Bis(4-hy­droxy-N,N-di-n-propyl­tryptammonium) fumarate tetra­hydrate

Chadeayne, A.R.; Pham, D.N.K.; Golen, J.A.; Manke, D.R.

doi:10.1107/S241431461901469X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 11| November 2019| x191469

https://doi.org/10.1107/S241431461901469X

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Bis(4-hydroxy-N,N-di-n-propyltryptammonium) fumarate tetrahydrate

Andrew R. Chadeayne,^a ^* Duyen N. K. Pham,^b James A. Golen ^b and David R. Manke ^b

^aCaaMTech, LLC, 58 East Sunset Way, Suite 209, Issaquah, WA 98027, USA, and ^b285 Old Westport Rd., North Dartmouth, MA, 02747, USA
^*Correspondence e-mail: andrew@caam.tech

Edited by K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 9 October 2019; accepted 29 October 2019; online 12 November 2019)

The title compound (systematic name: bis{[2-(4-hydroxy-1H-indol-3-yl)ethyl]bis(propan-2-yl)azanium} but-2-enedioate tetrahydrate), 2C₁₆H₂₅N₂O⁺·C₄H₂O₄²⁻·4H₂O, has a singly protonated DPT cation, one half of a fumarate dianion (completed by a crystallographic centre of symmetry) and two water molecules of crystallization in the asymmetric unit. A series of N—H⋯O and O—H⋯O hydrogen bonds form a three-dimensional network in the solid state.

Keywords: crystal structure; tryptamines; indoles; hydrogen bonding.

CCDC references: 1962339; 1962339

Structure description

4-Hydroxy-N,N-di-n-propyltryptamine, or 4-HO-DPT, is a derivative of psilocin, which is the primary active psychedelic in `magic' mushrooms. Psilocin is the metabolite of psilocybin and its synthetic analogue psilacetin, and is a serotonin-2a agonist which results in its mood-altering effects. Tryptamines, both naturally occurring [Psilocybin (Weber & Petcher, 1974 ), Psilocin (Petcher & Weber, 1974 ), and DMT (Falkenberg, 1972 )] and their synthetic derivatives [Psilacetin (Chadeayne et al. 2019a ,b ), MPT (Chadeayne et al. 2019c ), MiPT, and 4-HO-MiPT (Chadeayne, Pham et al. 2019 )] have garnered a great deal of interest because of their potential to treat depression and post-traumatic stress disorder (PTSD) (Carhart-Harris & Goodwin, 2017 ). The solid-state structures of bioactive tryptamine molecules are significant because they define each molecule's physical identity, thereby providing the foundation for all downstream research. For example, such fundamental structural characterization is essential for understanding each molecule's biological and clinical properties via structure-activity relationships. To help further elucidate these properties, we report the structure of 4-HO-DPT herein.

The synthesis of 4-HO-DPT was first reported by Repke et al. in 1977 (Repke et al., 1977 ). The molecular structure of bis(4-hydroxy-N,N-di-n-propyltryptammonium)fumarate is shown in Fig. 1. The asymmetric unit contains one 4-HO-DPT cation, protonated at the dipropylamine N atom. There are also two independent water molecules, and half of a fumarate ion present. The 4-hydroxy-N,N-di-n-propyltryptammonium cations, fumarate dianions and water molecules are linked to each other in an infinite three-dimensional network through hydrogen bonds (Fig. 2, Table 1). Both inequivalent O atoms on the fumarate dianion (i.e. O2 and O3) accept two hydrogen bonds. One oxygen accepts hydrogen bonds from the hydroxide of the DPT cation and one water molecule. The other oxygen interacts with the indole N atom and the second independent water molecule. The ammonium proton hydrogen bonds with one of the water molecules. A weak O—H⋯π interaction is observed between one hydrogen atom of one of the water molecules and the six-membered ring of an adjacent indole unit. The packing of the compound is shown in Fig. 3.

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.89 (3)	2.08 (3)	2.926 (2)	157 (2)
N2—H2⋯O1W	0.98 (2)	1.73 (3)	2.689 (2)	168 (2)
O1—H1⋯O2	0.88 (3)	1.74 (3)	2.625 (2)	174 (3)
O1W—H1WA⋯O2Wⁱⁱ	0.83 (3)	1.88 (3)	2.710 (3)	172 (3)
O1W—H1WB⋯O3	0.83 (3)	1.86 (3)	2.684 (3)	171 (3)
O2W—H2WB⋯O2	0.94 (3)	1.76 (3)	2.695 (2)	173 (3)
O2W—H2WA⋯Cgⁱⁱⁱ	0.82 (4)	2.69 (4)	3.488 (2)	167 (3)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x-1, y, z; (iii) $[-x+{\script{5\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of bis(4-hydroxy-N,N-di-n-propyltryptammonium)fumarate tetrahydrate, showing the atomic labeling. Displacement ellipsoids are drawn at 50% probability level. Hydrogen bonds are shown as dashed lines. Symmetry code: (i) 2 − x, 1 − y, −z.

Figure 2
The hydrogen bonding of the fumarate ion in the structure of the title compound (Table 1

), with hydrogen bonds shown as dashed lines. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms not involved in hydrogen bonds are omitted for clarity. Symmetry codes: (i) 2 − x, 1 − y, −z; (ii) − $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z; (iii) $[{5\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z.

Figure 3
The crystal packing of the title compound, viewed along the a axis. The N—H⋯O and O—H⋯O hydrogen bonds (Table 1

) are shown as dashed lines. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

Synthesis and crystallization

Single crystals of 4-HO-DPT fumarate suitable for X-ray analysis were obtained by the slow evaporation of an aqueous solution of a commercial sample of 4-hydroxy-N,N-di-n-propyltryptamine fumarate (The Indole Shop).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₂₅N₂O⁺·0.5C₄H₂O₄²⁻·2H₂O
M_r	354.44
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	8.3495 (8), 12.5138 (11), 18.6631 (17)
β (°)	100.902 (3)
V (Å³)	1914.8 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.705, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	52418, 3512, 2630
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.128, 1.05
No. of reflections	3512
No. of parameters	257
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.22
Computer programs: SAINT (Bruker, 2016), SHELXT2014 (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC references: 1962339; 1962339

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431461901469X/ff4032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461901469X/ff4032Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461901469X/ff4032Isup3.cml

checkCIF report

Computing details top

Cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Bis{[2-(4-hydroxy-1H-indol-3-yl)ethyl]bis(propan-2-yl)azanium} but-2-enedioate tetrahydrate top

Crystal data top

C₁₆H₂₅N₂O⁺·0.5C₄H₂O₄²⁻·2H₂O	F(000) = 768
M_r = 354.44	D_x = 1.229 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.3495 (8) Å	Cell parameters from 9972 reflections
b = 12.5138 (11) Å	θ = 2.9–25.2°
c = 18.6631 (17) Å	µ = 0.09 mm⁻¹
β = 100.902 (3)°	T = 200 K
V = 1914.8 (3) Å³	Shard, colourless
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	2630 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.061
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.4°, θ_min = 2.9°
T_min = 0.705, T_max = 0.745	h = −10→10
52418 measured reflections	k = −15→15
3512 independent reflections	l = −22→22

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.0556P)² + 0.997P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.128	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.59 e Å⁻³
3512 reflections	Δρ_min = −0.22 e Å⁻³
257 parameters	Extinction correction: SHELXL2018 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0155 (18)

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.

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

	x	y	z	U_iso*/U_eq
O1	0.94852 (17)	0.34667 (12)	0.25667 (7)	0.0394 (4)
O1W	0.5933 (3)	0.38719 (15)	0.16468 (15)	0.0764 (7)
O2	1.05696 (17)	0.46219 (12)	0.15852 (7)	0.0445 (4)
O2W	1.3681 (2)	0.53142 (15)	0.18964 (10)	0.0529 (5)
O3	0.82210 (18)	0.42826 (13)	0.08492 (7)	0.0457 (4)
N1	1.0659 (3)	0.16741 (15)	0.47495 (10)	0.0494 (5)
N2	0.60593 (19)	0.17587 (13)	0.19118 (8)	0.0321 (4)
C1	0.9055 (3)	0.15399 (17)	0.44334 (11)	0.0468 (6)
H1B	0.829526	0.112646	0.463512	0.056*
C2	1.1400 (3)	0.23028 (15)	0.43090 (10)	0.0381 (5)
C3	1.3016 (3)	0.26370 (17)	0.43917 (12)	0.0459 (6)
H3	1.380626	0.244438	0.480779	0.055*
C4	1.3413 (3)	0.32549 (18)	0.38466 (13)	0.0457 (5)
H4	1.450484	0.349755	0.388895	0.055*
C5	1.2268 (2)	0.35418 (16)	0.32296 (11)	0.0390 (5)
H5	1.259699	0.396749	0.286160	0.047*
C6	1.0666 (2)	0.32147 (15)	0.31481 (10)	0.0312 (4)
C7	1.0205 (2)	0.25791 (14)	0.36961 (10)	0.0307 (4)
C8	0.8697 (3)	0.20820 (15)	0.37881 (10)	0.0347 (5)
C9	0.7111 (2)	0.21074 (16)	0.32523 (11)	0.0372 (5)
H9A	0.683386	0.285434	0.310371	0.045*
H9B	0.622912	0.181941	0.348408	0.045*
C10	0.7250 (2)	0.14395 (16)	0.25814 (10)	0.0346 (5)
H10A	0.836979	0.150899	0.248342	0.042*
H10B	0.707217	0.067836	0.268820	0.042*
C11	0.6625 (3)	0.13956 (16)	0.12321 (11)	0.0379 (5)
H11A	0.584190	0.165736	0.080225	0.045*
H11B	0.769365	0.173093	0.122033	0.045*
C12	0.6794 (3)	0.02060 (19)	0.11654 (13)	0.0560 (6)
H12A	0.573370	−0.013926	0.117888	0.067*
H12B	0.760009	−0.006282	0.158518	0.067*
C13	0.7340 (3)	−0.0092 (2)	0.04618 (13)	0.0572 (6)
H13A	0.736537	−0.087204	0.041736	0.086*
H13B	0.843254	0.019698	0.046637	0.086*
H13C	0.657436	0.020577	0.004669	0.086*
C14	0.4340 (2)	0.14425 (17)	0.19474 (11)	0.0397 (5)
H14A	0.410134	0.165611	0.242711	0.048*
H14B	0.424083	0.065534	0.190902	0.048*
C15	0.3094 (3)	0.1947 (2)	0.13503 (14)	0.0594 (7)
H15A	0.319125	0.273426	0.138887	0.071*
H15B	0.333208	0.173394	0.087045	0.071*
C16	0.1391 (3)	0.1631 (2)	0.13865 (15)	0.0615 (7)
H16A	0.063310	0.198177	0.099119	0.092*
H16B	0.114132	0.185071	0.185742	0.092*
H16C	0.127829	0.085439	0.133480	0.092*
C17	0.9662 (2)	0.45901 (15)	0.09626 (10)	0.0317 (4)
C18	1.0407 (2)	0.49612 (15)	0.03381 (10)	0.0338 (4)
H18	1.152918	0.515150	0.043346	0.041*
H1	0.991 (3)	0.383 (2)	0.2241 (15)	0.066 (8)*
H2WA	1.372 (4)	0.591 (3)	0.1719 (19)	0.098 (12)*
H2	0.604 (3)	0.254 (2)	0.1887 (13)	0.052 (6)*
H2WB	1.261 (4)	0.505 (2)	0.1751 (15)	0.081 (9)*
H1A	1.121 (3)	0.135 (2)	0.5147 (15)	0.065 (8)*
H1WA	0.527 (4)	0.435 (2)	0.1698 (15)	0.072 (9)*
H1WB	0.670 (4)	0.403 (2)	0.1439 (17)	0.079 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0337 (8)	0.0537 (9)	0.0303 (7)	−0.0009 (7)	0.0044 (6)	0.0130 (7)
O1W	0.0541 (12)	0.0389 (10)	0.149 (2)	0.0080 (9)	0.0516 (13)	0.0289 (11)
O2	0.0450 (9)	0.0619 (10)	0.0258 (7)	−0.0141 (7)	0.0043 (6)	0.0076 (7)
O2W	0.0432 (10)	0.0484 (10)	0.0669 (11)	−0.0053 (8)	0.0104 (8)	0.0144 (9)
O3	0.0415 (9)	0.0666 (10)	0.0289 (7)	−0.0133 (7)	0.0065 (6)	0.0004 (7)
N1	0.0745 (14)	0.0405 (10)	0.0264 (9)	−0.0074 (10)	−0.0074 (9)	0.0056 (8)
N2	0.0315 (9)	0.0300 (9)	0.0347 (9)	0.0010 (7)	0.0063 (7)	0.0043 (7)
C1	0.0688 (16)	0.0388 (12)	0.0337 (11)	−0.0109 (11)	0.0117 (11)	0.0017 (9)
C2	0.0538 (13)	0.0286 (10)	0.0275 (10)	0.0017 (9)	−0.0034 (9)	−0.0034 (8)
C3	0.0488 (13)	0.0375 (12)	0.0420 (12)	0.0037 (10)	−0.0155 (10)	−0.0067 (10)
C4	0.0338 (11)	0.0431 (12)	0.0560 (14)	0.0007 (9)	−0.0026 (10)	−0.0107 (11)
C5	0.0356 (11)	0.0388 (11)	0.0431 (12)	−0.0002 (9)	0.0092 (9)	−0.0007 (9)
C6	0.0344 (10)	0.0311 (10)	0.0273 (9)	0.0046 (8)	0.0040 (8)	−0.0014 (8)
C7	0.0387 (11)	0.0270 (9)	0.0248 (9)	0.0017 (8)	0.0022 (8)	−0.0034 (7)
C8	0.0467 (12)	0.0301 (10)	0.0277 (10)	−0.0028 (8)	0.0077 (8)	−0.0024 (8)
C9	0.0369 (11)	0.0380 (11)	0.0385 (11)	−0.0034 (9)	0.0119 (9)	−0.0001 (9)
C10	0.0323 (10)	0.0351 (10)	0.0342 (10)	0.0015 (8)	0.0004 (8)	0.0009 (8)
C11	0.0367 (11)	0.0412 (12)	0.0362 (11)	−0.0001 (9)	0.0079 (9)	0.0034 (9)
C12	0.0807 (18)	0.0428 (13)	0.0442 (13)	0.0013 (12)	0.0111 (12)	−0.0023 (10)
C13	0.0663 (16)	0.0562 (15)	0.0494 (14)	0.0061 (12)	0.0114 (12)	−0.0111 (12)
C14	0.0304 (11)	0.0446 (12)	0.0443 (12)	−0.0030 (9)	0.0078 (9)	0.0030 (10)
C15	0.0373 (12)	0.0812 (18)	0.0563 (15)	−0.0030 (12)	0.0004 (11)	0.0113 (13)
C16	0.0371 (13)	0.0743 (18)	0.0691 (17)	0.0007 (12)	0.0000 (11)	0.0053 (14)
C17	0.0417 (11)	0.0306 (10)	0.0229 (9)	−0.0014 (8)	0.0067 (8)	−0.0015 (8)
C18	0.0403 (11)	0.0343 (10)	0.0281 (9)	−0.0032 (9)	0.0100 (8)	−0.0014 (8)

Geometric parameters (Å, º) top

O1—C6	1.358 (2)	C8—C9	1.501 (3)
O1—H1	0.88 (3)	C9—H9A	0.9900
O1W—H1WA	0.83 (3)	C9—H9B	0.9900
O1W—H1WB	0.83 (3)	C9—C10	1.528 (3)
O2—C17	1.262 (2)	C10—H10A	0.9900
O2W—H2WA	0.82 (4)	C10—H10B	0.9900
O2W—H2WB	0.94 (3)	C11—H11A	0.9900
O3—C17	1.243 (2)	C11—H11B	0.9900
N1—C1	1.368 (3)	C11—C12	1.503 (3)
N1—C2	1.367 (3)	C12—H12A	0.9900
N1—H1A	0.89 (3)	C12—H12B	0.9900
N2—C10	1.496 (2)	C12—C13	1.516 (3)
N2—C11	1.505 (3)	C13—H13A	0.9800
N2—C14	1.503 (2)	C13—H13B	0.9800
N2—H2	0.98 (2)	C13—H13C	0.9800
C1—H1B	0.9500	C14—H14A	0.9900
C1—C8	1.365 (3)	C14—H14B	0.9900
C2—C3	1.393 (3)	C14—C15	1.511 (3)
C2—C7	1.411 (3)	C15—H15A	0.9900
C3—H3	0.9500	C15—H15B	0.9900
C3—C4	1.368 (3)	C15—C16	1.489 (3)
C4—H4	0.9500	C16—H16A	0.9800
C4—C5	1.397 (3)	C16—H16B	0.9800
C5—H5	0.9500	C16—H16C	0.9800
C5—C6	1.380 (3)	C17—C18	1.495 (3)
C6—C7	1.406 (3)	C18—C18ⁱ	1.319 (4)
C7—C8	1.443 (3)	C18—H18	0.9500

C6—O1—H1	109.9 (17)	C9—C10—H10A	108.9
H1WA—O1W—H1WB	118 (3)	C9—C10—H10B	108.9
H2WA—O2W—H2WB	108 (3)	H10A—C10—H10B	107.7
C1—N1—H1A	127.6 (17)	N2—C11—H11A	108.6
C2—N1—C1	109.18 (17)	N2—C11—H11B	108.6
C2—N1—H1A	122.8 (17)	H11A—C11—H11B	107.6
C10—N2—C11	111.00 (15)	C12—C11—N2	114.73 (17)
C10—N2—C14	112.47 (15)	C12—C11—H11A	108.6
C10—N2—H2	107.9 (13)	C12—C11—H11B	108.6
C11—N2—H2	105.5 (14)	C11—C12—H12A	109.4
C14—N2—C11	114.36 (15)	C11—C12—H12B	109.4
C14—N2—H2	105.0 (13)	C11—C12—C13	111.4 (2)
N1—C1—H1B	124.7	H12A—C12—H12B	108.0
C8—C1—N1	110.7 (2)	C13—C12—H12A	109.4
C8—C1—H1B	124.7	C13—C12—H12B	109.4
N1—C2—C3	130.15 (19)	C12—C13—H13A	109.5
N1—C2—C7	107.29 (19)	C12—C13—H13B	109.5
C3—C2—C7	122.55 (19)	C12—C13—H13C	109.5
C2—C3—H3	121.5	H13A—C13—H13B	109.5
C4—C3—C2	116.94 (19)	H13A—C13—H13C	109.5
C4—C3—H3	121.5	H13B—C13—H13C	109.5
C3—C4—H4	118.9	N2—C14—H14A	109.0
C3—C4—C5	122.3 (2)	N2—C14—H14B	109.0
C5—C4—H4	118.9	N2—C14—C15	112.81 (17)
C4—C5—H5	119.6	H14A—C14—H14B	107.8
C6—C5—C4	120.8 (2)	C15—C14—H14A	109.0
C6—C5—H5	119.6	C15—C14—H14B	109.0
O1—C6—C5	124.15 (18)	C14—C15—H15A	109.1
O1—C6—C7	117.10 (17)	C14—C15—H15B	109.1
C5—C6—C7	118.74 (17)	H15A—C15—H15B	107.8
C2—C7—C8	107.28 (17)	C16—C15—C14	112.7 (2)
C6—C7—C2	118.64 (18)	C16—C15—H15A	109.1
C6—C7—C8	134.07 (17)	C16—C15—H15B	109.1
C1—C8—C7	105.59 (18)	C15—C16—H16A	109.5
C1—C8—C9	128.06 (19)	C15—C16—H16B	109.5
C7—C8—C9	126.23 (16)	C15—C16—H16C	109.5
C8—C9—H9A	109.7	H16A—C16—H16B	109.5
C8—C9—H9B	109.7	H16A—C16—H16C	109.5
C8—C9—C10	109.90 (16)	H16B—C16—H16C	109.5
H9A—C9—H9B	108.2	O2—C17—C18	116.23 (17)
C10—C9—H9A	109.7	O3—C17—O2	124.05 (17)
C10—C9—H9B	109.7	O3—C17—C18	119.71 (16)
N2—C10—C9	113.40 (16)	C17—C18—H18	118.2
N2—C10—H10A	108.9	C18ⁱ—C18—C17	123.6 (2)
N2—C10—H10B	108.9	C18ⁱ—C18—H18	118.2

O1—C6—C7—C2	−179.92 (16)	C3—C2—C7—C6	0.1 (3)
O1—C6—C7—C8	1.6 (3)	C3—C2—C7—C8	178.94 (18)
O2—C17—C18—C18ⁱ	−175.7 (2)	C3—C4—C5—C6	0.5 (3)
O3—C17—C18—C18ⁱ	3.7 (4)	C4—C5—C6—O1	179.62 (18)
N1—C1—C8—C7	0.7 (2)	C4—C5—C6—C7	−0.4 (3)
N1—C1—C8—C9	176.85 (19)	C5—C6—C7—C2	0.1 (3)
N1—C2—C3—C4	178.8 (2)	C5—C6—C7—C8	−178.3 (2)
N1—C2—C7—C6	−178.92 (17)	C6—C7—C8—C1	178.2 (2)
N1—C2—C7—C8	−0.1 (2)	C6—C7—C8—C9	2.0 (3)
N2—C11—C12—C13	179.03 (18)	C7—C2—C3—C4	0.0 (3)
N2—C14—C15—C16	179.9 (2)	C7—C8—C9—C10	69.5 (2)
C1—N1—C2—C3	−178.4 (2)	C8—C9—C10—N2	−156.21 (16)
C1—N1—C2—C7	0.5 (2)	C10—N2—C11—C12	61.6 (2)
C1—C8—C9—C10	−105.9 (2)	C10—N2—C14—C15	168.58 (19)
C2—N1—C1—C8	−0.8 (3)	C11—N2—C10—C9	158.64 (16)
C2—C3—C4—C5	−0.3 (3)	C11—N2—C14—C15	−63.6 (2)
C2—C7—C8—C1	−0.4 (2)	C14—N2—C10—C9	−71.8 (2)
C2—C7—C8—C9	−176.62 (18)	C14—N2—C11—C12	−66.9 (2)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱⁱ	0.89 (3)	2.08 (3)	2.926 (2)	157 (2)
N2—H2···O1W	0.98 (2)	1.73 (3)	2.689 (2)	168 (2)
O1—H1···O2	0.88 (3)	1.74 (3)	2.625 (2)	174 (3)
O1W—H1WA···O2Wⁱⁱⁱ	0.83 (3)	1.88 (3)	2.710 (3)	172 (3)
O1W—H1WB···O3	0.83 (3)	1.86 (3)	2.684 (3)	171 (3)
O2W—H2WB···O2	0.94 (3)	1.76 (3)	2.695 (2)	173 (3)
O2W—H2WA···Cg^iv	0.82 (4)	2.69 (4)	3.488 (2)	167 (3)

Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (iii) x−1, y, z; (iv) −x+5/2, y+1/2, −z+1/2.

Acknowledgements

Financial statements and conflict of interest: This study was funded by CaaMTech, LLC. ARC reports an ownership interest in CaaMTech, LLC, which has filed patent applications covering compositions of psilocybin derivatives.

Funding information

Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences (grant No. CHE-1429086).

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