Conformation–aggregation interplay in the simplest aliphatic ethers probed under high pressure

Sacharczuk, N.; Olejniczak, A.; Bujak, M.; Dziubek, K.F.; Katrusiak, A.; Podsiadło, M.

doi:10.1107/S2052252523009995

research papers

IUCrJ

Volume 11| Part 1| January 2024| Pages 57-61

ISSN: 2052-2525

https://doi.org/10.1107/S2052252523009995

CHEMISTRY | CRYSTENG

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Conformation–aggregation interplay in the simplest aliphatic ethers probed under high pressure

Natalia Sacharczuk,^a Anna Olejniczak,^a Maciej Bujak,^b Kamil Filip Dziubek,^c Andrzej Katrusiak ^a and Marcin Podsiadło ^a ^*

^aFaculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznanskiego 8, Poznan 61-614, Poland, ^bFaculty of Chemistry, University of Opole, Oleska 48, Opole 45-052, Poland, and ^cInstitut für Mineralogie und Kristallographie, Universität Wien, Josef-Holaubek-Platz 2, Wien A-1090, Austria
^*Correspondence e-mail: marcinp@amu.edu.pl

Edited by L. R. MacGillivray, University of Iowa, USA (Received 21 August 2023; accepted 16 November 2023)

The structures of the simplest symmetric primary ethers [(C_nH_2n+1)₂O, n = 1–3] determined under high pressure revealed their conformational preferences and intermolecular interactions. In three new polymorphs of diethyl ether (C₂H₅)₂O, high pressure promotes intermolecular CH⋯O contacts and enforces a conversion from the trans–trans conformer present in the α, β and γ phases to the trans–gauche conformer, which is higher in energy by 6.4 kJ mol⁻¹, in the δ phase. Two new polymorphs of dimethyl ether (CH₃)₂O display analogous transformations of the CH⋯O bonds. The crystal structure of di-n-propyl ether (C₃H₇)₂O, determined for the first time, is remarkably stable over the whole pressure range investigated from 1.70 up to 5.30 GPa.

Keywords: conformation–aggregation interplay; aliphatic ethers; in situ crystallization; high pressure.

CCDC references: 2282455; 2282456; 2282457; 2282458; 2282459; 2282460; 2282461; 2282462; 2282463; 2282464; 2282465; 2282466; 2282467; 2282468; 2282469; 2282470; 2282471; 2282472; 2282473; 2282474

1. Introduction

Pressure can drastically affect the association of molecules, i.e. one of the most essential properties of solvents (Boldyreva, 2008 ; Fabbiani & Pulham, 2006 ; Resnati et al., 2015 ). Ethoxyethane [diethyl ether, (C₂H₅)₂O, hereafter DEE] is a solvent commonly used in chemical practice and has also previously been applied as a general anaesthetic. Raman spectroscopy (Taga et al., 2006 ) was used to demonstrate that, in the gaseous and liquid states, the trans–trans (TT) conformer prevails over the trans–gauche conformers (TG⁺, TG⁻), which are less stable by ca 6.4 kJ mol⁻¹. For over a century, DEE has been known to freeze as stable and metastable polymorphs, melting at 157 and 150 K, respectively (Timmermans, 1911 ). The melting temperatures, 156.92 K for the stable form and 149.86 K for the metastable form, and the heats of fusion were precisely determined by Counsell et al. (1971 ). In the stable α phase, determined by André et al. (1972 ) in the space group P2₁2₁2₁ with Z = 8, the molecules assume the TT conformation. The crystal structure of the metastable form was not determined, but its vibrational spectra indicated that there are two independent molecules, both in the TT conformation (Durig & Church, 1981 ). The existence of the metastable modification and the tendency of DEE to vitrify were explained in terms of the fairly loose structure of the α phase, and hence the low value of stabilization energy compared with the amorphous state (André et al., 1972).

In the literature, there is much less information about the structure, interactions and properties of other aliphatic ethers. Dimethyl ether (DME) freezes at 93 K and its crystal structure was determined by Vojinović et al. (2004 ). The crystal structure of di-n-propyl ether (DPE) had not been determined. It was established that in the structure of tetrahydrofuran, a cyclic analogue of DEE, molecular aggregation is stabilized by CH⋯O interactions, which are strongly enhanced under high pressure (Dziubek et al., 2010 ; Chang et al., 2005 ). Such CH⋯O contacts are sterically hindered in the TT conformers, present in the structure of the α phase of DEE. Therefore, acyclic ethers such as DEE and higher ones are expected to change their TT conformations under high pressure. In the simplest ether DME, the molecular structure can be modified owing to the C—O—C angle and the methyl group rotations, whereas the intermolecular interactions can be changed by a rearrangements of molecules. Here, we describe the effect of high pressure on the crystal structure of DEE, and we also studied DME and DPE in order to obtain more general information about the role of molecular structure with respect to the interactions and aggregation for this class of compounds.

2. Experimental

DME (≥99.9%), DEE (≥99%) and DPE (≥99%), all purchased from Merck, were used as delivered. All three ethers were crystallized in situ in a modified Merrill–Bassett diamond-anvil cell (DAC) (Bassett, 2009 ). In each experiment, the DAC was equipped with a 0.3 mm-thick steel gasket with a hole 0.4 mm in diameter. At 295 K, DME, DEE and DPE froze at 2.95, 1.50 and 1.35 GPa, respectively, in the form of polycrystalline masses filling the volume of the DAC chamber. Single crystals were obtained under isochoric conditions (Fig. 1): the DAC containing the squeezed polycrystalline mass of the ether sample was heated with a hot-air gun until all but one grain melted. Then the DAC was slowly cooled to room temperature and the single crystal grew to eventually fill the whole chamber. The temperature inside the DAC was measured using an infrared thermometer. The pressure was calibrated by the ruby fluorescence method (Mao et al., 1986 ) before and after the X-ray diffraction measurements using a Photon Control spectrometer with an accuracy of 0.02 GPa. The experimental details and progress in growing the single crystals are shown in Figs. S1–S18 of the supporting information.

Figure 1
Single crystals grown in situ in the DAC. (a) β-DME at 3.90 GPa and 349 K, (b) γ-DME at 4.50 GPa and 359 K, (c) γ-DME at 5.60 GPa and 372 K, (d) β-DEE at 1.85 GPa and 327 K, (e) β-DEE at 2.45 GPa and 349 K, (f) γ-DEE at 2.65 GPa and 340 K, (g) δ-DEE at 2.80 GPa and 377 K, (h) δ-DEE at 3.45 GPa and 413 K, and (i) α-DPE at 2.10 GPa and 344 K.

The KUMA KM4-CCD diffractometer was used for the high-pressure X-ray diffraction studies. The DAC was centred by the gasket-shadow method (Budzianowski & Katrusiak, 2004 ). The CrysAlisPro suite was used for data collection, determination of the UB matrices and unit-cell parameters, and data reductions (Rigaku Oxford Diffraction, 2019 $[Rigaku Oxford Diffraction (2019). CrysAlisPro. Rigaku Oxford Diffraction, Yarnton, UK.]$ ). For all data, we accounted for the Lorentz, polarization and absorption effects. The programs SHELXT (Sheldrick, 2015a ) and SHELXL (Sheldrick, 2015b ) within the OLEX2 (Dolomanov et al., 2009 ) GUI were used to solve the structures by direct methods and refine the models by full-matrix least-squares on F². Anisotropic displacement parameters were applied for non-hydrogen atoms, but the isotropic thermal parameters were occasionally retained for atoms with unreasonable anisotropic factors or for lower-quality datasets. Hydrogen atoms were located from the molecular geometry, with the C—H distances equal to 0.97 Å (–CH₂–) or 0.96 Å (–CH₃) and their U_iso factors constrained to 1.2 or 1.5 times that of U_eq of the carriers. The crystal and experimental data are summarized in Table 1 and Tables S1–S4 of the supporting information.

Table 1
Selected crystal data of high-pressure phases of DME, DEE and DPE at 295 K (cf detailed data of all 20 determinations in Tables S1–S4)

	β DME	γ DME	β DEE	γ DEE	δ DEE	α DPE
P (GPa)	3.30 (2)	4.50 (2)	1.85 (2)	2.65 (2)	2.80 (2)	1.70 (2)
Space group	P2₁/c	P1	P2₁/c	I2/a	P1	P2₁/c
a (Å)	5.5541 (4)	4.3394 (12)	6.8268 (3)	7.7073 (12)	5.1196 (4)	9.416 (4)
b (Å)	6.6179 (11)	8.414 (2)	8.1428 (17)	4.0885 (4)	5.6659 (10)	4.1817 (3)
c (Å)	6.964 (3)	12.821 (6)	7.7731 (3)	13.233 (2)	7.2999 (4)	15.579 (7)
α (°)	90	90.55 (4)	90	90	97.275 (8)	90
β (°)	103.84 (2)	93.89 (6)	93.443 (4)	93.793 (16)	102.728 (6)	101.23 (5)
γ (°)	90	90.83 (2)	90	90	96.747 (10)	90
V (Å³)	248.56 (12)	467.0 (3)	431.32 (9)	416.07 (10)	202.56 (4)	601.7 (4)
Z, Z′	4, 1	8, 4	4, 1	4, 0.5	2, 1	4, 1
D_x (g cm⁻³)	1.231	1.311	1.141	1.183	1.215	1.128
R₁ [F² > 2σ(F²)]	0.0708	0.0554	0.0353	0.0371	0.0388	0.0455

A conformational analysis of the isolated DEE molecule in the gas phase was performed with the ab initio approach of the density functional theory (DFT) with the B3LYP/6–311++g(2d,2p) method using GAUSSIAN 16W (Frisch et al., 2016 ). The potential energy E_p map has been created as a function of the torsion angles C2—C1—O1—C3 and C4—C3—O1—C1 with a step of 30° (Dennington et al., 2016 ). The methyl hydrogen atoms (constraint AFIX 137) deviate by up to ca 8° in the H—C—C—O torsion angles for DEE compared with those obtained from the geometry optimization for the isolated molecule by GAUSSIAN 16W. The structure of DEE in the γ phase best agrees with the calculations, and the largest difference was observed for the δ phase.

3. Results and discussion

The lowest pressure for investigating the structure of the simplest primary ethers was chosen, about 0.3 GPa above their freezing pressure points, to ensure the stability of the single-crystal samples during the X-ray diffraction data collection experiments. The maximum pressure was the result of reaching the mechanical or thermal limitation of the DAC during the procedure to obtain the single crystals. The molecular volumes of the ethers studied as a function of pressure are plotted in Fig. 2.

Figure 2
Molecular volume (V/Z) of DME, DEE and DPE plotted as a function of pressure: solid high-pressure (circles, this work) and low-temperature [diamonds (André et al., 1972

; Vojinović et al., 2004

)] phases as well as liquid DEE [triangles (Bridgman, 1913

)]. Open circles indicate the V_m values estimated at the freezing-pressure points. The vertical dashed lines mark the solid–solid transition pressure points (this work). The ambient- and high-pressure points at 295 K are joined by dashed lines. The solid lines between points are guides for the eye only. The estimated standard deviations are smaller than the plotted symbols.

We have established that DEE freezes at 1.50 GPa when isothermally compressed at 295 K. Therefore, the single crystal was grown under isochoric conditions from the liquid in a DAC at 1.85 GPa (Fig. 1). The new β phase, built of TT conformers, is stable up to 2.65 GPa, when the γ phase, also built of the TT conformers, is formed. At even higher pressure, the DEE molecules adopt the TG conformation and the δ phase is formed, investigated between 2.80 and 4.90 GPa (Fig. 2). In the TG conformers, the reduced steric hindrance around the oxygen atom facilitates the formation of a larger number of CH⋯O contacts. When releasing pressure, the δ phase transforms to the β phase below 2.70 GPa.

In DME, the steric hindrance around the oxygen atom is smaller and the number of H⋯O contacts increases without conformational transformations. At 0.1 MPa and 93 K, DME crystallizes in the centrosymmetric α phase of the tetragonal space group P4₂/n (Vojinović et al., 2004). At 3.30 GPa and 295 K, DME forms the centrosymmetric β phase in the space group P2₁/c, and then, with increasing pressure, to 4.40 GPa, it transforms to the γ phase of the space-group symmetry P1 (Fig. 2). In DPE, the conformation is important for the molecular aggregation. The crystal structure of DPE at 0.1 MPa and low temperature has not yet been reported. At high pressure and 295 K, DPE crystallizes in the centrosymmetric space group P2₁/c. It was found that this phase (α phase) is stable from 1.70 to 5.30 GPa at least.

Our quantum-mechanical computations performed with Gaussian (Frisch et al., 2019) show that the idealized TT conformer (τ₁ = τ₂ = 180°) is 8.72 kJ mol⁻¹ more stable than the idealized TG conformers (τ₁ = 180°, τ₂ = ±60°). This E_p difference is somewhat larger than that previously determined by the B3LYP/6–311+G** method (Taga et al., 2006). Owing to the crystal-field effects, the E_p difference calculated by us between the TT and TG conformers present in the β (τ₁ = 172.47°, τ₂ = 179.45°) and δ (τ₁ = 177.70°, τ₂ = −77.55°) DEE phases is 6.43 kJ mol⁻¹ and between the γ (τ₁ = τ₂ = 168.53°) and δ phases it is 5.12 kJ mol⁻¹. Therefore, the volume reductions of 2.54 and 2.74 Å³ for the β–δ and γ–δ phase transitions, respectively, at 2.70 GPa, associated with the work component of the Gibbs free energies equal to 4.13 and 4.45 kJ mol⁻¹, is consistent with the energy gain of the system for a transition involving conformational changes. When assuming the initial density of the liquid at 293 K (0.7134 g cm⁻³), the work performed on the sample to 2.70 GPa amounts to about 59 kJ mol⁻¹, which is commensurate with the energy of the E_p barrier equal to about 11.3 kJ mol⁻¹ in the E_p map in Fig. 3.

Figure 3
Potential energy (E_p) map as a function of the torsion angles C4—C3—O1—C1 (τ₁) and C2—C1—O1—C3 (τ₂) for the isolated DEE molecule, with E_p = 0 for the TT conformer. The conformers present in the crystalline state for β DEE (square), γ DEE (circle) and δ DEE (triangle) are indicated in yellow.

According to intermolecular distances, the cohesion forces in DME, DEE and DPE crystals are dominated by CH⋯O bonds (Figs. 4, 5 and S19–S26). The approaching hydrogen atoms are roughly (within about 30°) grouped about the directions of the lone-electron pairs of oxygen atoms. For the β and γ phases of DEE, only the methyl hydrogen atoms participate in the hydrogen bonds, whereas in the α and δ phases of DEE, there are both methyl and methylene hydrogen donors. The CH⋯O bonds aggregate the molecules into different and characteristic architectures of rings (α DME), chains (α DEE, γ DEE, α DPE), ribbons (δ DEE), sheets (β DME, β DEE) and a three-dimensional pattern (γ DME). In DME, the number of CH⋯O contacts that are shorter than the sum of the van der Waals radii (Bondi, 1964 ) increases with pressure, hence the three-dimensional aggregation patterns are promoted. This relation does not apply for the DEE polymorphs.

Figure 4
Patterns of the CH⋯O bonds (dotted lines) in the structures of the DEE polymorphs (a) α, (b) β, (c) γ and (d) δ. The symmetry-independent structural units (0.5, 1 and 2 molecules) are indicated in green.

Figure 5
Evolution of the intermolecular distances for the different phases of DME (red), DEE (green) and DPE (blue) with pressure. The two shortest distances for the two types of interactions are presented: full shapes represent H⋯H and empty shapes represent H⋯O distances. The black horizontal lines show the sum of the van der Waals radii (Bondi, 1964

) of hydrogen and oxygen (2.72 Å) and of hydrogen and hydrogen (2.4 Å); the vertical dashed lines mark the limits of the pressure stability ranges of individual crystal phases. The estimated standard deviations are smaller than the plotted symbols.

The four phases of DEE clearly reveal the systematic transformation of patterns of intermolecular interactions at high pressure. The initial compression of H⋯H contacts and the small compression of H⋯O contacts between the α, β and γ phases are reversed in the δ phase, where the conformational change increases the access to the oxygen atom (Fig. S20). It promotes the formation of CH⋯O contacts at high pressure. The CH⋯O bonded molecules in the β, γ and δ phases are attracted with intermolecular interaction energies of about −12.0, −11.4 and −9.9 kJ mol⁻¹, respectively compared with about −4 kJ mol⁻¹ for the molecules with H⋯H contacts only (Gavezzotti, 1994 ; Gavezzotti & Filippini, 1994 ).

4. Conclusions

The interplay of preferences for the CH⋯O bond and low-E_p conformation govern the aggregation in solid phases of simple aliphatic ethers. We have found six new polymorphs: the β and γ phases of DME; the β, γ and δ phases of DEE; and the α phase of DPE. The conformational conversions can regulate access to the oxygen atom, and in this way can increase the number of stronger CH⋯O bonds and reduce the number of weak H⋯H contacts. Consequently, we observed a higher compressibility of CH⋯O distances in δ DEE compared with the compressibility of H⋯H within this phase. Though high pressure has proved to be a useful tool for inducing conformational changes in simple molecular compounds, it also shows the energetic landscape of thermally activated conformational conversions in liquids. Cohesion forces, molecular conformations and aggregation in the crystal structures of simple ethers still require further studies by theoretical methods. There are also asymmetric ethers, which can provide additional information about the structure–property relations of ethers, however their applications and availability are limited.

Supporting information

CCDC references: 2282455; 2282456; 2282457; 2282458; 2282459; 2282460; 2282461; 2282462; 2282463; 2282464; 2282465; 2282466; 2282467; 2282468; 2282469; 2282470; 2282471; 2282472; 2282473; 2282474

Crystal structure: contains datablocks global, dimethyl_ether_phase_beta_3_30GPa, dimethyl_ether_phase_beta_3_90GPa, dimethyl_ether_phase_beta_4_30GPa, dimethyl_ether_phase_gamma_4_50GPa, dimethyl_ether_phase_gamma_5_60GPa, dimethyl_ether_phase_gamma_7_30GPa, diethyl_ether_phase_beta_1_85GPa, diethyl_ether_phase_beta_2_15GPa, diethyl_ether_phase_beta_2_45GPa, diethyl_ether_phase_beta_2_65GPa, diethyl_ether_phase_gamma_2_65GPa, diethyl_ether_phase_delta_2_80GPa, diethyl_ether_phase_delta_3_45GPa, diethyl_ether_phase_delta_3_70GPa, diethyl_ether_phase_delta_4_90GPa, dipropyl_ether_phase_alpha_1_70GPa, dipropyl_ether_phase_alpha_2_10GPa, dipropyl_ether_phase_alpha_2_80GPa, dipropyl_ether_phase_alpha_3_85GPa, dipropyl_ether_phase_alpha_5_30GPa. DOI: https://doi.org/10.1107/S2052252523009995/lq5055sup1.cif

Supporting figures and tables. DOI: https://doi.org/10.1107/S2052252523009995/lq5055sup2.pdf

Computing details top

dimethyl ether (dimethyl_ether_phase_beta_3_30GPa) top

Crystal data top

C₂H₆O	F(000) = 104
M_r = 46.07	D_x = 1.231 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.5541 (4) Å	Cell parameters from 653 reflections
b = 6.6179 (11) Å	θ = 5.2–25.9°
c = 6.964 (3) Å	µ = 0.10 mm⁻¹
β = 103.835 (19)°	T = 295 K
V = 248.56 (12) Å³	Disc, colourless
Z = 4	0.30 × 0.29 × 0.25 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	132 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.065
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 25.9°, θ_min = 5.2°
T_min = 0.008, T_max = 1.000	h = −6→6
850 measured reflections	k = −7→7
147 independent reflections	l = −4→4

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.071	w = 1/[σ²(F_o²) + (0.1102P)² + 0.2366P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.193	(Δ/σ)_max < 0.001
S = 1.20	Δρ_max = 0.19 e Å⁻³
147 reflections	Δρ_min = −0.17 e Å⁻³
31 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 1.1 (7)
Primary atom site location: dual

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.7278 (6)	0.3356 (6)	0.1855 (8)	0.043 (3)
C1	0.9093 (9)	0.1818 (8)	0.2325 (13)	0.047 (4)
H11	0.917067	0.110106	0.114280	0.071*
H12	0.866040	0.089681	0.325303	0.071*
H13	1.067867	0.241268	0.289666	0.071*
C2	0.4941 (10)	0.2536 (8)	0.0858 (17)	0.050 (5)
H22	0.506093	0.198930	−0.039215	0.076*
H23	0.370885	0.358270	0.064545	0.076*
H21	0.448008	0.148453	0.164991	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.035 (2)	0.035 (4)	0.057 (10)	−0.0002 (13)	0.003 (3)	−0.0003 (16)
C1	0.039 (3)	0.031 (6)	0.071 (15)	0.006 (2)	0.011 (4)	0.004 (3)
C2	0.041 (3)	0.030 (6)	0.075 (17)	0.002 (2)	0.003 (4)	−0.001 (2)

Geometric parameters (Å, º) top

O1—C1	1.415 (6)	C1—H13	0.9600
O1—C2	1.425 (7)	C2—H22	0.9600
C1—H11	0.9600	C2—H23	0.9600
C1—H12	0.9600	C2—H21	0.9600

C1—O1—C2	110.7 (4)	O1—C2—H22	109.5
O1—C1—H11	109.5	O1—C2—H23	109.5
O1—C1—H12	109.5	O1—C2—H21	109.5
O1—C1—H13	109.5	H22—C2—H23	109.5
H11—C1—H12	109.5	H22—C2—H21	109.5
H11—C1—H13	109.5	H23—C2—H21	109.5
H12—C1—H13	109.5

dimethyl ether (dimethyl_ether_phase_beta_3_90GPa) top

Crystal data top

C₂H₆O	F(000) = 104
M_r = 46.07	D_x = 1.267 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.5277 (4) Å	Cell parameters from 488 reflections
b = 6.527 (10) Å	θ = 7.6–25.7°
c = 6.8941 (5) Å	µ = 0.10 mm⁻¹
β = 103.869 (6)°	T = 295 K
V = 241.5 (4) Å³	Disc, colourless
Z = 4	0.33 × 0.33 × 0.24 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	99 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.031
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 25.7°, θ_min = 7.6°
T_min = 0.082, T_max = 1.000	h = −6→6
634 measured reflections	k = −1→1
107 independent reflections	l = −8→8

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.069	H-atom parameters constrained
wR(F²) = 0.172	w = 1/[σ²(F_o²) + (0.1005P)² + 0.168P] where P = (F_o² + 2F_c²)/3
S = 1.19	(Δ/σ)_max < 0.001
107 reflections	Δρ_max = 0.17 e Å⁻³
15 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.7270 (4)	0.3359 (18)	0.1847 (3)	0.0310 (15)*
C1	0.9078 (7)	0.178 (2)	0.2323 (6)	0.0309 (16)*
H11	0.910795	0.101871	0.113639	0.046*
H12	0.865988	0.087541	0.329319	0.046*
H13	1.068887	0.236969	0.286165	0.046*
C2	0.4939 (7)	0.252 (2)	0.0882 (6)	0.0278 (16)*
H22	0.504422	0.193813	−0.037492	0.042*
H23	0.369749	0.357747	0.065583	0.042*
H21	0.449139	0.146997	0.170723	0.042*

Geometric parameters (Å, º) top

O1—C1	1.419 (16)	C1—H13	0.9600
O1—C2	1.411 (9)	C2—H22	0.9600
C1—H11	0.9600	C2—H23	0.9600
C1—H12	0.9600	C2—H21	0.9600

C2—O1—C1	109.8 (12)	O1—C2—H22	109.5
O1—C1—H11	109.5	O1—C2—H23	109.5
O1—C1—H12	109.5	O1—C2—H21	109.5
O1—C1—H13	109.5	H22—C2—H23	109.5
H11—C1—H12	109.5	H22—C2—H21	109.5
H11—C1—H13	109.5	H23—C2—H21	109.5
H12—C1—H13	109.5

dimethyl ether (dimethyl_ether_phase_beta_4_30GPa) top

Crystal data top

C₂H₆O	F(000) = 104
M_r = 46.07	D_x = 1.288 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.5073 (4) Å	Cell parameters from 560 reflections
b = 6.493 (5) Å	θ = 6.1–25.5°
c = 6.8431 (8) Å	µ = 0.10 mm⁻¹
β = 103.848 (8)°	T = 295 K
V = 237.58 (19) Å³	Disc, colourless
Z = 4	0.38 × 0.38 × 0.23 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	118 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.030
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.1°, θ_min = 6.1°
T_min = 0.031, T_max = 1.000	h = −6→6
721 measured reflections	k = −3→3
129 independent reflections	l = −7→7

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.053	w = 1/[σ²(F_o²) + (0.1045P)² + 0.0355P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.140	(Δ/σ)_max < 0.001
S = 1.18	Δρ_max = 0.14 e Å⁻³
129 reflections	Δρ_min = −0.11 e Å⁻³
31 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 1.1 (3)
Primary atom site location: structure-invariant direct methods

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.7272 (3)	0.3391 (10)	0.1848 (3)	0.024 (5)
C1	0.9077 (5)	0.1760 (14)	0.2313 (5)	0.031 (5)
H11	0.908494	0.100137	0.111070	0.046*
H12	0.864582	0.085386	0.328685	0.046*
H13	1.070601	0.233258	0.285415	0.046*
C2	0.4927 (5)	0.2529 (10)	0.0854 (5)	0.020 (6)
H22	0.508326	0.185891	−0.036109	0.031*
H23	0.369889	0.360298	0.052970	0.031*
H21	0.441758	0.154211	0.172140	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0257 (15)	0.008 (14)	0.038 (2)	0.0004 (16)	0.0069 (10)	0.0007 (10)
C1	0.026 (2)	0.031 (18)	0.037 (3)	0.006 (2)	0.0104 (14)	0.006 (2)
C2	0.027 (2)	0.008 (18)	0.026 (3)	0.003 (2)	0.0058 (12)	−0.0012 (16)

Geometric parameters (Å, º) top

O1—C1	1.435 (10)	C1—H13	0.9600
O1—C2	1.422 (5)	C2—H22	0.9600
C1—H11	0.9600	C2—H23	0.9600
C1—H12	0.9600	C2—H21	0.9600

C2—O1—C1	108.5 (6)	O1—C2—H22	109.5
O1—C1—H11	109.5	O1—C2—H23	109.5
O1—C1—H12	109.5	O1—C2—H21	109.5
O1—C1—H13	109.5	H22—C2—H23	109.5
H11—C1—H12	109.5	H22—C2—H21	109.5
H11—C1—H13	109.5	H23—C2—H21	109.5
H12—C1—H13	109.5

dimethyl ether (dimethyl_ether_phase_gamma_4_50GPa) top

Crystal data top

C₂H₆O	Z = 8
M_r = 46.07	F(000) = 208
Triclinic, P1	D_x = 1.311 Mg m⁻³
a = 4.3394 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.414 (2) Å	Cell parameters from 1331 reflections
c = 12.821 (6) Å	θ = 4.7–25.7°
α = 90.55 (4)°	µ = 0.10 mm⁻¹
β = 93.89 (6)°	T = 295 K
γ = 90.83 (2)°	Disc, colourless
V = 467.0 (3) Å³	0.34 × 0.32 × 0.22 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	481 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.034
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.2°, θ_min = 4.9°
T_min = 0.508, T_max = 1.000	h = −5→5
2659 measured reflections	k = −10→10
556 independent reflections	l = −5→6

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.155	w = 1/[σ²(F_o²) + (0.0885P)² + 0.3224P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
556 reflections	Δρ_max = 0.15 e Å⁻³
117 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.2353 (9)	0.8266 (5)	−0.0051 (11)	0.062 (9)
C1	−0.0287 (9)	0.7298 (5)	−0.0134 (10)	0.044 (8)
H13	−0.043845	0.676938	−0.080241	0.065*
H11	−0.207859	0.793660	−0.006548	0.065*
H12	−0.016169	0.652057	0.041042	0.065*
C2	0.2688 (14)	0.9025 (8)	0.0925 (17)	0.065 (14)
H23	0.450244	0.969563	0.095980	0.098*
H21	0.288592	0.824268	0.146477	0.098*
H22	0.090664	0.965959	0.102216	0.098*
O2	0.8338 (5)	0.5159 (3)	0.1951 (6)	0.053 (7)
C3	0.5369 (8)	0.4961 (6)	0.1440 (10)	0.050 (9)
H33	0.538992	0.409885	0.094456	0.075*
H31	0.480134	0.592040	0.108156	0.075*
H32	0.389909	0.472796	0.194624	0.075*
C4	0.8463 (10)	0.6574 (5)	0.2578 (12)	0.061 (11)
H42	0.788825	0.746478	0.214836	0.092*
H43	1.052462	0.673782	0.288411	0.092*
H41	0.705954	0.647051	0.312144	0.092*
O3	0.7072 (5)	0.0121 (3)	0.2903 (6)	0.043 (6)
C5	0.4487 (9)	−0.0198 (6)	0.3482 (11)	0.068 (11)
H51	0.262856	−0.006975	0.304254	0.103*
H52	0.449390	0.052624	0.406528	0.103*
H53	0.457795	−0.126945	0.373262	0.103*
C6	0.6947 (12)	0.1668 (6)	0.2465 (11)	0.056 (11)
H62	0.513907	0.174374	0.199385	0.083*
H63	0.875650	0.185774	0.208993	0.083*
H61	0.686102	0.244659	0.301374	0.083*
O4	0.2707 (5)	0.3082 (3)	0.4954 (7)	0.042 (7)
C7	0.0047 (8)	0.2104 (5)	0.5040 (10)	0.040 (8)
H73	0.034023	0.144502	0.564476	0.060*
H71	−0.027707	0.144552	0.442571	0.060*
H72	−0.172111	0.276006	0.510812	0.060*
C8	0.2335 (9)	0.4051 (5)	0.4043 (10)	0.050 (10)
H81	0.047544	0.465073	0.406699	0.076*
H82	0.220763	0.338591	0.342861	0.076*
H83	0.407307	0.476676	0.402276	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0247 (17)	0.034 (2)	0.13 (3)	−0.0098 (18)	−0.004 (4)	0.003 (7)
C1	0.0222 (18)	0.030 (2)	0.08 (3)	−0.0062 (15)	−0.001 (4)	0.002 (6)
C2	0.028 (3)	0.033 (3)	0.13 (4)	0.000 (3)	0.004 (7)	0.029 (10)
O2	0.0233 (14)	0.0224 (16)	0.11 (2)	0.0011 (10)	−0.014 (3)	0.006 (5)
C3	0.0206 (18)	0.030 (2)	0.10 (3)	−0.0018 (14)	−0.006 (4)	0.007 (6)
C4	0.040 (2)	0.030 (3)	0.11 (3)	−0.0015 (18)	−0.002 (6)	0.004 (8)
O3	0.0262 (14)	0.0219 (15)	0.080 (18)	−0.0001 (10)	0.005 (3)	0.010 (4)
C5	0.0226 (19)	0.032 (2)	0.15 (3)	−0.0008 (16)	−0.005 (5)	0.016 (8)
C6	0.047 (3)	0.030 (3)	0.09 (3)	−0.003 (2)	−0.009 (5)	0.024 (8)
O4	0.0239 (14)	0.0280 (17)	0.07 (2)	−0.0059 (11)	0.001 (3)	0.014 (5)
C7	0.0251 (19)	0.025 (2)	0.07 (3)	−0.0064 (15)	−0.009 (4)	0.013 (6)
C8	0.038 (2)	0.027 (2)	0.08 (3)	−0.0053 (17)	−0.008 (5)	0.015 (7)

Geometric parameters (Å, º) top

O1—C1	1.393 (5)	O3—C5	1.411 (10)
O1—C2	1.40 (3)	O3—C6	1.423 (6)
C1—H13	0.9600	C5—H51	0.9600
C1—H11	0.9600	C5—H52	0.9600
C1—H12	0.9600	C5—H53	0.9600
C2—H23	0.9600	C6—H62	0.9600
C2—H21	0.9600	C6—H63	0.9600
C2—H22	0.9600	C6—H61	0.9600
O2—C3	1.412 (7)	O4—C7	1.419 (4)
O2—C4	1.428 (12)	O4—C8	1.432 (11)
C3—H33	0.9600	C7—H73	0.9600
C3—H31	0.9600	C7—H71	0.9600
C3—H32	0.9600	C7—H72	0.9600
C4—H42	0.9600	C8—H81	0.9600
C4—H43	0.9600	C8—H82	0.9600
C4—H41	0.9600	C8—H83	0.9600

C1—O1—C2	111.0 (13)	C5—O3—C6	111.5 (5)
O1—C1—H13	109.5	O3—C5—H51	109.5
O1—C1—H11	109.5	O3—C5—H52	109.5
O1—C1—H12	109.5	O3—C5—H53	109.5
H13—C1—H11	109.5	H51—C5—H52	109.5
H13—C1—H12	109.5	H51—C5—H53	109.5
H11—C1—H12	109.5	H52—C5—H53	109.5
O1—C2—H23	109.5	O3—C6—H62	109.5
O1—C2—H21	109.5	O3—C6—H63	109.5
O1—C2—H22	109.5	O3—C6—H61	109.5
H23—C2—H21	109.5	H62—C6—H63	109.5
H23—C2—H22	109.5	H62—C6—H61	109.5
H21—C2—H22	109.5	H63—C6—H61	109.5
C3—O2—C4	110.1 (4)	C7—O4—C8	110.2 (5)
O2—C3—H33	109.5	O4—C7—H73	109.5
O2—C3—H31	109.5	O4—C7—H71	109.5
O2—C3—H32	109.5	O4—C7—H72	109.5
H33—C3—H31	109.5	H73—C7—H71	109.5
H33—C3—H32	109.5	H73—C7—H72	109.5
H31—C3—H32	109.5	H71—C7—H72	109.5
O2—C4—H42	109.5	O4—C8—H81	109.5
O2—C4—H43	109.5	O4—C8—H82	109.5
O2—C4—H41	109.5	O4—C8—H83	109.5
H42—C4—H43	109.5	H81—C8—H82	109.5
H42—C4—H41	109.5	H81—C8—H83	109.5
H43—C4—H41	109.5	H82—C8—H83	109.5

dimethyl ether (dimethyl_ether_phase_gamma_5_60GPa) top

Crystal data top

C₂H₆O	Z = 8
M_r = 46.07	F(000) = 208
Triclinic, P1	D_x = 1.346 Mg m⁻³
a = 4.2888 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.3045 (18) Å	Cell parameters from 1388 reflections
c = 12.7912 (13) Å	θ = 4.9–25.6°
α = 90.249 (12)°	µ = 0.10 mm⁻¹
β = 93.92 (2)°	T = 295 K
γ = 90.14 (3)°	Disc, colourless
V = 454.5 (2) Å³	0.37 × 0.35 × 0.21 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	486 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.031
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.3°, θ_min = 4.8°
T_min = 0.788, T_max = 1.000	h = −2→2
2631 measured reflections	k = −10→9
559 independent reflections	l = −15→15

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.117	w = 1/[σ²(F_o²) + (0.0699P)² + 2.7136P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.260	(Δ/σ)_max < 0.001
S = 1.14	Δρ_max = 0.23 e Å⁻³
559 reflections	Δρ_min = −0.19 e Å⁻³
58 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.12 (5)
Primary atom site location: structure-invariant direct methods

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.242 (3)	0.8248 (9)	−0.0022 (4)	0.0355 (18)*
C1	−0.044 (6)	0.7338 (16)	−0.0090 (7)	0.044 (3)*
H13	−0.090194	0.698647	−0.079991	0.066*
H11	−0.211365	0.800321	0.012419	0.066*
H12	−0.022179	0.641798	0.036022	0.066*
C2	0.253 (5)	0.9101 (16)	0.0956 (7)	0.035 (2)*
H23	0.401532	0.996640	0.094303	0.053*
H21	0.315057	0.837755	0.151533	0.053*
H22	0.050127	0.952873	0.106470	0.053*
O2	0.839 (4)	0.5131 (9)	0.1969 (4)	0.0355 (19)*
C3	0.583 (6)	0.4931 (16)	0.1409 (8)	0.044 (3)*
H33	0.597037	0.397973	0.098645	0.066*
H31	0.545875	0.584812	0.096426	0.066*
H32	0.413976	0.481568	0.185831	0.066*
C4	0.826 (5)	0.6641 (14)	0.2545 (7)	0.033 (2)*
H42	0.736833	0.746038	0.208976	0.050*
H43	1.033412	0.695640	0.279589	0.050*
H41	0.699224	0.650412	0.312783	0.050*
O3	0.711 (4)	0.0119 (9)	0.2914 (4)	0.039 (2)*
C5	0.423 (6)	−0.0119 (17)	0.3472 (8)	0.048 (3)*
H51	0.261497	0.056876	0.317384	0.072*
H52	0.464730	0.014100	0.419992	0.072*
H53	0.357516	−0.122233	0.340226	0.072*
C6	0.678 (6)	0.1662 (14)	0.2479 (7)	0.038 (2)*
H62	0.509187	0.165541	0.194479	0.057*
H63	0.867947	0.196660	0.217750	0.057*
H61	0.632919	0.242027	0.301708	0.057*
O4	0.274 (4)	0.3116 (10)	0.4989 (4)	0.0381 (19)*
C7	−0.032 (6)	0.2154 (16)	0.5048 (7)	0.038 (3)*
H73	−0.012530	0.143250	0.563344	0.058*
H71	−0.072304	0.154542	0.441314	0.058*
H72	−0.201529	0.288377	0.513443	0.058*
C8	0.222 (6)	0.4120 (15)	0.4061 (6)	0.033 (2)*
H81	0.111214	0.507395	0.423767	0.050*
H82	0.101913	0.353007	0.352648	0.050*
H83	0.420049	0.441628	0.380646	0.050*

Geometric parameters (Å, º) top

O1—C1	1.44 (2)	O3—C5	1.48 (3)
O1—C2	1.433 (11)	O3—C6	1.403 (15)
C1—H13	0.9600	C5—H51	0.9600
C1—H11	0.9600	C5—H52	0.9600
C1—H12	0.9600	C5—H53	0.9600
C2—H23	0.9600	C6—H62	0.9600
C2—H21	0.9600	C6—H63	0.9600
C2—H22	0.9600	C6—H61	0.9600
O2—C3	1.28 (3)	O4—C7	1.543 (19)
O2—C4	1.455 (13)	O4—C8	1.459 (13)
C3—H33	0.9600	C7—H73	0.9600
C3—H31	0.9600	C7—H71	0.9600
C3—H32	0.9600	C7—H72	0.9600
C4—H42	0.9600	C8—H81	0.9600
C4—H43	0.9600	C8—H82	0.9600
C4—H41	0.9600	C8—H83	0.9600

C2—O1—C1	106.6 (11)	C6—O3—C5	104.3 (15)
O1—C1—H13	109.5	O3—C5—H51	109.5
O1—C1—H11	109.5	O3—C5—H52	109.5
O1—C1—H12	109.5	O3—C5—H53	109.5
H13—C1—H11	109.5	H51—C5—H52	109.5
H13—C1—H12	109.5	H51—C5—H53	109.5
H11—C1—H12	109.5	H52—C5—H53	109.5
O1—C2—H23	109.5	O3—C6—H62	109.5
O1—C2—H21	109.5	O3—C6—H63	109.5
O1—C2—H22	109.5	O3—C6—H61	109.5
H23—C2—H21	109.5	H62—C6—H63	109.5
H23—C2—H22	109.5	H62—C6—H61	109.5
H21—C2—H22	109.5	H63—C6—H61	109.5
C3—O2—C4	109.2 (16)	C8—O4—C7	104.7 (11)
O2—C3—H33	109.5	O4—C7—H73	109.5
O2—C3—H31	109.5	O4—C7—H71	109.5
O2—C3—H32	109.5	O4—C7—H72	109.5
H33—C3—H31	109.5	H73—C7—H71	109.5
H33—C3—H32	109.5	H73—C7—H72	109.5
H31—C3—H32	109.5	H71—C7—H72	109.5
O2—C4—H42	109.5	O4—C8—H81	109.5
O2—C4—H43	109.5	O4—C8—H82	109.5
O2—C4—H41	109.5	O4—C8—H83	109.5
H42—C4—H43	109.5	H81—C8—H82	109.5
H42—C4—H41	109.5	H81—C8—H83	109.5
H43—C4—H41	109.5	H82—C8—H83	109.5

dimethyl ether (dimethyl_ether_phase_gamma_7_30GPa) top

Crystal data top

C₂H₆O	Z = 8
M_r = 46.07	F(000) = 208
Triclinic, P1	D_x = 1.396 Mg m⁻³
a = 4.250 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.198 (3) Å	Cell parameters from 842 reflections
c = 12.6105 (19) Å	θ = 5.0–23.5°
α = 90.641 (19)°	µ = 0.11 mm⁻¹
β = 93.97 (3)°	T = 295 K
γ = 90.04 (5)°	Disc, colourless
V = 438.3 (4) Å³	0.40 × 0.38 × 0.20 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	389 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.042
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.1°, θ_min = 4.9°
T_min = 0.768, T_max = 1.000	h = −2→2
2349 measured reflections	k = −9→9
523 independent reflections	l = −15→15

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.079	w = 1/[σ²(F_o²) + (0.0557P)² + 1.6787P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.187	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.16 e Å⁻³
523 reflections	Δρ_min = −0.14 e Å⁻³
118 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.15 (4)
Primary atom site location: structure-invariant direct methods

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.240 (3)	0.8292 (9)	−0.0037 (4)	0.082 (12)
C1	−0.041 (5)	0.7358 (14)	−0.0105 (6)	0.048 (16)
H13	−0.142119	0.743904	−0.080735	0.073*
H11	−0.180702	0.776448	0.040411	0.073*
H12	0.008136	0.623754	0.004302	0.073*
C2	0.250 (5)	0.9124 (13)	0.0985 (6)	0.038 (14)
H23	0.413437	0.993563	0.101686	0.057*
H21	0.292871	0.834845	0.154095	0.057*
H22	0.050583	0.963852	0.107354	0.057*
O2	0.845 (3)	0.5126 (8)	0.1935 (4)	0.034 (10)
C3	0.552 (5)	0.5002 (13)	0.1409 (7)	0.037 (14)
H33	0.542484	0.403031	0.097564	0.056*
H31	0.515165	0.593709	0.096605	0.056*
H32	0.394248	0.495181	0.191592	0.056*
C4	0.863 (5)	0.6591 (12)	0.2548 (7)	0.075 (16)
H42	0.783470	0.748082	0.211966	0.112*
H43	1.078333	0.680152	0.278883	0.112*
H41	0.738439	0.648119	0.315095	0.112*
O3	0.714 (4)	0.0122 (9)	0.2895 (4)	0.085 (11)
C5	0.429 (6)	−0.0141 (15)	0.3470 (7)	0.066 (17)
H51	0.245633	0.012962	0.301779	0.099*
H52	0.437070	0.053987	0.409528	0.099*
H53	0.417646	−0.126455	0.367076	0.099*
C6	0.680 (5)	0.1709 (12)	0.2492 (8)	0.063 (16)
H62	0.510643	0.172508	0.194618	0.094*
H63	0.872158	0.203780	0.219885	0.094*
H61	0.632894	0.244860	0.305507	0.094*
O4	0.261 (3)	0.3117 (8)	0.4976 (4)	0.042 (11)
C7	−0.009 (5)	0.2107 (14)	0.5049 (6)	0.058 (17)
H73	0.005406	0.156050	0.571974	0.088*
H71	−0.017860	0.131259	0.448232	0.088*
H72	−0.195690	0.276561	0.499377	0.088*
C8	0.234 (6)	0.4113 (12)	0.4053 (6)	0.059 (16)
H81	0.067885	0.489404	0.412051	0.088*
H82	0.185615	0.343922	0.343505	0.088*
H83	0.429215	0.467453	0.398230	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.15 (3)	0.046 (6)	0.049 (3)	−0.043 (15)	−0.012 (6)	0.005 (3)
C1	0.05 (4)	0.044 (9)	0.048 (5)	−0.02 (2)	0.009 (8)	0.000 (5)
C2	0.03 (4)	0.030 (8)	0.056 (5)	0.009 (17)	−0.004 (9)	−0.004 (5)
O2	0.03 (3)	0.021 (5)	0.048 (3)	0.006 (11)	0.001 (6)	−0.005 (3)
C3	0.03 (4)	0.037 (8)	0.044 (4)	−0.005 (17)	0.014 (9)	−0.003 (4)
C4	0.13 (4)	0.029 (7)	0.057 (5)	−0.024 (18)	−0.019 (9)	0.004 (5)
O3	0.16 (3)	0.044 (6)	0.050 (3)	−0.045 (13)	0.002 (6)	0.008 (3)
C5	0.09 (5)	0.050 (9)	0.061 (5)	−0.01 (2)	0.001 (11)	0.007 (6)
C6	0.11 (4)	0.029 (7)	0.054 (5)	−0.002 (18)	0.000 (9)	−0.005 (5)
O4	0.03 (3)	0.042 (6)	0.051 (3)	−0.010 (13)	0.005 (6)	0.004 (3)
C7	0.09 (5)	0.045 (9)	0.041 (4)	−0.02 (2)	0.019 (9)	−0.005 (4)
C8	0.10 (4)	0.022 (7)	0.052 (5)	0.007 (18)	0.004 (9)	−0.002 (4)

Geometric parameters (Å, º) top

O1—C1	1.416 (16)	O3—C5	1.47 (2)
O1—C2	1.449 (11)	O3—C6	1.406 (12)
C1—H13	0.9600	C5—H51	0.9600
C1—H11	0.9600	C5—H52	0.9600
C1—H12	0.9600	C5—H53	0.9600
C2—H23	0.9600	C6—H62	0.9600
C2—H21	0.9600	C6—H63	0.9600
C2—H22	0.9600	C6—H61	0.9600
O2—C3	1.37 (2)	O4—C7	1.421 (15)
O2—C4	1.420 (11)	O4—C8	1.427 (9)
C3—H33	0.9600	C7—H73	0.9600
C3—H31	0.9600	C7—H71	0.9600
C3—H32	0.9600	C7—H72	0.9600
C4—H42	0.9600	C8—H81	0.9600
C4—H43	0.9600	C8—H82	0.9600
C4—H41	0.9600	C8—H83	0.9600

C1—O1—C2	106.0 (11)	C6—O3—C5	104.5 (14)
O1—C1—H13	109.5	O3—C5—H51	109.5
O1—C1—H11	109.5	O3—C5—H52	109.5
O1—C1—H12	109.5	O3—C5—H53	109.5
H13—C1—H11	109.5	H51—C5—H52	109.5
H13—C1—H12	109.5	H51—C5—H53	109.5
H11—C1—H12	109.5	H52—C5—H53	109.5
O1—C2—H23	109.5	O3—C6—H62	109.5
O1—C2—H21	109.5	O3—C6—H63	109.5
O1—C2—H22	109.5	O3—C6—H61	109.5
H23—C2—H21	109.5	H62—C6—H63	109.5
H23—C2—H22	109.5	H62—C6—H61	109.5
H21—C2—H22	109.5	H63—C6—H61	109.5
C3—O2—C4	109.5 (14)	C7—O4—C8	111.8 (10)
O2—C3—H33	109.5	O4—C7—H73	109.5
O2—C3—H31	109.5	O4—C7—H71	109.5
O2—C3—H32	109.5	O4—C7—H72	109.5
H33—C3—H31	109.5	H73—C7—H71	109.5
H33—C3—H32	109.5	H73—C7—H72	109.5
H31—C3—H32	109.5	H71—C7—H72	109.5
O2—C4—H42	109.5	O4—C8—H81	109.5
O2—C4—H43	109.5	O4—C8—H82	109.5
O2—C4—H41	109.5	O4—C8—H83	109.5
H42—C4—H43	109.5	H81—C8—H82	109.5
H42—C4—H41	109.5	H81—C8—H83	109.5
H43—C4—H41	109.5	H82—C8—H83	109.5

diethyl ether (diethyl_ether_phase_beta_1_85GPa) top

Crystal data top

C₄H₁₀O	F(000) = 168
M_r = 74.12	D_x = 1.141 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.8268 (3) Å	Cell parameters from 1485 reflections
b = 8.1428 (17) Å	θ = 4.6–25.7°
c = 7.7731 (3) Å	µ = 0.08 mm⁻¹
β = 93.443 (4)°	T = 295 K
V = 431.32 (9) Å³	Disc, colourless
Z = 4	0.37 × 0.36 × 0.27 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	352 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.024
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.4°, θ_min = 4.6°
T_min = 0.147, T_max = 1.000	h = −8→8
2198 measured reflections	k = −5→5
386 independent reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0644P)² + 0.0373P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
386 reflections	Δρ_max = 0.10 e Å⁻³
48 parameters	Δρ_min = −0.11 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.17812 (13)	0.3152 (3)	0.16798 (12)	0.0291 (11)
C1	0.0752 (2)	0.4539 (4)	0.23017 (19)	0.0298 (12)
H11	0.034261	0.525699	0.135100	0.036*
H12	0.159911	0.515689	0.311258	0.036*
C2	−0.1009 (2)	0.3922 (4)	0.3172 (2)	0.0394 (11)
H21	−0.181221	0.327688	0.237235	0.059*
H23	−0.175377	0.483714	0.355583	0.059*
H22	−0.058707	0.325581	0.414383	0.059*
C3	0.3451 (2)	0.3672 (4)	0.08199 (19)	0.0382 (12)
H31	0.424305	0.440801	0.155581	0.046*
H32	0.304025	0.425712	−0.022745	0.046*
C4	0.4627 (3)	0.2191 (4)	0.0393 (2)	0.0327 (12)
H42	0.384451	0.148172	−0.035782	0.049*
H41	0.501668	0.161254	0.143395	0.049*
H43	0.577325	0.252798	−0.017171	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0302 (9)	0.018 (4)	0.0399 (7)	−0.0026 (6)	0.0114 (5)	−0.0034 (6)
C1	0.0316 (10)	0.026 (4)	0.0319 (7)	0.0014 (10)	0.0015 (6)	−0.0041 (9)
C2	0.0280 (11)	0.051 (4)	0.0397 (8)	0.0040 (9)	0.0092 (7)	−0.0051 (11)
C3	0.0262 (11)	0.055 (4)	0.0348 (8)	−0.0023 (10)	0.0094 (8)	0.0036 (11)
C4	0.0295 (11)	0.033 (4)	0.0365 (8)	−0.0013 (9)	0.0063 (7)	−0.0027 (10)

Geometric parameters (Å, º) top

O1—C1	1.430 (3)	C2—H22	0.9600
O1—C3	1.421 (2)	C3—H31	0.9700
C1—H11	0.9700	C3—H32	0.9700
C1—H12	0.9700	C3—C4	1.497 (4)
C1—C2	1.501 (3)	C4—H42	0.9600
C2—H21	0.9600	C4—H41	0.9600
C2—H23	0.9600	C4—H43	0.9600

C3—O1—C1	110.3 (2)	O1—C3—H31	110.0
O1—C1—H11	110.1	O1—C3—H32	110.0
O1—C1—H12	110.1	O1—C3—C4	108.7 (3)
O1—C1—C2	108.1 (3)	H31—C3—H32	108.3
H11—C1—H12	108.4	C4—C3—H31	110.0
C2—C1—H11	110.1	C4—C3—H32	110.0
C2—C1—H12	110.1	C3—C4—H42	109.5
C1—C2—H21	109.5	C3—C4—H41	109.5
C1—C2—H23	109.5	C3—C4—H43	109.5
C1—C2—H22	109.5	H42—C4—H41	109.5
H21—C2—H23	109.5	H42—C4—H43	109.5
H21—C2—H22	109.5	H41—C4—H43	109.5
H23—C2—H22	109.5

C1—O1—C3—C4	172.74 (12)	C3—O1—C1—C2	179.15 (10)

diethyl ether (diethyl_ether_phase_beta_2_15GPa) top

Crystal data top

C₄H₁₀O	F(000) = 168
M_r = 74.12	D_x = 1.161 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.7948 (3) Å	Cell parameters from 1468 reflections
b = 8.0952 (12) Å	θ = 4.6–26.6°
c = 7.7259 (2) Å	µ = 0.08 mm⁻¹
β = 93.621 (3)°	T = 295 K
V = 424.12 (7) Å³	Dosc, colourless
Z = 4	0.38 × 0.34 × 0.26 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	353 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.025
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.6°, θ_min = 4.6°
T_min = 0.183, T_max = 1.000	h = −8→8
2208 measured reflections	k = −5→5
386 independent reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0569P)² + 0.0332P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max < 0.001
386 reflections	Δρ_max = 0.09 e Å⁻³
48 parameters	Δρ_min = −0.09 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.17730 (13)	0.3155 (3)	0.16712 (12)	0.0317 (9)
C1	0.0747 (2)	0.4556 (3)	0.23053 (18)	0.0282 (10)
H11	0.033284	0.528400	0.135343	0.034*
H12	0.160117	0.517092	0.312664	0.034*
C2	−0.1022 (2)	0.3919 (3)	0.31758 (18)	0.0336 (8)
H21	−0.183929	0.328916	0.235931	0.050*
H23	−0.176267	0.483315	0.358649	0.050*
H22	−0.059370	0.322789	0.413669	0.050*
C3	0.3452 (2)	0.3685 (4)	0.08107 (18)	0.0343 (10)
H31	0.424990	0.442146	0.155577	0.041*
H32	0.303901	0.427692	−0.024215	0.041*
C4	0.4633 (2)	0.2178 (4)	0.0378 (2)	0.0346 (10)
H42	0.384843	0.147670	−0.039303	0.052*
H41	0.500664	0.158572	0.142367	0.052*
H43	0.579618	0.251431	−0.017272	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0277 (8)	0.032 (3)	0.0369 (6)	−0.0021 (5)	0.0127 (5)	−0.0041 (6)
C1	0.0293 (9)	0.025 (4)	0.0301 (7)	0.0019 (8)	0.0024 (6)	−0.0012 (8)
C2	0.0298 (10)	0.034 (3)	0.0377 (8)	0.0044 (8)	0.0089 (7)	−0.0047 (9)
C3	0.0279 (11)	0.044 (4)	0.0321 (8)	−0.0019 (9)	0.0088 (8)	0.0033 (8)
C4	0.0283 (10)	0.042 (4)	0.0345 (7)	−0.0011 (9)	0.0078 (7)	−0.0044 (9)

Geometric parameters (Å, º) top

O1—C1	1.434 (3)	C2—H22	0.9600
O1—C3	1.423 (2)	C3—H31	0.9700
C1—H11	0.9700	C3—H32	0.9700
C1—H12	0.9700	C3—C4	1.509 (4)
C1—C2	1.505 (3)	C4—H42	0.9600
C2—H21	0.9600	C4—H41	0.9600
C2—H23	0.9600	C4—H43	0.9600

C3—O1—C1	110.0 (2)	O1—C3—H31	110.1
O1—C1—H11	110.2	O1—C3—H32	110.1
O1—C1—H12	110.2	O1—C3—C4	108.2 (3)
O1—C1—C2	107.5 (2)	H31—C3—H32	108.4
H11—C1—H12	108.5	C4—C3—H31	110.1
C2—C1—H11	110.2	C4—C3—H32	110.1
C2—C1—H12	110.2	C3—C4—H42	109.5
C1—C2—H21	109.5	C3—C4—H41	109.5
C1—C2—H23	109.5	C3—C4—H43	109.5
C1—C2—H22	109.5	H42—C4—H41	109.5
H21—C2—H23	109.5	H42—C4—H43	109.5
H21—C2—H22	109.5	H41—C4—H43	109.5
H23—C2—H22	109.5

C1—O1—C3—C4	172.54 (12)	C3—O1—C1—C2	179.20 (9)

diethyl ether (diethyl_ether_phase_beta_2_45GPa) top

Crystal data top

C₄H₁₀O	F(000) = 168
M_r = 74.12	D_x = 1.176 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.7759 (3) Å	Cell parameters from 1419 reflections
b = 8.0552 (14) Å	θ = 4.6–26.3°
c = 7.6873 (2) Å	µ = 0.08 mm⁻¹
β = 93.713 (3)°	T = 295 K
V = 418.70 (8) Å³	Disc, colourless
Z = 4	0.39 × 0.36 × 0.25 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	346 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.025
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.5°, θ_min = 4.9°
T_min = 0.207, T_max = 1.000	h = −8→8
2154 measured reflections	k = −5→5
377 independent reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0773P)² + 0.0273P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max < 0.001
377 reflections	Δρ_max = 0.12 e Å⁻³
48 parameters	Δρ_min = −0.11 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.17681 (14)	0.3159 (3)	0.16662 (13)	0.0312 (12)
C1	0.0741 (3)	0.4562 (4)	0.23044 (19)	0.0241 (12)
H11	0.032470	0.529428	0.134822	0.029*
H12	0.160060	0.517948	0.312958	0.029*
C2	−0.1030 (2)	0.3927 (4)	0.3180 (2)	0.0326 (11)
H21	−0.184224	0.328073	0.236481	0.049*
H23	−0.177930	0.484773	0.357653	0.049*
H22	−0.059845	0.324591	0.415643	0.049*
C3	0.3452 (2)	0.3678 (5)	0.0805 (2)	0.0333 (12)
H31	0.425157	0.441993	0.155287	0.040*
H32	0.303905	0.427143	−0.025482	0.040*
C4	0.4639 (3)	0.2183 (4)	0.0373 (2)	0.0313 (13)
H42	0.385406	0.147174	−0.039892	0.047*
H41	0.502376	0.159088	0.142415	0.047*
H43	0.579839	0.252722	−0.018446	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0273 (10)	0.032 (4)	0.0362 (7)	−0.0022 (6)	0.0123 (6)	−0.0041 (6)
C1	0.0291 (10)	0.015 (4)	0.0288 (8)	0.0005 (9)	0.0021 (7)	−0.0023 (9)
C2	0.0297 (12)	0.034 (4)	0.0349 (8)	0.0036 (10)	0.0088 (8)	−0.0045 (10)
C3	0.0274 (14)	0.042 (5)	0.0313 (9)	−0.0014 (11)	0.0096 (9)	0.0030 (10)
C4	0.0287 (12)	0.033 (5)	0.0324 (8)	−0.0032 (10)	0.0062 (7)	−0.0057 (10)

Geometric parameters (Å, º) top

O1—C1	1.431 (3)	C2—H22	0.9600
O1—C3	1.419 (2)	C3—H31	0.9700
C1—H11	0.9700	C3—H32	0.9700
C1—H12	0.9700	C3—C4	1.497 (4)
C1—C2	1.503 (3)	C4—H42	0.9600
C2—H21	0.9600	C4—H41	0.9600
C2—H23	0.9600	C4—H43	0.9600

C3—O1—C1	110.5 (3)	O1—C3—H31	109.9
O1—C1—H11	110.2	O1—C3—H32	109.9
O1—C1—H12	110.2	O1—C3—C4	109.0 (3)
O1—C1—C2	107.7 (3)	H31—C3—H32	108.3
H11—C1—H12	108.5	C4—C3—H31	109.9
C2—C1—H11	110.2	C4—C3—H32	109.9
C2—C1—H12	110.2	C3—C4—H42	109.5
C1—C2—H21	109.5	C3—C4—H41	109.5
C1—C2—H23	109.5	C3—C4—H43	109.5
C1—C2—H22	109.5	H42—C4—H41	109.5
H21—C2—H23	109.5	H42—C4—H43	109.5
H21—C2—H22	109.5	H41—C4—H43	109.5
H23—C2—H22	109.5

C1—O1—C3—C4	172.31 (13)	C3—O1—C1—C2	179.37 (10)

diethyl ether (diethyl_ether_phase_beta_2_65GPa) top

Crystal data top

C₄H₁₀O	F(000) = 168
M_r = 74.12	D_x = 1.185 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.7612 (3) Å	Cell parameters from 1414 reflections
b = 8.0271 (15) Å	θ = 4.6–26.3°
c = 7.6687 (3) Å	µ = 0.08 mm⁻¹
β = 93.784 (4)°	T = 295 K
V = 415.29 (8) Å³	Disc, colourless
Z = 4	0.40 × 0.37 × 0.24 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	342 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.022
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.4°, θ_min = 4.9°
T_min = 0.140, T_max = 1.000	h = −8→7
2120 measured reflections	k = −5→5
375 independent reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0819P)² + 0.0302P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
375 reflections	Δρ_max = 0.14 e Å⁻³
48 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.17622 (14)	0.3155 (3)	0.16649 (13)	0.0278 (11)
C1	0.0735 (3)	0.4566 (4)	0.22999 (19)	0.0268 (13)
H11	0.031527	0.529766	0.133855	0.032*
H12	0.159858	0.518882	0.312373	0.032*
C2	−0.1039 (2)	0.3932 (4)	0.3183 (2)	0.0319 (11)
H21	−0.186243	0.329073	0.236584	0.048*
H23	−0.178158	0.485834	0.358769	0.048*
H22	−0.060485	0.324379	0.415731	0.048*
C3	0.3450 (2)	0.3690 (5)	0.0800 (2)	0.0334 (13)
H31	0.425138	0.443431	0.155130	0.040*
H32	0.303322	0.428584	−0.026219	0.040*
C4	0.4637 (3)	0.2176 (4)	0.0368 (2)	0.0291 (13)
H42	0.384657	0.146419	−0.040428	0.044*
H41	0.502092	0.158327	0.142362	0.044*
H43	0.580088	0.251639	−0.019055	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0255 (9)	0.024 (4)	0.0350 (7)	−0.0023 (5)	0.0111 (6)	−0.0031 (6)
C1	0.0255 (10)	0.028 (4)	0.0274 (8)	0.0015 (10)	0.0024 (7)	−0.0028 (9)
C2	0.0266 (12)	0.037 (4)	0.0331 (8)	0.0024 (9)	0.0077 (8)	−0.0035 (10)
C3	0.0249 (13)	0.046 (5)	0.0299 (9)	−0.0011 (10)	0.0087 (9)	0.0026 (10)
C4	0.0268 (12)	0.030 (5)	0.0309 (8)	−0.0017 (10)	0.0053 (7)	−0.0030 (10)

Geometric parameters (Å, º) top

O1—C1	1.431 (3)	C2—H22	0.9600
O1—C3	1.424 (2)	C3—H31	0.9700
C1—H11	0.9700	C3—H32	0.9700
C1—H12	0.9700	C3—C4	1.505 (5)
C1—C2	1.504 (3)	C4—H42	0.9600
C2—H21	0.9600	C4—H41	0.9600
C2—H23	0.9600	C4—H43	0.9600

C3—O1—C1	110.0 (3)	O1—C3—H31	110.0
O1—C1—H11	110.2	O1—C3—H32	110.0
O1—C1—H12	110.2	O1—C3—C4	108.3 (3)
O1—C1—C2	107.7 (3)	H31—C3—H32	108.4
H11—C1—H12	108.5	C4—C3—H31	110.0
C2—C1—H11	110.2	C4—C3—H32	110.0
C2—C1—H12	110.2	C3—C4—H42	109.5
C1—C2—H21	109.5	C3—C4—H41	109.5
C1—C2—H23	109.5	C3—C4—H43	109.5
C1—C2—H22	109.5	H42—C4—H41	109.5
H21—C2—H23	109.5	H42—C4—H43	109.5
H21—C2—H22	109.5	H41—C4—H43	109.5
H23—C2—H22	109.5

C1—O1—C3—C4	172.46 (12)	C3—O1—C1—C2	179.44 (10)

diethyl ether (diethyl_ether_phase_gamma_2_65GPa) top

Crystal data top

C₄H₁₀O	F(000) = 168
M_r = 74.12	D_x = 1.183 Mg m⁻³
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 7.7073 (12) Å	Cell parameters from 695 reflections
b = 4.0885 (4) Å	θ = 5.2–26.4°
c = 13.233 (2) Å	µ = 0.08 mm⁻¹
β = 93.793 (16)°	T = 295 K
V = 416.07 (10) Å³	Disc, colourless
Z = 4	0.40 × 0.36 × 0.24 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	202 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.013
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.4°, θ_min = 5.2°
T_min = 0.752, T_max = 1.000	h = −7→8
1160 measured reflections	k = −4→4
223 independent reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.0545P)² + 0.1653P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
223 reflections	Δρ_max = 0.09 e Å⁻³
25 parameters	Δρ_min = −0.11 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.250000	0.1448 (3)	0.000000	0.0334 (9)
C1	0.1949 (3)	0.3422 (4)	0.08002 (14)	0.0321 (9)
H11	0.116628	0.510954	0.052854	0.039*
H12	0.294801	0.447906	0.114514	0.039*
C2	0.1045 (3)	0.1352 (4)	0.15316 (15)	0.0364 (9)
H23	0.066841	0.269719	0.207006	0.055*
H22	0.182974	−0.029239	0.180696	0.055*
H21	0.005409	0.031963	0.118826	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0415 (18)	0.0255 (10)	0.0337 (14)	0.000	0.0053 (13)	0.000
C1	0.0345 (18)	0.0284 (11)	0.0335 (16)	0.0015 (6)	0.0021 (15)	−0.0043 (6)
C2	0.0362 (19)	0.0371 (12)	0.0361 (16)	0.0006 (7)	0.0035 (15)	−0.0072 (6)

Geometric parameters (Å, º) top

O1—C1ⁱ	1.418 (2)	C1—C2	1.493 (3)
O1—C1	1.418 (2)	C2—H23	0.9600
C1—H11	0.9700	C2—H22	0.9600
C1—H12	0.9700	C2—H21	0.9600

C1ⁱ—O1—C1	110.64 (18)	C1—C2—H23	109.5
O1—C1—H11	109.7	C1—C2—H22	109.5
O1—C1—H12	109.7	C1—C2—H21	109.5
O1—C1—C2	109.69 (14)	H23—C2—H22	109.5
H11—C1—H12	108.2	H23—C2—H21	109.5
C2—C1—H11	109.7	H22—C2—H21	109.5
C2—C1—H12	109.7

C1ⁱ—O1—C1—C2	168.50 (15)

Symmetry code: (i) −x+1/2, y, −z.

diethyl ether (diethyl_ether_phase_delta_2_80GPa) top

Crystal data top

C₄H₁₀O	Z = 2
M_r = 74.12	F(000) = 84
Triclinic, P1	D_x = 1.215 Mg m⁻³
a = 5.1196 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.6659 (10) Å	Cell parameters from 846 reflections
c = 7.2999 (4) Å	θ = 5.1–26.1°
α = 97.275 (8)°	µ = 0.08 mm⁻¹
β = 102.728 (6)°	T = 295 K
γ = 96.747 (10)°	Disc, colourless
V = 202.56 (4) Å³	0.36 × 0.36 × 0.23 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	225 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.014
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.1°, θ_min = 5.1°
T_min = 0.675, T_max = 1.000	h = −6→6
1217 measured reflections	k = −4→4
244 independent reflections	l = −8→8

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0403P)² + 0.0893P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max < 0.001
244 reflections	Δρ_max = 0.09 e Å⁻³
48 parameters	Δρ_min = −0.08 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.5029 (7)	0.2073 (11)	0.3190 (3)	0.042 (4)
C1	0.5498 (12)	0.4352 (18)	0.2653 (4)	0.043 (6)
H11	0.628013	0.422259	0.155505	0.052*
H12	0.676772	0.543641	0.368504	0.052*
C2	0.2856 (8)	0.5336 (14)	0.2175 (4)	0.041 (5)
H21	0.167648	0.435123	0.106701	0.061*
H23	0.319899	0.695440	0.192897	0.061*
H22	0.201188	0.532848	0.322611	0.061*
C3	0.7439 (8)	0.0987 (13)	0.3593 (3)	0.045 (5)
H31	0.717200	−0.027165	0.434745	0.054*
H32	0.892291	0.218957	0.434044	0.054*
C4	0.8197 (10)	−0.0082 (16)	0.1798 (3)	0.052 (5)
H41	0.679133	−0.135463	0.109703	0.079*
H43	0.986759	−0.071269	0.213696	0.079*
H42	0.840957	0.114565	0.102610	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.031 (3)	0.071 (11)	0.0349 (11)	0.026 (6)	0.0132 (13)	0.017 (2)
C1	0.036 (4)	0.072 (17)	0.0281 (14)	0.026 (9)	0.0093 (17)	0.012 (3)
C2	0.036 (4)	0.060 (15)	0.0327 (12)	0.024 (8)	0.0094 (14)	0.012 (2)
C3	0.038 (4)	0.074 (13)	0.0291 (12)	0.036 (7)	0.0065 (14)	0.009 (2)
C4	0.044 (4)	0.086 (15)	0.0344 (13)	0.036 (8)	0.0125 (16)	0.008 (3)

Geometric parameters (Å, º) top

O1—C1	1.405 (13)	C2—H22	0.9600
O1—C3	1.432 (3)	C3—H31	0.9700
C1—H11	0.9700	C3—H32	0.9700
C1—H12	0.9700	C3—C4	1.521 (3)
C1—C2	1.510 (3)	C4—H41	0.9600
C2—H21	0.9600	C4—H43	0.9600
C2—H23	0.9600	C4—H42	0.9600

C1—O1—C3	112.5 (5)	O1—C3—H31	109.1
O1—C1—H11	109.8	O1—C3—H32	109.1
O1—C1—H12	109.8	O1—C3—C4	112.51 (18)
O1—C1—C2	109.5 (7)	H31—C3—H32	107.8
H11—C1—H12	108.2	C4—C3—H31	109.1
C2—C1—H11	109.8	C4—C3—H32	109.1
C2—C1—H12	109.8	C3—C4—H41	109.5
C1—C2—H21	109.5	C3—C4—H43	109.5
C1—C2—H23	109.5	C3—C4—H42	109.5
C1—C2—H22	109.5	H41—C4—H43	109.5
H21—C2—H23	109.5	H41—C4—H42	109.5
H21—C2—H22	109.5	H43—C4—H42	109.5
H23—C2—H22	109.5

C1—O1—C3—C4	−77.9 (7)	C3—O1—C1—C2	177.7 (2)

diethyl ether (diethyl_ether_phase_delta_3_45GPa) top

Crystal data top

C₄H₁₀O	Z = 2
M_r = 74.12	F(000) = 84
Triclinic, P1	D_x = 1.242 Mg m⁻³
a = 5.0809 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.6329 (10) Å	Cell parameters from 828 reflections
c = 7.2451 (10) Å	θ = 5.1–26.0°
α = 97.382 (13)°	µ = 0.09 mm⁻¹
β = 102.749 (10)°	T = 295 K
γ = 97.002 (11)°	Disc, colourless
V = 198.13 (5) Å³	0.37 × 0.37 × 0.22 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	218 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.018
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.1°, θ_min = 5.1°
T_min = 0.036, T_max = 1.000	h = −6→6
1179 measured reflections	k = −5→4
243 independent reflections	l = −8→8

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.101	H-atom parameters constrained
wR(F²) = 0.361	w = 1/[σ²(F_o²) + (0.2P)²] where P = (F_o² + 2F_c²)/3
S = 1.79	(Δ/σ)_max < 0.001
243 reflections	Δρ_max = 0.30 e Å⁻³
23 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.5037 (8)	0.2114 (12)	0.3175 (4)	0.0284 (16)*
C1	0.5525 (13)	0.442 (2)	0.2643 (7)	0.0307 (17)*
H11	0.631428	0.429983	0.153823	0.037*
H12	0.679908	0.551643	0.368952	0.037*
C2	0.2846 (12)	0.5367 (19)	0.2166 (9)	0.0303 (17)*
H21	0.173772	0.446966	0.097511	0.045*
H23	0.318515	0.704999	0.205312	0.045*
H22	0.191093	0.518451	0.316722	0.045*
C3	0.7420 (11)	0.0974 (16)	0.3593 (7)	0.0279 (17)*
H31	0.709314	−0.029712	0.433682	0.033*
H32	0.893508	0.215939	0.436765	0.033*
C4	0.8200 (11)	−0.0114 (16)	0.1783 (6)	0.0311 (17)*
H41	0.679282	−0.141256	0.108049	0.047*
H43	0.989265	−0.072654	0.213373	0.047*
H42	0.840480	0.111312	0.099832	0.047*

Geometric parameters (Å, º) top

O1—C1	1.410 (14)	C2—H22	0.9600
O1—C3	1.431 (4)	C3—H31	0.9700
C1—H11	0.9700	C3—H32	0.9700
C1—H12	0.9700	C3—C4	1.528 (6)
C1—C2	1.508 (5)	C4—H41	0.9600
C2—H21	0.9600	C4—H43	0.9600
C2—H23	0.9600	C4—H42	0.9600

C1—O1—C3	113.9 (7)	O1—C3—H31	109.1
O1—C1—H11	110.0	O1—C3—H32	109.1
O1—C1—H12	110.0	O1—C3—C4	112.5 (4)
O1—C1—C2	108.5 (8)	H31—C3—H32	107.8
H11—C1—H12	108.4	C4—C3—H31	109.1
C2—C1—H11	110.0	C4—C3—H32	109.1
C2—C1—H12	110.0	C3—C4—H41	109.5
C1—C2—H21	109.5	C3—C4—H43	109.5
C1—C2—H23	109.5	C3—C4—H42	109.5
C1—C2—H22	109.5	H41—C4—H43	109.5
H21—C2—H23	109.5	H41—C4—H42	109.5
H21—C2—H22	109.5	H43—C4—H42	109.5
H23—C2—H22	109.5

C1—O1—C3—C4	−77.6 (7)	C3—O1—C1—C2	177.7 (2)

diethyl ether (diethyl_ether_phase_delta_3_70GPa) top

Crystal data top

C₄H₁₀O	Z = 2
M_r = 74.12	F(000) = 84
Triclinic, P1	D_x = 1.252 Mg m⁻³
a = 5.072 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.629 (2) Å	Cell parameters from 822 reflections
c = 7.215 (5) Å	θ = 3.7–27.7°
α = 97.43 (5)°	µ = 0.09 mm⁻¹
β = 102.91 (6)°	T = 295 K
γ = 97.15 (5)°	Disc, colourless
V = 196.6 (2) Å³	0.38 × 0.38 × 0.21 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	177 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.038
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 27.7°, θ_min = 3.7°
T_min = 0.216, T_max = 1.000	h = −5→5
1025 measured reflections	k = −7→7
199 independent reflections	l = −7→7

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.141	w = 1/[σ²(F_o²) + (0.0907P)² + 0.0311P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max < 0.001
199 reflections	Δρ_max = 0.09 e Å⁻³
23 parameters	Δρ_min = −0.10 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.5003 (10)	0.2063 (3)	0.3186 (9)	0.0240 (8)*
C1	0.5440 (16)	0.4379 (5)	0.2617 (14)	0.0224 (8)*
H11	0.619886	0.424228	0.149405	0.027*
H12	0.674185	0.549334	0.365025	0.027*
C2	0.2853 (16)	0.5315 (6)	0.2166 (13)	0.0257 (9)*
H21	0.164595	0.431191	0.104563	0.039*
H23	0.319056	0.694628	0.191837	0.039*
H22	0.202190	0.530086	0.323708	0.039*
C3	0.7453 (17)	0.0991 (5)	0.3606 (15)	0.0253 (9)*
H31	0.719288	−0.027435	0.437150	0.030*
H32	0.895743	0.221737	0.436015	0.030*
C4	0.8184 (17)	−0.0086 (6)	0.1773 (15)	0.0267 (10)*
H41	0.679656	−0.142617	0.109732	0.040*
H43	0.991835	−0.064044	0.210200	0.040*
H42	0.829900	0.113155	0.096428	0.040*

Geometric parameters (Å, º) top

O1—C1	1.423 (6)	C2—H22	0.9600
O1—C3	1.437 (9)	C3—H31	0.9700
C1—H11	0.9700	C3—H32	0.9700
C1—H12	0.9700	C3—C4	1.524 (8)
C1—C2	1.460 (11)	C4—H41	0.9600
C2—H21	0.9600	C4—H43	0.9600
C2—H23	0.9600	C4—H42	0.9600

C1—O1—C3	113.2 (3)	O1—C3—H31	109.3
O1—C1—H11	109.7	O1—C3—H32	109.3
O1—C1—H12	109.7	O1—C3—C4	111.7 (9)
O1—C1—C2	109.9 (3)	H31—C3—H32	107.9
H11—C1—H12	108.2	C4—C3—H31	109.3
C2—C1—H11	109.7	C4—C3—H32	109.3
C2—C1—H12	109.7	C3—C4—H41	109.5
C1—C2—H21	109.5	C3—C4—H43	109.5
C1—C2—H23	109.5	C3—C4—H42	109.5
C1—C2—H22	109.5	H41—C4—H43	109.5
H21—C2—H23	109.5	H41—C4—H42	109.5
H21—C2—H22	109.5	H43—C4—H42	109.5
H23—C2—H22	109.5

C1—O1—C3—C4	−77.6 (5)	C3—O1—C1—C2	178.5 (6)

diethyl ether (diethyl_ether_phase_delta_4_90GPa) top

Crystal data top

C₄H₁₀O	Z = 2
M_r = 74.12	F(000) = 84
Triclinic, P1	D_x = 1.293 Mg m⁻³
a = 5.0182 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.575 (3) Å	Cell parameters from 655 reflections
c = 7.136 (3) Å	θ = 4.4–27.9°
α = 97.36 (4)°	µ = 0.09 mm⁻¹
β = 102.81 (3)°	T = 295 K
γ = 97.72 (4)°	Disc, colourless
V = 190.31 (14) Å³	0.40 × 0.40 × 0.20 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	153 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.095
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 27.9°, θ_min = 4.4°
T_min = 0.136, T_max = 1.000	h = −5→5
944 measured reflections	k = −6→6
195 independent reflections	l = −8→8

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.061	H-atom parameters constrained
wR(F²) = 0.182	w = 1/[σ²(F_o²) + (0.1287P)² + 0.0085P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
195 reflections	Δρ_max = 0.12 e Å⁻³
23 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.4987 (12)	0.2042 (9)	0.3204 (7)	0.0254 (10)*
C1	0.545 (2)	0.4379 (17)	0.2630 (13)	0.0256 (12)*
H11	0.623129	0.424073	0.149948	0.031*
H12	0.677056	0.550931	0.367720	0.031*
C2	0.281 (2)	0.5333 (18)	0.2156 (13)	0.0302 (13)*
H21	0.155921	0.426996	0.105977	0.045*
H23	0.316270	0.695125	0.184223	0.045*
H22	0.200598	0.539633	0.325745	0.045*
C3	0.747 (2)	0.1009 (15)	0.3620 (11)	0.0254 (12)*
H31	0.723207	−0.026309	0.440691	0.030*
H32	0.898771	0.227237	0.436653	0.030*
C4	0.818 (2)	−0.0086 (16)	0.1748 (13)	0.0320 (12)*
H41	0.686668	−0.153869	0.113600	0.048*
H43	1.001199	−0.049546	0.205957	0.048*
H42	0.812374	0.109210	0.087502	0.048*

Geometric parameters (Å, º) top

O1—C1	1.421 (8)	C2—H22	0.9600
O1—C3	1.429 (6)	C3—H31	0.9700
C1—H11	0.9700	C3—H32	0.9700
C1—H12	0.9700	C3—C4	1.533 (8)
C1—C2	1.479 (8)	C4—H41	0.9600
C2—H21	0.9600	C4—H43	0.9600
C2—H23	0.9600	C4—H42	0.9600

C1—O1—C3	112.1 (5)	O1—C3—H31	109.3
O1—C1—H11	109.7	O1—C3—H32	109.3
O1—C1—H12	109.7	O1—C3—C4	111.5 (7)
O1—C1—C2	110.0 (7)	H31—C3—H32	108.0
H11—C1—H12	108.2	C4—C3—H31	109.3
C2—C1—H11	109.7	C4—C3—H32	109.3
C2—C1—H12	109.7	C3—C4—H41	109.5
C1—C2—H21	109.5	C3—C4—H43	109.5
C1—C2—H23	109.5	C3—C4—H42	109.5
C1—C2—H22	109.5	H41—C4—H43	109.5
H21—C2—H23	109.5	H41—C4—H42	109.5
H21—C2—H22	109.5	H43—C4—H42	109.5
H23—C2—H22	109.5

C1—O1—C3—C4	−78.2 (7)	C3—O1—C1—C2	178.2 (7)

dipropyl ether (dipropyl_ether_phase_alpha_1_70GPa) top

Crystal data top

C₆H₁₄O	F(000) = 232
M_r = 102.17	D_x = 1.128 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.416 (4) Å	Cell parameters from 1225 reflections
b = 4.1817 (3) Å	θ = 5.0–24.3°
c = 15.579 (7) Å	µ = 0.07 mm⁻¹
β = 101.23 (5)°	T = 295 K
V = 601.7 (4) Å³	Disc, colourless
Z = 4	0.39 × 0.37 × 0.25 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	286 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.025
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.4°, θ_min = 5.1°
T_min = 0.507, T_max = 1.000	h = −8→8
3001 measured reflections	k = −5→5
386 independent reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.151	w = 1/[σ²(F_o²) + (0.1115P)² + 0.0052P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
386 reflections	Δρ_max = 0.10 e Å⁻³
66 parameters	Δρ_min = −0.09 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.4584 (3)	0.8467 (3)	0.1317 (2)	0.060 (4)
C1	0.3752 (5)	0.7145 (5)	0.0533 (3)	0.058 (5)
H11	0.381195	0.482954	0.055219	0.070*
H12	0.412714	0.788437	0.003069	0.070*
C2	0.2192 (5)	0.8192 (5)	0.0453 (3)	0.055 (5)
H22	0.215342	1.049577	0.051684	0.066*
H21	0.178636	0.722202	0.091687	0.066*
C3	0.1296 (7)	0.7211 (5)	−0.0435 (4)	0.070 (5)
H33	0.033105	0.804050	−0.049320	0.105*
H31	0.125959	0.492113	−0.047613	0.105*
H32	0.173411	0.805742	−0.089436	0.105*
C4	0.6010 (5)	0.7224 (6)	0.1490 (3)	0.054 (5)
H41	0.651228	0.788187	0.103195	0.065*
H42	0.597459	0.490543	0.149471	0.065*
C5	0.6821 (5)	0.8410 (5)	0.2361 (3)	0.057 (5)
H52	0.636877	0.757803	0.282339	0.068*
H51	0.676959	1.072595	0.237591	0.068*
C6	0.8394 (6)	0.7377 (5)	0.2520 (4)	0.064 (6)
H63	0.890335	0.830768	0.305550	0.096*
H61	0.882544	0.807961	0.204295	0.096*
H62	0.844893	0.508801	0.256252	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.049 (5)	0.0445 (10)	0.071 (5)	0.0031 (10)	−0.025 (5)	−0.0060 (11)
C1	0.055 (7)	0.0386 (12)	0.065 (7)	−0.0009 (15)	−0.026 (7)	0.0007 (16)
C2	0.045 (7)	0.0441 (13)	0.066 (7)	0.0021 (16)	−0.014 (7)	−0.0012 (17)
C3	0.060 (7)	0.0557 (14)	0.076 (7)	−0.0001 (17)	−0.032 (7)	0.0025 (18)
C4	0.041 (7)	0.0416 (13)	0.067 (7)	0.0010 (14)	−0.019 (7)	0.0046 (16)
C5	0.049 (6)	0.0449 (12)	0.065 (6)	0.0004 (16)	−0.018 (6)	0.0025 (18)
C6	0.051 (8)	0.0605 (15)	0.066 (7)	−0.0066 (18)	−0.025 (7)	0.0095 (19)

Geometric parameters (Å, º) top

O1—C1	1.428 (4)	C3—H32	0.9600
O1—C4	1.416 (5)	C4—H41	0.9700
C1—H11	0.9700	C4—H42	0.9700
C1—H12	0.9700	C4—C5	1.505 (4)
C1—C2	1.514 (7)	C5—H52	0.9700
C2—H22	0.9700	C5—H51	0.9700
C2—H21	0.9700	C5—C6	1.516 (7)
C2—C3	1.530 (5)	C6—H63	0.9600
C3—H33	0.9600	C6—H61	0.9600
C3—H31	0.9600	C6—H62	0.9600

C4—O1—C1	111.3 (4)	O1—C4—H41	109.6
O1—C1—H11	110.0	O1—C4—H42	109.6
O1—C1—H12	110.0	O1—C4—C5	110.3 (4)
O1—C1—C2	108.7 (4)	H41—C4—H42	108.1
H11—C1—H12	108.3	C5—C4—H41	109.6
C2—C1—H11	110.0	C5—C4—H42	109.6
C2—C1—H12	110.0	C4—C5—H52	109.4
C1—C2—H22	109.5	C4—C5—H51	109.4
C1—C2—H21	109.5	C4—C5—C6	111.2 (5)
C1—C2—C3	110.7 (5)	H52—C5—H51	108.0
H22—C2—H21	108.1	C6—C5—H52	109.4
C3—C2—H22	109.5	C6—C5—H51	109.4
C3—C2—H21	109.5	C5—C6—H63	109.5
C2—C3—H33	109.5	C5—C6—H61	109.5
C2—C3—H31	109.5	C5—C6—H62	109.5
C2—C3—H32	109.5	H63—C6—H61	109.5
H33—C3—H31	109.5	H63—C6—H62	109.5
H33—C3—H32	109.5	H61—C6—H62	109.5
H31—C3—H32	109.5

O1—C1—C2—C3	172.4 (3)	C1—O1—C4—C5	−174.7 (4)
O1—C4—C5—C6	−174.4 (3)	C4—O1—C1—C2	172.0 (3)

dipropyl ether (dipropyl_ether_phase_alpha_2_10GPa) top

Crystal data top

C₆H₁₄O	F(000) = 232
M_r = 102.17	D_x = 1.159 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.368 (8) Å	Cell parameters from 1024 reflections
b = 4.1229 (4) Å	θ = 5.1–24.5°
c = 15.434 (4) Å	µ = 0.08 mm⁻¹
β = 100.84 (6)°	T = 295 K
V = 585.5 (6) Å³	Disc, colourless
Z = 4	0.39 × 0.38 × 0.24 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	287 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.030
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.5°, θ_min = 5.1°
T_min = 0.517, T_max = 1.000	h = −6→6
2850 measured reflections	k = −5→5
383 independent reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.052	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0676P)² + 0.3061P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
383 reflections	Δρ_max = 0.10 e Å⁻³
66 parameters	Δρ_min = −0.10 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.4584 (5)	0.8479 (5)	0.1318 (2)	0.060 (4)
C1	0.3745 (8)	0.7127 (7)	0.0543 (3)	0.050 (5)
H11	0.379792	0.477886	0.057313	0.060*
H12	0.412771	0.782871	0.003253	0.060*
C2	0.2200 (8)	0.8189 (7)	0.0454 (3)	0.051 (6)
H22	0.216710	1.052744	0.051755	0.061*
H21	0.178157	0.722236	0.092211	0.061*
C3	0.1293 (10)	0.7207 (8)	−0.0443 (3)	0.067 (6)
H33	0.030640	0.790486	−0.047620	0.100*
H31	0.131747	0.489262	−0.050547	0.100*
H32	0.168837	0.821113	−0.090695	0.100*
C4	0.6019 (8)	0.7218 (7)	0.1489 (3)	0.052 (6)
H41	0.652655	0.790134	0.102695	0.062*
H42	0.598404	0.486637	0.148855	0.062*
C5	0.6824 (8)	0.8402 (7)	0.2367 (3)	0.057 (6)
H52	0.636847	0.753664	0.283253	0.069*
H51	0.676855	1.074957	0.238738	0.069*
C6	0.8411 (8)	0.7362 (8)	0.2522 (3)	0.068 (6)
H63	0.891490	0.826082	0.306852	0.101*
H61	0.885090	0.813085	0.204682	0.101*
H62	0.846918	0.503821	0.254860	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.071 (9)	0.0434 (13)	0.052 (3)	0.0061 (17)	−0.019 (5)	−0.0083 (11)
C1	0.063 (12)	0.0385 (17)	0.041 (3)	0.002 (3)	−0.011 (6)	0.0000 (16)
C2	0.063 (13)	0.0423 (18)	0.043 (4)	0.000 (3)	−0.003 (7)	−0.0001 (16)
C3	0.091 (13)	0.050 (2)	0.047 (4)	0.002 (3)	−0.016 (7)	−0.0013 (18)
C4	0.059 (12)	0.0393 (18)	0.048 (4)	−0.001 (3)	−0.012 (6)	0.0046 (16)
C5	0.069 (13)	0.0419 (17)	0.051 (4)	−0.001 (3)	−0.016 (7)	0.0003 (17)
C6	0.083 (13)	0.051 (2)	0.055 (4)	−0.003 (3)	−0.023 (7)	0.0028 (18)

Geometric parameters (Å, º) top

O1—C1	1.416 (4)	C3—H32	0.9600
O1—C4	1.419 (8)	C4—H41	0.9700
C1—H11	0.9700	C4—H42	0.9700
C1—H12	0.9700	C4—C5	1.504 (4)
C1—C2	1.493 (10)	C5—H52	0.9700
C2—H22	0.9700	C5—H51	0.9700
C2—H21	0.9700	C5—C6	1.523 (9)
C2—C3	1.536 (4)	C6—H63	0.9600
C3—H33	0.9600	C6—H61	0.9600
C3—H31	0.9600	C6—H62	0.9600

C1—O1—C4	111.6 (4)	O1—C4—H41	109.6
O1—C1—H11	109.7	O1—C4—H42	109.6
O1—C1—H12	109.7	O1—C4—C5	110.2 (5)
O1—C1—C2	109.7 (5)	H41—C4—H42	108.1
H11—C1—H12	108.2	C5—C4—H41	109.6
C2—C1—H11	109.7	C5—C4—H42	109.6
C2—C1—H12	109.7	C4—C5—H52	109.4
C1—C2—H22	109.3	C4—C5—H51	109.4
C1—C2—H21	109.3	C4—C5—C6	111.1 (5)
C1—C2—C3	111.6 (6)	H52—C5—H51	108.0
H22—C2—H21	108.0	C6—C5—H52	109.4
C3—C2—H22	109.3	C6—C5—H51	109.4
C3—C2—H21	109.3	C5—C6—H63	109.5
C2—C3—H33	109.5	C5—C6—H61	109.5
C2—C3—H31	109.5	C5—C6—H62	109.5
C2—C3—H32	109.5	H63—C6—H61	109.5
H33—C3—H31	109.5	H63—C6—H62	109.5
H33—C3—H32	109.5	H61—C6—H62	109.5
H31—C3—H32	109.5

O1—C1—C2—C3	171.5 (4)	C1—O1—C4—C5	−173.4 (4)
O1—C4—C5—C6	−174.2 (4)	C4—O1—C1—C2	172.7 (4)

dipropyl ether (dipropyl_ether_phase_alpha_2_80GPa) top

Crystal data top

C₆H₁₄O	F(000) = 232
M_r = 102.17	D_x = 1.202 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.293 (7) Å	Cell parameters from 1241 reflections
b = 4.0686 (2) Å	θ = 5.2–25.5°
c = 15.1855 (10) Å	µ = 0.08 mm⁻¹
β = 100.35 (3)°	T = 295 K
V = 564.8 (4) Å³	Disc, colourless
Z = 4	0.46 × 0.43 × 0.23 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	282 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.027
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.6°, θ_min = 5.2°
T_min = 0.715, T_max = 1.000	h = −4→4
2881 measured reflections	k = −5→5
356 independent reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.145	w = 1/[σ²(F_o²) + (0.095P)² + 0.1072P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
356 reflections	Δρ_max = 0.09 e Å⁻³
66 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.4592 (8)	0.8515 (6)	0.13181 (16)	0.048 (5)
C1	0.3710 (14)	0.7144 (8)	0.0534 (3)	0.057 (7)
H11	0.375837	0.476428	0.056591	0.069*
H12	0.408763	0.783597	0.000841	0.069*
C2	0.2183 (15)	0.8207 (9)	0.0454 (3)	0.059 (8)
H22	0.215089	1.057762	0.051505	0.070*
H21	0.176415	0.723991	0.093491	0.070*
C3	0.1275 (10)	0.7202 (6)	−0.04411 (19)	0.061 (6)
H33	0.030515	0.808317	−0.049194	0.091*
H31	0.122554	0.484845	−0.047821	0.091*
H32	0.172152	0.804195	−0.091816	0.091*
C4	0.6028 (12)	0.7222 (8)	0.1489 (2)	0.049 (7)
H41	0.654202	0.788314	0.101489	0.059*
H42	0.598606	0.484045	0.149522	0.059*
C5	0.6839 (15)	0.8434 (9)	0.2368 (3)	0.047 (9)
H52	0.637162	0.759927	0.284476	0.056*
H51	0.679331	1.081472	0.238059	0.056*
C6	0.8413 (16)	0.7369 (10)	0.2531 (3)	0.070 (9)
H63	0.890833	0.827079	0.308776	0.104*
H61	0.887268	0.814327	0.205228	0.104*
H62	0.846320	0.501371	0.255674	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.070 (16)	0.0361 (14)	0.0318 (16)	0.001 (2)	−0.008 (4)	−0.0059 (9)
C1	0.11 (2)	0.0296 (18)	0.0280 (19)	−0.004 (3)	0.010 (6)	−0.0011 (13)
C2	0.11 (3)	0.035 (2)	0.035 (2)	0.001 (3)	0.012 (6)	−0.0029 (14)
C3	0.109 (19)	0.0418 (16)	0.0286 (18)	−0.006 (3)	0.002 (5)	−0.0006 (10)
C4	0.08 (2)	0.0324 (18)	0.028 (2)	0.006 (4)	0.001 (6)	0.0039 (13)
C5	0.07 (3)	0.034 (2)	0.033 (2)	−0.002 (3)	0.002 (7)	0.0017 (13)
C6	0.13 (3)	0.044 (2)	0.030 (2)	−0.002 (4)	0.006 (7)	0.0046 (15)

Geometric parameters (Å, º) top

O1—C1	1.432 (10)	C3—H32	0.9600
O1—C4	1.414 (14)	C4—H41	0.9700
C1—H11	0.9700	C4—H42	0.9700
C1—H12	0.9700	C4—C5	1.495 (10)
C1—C2	1.468 (19)	C5—H52	0.9700
C2—H22	0.9700	C5—H51	0.9700
C2—H21	0.9700	C5—C6	1.50 (2)
C2—C3	1.522 (10)	C6—H63	0.9600
C3—H33	0.9600	C6—H61	0.9600
C3—H31	0.9600	C6—H62	0.9600

C4—O1—C1	112.8 (5)	O1—C4—H41	109.6
O1—C1—H11	109.5	O1—C4—H42	109.6
O1—C1—H12	109.5	O1—C4—C5	110.4 (5)
O1—C1—C2	110.8 (4)	H41—C4—H42	108.1
H11—C1—H12	108.1	C5—C4—H41	109.6
C2—C1—H11	109.5	C5—C4—H42	109.6
C2—C1—H12	109.5	C4—C5—H52	109.3
C1—C2—H22	109.3	C4—C5—H51	109.3
C1—C2—H21	109.3	C4—C5—C6	111.8 (5)
C1—C2—C3	111.6 (4)	H52—C5—H51	107.9
H22—C2—H21	108.0	C6—C5—H52	109.3
C3—C2—H22	109.3	C6—C5—H51	109.3
C3—C2—H21	109.3	C5—C6—H63	109.5
C2—C3—H33	109.5	C5—C6—H61	109.5
C2—C3—H31	109.5	C5—C6—H62	109.5
C2—C3—H32	109.5	H63—C6—H61	109.5
H33—C3—H31	109.5	H63—C6—H62	109.5
H33—C3—H32	109.5	H61—C6—H62	109.5
H31—C3—H32	109.5

O1—C1—C2—C3	171.5 (2)	C1—O1—C4—C5	−173.3 (3)
O1—C4—C5—C6	−174.6 (5)	C4—O1—C1—C2	172.1 (4)

dipropyl ether (dipropyl_ether_phase_alpha_3_85GPa) top

Crystal data top

C₆H₁₄O	F(000) = 232
M_r = 102.17	D_x = 1.249 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.198 (9) Å	Cell parameters from 1140 reflections
b = 4.0064 (3) Å	θ = 5.2–24.9°
c = 14.9459 (15) Å	µ = 0.08 mm⁻¹
β = 99.54 (4)°	T = 295 K
V = 543.1 (5) Å³	Disc, colourless
Z = 4	0.38 × 0.36 × 0.22 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	281 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.030
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.5°, θ_min = 5.3°
T_min = 0.650, T_max = 1.000	h = −4→4
2785 measured reflections	k = −5→5
347 independent reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0571P)² + 0.017P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
347 reflections	Δρ_max = 0.06 e Å⁻³
66 parameters	Δρ_min = −0.06 e Å⁻³
0 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.4590 (6)	0.8573 (4)	0.13140 (11)	0.032 (3)
C1	0.3718 (9)	0.7137 (6)	0.05340 (17)	0.038 (5)
H11	0.376898	0.472271	0.057771	0.045*
H12	0.410512	0.780373	−0.000437	0.045*
C2	0.2172 (11)	0.8215 (6)	0.04531 (19)	0.040 (5)
H22	0.213852	1.062364	0.051246	0.049*
H21	0.174194	0.724233	0.094321	0.049*
C3	0.1266 (7)	0.7189 (4)	−0.04495 (14)	0.038 (4)
H33	0.030179	0.816785	−0.050866	0.056*
H31	0.117814	0.480141	−0.047387	0.056*
H32	0.174456	0.794864	−0.093598	0.056*
C4	0.6039 (8)	0.7236 (5)	0.14848 (16)	0.033 (5)
H41	0.656253	0.787994	0.099948	0.039*
H42	0.598715	0.481810	0.149553	0.039*
C5	0.6864 (10)	0.8467 (6)	0.23728 (17)	0.041 (6)
H51	0.682788	1.088614	0.238299	0.049*
H52	0.638802	0.764234	0.286161	0.049*
C6	0.8428 (10)	0.7367 (7)	0.25265 (18)	0.037 (5)
H63	0.892849	0.828515	0.308717	0.055*
H61	0.889671	0.813054	0.203603	0.055*
H62	0.846929	0.497451	0.255561	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.028 (10)	0.0343 (10)	0.0316 (10)	0.0025 (15)	−0.005 (3)	−0.0050 (6)
C1	0.061 (15)	0.0259 (12)	0.0248 (13)	−0.002 (2)	0.004 (4)	−0.0016 (9)
C2	0.061 (16)	0.0286 (13)	0.0321 (15)	0.005 (2)	0.009 (4)	−0.0007 (9)
C3	0.044 (12)	0.0368 (11)	0.0302 (13)	0.0008 (18)	0.001 (3)	0.0003 (7)
C4	0.040 (15)	0.0298 (12)	0.0263 (15)	0.004 (2)	−0.001 (4)	0.0037 (8)
C5	0.063 (18)	0.0299 (13)	0.0285 (14)	0.004 (2)	0.005 (4)	0.0028 (9)
C6	0.041 (18)	0.0367 (16)	0.0287 (15)	−0.005 (3)	−0.004 (4)	0.0030 (9)

Geometric parameters (Å, º) top

O1—C1	1.423 (7)	C3—H32	0.9600
O1—C4	1.419 (9)	C4—H41	0.9700
C1—H11	0.9700	C4—H42	0.9700
C1—H12	0.9700	C4—C5	1.499 (6)
C1—C2	1.472 (14)	C5—H51	0.9700
C2—H22	0.9700	C5—H52	0.9700
C2—H21	0.9700	C5—C6	1.485 (13)
C2—C3	1.520 (7)	C6—H63	0.9600
C3—H33	0.9600	C6—H61	0.9600
C3—H31	0.9600	C6—H62	0.9600

C4—O1—C1	112.3 (3)	O1—C4—H41	109.4
O1—C1—H11	109.5	O1—C4—H42	109.4
O1—C1—H12	109.5	O1—C4—C5	111.0 (4)
O1—C1—C2	110.8 (3)	H41—C4—H42	108.0
H11—C1—H12	108.1	C5—C4—H41	109.4
C2—C1—H11	109.5	C5—C4—H42	109.4
C2—C1—H12	109.5	C4—C5—H51	109.2
C1—C2—H22	109.2	C4—C5—H52	109.2
C1—C2—H21	109.2	H51—C5—H52	107.9
C1—C2—C3	111.9 (3)	C6—C5—C4	112.0 (4)
H22—C2—H21	107.9	C6—C5—H51	109.2
C3—C2—H22	109.2	C6—C5—H52	109.2
C3—C2—H21	109.2	C5—C6—H63	109.5
C2—C3—H33	109.5	C5—C6—H61	109.5
C2—C3—H31	109.5	C5—C6—H62	109.5
C2—C3—H32	109.5	H63—C6—H61	109.5
H33—C3—H31	109.5	H63—C6—H62	109.5
H33—C3—H32	109.5	H61—C6—H62	109.5
H31—C3—H32	109.5

O1—C1—C2—C3	170.71 (15)	C1—O1—C4—C5	−172.7 (2)
O1—C4—C5—C6	−174.5 (4)	C4—O1—C1—C2	171.8 (3)

dipropyl ether (dipropyl_ether_phase_alpha_5_30GPa) top

Crystal data top

C₆H₁₄O	F(000) = 232
M_r = 102.17	D_x = 1.304 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.099 (12) Å	Cell parameters from 1024 reflections
b = 3.9465 (3) Å	θ = 5.3–26.1°
c = 14.649 (8) Å	µ = 0.09 mm⁻¹
β = 98.32 (10)°	T = 295 K
V = 520.5 (7) Å³	Disc, colourless
Z = 4	0.44 × 0.40 × 0.21 mm

Data collection top

KUMA KM4-CCD, Eos diffractometer	232 reflections with I > 2σ(I)
φ– and ω–scans	R_int = 0.035
Absorption correction: multi-scan CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θ_max = 26.3°, θ_min = 5.4°
T_min = 0.725, T_max = 1.000	h = −7→7
2594 measured reflections	k = −4→4
310 independent reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0445P)² + 0.3422P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
310 reflections	Δρ_max = 0.10 e Å⁻³
66 parameters	Δρ_min = −0.08 e Å⁻³
6 restraints

Special details top

Refinement. The diamond-anvil cell (DAC) imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.4627 (19)	0.8650 (7)	0.1325 (8)	0.050 (9)
C1	0.371 (3)	0.7166 (10)	0.0531 (12)	0.023 (12)
H12	0.409912	0.780801	−0.002578	0.028*
H11	0.375152	0.471618	0.058045	0.028*
C2	0.217 (2)	0.8244 (10)	0.0454 (9)	0.049 (11)
H22	0.213116	1.069016	0.051235	0.059*
H21	0.172236	0.726698	0.095760	0.059*
C3	0.127 (2)	0.7196 (10)	−0.0455 (8)	0.046 (10)
H33	0.029615	0.820062	−0.050986	0.069*
H31	0.117300	0.477280	−0.047607	0.069*
H32	0.175853	0.795027	−0.095538	0.069*
C4	0.605 (3)	0.7270 (11)	0.1482 (13)	0.033 (14)
H41	0.658536	0.789594	0.097857	0.040*
H42	0.598453	0.481867	0.149304	0.040*
C5	0.693 (2)	0.8507 (9)	0.2395 (8)	0.044 (11)
H51	0.691123	1.096390	0.240938	0.052*
H52	0.644999	0.768628	0.290271	0.052*
C6	0.846 (2)	0.7360 (12)	0.2521 (9)	0.066 (10)
H63	0.896718	0.821768	0.309438	0.100*
H61	0.893893	0.817475	0.202188	0.100*
H62	0.848248	0.492831	0.253003	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.07 (2)	0.0270 (14)	0.056 (9)	0.006 (5)	0.034 (14)	−0.002 (3)
C1	0.01 (3)	0.0240 (18)	0.037 (17)	0.001 (10)	0.00 (2)	0.000 (6)
C2	0.07 (3)	0.0260 (18)	0.059 (12)	0.005 (5)	0.042 (18)	0.001 (3)
C3	0.07 (3)	0.0302 (19)	0.039 (11)	−0.004 (6)	0.021 (16)	−0.002 (4)
C4	0.02 (4)	0.0253 (19)	0.055 (17)	0.007 (10)	0.02 (2)	0.006 (6)
C5	0.08 (3)	0.0245 (18)	0.028 (10)	0.006 (5)	0.015 (17)	0.004 (3)
C6	0.12 (3)	0.030 (2)	0.064 (12)	0.008 (6)	0.053 (17)	0.005 (4)

Geometric parameters (Å, º) top

O1—C1	1.46 (4)	C3—H32	0.9600
O1—C4	1.40 (4)	C4—H41	0.9700
C1—H12	0.9700	C4—H42	0.9700
C1—H11	0.9700	C4—C5	1.53 (4)
C1—C2	1.45 (4)	C5—H51	0.9700
C2—H22	0.9700	C5—H52	0.9700
C2—H21	0.9700	C5—C6	1.45 (3)
C2—C3	1.52 (3)	C6—H63	0.9600
C3—H33	0.9600	C6—H61	0.9600
C3—H31	0.9600	C6—H62	0.9600

C4—O1—C1	112.9 (6)	O1—C4—H41	109.2
O1—C1—H12	109.1	O1—C4—H42	109.2
O1—C1—H11	109.1	O1—C4—C5	111.8 (6)
H12—C1—H11	107.9	H41—C4—H42	107.9
C2—C1—O1	112.4 (5)	C5—C4—H41	109.2
C2—C1—H12	109.1	C5—C4—H42	109.2
C2—C1—H11	109.1	C4—C5—H51	109.2
C1—C2—H22	109.1	C4—C5—H52	109.2
C1—C2—H21	109.1	H51—C5—H52	107.9
C1—C2—C3	112.3 (6)	C6—C5—C4	112.2 (6)
H22—C2—H21	107.9	C6—C5—H51	109.2
C3—C2—H22	109.1	C6—C5—H52	109.2
C3—C2—H21	109.1	C5—C6—H63	109.5
C2—C3—H33	109.5	C5—C6—H61	109.5
C2—C3—H31	109.5	C5—C6—H62	109.5
C2—C3—H32	109.5	H63—C6—H61	109.5
H33—C3—H31	109.5	H63—C6—H62	109.5
H33—C3—H32	109.5	H61—C6—H62	109.5
H31—C3—H32	109.5

O1—C1—C2—C3	170.2 (4)	C1—O1—C4—C5	−172.0 (4)
O1—C4—C5—C6	−174.3 (4)	C4—O1—C1—C2	171.4 (4)

Funding information

This study was supported by the National Science Centre, Poland (grant No. 2020/37/B/ST4/00982).

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IUCrJ

Volume 11| Part 1| January 2024| Pages 57-61

ISSN: 2052-2525

https://doi.org/10.1107/S2052252523009995

CHEMISTRY | CRYSTENG

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access