6,6′-[(3,3′-Di-tert-butyl-5,5′-dimeth­oxy-1,1′-biphenyl-2,2′-di­yl)bis(oxy)]bis­(dibenzo[d,f][1,3,2]dioxaphosphepine) benzene monosolvate

Leidecker, B.N.; Kubis, C.; Spannenberg, A.; Franke, R.; Börner, A.

doi:10.1107/S2414314619016365

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 12| December 2019| x191636

https://doi.org/10.1107/S2414314619016365

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access

6,6′-[(3,3′-Di-tert-butyl-5,5′-dimethoxy-1,1′-biphenyl-2,2′-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepine) benzene monosolvate

Benedict N. Leidecker,^a Christoph Kubis,^a ^* Anke Spannenberg,^a Robert Franke ^b,^c ^* and Armin Börner ^a

^aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany, ^bEvonik Performance Materials GmbH, Paul-Baumann-Str. 1, 45772 Marl, Germany, and ^cLehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany
^*Correspondence e-mail: christoph.kubis@catalysis.de, robert.franke@evonik.com

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 21 November 2019; accepted 4 December 2019; online 10 December 2019)

The crystal structure of the benzene monosolvate of the well known organic diphosphite ligand BIPHEPHOS, C₄₆H₄₄O₈P₂·C₆H₆, is reported for the first time. Single crystals of BIPHEPHOS were obtained from a benzene solution after layering with n-heptane at room temperature. One specific property of this type of diphosphite structure is the twisting of the biphenyl units. In the crystal, C—H⋯π contacts and π–π stacking interactions [centroid-to-centroid distance = 3.8941 (15) Å] are observed.

Keywords: crystal structure; diphosphite; BIPHEPHOS; biphenyl unit.

CCDC reference: 1970077

Structure description

BIPHEPHOS is a very prominent organic diphosphite ligand applied as co-catalyst in the field of highly n-regioselective rhodium-catalysed alkene hydroformylation (Börner & Franke, 2016 ). Atropisomerism of the dibenzo[d,f][1,3,2]dioxaphosphepine moiety in related diphosphites has been studied in solution and by DFT methods (Whiteker et al., 1995 , Briggs & Whiteker, 2001 , Franke et al., 2003 ). Interestingly, until now no crystal structure of BIPHEPHOS has been reported. Crystal structures have been published for similar diphosphites containing the same dibenzo[d,f][1,3,2]dioxaphosphepine unit but with the unsubstituted 2,2′-dihydroxybiphenyl and the 2,2′-dihydroxy-3,3′,5,5′-tetra(t-butyl)biphenyl backbone (Baker et al., 1991 ; Meyer et al., 1993 ; Hao et al., 2012 ; Liu et al., 2014 ). The common feature of these types of ligands is the twisting about the biphenyl linkages. For the title compound (Fig. 1), the dihedral angle about the biphenyl axis of the backbone between the C1–C6 and C7–C12 planes is 61.79 (10)°. Within the seven-membered rings, the dihedral angles about the biphenyl units are 43.83 (11)° for C2–C28/C29–C34 and 41.78 (11)° for C35–C40/C41–C46.

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. Hydrogen atoms are omitted for clarity.

Crystals of the title compound contain co-crystallized solvent (one benzene per one molecule diphosphite), which interacts with the ligand via C—H⋯π interactions (Table 1). In the crystal, centrosymmetrically related molecules are linked by a π–π stacking interaction involving the C23–C28 rings with a centroid-to-centroid distance of 3.8941 (15) Å.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C47–C52 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C39—H39⋯Cg1ⁱ	0.95	2.75	3.678 (3)	165
Symmetry code: (i) x, y-1, z.

Synthesis and crystallization

The diphosphite was provided by Evonik Performance Materials GmbH (OxoPhos^® 17). A solution of C₄₆H₄₄O₈P₂ (0.08 mmol, 0.063 g) in benzene (2 ml) was prepared under argon using standard Schlenk techniques. The solution was brought to 50°C for dissolving the solid material. At room temperature the solution was then layered with ca 0.4 ml of n-heptane. Crystallization as fine needles took place at room temperature after several days.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₄₆H₄₄O₈P₂·C₆H₆
M_r	864.86
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	25.1072 (5), 8.8634 (2), 21.3401 (4)
β (°)	112.4441 (12)
V (Å³)	4389.20 (16)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.36
Crystal size (mm)	0.34 × 0.04 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.80, 0.95
No. of measured, independent and observed [I > 2σ(I)] reflections	41898, 7745, 5805
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.107, 1.01
No. of reflections	7745
No. of parameters	567
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.34
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2013 ), XP in SHELXTL and SHELXS97 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1970077

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619016365/rz4035sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619016365/rz4035Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

6,6'-[(3,3'-Di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepine) benzene monosolvate top

Crystal data top

C₄₆H₄₄O₈P₂·C₆H₆	F(000) = 1824
M_r = 864.86	D_x = 1.309 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 25.1072 (5) Å	Cell parameters from 4431 reflections
b = 8.8634 (2) Å	θ = 3.8–66.5°
c = 21.3401 (4) Å	µ = 1.36 mm⁻¹
β = 112.4441 (12)°	T = 150 K
V = 4389.20 (16) Å³	Needle, colourless
Z = 4	0.34 × 0.04 × 0.04 mm

Data collection top

Bruker APEXII CCD diffractometer	7745 independent reflections
Radiation source: microfocus	5805 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.067
Detector resolution: 8.3333 pixels mm^-1	θ_max = 66.7°, θ_min = 1.9°
φ and ω scans	h = −29→29
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −10→9
T_min = 0.80, T_max = 0.95	l = −25→25
41898 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0532P)² + 0.4402P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
7745 reflections	Δρ_max = 0.25 e Å⁻³
567 parameters	Δρ_min = −0.34 e Å⁻³

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. All H atoms were placed geometrically and refined using a riding atom approximation, with C–H = 0.95–0.98 Å, and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H atoms. A rotating model was used for the methyl groups.

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

	x	y	z	U_iso*/U_eq
C1	0.21470 (8)	0.4417 (2)	0.51667 (10)	0.0260 (4)
C2	0.15970 (9)	0.3898 (3)	0.47514 (10)	0.0296 (4)
C3	0.11333 (9)	0.4728 (3)	0.47748 (10)	0.0318 (4)
H3	0.0754	0.4417	0.4499	0.038*
C4	0.12035 (9)	0.5992 (3)	0.51846 (10)	0.0318 (4)
C5	0.17481 (9)	0.6423 (2)	0.56151 (10)	0.0290 (4)
H5	0.1798	0.7261	0.5909	0.035*
C6	0.22288 (8)	0.5612 (2)	0.56154 (9)	0.0260 (4)
C7	0.28090 (8)	0.6109 (2)	0.61018 (9)	0.0257 (4)
C8	0.29895 (9)	0.7562 (2)	0.60285 (9)	0.0275 (4)
H8	0.2752	0.8192	0.5671	0.033*
C9	0.35139 (9)	0.8083 (2)	0.64762 (10)	0.0271 (4)
C10	0.38784 (8)	0.7113 (2)	0.69685 (10)	0.0274 (4)
H10	0.4253	0.7457	0.7246	0.033*
C11	0.37152 (8)	0.5665 (2)	0.70686 (9)	0.0255 (4)
C12	0.31566 (8)	0.5203 (2)	0.66410 (9)	0.0248 (4)
C13	0.14907 (9)	0.2501 (3)	0.42951 (11)	0.0357 (5)
C14	0.18159 (10)	0.1141 (3)	0.47133 (12)	0.0382 (5)
H14A	0.2231	0.1340	0.4890	0.057*
H14B	0.1731	0.0241	0.4425	0.057*
H14C	0.1693	0.0974	0.5092	0.057*
C15	0.16772 (11)	0.2851 (3)	0.37019 (11)	0.0430 (6)
H15A	0.1452	0.3702	0.3440	0.065*
H15B	0.1611	0.1962	0.3408	0.065*
H15C	0.2088	0.3110	0.3880	0.065*
C16	0.08521 (11)	0.2061 (3)	0.39926 (15)	0.0552 (7)
H16A	0.0713	0.1908	0.4359	0.083*
H16B	0.0806	0.1125	0.3732	0.083*
H16C	0.0630	0.2868	0.3693	0.083*
C17	0.07469 (11)	0.7922 (3)	0.55768 (15)	0.0536 (7)
H17A	0.0915	0.7573	0.6048	0.080*
H17B	0.0364	0.8344	0.5484	0.080*
H17C	0.0995	0.8700	0.5504	0.080*
C18	0.33003 (10)	1.0591 (2)	0.60870 (11)	0.0333 (5)
H18A	0.3148	1.0291	0.5609	0.050*
H18B	0.3483	1.1585	0.6135	0.050*
H18C	0.2985	1.0639	0.6250	0.050*
C19	0.41356 (8)	0.4679 (2)	0.76405 (10)	0.0278 (4)
C20	0.39320 (9)	0.4608 (3)	0.82366 (10)	0.0317 (4)
H20A	0.3545	0.4168	0.8080	0.048*
H20B	0.3923	0.5629	0.8409	0.048*
H20C	0.4199	0.3982	0.8599	0.048*
C21	0.47487 (9)	0.5340 (3)	0.79171 (11)	0.0360 (5)
H21A	0.5011	0.4640	0.8247	0.054*
H21B	0.4748	0.6310	0.8138	0.054*
H21C	0.4878	0.5492	0.7542	0.054*
C22	0.41810 (9)	0.3085 (3)	0.73876 (10)	0.0317 (4)
H22A	0.4303	0.3145	0.7003	0.048*
H22B	0.3805	0.2587	0.7244	0.048*
H22C	0.4465	0.2503	0.7754	0.048*
C23	0.42077 (9)	0.4076 (3)	0.56208 (10)	0.0300 (4)
C24	0.45812 (9)	0.5236 (3)	0.59366 (10)	0.0343 (5)
H24	0.4453	0.6070	0.6121	0.041*
C25	0.51494 (10)	0.5166 (3)	0.59814 (11)	0.0397 (5)
H25	0.5411	0.5958	0.6194	0.048*
C26	0.53311 (9)	0.3941 (3)	0.57156 (11)	0.0408 (6)
H26	0.5718	0.3895	0.5746	0.049*
C27	0.49539 (9)	0.2779 (3)	0.54057 (11)	0.0368 (5)
H27	0.5086	0.1939	0.5229	0.044*
C28	0.43789 (9)	0.2825 (3)	0.53483 (10)	0.0310 (4)
C29	0.39772 (9)	0.1581 (3)	0.50225 (10)	0.0309 (4)
C30	0.41526 (10)	0.0076 (3)	0.51498 (11)	0.0352 (5)
H30	0.4534	−0.0142	0.5456	0.042*
C31	0.37855 (10)	−0.1101 (3)	0.48411 (11)	0.0385 (5)
H31	0.3912	−0.2114	0.4946	0.046*
C32	0.32335 (10)	−0.0804 (3)	0.43777 (11)	0.0375 (5)
H32	0.2984	−0.1613	0.4158	0.045*
C33	0.30467 (9)	0.0682 (3)	0.42360 (10)	0.0332 (5)
H33	0.2672	0.0895	0.3912	0.040*
C34	0.34123 (9)	0.1848 (3)	0.45714 (10)	0.0293 (4)
C35	0.15006 (9)	0.2095 (3)	0.64810 (10)	0.0298 (4)
C36	0.09582 (10)	0.2675 (3)	0.61247 (11)	0.0363 (5)
H36	0.0911	0.3526	0.5838	0.044*
C37	0.04799 (10)	0.2002 (3)	0.61888 (12)	0.0401 (5)
H37	0.0105	0.2392	0.5947	0.048*
C38	0.05564 (9)	0.0756 (3)	0.66094 (12)	0.0375 (5)
H38	0.0231	0.0287	0.6651	0.045*
C39	0.11007 (9)	0.0195 (3)	0.69661 (11)	0.0330 (5)
H39	0.1147	−0.0653	0.7254	0.040*
C40	0.15884 (9)	0.0861 (2)	0.69093 (10)	0.0288 (4)
C41	0.21719 (9)	0.0226 (2)	0.72726 (10)	0.0279 (4)
C42	0.22625 (9)	−0.1325 (3)	0.73141 (10)	0.0320 (4)
H42	0.1944	−0.1984	0.7113	0.038*
C43	0.28060 (10)	−0.1929 (3)	0.76411 (11)	0.0369 (5)
H43	0.2859	−0.2992	0.7664	0.044*
C44	0.32739 (10)	−0.0979 (3)	0.79350 (11)	0.0372 (5)
H44	0.3649	−0.1391	0.8151	0.045*
C45	0.31965 (9)	0.0563 (3)	0.79145 (10)	0.0334 (5)
H45	0.3516	0.1213	0.8126	0.040*
C46	0.26507 (9)	0.1158 (2)	0.75833 (9)	0.0284 (4)
C47	0.04143 (12)	0.7196 (4)	0.77065 (14)	0.0537 (7)
H47	0.0019	0.7458	0.7563	0.064*
C48	0.05877 (12)	0.6181 (4)	0.73342 (14)	0.0540 (7)
H48	0.0311	0.5740	0.6937	0.065*
C49	0.11611 (13)	0.5804 (3)	0.75358 (15)	0.0550 (7)
H49	0.1281	0.5103	0.7280	0.066*
C50	0.15594 (13)	0.6450 (4)	0.81117 (17)	0.0627 (9)
H50	0.1956	0.6203	0.8252	0.075*
C51	0.13798 (15)	0.7463 (4)	0.84858 (15)	0.0629 (8)
H51	0.1654	0.7903	0.8885	0.076*
C52	0.08077 (14)	0.7832 (4)	0.82824 (14)	0.0590 (7)
H52	0.0685	0.8524	0.8540	0.071*
O1	0.26355 (6)	0.36536 (16)	0.51544 (7)	0.0273 (3)
O2	0.36542 (6)	0.40936 (17)	0.56232 (7)	0.0294 (3)
O3	0.32105 (6)	0.33231 (17)	0.44072 (7)	0.0309 (3)
O4	0.29329 (6)	0.38073 (16)	0.67427 (7)	0.0265 (3)
O5	0.19750 (6)	0.27103 (17)	0.63783 (7)	0.0309 (3)
O6	0.25769 (6)	0.27110 (17)	0.76141 (7)	0.0310 (3)
O7	0.06992 (7)	0.6688 (2)	0.51339 (8)	0.0427 (4)
O8	0.37168 (7)	0.95099 (17)	0.64772 (7)	0.0337 (3)
P1	0.31057 (2)	0.45307 (6)	0.49248 (2)	0.02799 (13)
P2	0.23811 (2)	0.38617 (6)	0.69709 (3)	0.02787 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0238 (9)	0.0298 (11)	0.0245 (9)	0.0053 (8)	0.0094 (8)	0.0046 (8)
C2	0.0302 (10)	0.0345 (12)	0.0224 (9)	0.0016 (8)	0.0081 (8)	−0.0001 (8)
C3	0.0246 (10)	0.0404 (13)	0.0268 (10)	0.0017 (8)	0.0057 (8)	−0.0021 (8)
C4	0.0266 (10)	0.0397 (13)	0.0273 (10)	0.0085 (9)	0.0083 (8)	0.0012 (9)
C5	0.0301 (10)	0.0300 (11)	0.0259 (9)	0.0030 (8)	0.0096 (8)	−0.0008 (8)
C6	0.0268 (10)	0.0276 (11)	0.0231 (9)	0.0009 (8)	0.0090 (8)	0.0032 (7)
C7	0.0267 (10)	0.0297 (11)	0.0229 (9)	0.0006 (8)	0.0119 (8)	−0.0013 (7)
C8	0.0307 (10)	0.0286 (11)	0.0228 (9)	0.0024 (8)	0.0100 (8)	0.0026 (8)
C9	0.0310 (10)	0.0268 (11)	0.0258 (9)	−0.0033 (8)	0.0132 (8)	−0.0003 (8)
C10	0.0258 (10)	0.0332 (12)	0.0237 (9)	−0.0031 (8)	0.0100 (8)	−0.0029 (8)
C11	0.0263 (10)	0.0294 (11)	0.0241 (9)	0.0004 (8)	0.0133 (8)	−0.0007 (7)
C12	0.0269 (10)	0.0255 (11)	0.0248 (9)	−0.0008 (8)	0.0131 (8)	−0.0010 (7)
C13	0.0310 (11)	0.0398 (13)	0.0325 (10)	0.0000 (9)	0.0079 (9)	−0.0093 (9)
C14	0.0420 (12)	0.0331 (12)	0.0401 (12)	−0.0030 (9)	0.0162 (10)	−0.0069 (9)
C15	0.0471 (14)	0.0492 (15)	0.0258 (10)	0.0085 (11)	0.0061 (10)	−0.0075 (9)
C16	0.0358 (13)	0.0578 (18)	0.0619 (17)	−0.0049 (11)	0.0075 (12)	−0.0290 (14)
C17	0.0395 (14)	0.0598 (18)	0.0567 (15)	0.0138 (12)	0.0130 (12)	−0.0185 (13)
C18	0.0458 (13)	0.0247 (11)	0.0308 (10)	0.0010 (9)	0.0162 (9)	0.0020 (8)
C19	0.0261 (10)	0.0337 (12)	0.0229 (9)	0.0010 (8)	0.0086 (8)	0.0018 (8)
C20	0.0336 (11)	0.0388 (12)	0.0225 (9)	0.0013 (9)	0.0105 (8)	0.0014 (8)
C21	0.0276 (11)	0.0433 (13)	0.0328 (10)	−0.0002 (9)	0.0069 (9)	0.0054 (9)
C22	0.0328 (11)	0.0356 (12)	0.0266 (10)	0.0062 (9)	0.0112 (8)	0.0029 (8)
C23	0.0276 (10)	0.0404 (13)	0.0245 (9)	0.0022 (8)	0.0128 (8)	0.0025 (8)
C24	0.0343 (11)	0.0431 (13)	0.0269 (10)	−0.0024 (9)	0.0133 (9)	−0.0038 (9)
C25	0.0297 (11)	0.0571 (16)	0.0311 (11)	−0.0083 (10)	0.0104 (9)	−0.0037 (10)
C26	0.0265 (11)	0.0679 (17)	0.0294 (10)	−0.0005 (10)	0.0122 (9)	−0.0010 (10)
C27	0.0316 (11)	0.0525 (15)	0.0287 (10)	0.0071 (10)	0.0144 (9)	0.0026 (9)
C28	0.0307 (10)	0.0397 (13)	0.0250 (9)	0.0054 (9)	0.0134 (8)	0.0037 (8)
C29	0.0340 (11)	0.0380 (12)	0.0255 (9)	0.0045 (9)	0.0169 (9)	0.0002 (8)
C30	0.0366 (11)	0.0419 (13)	0.0299 (10)	0.0095 (9)	0.0158 (9)	0.0003 (9)
C31	0.0487 (13)	0.0351 (13)	0.0383 (11)	0.0065 (10)	0.0238 (11)	0.0002 (9)
C32	0.0425 (13)	0.0394 (13)	0.0359 (11)	−0.0028 (10)	0.0207 (10)	−0.0079 (9)
C33	0.0347 (11)	0.0418 (13)	0.0253 (9)	0.0018 (9)	0.0140 (9)	−0.0031 (8)
C34	0.0346 (11)	0.0345 (12)	0.0232 (9)	0.0051 (9)	0.0161 (8)	0.0013 (8)
C35	0.0290 (10)	0.0349 (12)	0.0268 (9)	−0.0040 (8)	0.0121 (8)	−0.0025 (8)
C36	0.0324 (11)	0.0399 (13)	0.0340 (11)	−0.0007 (9)	0.0099 (9)	0.0035 (9)
C37	0.0282 (11)	0.0482 (15)	0.0418 (12)	0.0007 (9)	0.0111 (10)	−0.0012 (10)
C38	0.0291 (11)	0.0461 (14)	0.0403 (11)	−0.0059 (9)	0.0167 (9)	−0.0050 (10)
C39	0.0352 (11)	0.0360 (13)	0.0323 (10)	−0.0048 (9)	0.0179 (9)	−0.0027 (9)
C40	0.0282 (10)	0.0344 (12)	0.0255 (9)	−0.0032 (8)	0.0121 (8)	−0.0046 (8)
C41	0.0311 (10)	0.0327 (12)	0.0239 (9)	−0.0021 (8)	0.0149 (8)	−0.0015 (8)
C42	0.0342 (11)	0.0349 (12)	0.0287 (10)	−0.0028 (9)	0.0139 (9)	−0.0030 (8)
C43	0.0430 (12)	0.0338 (13)	0.0338 (11)	0.0029 (9)	0.0147 (10)	−0.0019 (9)
C44	0.0332 (11)	0.0451 (14)	0.0310 (10)	0.0078 (10)	0.0099 (9)	0.0001 (9)
C45	0.0317 (11)	0.0438 (13)	0.0238 (9)	−0.0033 (9)	0.0095 (8)	−0.0029 (8)
C46	0.0324 (10)	0.0332 (11)	0.0221 (9)	−0.0015 (8)	0.0131 (8)	0.0000 (8)
C47	0.0491 (15)	0.0670 (19)	0.0527 (15)	−0.0009 (13)	0.0281 (13)	0.0081 (13)
C48	0.0528 (16)	0.0603 (18)	0.0471 (14)	−0.0054 (13)	0.0170 (12)	0.0015 (12)
C49	0.0605 (17)	0.0547 (18)	0.0553 (16)	0.0096 (13)	0.0284 (14)	0.0104 (13)
C50	0.0435 (15)	0.068 (2)	0.072 (2)	0.0043 (13)	0.0163 (14)	0.0379 (17)
C51	0.071 (2)	0.061 (2)	0.0418 (14)	−0.0161 (15)	0.0046 (14)	0.0121 (13)
C52	0.074 (2)	0.0626 (19)	0.0441 (14)	−0.0003 (15)	0.0271 (14)	0.0040 (13)
O1	0.0252 (7)	0.0294 (8)	0.0279 (7)	0.0021 (5)	0.0109 (6)	0.0002 (5)
O2	0.0253 (7)	0.0385 (9)	0.0265 (7)	0.0002 (6)	0.0122 (6)	−0.0024 (6)
O3	0.0357 (8)	0.0337 (8)	0.0245 (7)	0.0034 (6)	0.0129 (6)	0.0021 (6)
O4	0.0268 (7)	0.0266 (7)	0.0274 (7)	−0.0005 (5)	0.0120 (6)	0.0007 (5)
O5	0.0300 (7)	0.0366 (8)	0.0263 (7)	−0.0065 (6)	0.0111 (6)	0.0007 (6)
O6	0.0363 (8)	0.0314 (8)	0.0262 (7)	−0.0050 (6)	0.0131 (6)	−0.0023 (6)
O7	0.0274 (8)	0.0520 (11)	0.0421 (9)	0.0098 (7)	0.0058 (7)	−0.0125 (7)
O8	0.0359 (8)	0.0289 (8)	0.0325 (7)	−0.0056 (6)	0.0089 (6)	0.0040 (6)
P1	0.0297 (3)	0.0298 (3)	0.0263 (2)	0.0013 (2)	0.0127 (2)	0.00127 (19)
P2	0.0283 (3)	0.0292 (3)	0.0284 (2)	−0.0014 (2)	0.0133 (2)	−0.0002 (2)

Geometric parameters (Å, º) top

C1—C6	1.390 (3)	C25—C26	1.381 (4)
C1—C2	1.403 (3)	C25—H25	0.9500
C1—O1	1.409 (2)	C26—C27	1.384 (4)
C2—C3	1.394 (3)	C26—H26	0.9500
C2—C13	1.534 (3)	C27—C28	1.402 (3)
C3—C4	1.390 (3)	C27—H27	0.9500
C3—H3	0.9500	C28—C29	1.476 (3)
C4—O7	1.375 (3)	C29—C34	1.397 (3)
C4—C5	1.379 (3)	C29—C30	1.398 (3)
C5—C6	1.404 (3)	C30—C31	1.381 (4)
C5—H5	0.9500	C30—H30	0.9500
C6—C7	1.496 (3)	C31—C32	1.386 (3)
C7—C8	1.394 (3)	C31—H31	0.9500
C7—C12	1.401 (3)	C32—C33	1.393 (3)
C8—C9	1.378 (3)	C32—H32	0.9500
C8—H8	0.9500	C33—C34	1.386 (3)
C9—O8	1.364 (3)	C33—H33	0.9500
C9—C10	1.395 (3)	C34—O3	1.397 (3)
C10—C11	1.389 (3)	C35—C36	1.380 (3)
C10—H10	0.9500	C35—C40	1.388 (3)
C11—C12	1.411 (3)	C35—O5	1.401 (2)
C11—C19	1.544 (3)	C36—C37	1.394 (3)
C12—O4	1.409 (2)	C36—H36	0.9500
C13—C16	1.533 (3)	C37—C38	1.390 (4)
C13—C14	1.536 (3)	C37—H37	0.9500
C13—C15	1.540 (3)	C38—C39	1.379 (3)
C14—H14A	0.9800	C38—H38	0.9500
C14—H14B	0.9800	C39—C40	1.406 (3)
C14—H14C	0.9800	C39—H39	0.9500
C15—H15A	0.9800	C40—C41	1.482 (3)
C15—H15B	0.9800	C41—C42	1.391 (3)
C15—H15C	0.9800	C41—C46	1.399 (3)
C16—H16A	0.9800	C42—C43	1.381 (3)
C16—H16B	0.9800	C42—H42	0.9500
C16—H16C	0.9800	C43—C44	1.386 (3)
C17—O7	1.420 (3)	C43—H43	0.9500
C17—H17A	0.9800	C44—C45	1.379 (3)
C17—H17B	0.9800	C44—H44	0.9500
C17—H17C	0.9800	C45—C46	1.384 (3)
C18—O8	1.428 (3)	C45—H45	0.9500
C18—H18A	0.9800	C46—O6	1.394 (3)
C18—H18B	0.9800	C47—C52	1.370 (4)
C18—H18C	0.9800	C47—C48	1.376 (4)
C19—C22	1.532 (3)	C47—H47	0.9500
C19—C21	1.539 (3)	C48—C49	1.377 (4)
C19—C20	1.543 (3)	C48—H48	0.9500
C20—H20A	0.9800	C49—C50	1.379 (5)
C20—H20B	0.9800	C49—H49	0.9500
C20—H20C	0.9800	C50—C51	1.386 (5)
C21—H21A	0.9800	C50—H50	0.9500
C21—H21B	0.9800	C51—C52	1.372 (5)
C21—H21C	0.9800	C51—H51	0.9500
C22—H22A	0.9800	C52—H52	0.9500
C22—H22B	0.9800	O1—P1	1.6372 (14)
C22—H22C	0.9800	O2—P1	1.6433 (14)
C23—C24	1.381 (3)	O3—P1	1.6300 (15)
C23—O2	1.392 (2)	O4—P2	1.6352 (13)
C23—C28	1.394 (3)	O5—P2	1.6419 (15)
C24—C25	1.394 (3)	O6—P2	1.6282 (15)
C24—H24	0.9500

C6—C1—C2	122.39 (18)	C23—C24—H24	120.4
C6—C1—O1	118.55 (17)	C25—C24—H24	120.4
C2—C1—O1	118.98 (18)	C26—C25—C24	119.8 (2)
C3—C2—C1	116.0 (2)	C26—C25—H25	120.1
C3—C2—C13	120.23 (19)	C24—C25—H25	120.1
C1—C2—C13	123.77 (19)	C25—C26—C27	120.5 (2)
C4—C3—C2	122.7 (2)	C25—C26—H26	119.7
C4—C3—H3	118.6	C27—C26—H26	119.7
C2—C3—H3	118.6	C26—C27—C28	121.0 (2)
O7—C4—C5	125.3 (2)	C26—C27—H27	119.5
O7—C4—C3	114.84 (19)	C28—C27—H27	119.5
C5—C4—C3	119.86 (19)	C23—C28—C27	117.2 (2)
C4—C5—C6	119.48 (19)	C23—C28—C29	121.77 (19)
C4—C5—H5	120.3	C27—C28—C29	121.0 (2)
C6—C5—H5	120.3	C34—C29—C30	117.2 (2)
C1—C6—C5	119.26 (18)	C34—C29—C28	121.9 (2)
C1—C6—C7	123.42 (18)	C30—C29—C28	120.9 (2)
C5—C6—C7	117.31 (18)	C31—C30—C29	121.6 (2)
C8—C7—C12	119.64 (18)	C31—C30—H30	119.2
C8—C7—C6	117.78 (17)	C29—C30—H30	119.2
C12—C7—C6	122.49 (18)	C30—C31—C32	120.0 (2)
C9—C8—C7	119.79 (18)	C30—C31—H31	120.0
C9—C8—H8	120.1	C32—C31—H31	120.0
C7—C8—H8	120.1	C31—C32—C33	119.8 (2)
O8—C9—C8	124.69 (19)	C31—C32—H32	120.1
O8—C9—C10	115.65 (18)	C33—C32—H32	120.1
C8—C9—C10	119.66 (19)	C34—C33—C32	119.4 (2)
C11—C10—C9	122.54 (19)	C34—C33—H33	120.3
C11—C10—H10	118.7	C32—C33—H33	120.3
C9—C10—H10	118.7	C33—C34—C29	121.8 (2)
C10—C11—C12	116.61 (18)	C33—C34—O3	117.58 (19)
C10—C11—C19	119.47 (18)	C29—C34—O3	120.5 (2)
C12—C11—C19	123.90 (18)	C36—C35—C40	122.08 (19)
C7—C12—O4	118.00 (17)	C36—C35—O5	119.21 (19)
C7—C12—C11	121.21 (19)	C40—C35—O5	118.60 (18)
O4—C12—C11	120.78 (17)	C35—C36—C37	119.5 (2)
C16—C13—C2	111.91 (19)	C35—C36—H36	120.2
C16—C13—C14	106.5 (2)	C37—C36—H36	120.2
C2—C13—C14	109.85 (18)	C38—C37—C36	119.5 (2)
C16—C13—C15	107.6 (2)	C38—C37—H37	120.3
C2—C13—C15	109.0 (2)	C36—C37—H37	120.3
C14—C13—C15	112.01 (19)	C39—C38—C37	120.5 (2)
C13—C14—H14A	109.5	C39—C38—H38	119.8
C13—C14—H14B	109.5	C37—C38—H38	119.8
H14A—C14—H14B	109.5	C38—C39—C40	120.9 (2)
C13—C14—H14C	109.5	C38—C39—H39	119.5
H14A—C14—H14C	109.5	C40—C39—H39	119.5
H14B—C14—H14C	109.5	C35—C40—C39	117.6 (2)
C13—C15—H15A	109.5	C35—C40—C41	121.36 (18)
C13—C15—H15B	109.5	C39—C40—C41	121.0 (2)
H15A—C15—H15B	109.5	C42—C41—C46	117.6 (2)
C13—C15—H15C	109.5	C42—C41—C40	120.90 (19)
H15A—C15—H15C	109.5	C46—C41—C40	121.5 (2)
H15B—C15—H15C	109.5	C43—C42—C41	121.4 (2)
C13—C16—H16A	109.5	C43—C42—H42	119.3
C13—C16—H16B	109.5	C41—C42—H42	119.3
H16A—C16—H16B	109.5	C42—C43—C44	119.8 (2)
C13—C16—H16C	109.5	C42—C43—H43	120.1
H16A—C16—H16C	109.5	C44—C43—H43	120.1
H16B—C16—H16C	109.5	C45—C44—C43	120.2 (2)
O7—C17—H17A	109.5	C45—C44—H44	119.9
O7—C17—H17B	109.5	C43—C44—H44	119.9
H17A—C17—H17B	109.5	C44—C45—C46	119.6 (2)
O7—C17—H17C	109.5	C44—C45—H45	120.2
H17A—C17—H17C	109.5	C46—C45—H45	120.2
H17B—C17—H17C	109.5	C45—C46—O6	118.40 (19)
O8—C18—H18A	109.5	C45—C46—C41	121.4 (2)
O8—C18—H18B	109.5	O6—C46—C41	119.96 (18)
H18A—C18—H18B	109.5	C52—C47—C48	120.5 (3)
O8—C18—H18C	109.5	C52—C47—H47	119.7
H18A—C18—H18C	109.5	C48—C47—H47	119.7
H18B—C18—H18C	109.5	C47—C48—C49	120.1 (3)
C22—C19—C21	106.76 (17)	C47—C48—H48	119.9
C22—C19—C20	110.18 (17)	C49—C48—H48	119.9
C21—C19—C20	107.29 (17)	C48—C49—C50	119.6 (3)
C22—C19—C11	111.34 (16)	C48—C49—H49	120.2
C21—C19—C11	111.70 (17)	C50—C49—H49	120.2
C20—C19—C11	109.46 (16)	C49—C50—C51	119.9 (3)
C19—C20—H20A	109.5	C49—C50—H50	120.1
C19—C20—H20B	109.5	C51—C50—H50	120.1
H20A—C20—H20B	109.5	C52—C51—C50	120.2 (3)
C19—C20—H20C	109.5	C52—C51—H51	119.9
H20A—C20—H20C	109.5	C50—C51—H51	119.9
H20B—C20—H20C	109.5	C47—C52—C51	119.7 (3)
C19—C21—H21A	109.5	C47—C52—H52	120.2
C19—C21—H21B	109.5	C51—C52—H52	120.2
H21A—C21—H21B	109.5	C1—O1—P1	120.65 (13)
C19—C21—H21C	109.5	C23—O2—P1	119.44 (12)
H21A—C21—H21C	109.5	C34—O3—P1	125.54 (12)
H21B—C21—H21C	109.5	C12—O4—P2	116.93 (12)
C19—C22—H22A	109.5	C35—O5—P2	115.87 (12)
C19—C22—H22B	109.5	C46—O6—P2	125.57 (12)
H22A—C22—H22B	109.5	C4—O7—C17	116.87 (18)
C19—C22—H22C	109.5	C9—O8—C18	115.57 (17)
H22A—C22—H22C	109.5	O3—P1—O1	102.27 (8)
H22B—C22—H22C	109.5	O3—P1—O2	99.42 (8)
C24—C23—O2	118.85 (19)	O1—P1—O2	93.84 (7)
C24—C23—C28	122.4 (2)	O6—P2—O4	102.43 (8)
O2—C23—C28	118.5 (2)	O6—P2—O5	99.14 (8)
C23—C24—C25	119.1 (2)	O4—P2—O5	95.73 (7)

C6—C1—C2—C3	4.9 (3)	C31—C32—C33—C34	−1.3 (3)
O1—C1—C2—C3	−178.35 (17)	C32—C33—C34—C29	3.6 (3)
C6—C1—C2—C13	−174.64 (19)	C32—C33—C34—O3	179.15 (17)
O1—C1—C2—C13	2.1 (3)	C30—C29—C34—C33	−3.1 (3)
C1—C2—C3—C4	−0.3 (3)	C28—C29—C34—C33	176.17 (18)
C13—C2—C3—C4	179.2 (2)	C30—C29—C34—O3	−178.52 (16)
C2—C3—C4—O7	178.8 (2)	C28—C29—C34—O3	0.8 (3)
C2—C3—C4—C5	−3.3 (3)	C40—C35—C36—C37	−0.5 (3)
O7—C4—C5—C6	−179.9 (2)	O5—C35—C36—C37	175.6 (2)
C3—C4—C5—C6	2.5 (3)	C35—C36—C37—C38	−0.2 (4)
C2—C1—C6—C5	−5.7 (3)	C36—C37—C38—C39	0.6 (4)
O1—C1—C6—C5	177.48 (17)	C37—C38—C39—C40	−0.5 (3)
C2—C1—C6—C7	175.04 (18)	C36—C35—C40—C39	0.6 (3)
O1—C1—C6—C7	−1.7 (3)	O5—C35—C40—C39	−175.47 (17)
C4—C5—C6—C1	1.9 (3)	C36—C35—C40—C41	178.2 (2)
C4—C5—C6—C7	−178.85 (18)	O5—C35—C40—C41	2.1 (3)
C1—C6—C7—C8	117.3 (2)	C38—C39—C40—C35	−0.1 (3)
C5—C6—C7—C8	−61.9 (2)	C38—C39—C40—C41	−177.74 (19)
C1—C6—C7—C12	−66.1 (3)	C35—C40—C41—C42	−136.9 (2)
C5—C6—C7—C12	114.7 (2)	C39—C40—C41—C42	40.6 (3)
C12—C7—C8—C9	1.6 (3)	C35—C40—C41—C46	42.9 (3)
C6—C7—C8—C9	178.23 (17)	C39—C40—C41—C46	−139.6 (2)
C7—C8—C9—O8	−175.82 (17)	C46—C41—C42—C43	−0.9 (3)
C7—C8—C9—C10	4.7 (3)	C40—C41—C42—C43	178.84 (18)
O8—C9—C10—C11	174.68 (17)	C41—C42—C43—C44	−0.1 (3)
C8—C9—C10—C11	−5.8 (3)	C42—C43—C44—C45	1.4 (3)
C9—C10—C11—C12	0.4 (3)	C43—C44—C45—C46	−1.7 (3)
C9—C10—C11—C19	−177.90 (17)	C44—C45—C46—O6	175.18 (17)
C8—C7—C12—O4	173.19 (16)	C44—C45—C46—C41	0.6 (3)
C6—C7—C12—O4	−3.3 (3)	C42—C41—C46—C45	0.6 (3)
C8—C7—C12—C11	−7.1 (3)	C40—C41—C46—C45	−179.11 (17)
C6—C7—C12—C11	176.38 (17)	C42—C41—C46—O6	−173.83 (16)
C10—C11—C12—C7	6.0 (3)	C40—C41—C46—O6	6.4 (3)
C19—C11—C12—C7	−175.73 (17)	C52—C47—C48—C49	−0.5 (4)
C10—C11—C12—O4	−174.29 (16)	C47—C48—C49—C50	−0.1 (4)
C19—C11—C12—O4	3.9 (3)	C48—C49—C50—C51	0.5 (4)
C3—C2—C13—C16	−8.9 (3)	C49—C50—C51—C52	−0.5 (4)
C1—C2—C13—C16	170.6 (2)	C48—C47—C52—C51	0.6 (4)
C3—C2—C13—C14	−126.9 (2)	C50—C51—C52—C47	−0.1 (4)
C1—C2—C13—C14	52.6 (3)	C6—C1—O1—P1	−63.9 (2)
C3—C2—C13—C15	110.0 (2)	C2—C1—O1—P1	119.26 (17)
C1—C2—C13—C15	−70.5 (3)	C24—C23—O2—P1	105.80 (19)
C10—C11—C19—C22	−133.04 (19)	C28—C23—O2—P1	−79.4 (2)
C12—C11—C19—C22	48.8 (2)	C33—C34—O3—P1	116.70 (17)
C10—C11—C19—C21	−13.8 (2)	C29—C34—O3—P1	−67.7 (2)
C12—C11—C19—C21	168.04 (18)	C7—C12—O4—P2	−66.19 (19)
C10—C11—C19—C20	104.9 (2)	C11—C12—O4—P2	114.13 (17)
C12—C11—C19—C20	−73.3 (2)	C36—C35—O5—P2	102.7 (2)
O2—C23—C24—C25	175.12 (19)	C40—C35—O5—P2	−81.1 (2)
C28—C23—C24—C25	0.5 (3)	C45—C46—O6—P2	116.01 (18)
C23—C24—C25—C26	−0.5 (3)	C41—C46—O6—P2	−69.4 (2)
C24—C25—C26—C27	−0.1 (4)	C5—C4—O7—C17	−1.9 (3)
C25—C26—C27—C28	0.6 (3)	C3—C4—O7—C17	175.8 (2)
C24—C23—C28—C27	0.0 (3)	C8—C9—O8—C18	14.4 (3)
O2—C23—C28—C27	−174.62 (17)	C10—C9—O8—C18	−166.10 (17)
C24—C23—C28—C29	178.94 (19)	C34—O3—P1—O1	−59.05 (17)
O2—C23—C28—C29	4.3 (3)	C34—O3—P1—O2	37.00 (17)
C26—C27—C28—C23	−0.6 (3)	C1—O1—P1—O3	−134.20 (14)
C26—C27—C28—C29	−179.5 (2)	C1—O1—P1—O2	125.29 (14)
C23—C28—C29—C34	43.9 (3)	C23—O2—P1—O3	53.57 (17)
C27—C28—C29—C34	−137.1 (2)	C23—O2—P1—O1	156.69 (16)
C23—C28—C29—C30	−136.8 (2)	C46—O6—P2—O4	−66.92 (16)
C27—C28—C29—C30	42.1 (3)	C46—O6—P2—O5	31.07 (17)
C34—C29—C30—C31	0.4 (3)	C12—O4—P2—O6	−131.10 (13)
C28—C29—C30—C31	−178.94 (19)	C12—O4—P2—O5	128.21 (13)
C29—C30—C31—C32	1.9 (3)	C35—O5—P2—O6	60.03 (15)
C30—C31—C32—C33	−1.4 (3)	C35—O5—P2—O4	163.63 (14)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C47–C52 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C39—H39···Cg1ⁱ	0.95	2.75	3.678 (3)	165

Symmetry code: (i) x, y−1, z.

References

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Volume 4| Part 12| December 2019| x191636

https://doi.org/10.1107/S2414314619016365

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6,6′-[(3,3′-Di-tert-butyl-5,5′-dimeth­­oxy-1,1′-bi­phenyl-2,2′-di­yl)bis­(­oxy)]bis­­(dibenzo[d,f][1,3,2]dioxaphosphepine) benzene monosolvate

Structure description

Synthesis and crystallization

Refinement

Structural data

References

organic compounds

6,6′-[(3,3′-Di-tert-butyl-5,5′-dimethoxy-1,1′-biphenyl-2,2′-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepine) benzene monosolvate