`Foxtrot' fumarate: a water-soluble salt of N,N-di­allyl-5-methoxytryptamine (5-MeO-DALT)

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

doi:10.1107/S2056989021002838

research communications

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ISSN: 2056-9890

Volume 77| Part 4| April 2021| Pages 416-419

https://doi.org/10.1107/S2056989021002838

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`Foxtrot' fumarate: a water-soluble salt of N,N-diallyl-5-methoxytryptamine (5-MeO-DALT)

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

^aUniversity of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA, and ^bCaaMTech, Inc., 58 East Sunset Way, Suite 209, Issaquah, WA 98027, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by D. Gray, University of Illinois Urbana-Champaign, USA (Received 19 January 2021; accepted 16 March 2021; online 19 March 2021)

The title compound, bis(N,N-diallyl-5-methoxytryptammonium) (5-MeO-DALT) fumarate (systematic name: bis{N-[2-(5-methoxy-1H-indol-3-yl)ethyl]- N-(prop-2-en-1-yl)prop-2-en-1-aminium} (E)-but-2-enedioate), 2C₁₇H₂₃N₂O⁺·C₄H₂O₄²⁻, has a single tryptammonium cation and half of a fumarate dianion in the asymmetric unit. The tryptammonium and fumarate ions are held together in one-dimensional chains by a series of N—H⋯O hydrogen bonds. These chains are combinations of R⁴₄(22) rings, and C²₂(14) and C⁴₄(28) parallel chains along [111].

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

CCDC reference: 2070873

1. Chemical context

Psychotropic compounds have gained a lot of attention in recent years for their potential as therapeutics to treat depression, anxiety, post-traumatic stress disorder, and addiction, among other disorders (Nichols & Hendricks, 2020 ). 5-Methoxy-N,N-dimethyltryptamine (5-MeO-DMT) is a naturally occurring tryptamine found in the parotid gland of some toads, and this compound has been explored for its clinical effects in treating mood disorders (Davis et al., 2018 ). 5-MeO-DMT is highly active at the serotonin (5-hydroxytryptamine, 5-HT) 2A receptor, which is the origin of its psychotropic activity. It can be administered via inhalation or injection, but does not function as a psychedelic when consumed orally (Weil & Davis, 1994 ). A recent report described the synthesis of a water-soluble succinate salt of 5-MeO-DMT (Sherwood et al., 2020 ).

5-Methoxy-N,N-diallyltryptamine (5-MeO-DALT) is a synthetic analogue of 5-MeO-DMT, which was synthesized in 2004 by Alexander Shulgin (Shulgin & Shulgin, 2016 ). The compound has potential as a therapeutic because it has a quick onset and rapid drop-off relative to other psychotropic tryptamines (Corkery et al., 2012 ). Unlike 5-MeO-DMT, 5-MeO-DALT demonstrates activity when consumed orally, further improving its potential as a drug candidate. 5-MeO-DALT shows activity at a number of serotonin receptors, including 5-HT_1A, 5-HT_1D, 5-HT_2A, 5-HT_2B, 5-HT₆ and 5-HT₇ (Cozzi & Daley, 2016 ). As this class of molecules become more significant in the treatment of mood disorders, it is important to have analytically pure, well-characterized, crystalline material to study the unique impact of individual compounds from the diverse range of compounds. It is also important to explore the effects of analytically pure combinations of these compounds to explore potential entourage effects. To best administer these compounds orally active, water-soluble crystalline materials are ideal. To that end, we set out to synthesize a water-soluble salt of 5-MeO-DALT, and report the synthesis and structure of bis(5-methoxy-N,N-diallyltryptammonium) fumarate herein.

2. Structural commentary

The asymmetric unit of bis(5-methoxy-N,N-diallyltryptammonium) fumarate contains one tryptammonium cation and one half of a fumarate dianion (Fig. 1). The cation possesses a near planar indole ring, with a mean deviation from planarity of 0.011 Å. The methoxy group is turned slightly away from this plane, with a C2—C3—O1—C17 torsion angle of −13.9 (2)°. The ethylamino group is turned away from this plane, with a C7—C8—C9—C10 torsion angle of −103.9 (2)°. The second half of the fumarate dianion is generated by inversion, and the dianion is near planar, with a mean deviation from planarity of 0.057 Å. The carboxylate unit is delocalized, with C—O distances of 1.271 (2) and 1.240 (2) Å. The nature of this salt allows for it to have high solubility in water, while the freebase does not.

Figure 1
The molecular structure of bis(5-methoxy-N,N-diallyltryptammonium) fumarate, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. Symmetry code: (i) −x, 1 − y, −z.

3. Supramolecular features

The tryptammonium cation and the fumarate dianion are linked together in the asymmetric unit through an N—H⋯O hydrogen bond between the ammonium nitrogen and a carboxylate oxygen (Table 1, Fig. 2). The indole nitrogen also exhibits an N—H⋯O hydrogen bond with another symmetry generated fumarate dianion. Two tryptammonium cations and two fumarate dianions are joined together through the N—H⋯O hydrogen bonds to form rings with graph-set notation R₄⁴(22) (Etter et al., 1990 ). The rings are joined together by two parallel chains along [111]. These chains have graph-set notation C₂²(14) and C₄⁴(28). The chains and rings are shown in Fig. 3. The hydrogen bond donor–acceptor distances of 2.5669 (16) Å and 2.7729 (17) Å indicate strong hydrogen bonds, with the N2—H2⋯O3 bond being stronger due to a charged donor and acceptor (Desiraju & Steiner, 2001 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.87 (1)	1.91 (1)	2.7729 (17)	175 (2)
N2—H2⋯O3	0.90 (1)	1.68 (1)	2.5669 (16)	171 (2)
Symmetry code: (i) .

Figure 2
The crystal packing of bis(5-methoxy-N,N-diallyltryptammonium) fumarate, viewed along the b axis. The N—H⋯O hydrogen bonds (Table 1

) are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

Figure 3
The hydrogen-bonding network along [111], which consists of R₄⁴(22) rings that are joined together by two parallel C₂²(14) and C₄⁴(28) chains. The three components described in graph-set notation and the combined chain are shown. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity. Hydrogen bonds are shown as dashed lines.

4. Database survey

The structure of the freebase of 5-MeO-DALT has previously been reported (CCDC 1995802; Chadeayne et al., 2020d ). The other tryptamine fumarate salts reported are those of 4-hydroxy-N-methyl-N-isopropyltryptamine (4-HO-MiPT) (TUFQAP; Chadeayne et al., 2020a ), norpsilocin (4-HO-NMT) (MULXEZ; Chadeayne et al., 2020b ), 4-acetoxy-N,N-dimethyltryptamine (4-AcO-DMT) (XOFDOO; Chadeayne, Golen & Manke, 2019a ) and 4-hydroxy-N,N-di-n-propyltryptamine (4-HO-DPT) (WUCGAF; Chadeayne, Pham et al., 2019b ). There have also been a number of hydrofumarate tryptamine salts reported, namely those of 4-AcO-DMT (HOCJUH; Chadeayne, Golen & Manke, 2019b ), N-methyl-N-isopropyltryptamine (MiPT) and 4-HO-MiPT (RONSOF and RONSUL; Chadeayne, Pham et al., 2019a ), N-ethyl-N-n-propyltryptamine (EPT) and N-methyl-N-allyltryptamine (MALT) (GUPBOL and GUPBUR; Chadeayne et al., 2020c ). The MALT structure is the only other structure of an N-allyl tryptamine reported. There are a number of other 5-O-substituted tryptamines whose structures have been reported, including bufotenine (BUFTEN; Falkenberg, 1972 ), 5-MeO-DMT hydrochloride (MOTYPT; Falkenberg & Carlström, 1971 ), 5-methoxytryptamine (MXTRUP; Quarles et al., 1974 ), 5-MeO-DMT and 5-methoxymonomethyltryptamine (QQQAGY and QQQAHA; Bergin et al., 1968 ). Three 2-Me-substituted 5-MeO-tryptamines were recently reported (CCDC 2058143, 2058144, 2058145; Pham et al. 2021 ).

5. Synthesis and crystallization

110 mg of 5-MeO-DALT freebase were dissolved in 10 mL of methanol and 47 mg of fumaric acid was added and refluxed overnight. 129 mg (82% yield) of white powder was obtained upon removal of solvent in vacuo. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an aqueous solution. The product was analysed by ¹H NMR and ¹³C NMR. ¹H NMR (400 MHz, D₂O): δ 7.44 (d, J = 8.8 Hz, 1 H, ArH), 7.27 (s, 1 H, ArH), 7.10 (d, J = 2.3 Hz, 1 H, ArH), 6.94 (dd, J = 8.8, 2.4 Hz, 1 H, ArH), 6.67 (s, 2 H, CH), 5.91–5.81 (m, 2 H, CH), 5.62–5.56 (m, 4 H, CH₂), 3.87 (s, 3 H, CH₃), 3.79 (d, J = 7.2 Hz, 4 H, CH₂), 3.42–3.38 (m, 2 H, CH₂), 3.17–3.13 (m, 2 H, CH₂); ¹³C NMR (100 MHz, D₂O): δ 172.1 (COO), 152.7 (CH), 135.3 (ArC), 132.5 (ArC), 127.22 (ArC), 127.20 (ArC), 126.2 (ArC), 125.8 (ArC), 113.7 (ArC), 112.6 (ArC), 108.9 (CH=CH₂), 101.3 (CH=CH₂), 56.8 (AkC), 55.7 (AkC), 52.2 (AkC), 20.4 (AkC).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydrogen atoms on the indole nitrogen (H1), and the amine (H2), were found in a difference-Fourier map and were refined isotropically, using DFIX restraints with N—H distances of 0.87 (1) Å. Isotropic displacement parameters were set to 1.2U_eq of the parent nitrogen atom. All other hydrogen atoms were placed in calculated positions (C—H = 0.93–0.97 Å). Isotropic displacement parameters were set to 1.2U_eq (CH,CH₂) or 1.5U_eq (CH₃).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₂₃N₂O⁺·0.5C₄H₂O₄²⁻
M_r	328.40
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	297
a, b, c (Å)	7.8791 (7), 9.2908 (7), 13.5352 (11)
α, β, γ (°)	108.081 (3), 104.365 (3), 95.903 (3)
V (Å³)	894.87 (13)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.34 × 0.28 × 0.22

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2018 )
T_min, T_max	0.711, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	27913, 3383, 2788
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.611

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.114, 1.05
No. of reflections	3383
No. of parameters	226
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.16
Computer programs: APEX3 and SAINT (Bruker, 2018), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2070873

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002838/ey2005sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002838/ey2005Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021002838/ey2005Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis{N-[2-(5-methoxy-1H-indol-3-yl)ethyl]- N-(prop-2-en-1-yl)prop-2-en-1-aminium} (E)-but-2-enedioate top

Crystal data top

C₁₇H₂₃N₂O⁺·0.5C₄H₂O₄²⁻	Z = 2
M_r = 328.40	F(000) = 352
Triclinic, P1	D_x = 1.219 Mg m⁻³
a = 7.8791 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2908 (7) Å	Cell parameters from 9847 reflections
c = 13.5352 (11) Å	θ = 2.7–25.7°
α = 108.081 (3)°	µ = 0.08 mm⁻¹
β = 104.365 (3)°	T = 297 K
γ = 95.903 (3)°	Block, orange
V = 894.87 (13) Å³	0.34 × 0.28 × 0.22 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	2788 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.035
Absorption correction: multi-scan (SADABS; Bruker, 2018)	θ_max = 25.7°, θ_min = 2.7°
T_min = 0.711, T_max = 0.745	h = −9→9
27913 measured reflections	k = −11→11
3383 independent reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0485P)² + 0.266P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3383 reflections	Δρ_max = 0.26 e Å⁻³
226 parameters	Δρ_min = −0.16 e Å⁻³
2 restraints

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
O3	0.32558 (15)	0.59832 (14)	0.09859 (10)	0.0582 (3)
O2	0.21841 (18)	0.81313 (14)	0.10656 (11)	0.0675 (4)
O1	0.7398 (2)	0.32650 (13)	0.56660 (10)	0.0647 (4)
N1	0.7725 (2)	0.95161 (15)	0.70532 (10)	0.0491 (3)
H1	0.773 (2)	1.0212 (17)	0.7654 (10)	0.058 (5)*
N2	0.63718 (16)	0.74775 (14)	0.22313 (9)	0.0392 (3)
H2	0.5248 (15)	0.704 (2)	0.1812 (15)	0.078 (6)*
C1	0.77565 (19)	0.72996 (16)	0.57820 (11)	0.0372 (3)
C2	0.7682 (2)	0.57053 (17)	0.53501 (11)	0.0412 (3)
H2A	0.774806	0.524400	0.464848	0.049*
C3	0.7507 (2)	0.48447 (17)	0.59951 (12)	0.0453 (4)
C4	0.7447 (2)	0.55271 (19)	0.70629 (13)	0.0503 (4)
H4	0.735505	0.491381	0.748234	0.060*
C5	0.7522 (2)	0.70801 (19)	0.74980 (12)	0.0494 (4)
H5	0.747839	0.753096	0.820581	0.059*
C6	0.7667 (2)	0.79678 (17)	0.68493 (11)	0.0420 (3)
C7	0.7879 (2)	0.98335 (18)	0.61541 (12)	0.0460 (4)
H7	0.795238	1.080810	0.609612	0.055*
C8	0.79099 (19)	0.85197 (16)	0.53544 (11)	0.0386 (3)
C9	0.80805 (19)	0.83539 (17)	0.42450 (11)	0.0400 (3)
H9A	0.894016	0.770455	0.409345	0.048*
H9B	0.852886	0.936130	0.423723	0.048*
C10	0.63041 (19)	0.76520 (17)	0.33583 (11)	0.0386 (3)
H10A	0.587159	0.664307	0.336960	0.046*
H10B	0.544568	0.829401	0.352776	0.046*
C11	0.7478 (2)	0.63509 (19)	0.18188 (13)	0.0508 (4)
H11A	0.750182	0.632850	0.110119	0.061*
H11B	0.869410	0.668790	0.229759	0.061*
C12	0.6761 (3)	0.4763 (2)	0.17570 (15)	0.0624 (5)
H12	0.555703	0.436157	0.138805	0.075*
C13	0.7660 (4)	0.3904 (3)	0.2168 (2)	0.0886 (7)
H13A	0.886868	0.425891	0.254358	0.106*
H13B	0.710420	0.292544	0.209010	0.106*
C14	0.6880 (2)	0.90039 (18)	0.21243 (12)	0.0501 (4)
H14A	0.623177	0.972370	0.248743	0.060*
H14B	0.814472	0.939713	0.249493	0.060*
C17	0.7066 (3)	0.2475 (2)	0.45399 (15)	0.0660 (5)
H17A	0.673648	0.138566	0.438067	0.099*
H17B	0.812447	0.268352	0.433750	0.099*
H17C	0.611040	0.282080	0.413694	0.099*
C15	0.6516 (3)	0.8949 (2)	0.09796 (13)	0.0570 (4)
H15	0.538880	0.845917	0.049925	0.068*
C16	0.7676 (3)	0.9543 (3)	0.06119 (18)	0.0783 (6)
H16A	0.881409	1.004033	0.107318	0.094*
H16B	0.737080	0.947286	−0.011317	0.094*
C19	0.02229 (19)	0.57392 (16)	0.00887 (11)	0.0392 (3)
H19	−0.063089	0.621325	−0.022769	0.047*
C18	0.2012 (2)	0.67065 (17)	0.07656 (11)	0.0416 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0431 (6)	0.0573 (7)	0.0615 (7)	−0.0031 (5)	−0.0059 (5)	0.0244 (6)
O2	0.0745 (9)	0.0416 (7)	0.0662 (8)	−0.0010 (6)	0.0246 (7)	−0.0080 (6)
O1	0.1008 (10)	0.0379 (6)	0.0513 (7)	0.0104 (6)	0.0145 (7)	0.0174 (5)
N1	0.0683 (9)	0.0402 (7)	0.0320 (6)	0.0074 (6)	0.0156 (6)	0.0039 (5)
N2	0.0384 (7)	0.0423 (7)	0.0301 (6)	0.0001 (5)	0.0070 (5)	0.0083 (5)
C1	0.0399 (7)	0.0378 (7)	0.0291 (6)	0.0026 (6)	0.0067 (6)	0.0096 (6)
C2	0.0487 (8)	0.0389 (8)	0.0314 (7)	0.0058 (6)	0.0097 (6)	0.0086 (6)
C3	0.0518 (9)	0.0386 (8)	0.0404 (8)	0.0040 (7)	0.0070 (7)	0.0137 (6)
C4	0.0587 (10)	0.0528 (10)	0.0397 (8)	0.0012 (7)	0.0100 (7)	0.0231 (7)
C5	0.0597 (10)	0.0556 (10)	0.0299 (7)	0.0036 (8)	0.0138 (7)	0.0127 (7)
C6	0.0478 (8)	0.0411 (8)	0.0308 (7)	0.0040 (6)	0.0094 (6)	0.0073 (6)
C7	0.0574 (9)	0.0367 (8)	0.0388 (8)	0.0033 (7)	0.0097 (7)	0.0115 (6)
C8	0.0423 (8)	0.0369 (7)	0.0311 (7)	0.0015 (6)	0.0064 (6)	0.0097 (6)
C9	0.0420 (8)	0.0421 (8)	0.0323 (7)	0.0006 (6)	0.0077 (6)	0.0132 (6)
C10	0.0393 (7)	0.0416 (8)	0.0316 (7)	0.0020 (6)	0.0111 (6)	0.0096 (6)
C11	0.0533 (9)	0.0577 (10)	0.0385 (8)	0.0129 (8)	0.0176 (7)	0.0089 (7)
C12	0.0685 (12)	0.0557 (11)	0.0576 (11)	0.0183 (9)	0.0149 (9)	0.0133 (9)
C13	0.0978 (18)	0.0812 (16)	0.0977 (17)	0.0381 (14)	0.0339 (14)	0.0358 (14)
C14	0.0596 (10)	0.0456 (9)	0.0391 (8)	−0.0012 (7)	0.0108 (7)	0.0134 (7)
C17	0.0925 (15)	0.0400 (9)	0.0539 (10)	0.0135 (9)	0.0097 (10)	0.0099 (8)
C15	0.0681 (11)	0.0579 (10)	0.0403 (8)	0.0039 (8)	0.0085 (8)	0.0191 (8)
C16	0.1000 (17)	0.0871 (15)	0.0617 (12)	0.0149 (13)	0.0341 (12)	0.0381 (11)
C19	0.0391 (7)	0.0439 (7)	0.0314 (7)	0.0085 (6)	0.0087 (6)	0.0097 (6)
C18	0.0472 (8)	0.0436 (8)	0.0272 (7)	0.0006 (7)	0.0120 (6)	0.0049 (6)

Geometric parameters (Å, º) top

O3—C18	1.2709 (19)	C9—H9B	0.9700
O2—C18	1.2400 (19)	C9—C10	1.5224 (19)
O1—C3	1.3817 (19)	C10—H10A	0.9700
O1—C17	1.414 (2)	C10—H10B	0.9700
N1—H1	0.865 (9)	C11—H11A	0.9700
N1—C6	1.372 (2)	C11—H11B	0.9700
N1—C7	1.368 (2)	C11—C12	1.494 (3)
N2—H2	0.897 (9)	C12—H12	0.9300
N2—C10	1.4982 (17)	C12—C13	1.282 (3)
N2—C11	1.494 (2)	C13—H13A	0.9300
N2—C14	1.494 (2)	C13—H13B	0.9300
C1—C2	1.402 (2)	C14—H14A	0.9700
C1—C6	1.4073 (19)	C14—H14B	0.9700
C1—C8	1.431 (2)	C14—C15	1.488 (2)
C2—H2A	0.9300	C17—H17A	0.9600
C2—C3	1.375 (2)	C17—H17B	0.9600
C3—C4	1.402 (2)	C17—H17C	0.9600
C4—H4	0.9300	C15—H15	0.9300
C4—C5	1.367 (2)	C15—C16	1.297 (3)
C5—H5	0.9300	C16—H16A	0.9300
C5—C6	1.394 (2)	C16—H16B	0.9300
C7—H7	0.9300	C19—C19ⁱ	1.312 (3)
C7—C8	1.364 (2)	C19—H19	0.9300
C8—C9	1.5025 (19)	C19—C18	1.491 (2)
C9—H9A	0.9700

C3—O1—C17	116.62 (13)	N2—C10—H10A	108.6
C6—N1—H1	127.5 (13)	N2—C10—H10B	108.6
C7—N1—H1	123.8 (13)	C9—C10—H10A	108.6
C7—N1—C6	108.60 (12)	C9—C10—H10B	108.6
C10—N2—H2	103.9 (13)	H10A—C10—H10B	107.5
C11—N2—H2	105.0 (13)	N2—C11—H11A	109.3
C11—N2—C10	113.75 (12)	N2—C11—H11B	109.3
C14—N2—H2	109.2 (13)	H11A—C11—H11B	107.9
C14—N2—C10	111.74 (11)	C12—C11—N2	111.77 (14)
C14—N2—C11	112.46 (13)	C12—C11—H11A	109.3
C2—C1—C6	119.75 (13)	C12—C11—H11B	109.3
C2—C1—C8	133.20 (13)	C11—C12—H12	117.1
C6—C1—C8	107.05 (12)	C13—C12—C11	125.7 (2)
C1—C2—H2A	121.0	C13—C12—H12	117.1
C3—C2—C1	118.00 (13)	C12—C13—H13A	120.0
C3—C2—H2A	121.0	C12—C13—H13B	120.0
O1—C3—C4	114.40 (14)	H13A—C13—H13B	120.0
C2—C3—O1	123.88 (14)	N2—C14—H14A	108.8
C2—C3—C4	121.71 (14)	N2—C14—H14B	108.8
C3—C4—H4	119.5	H14A—C14—H14B	107.6
C5—C4—C3	121.06 (14)	C15—C14—N2	114.01 (13)
C5—C4—H4	119.5	C15—C14—H14A	108.8
C4—C5—H5	121.0	C15—C14—H14B	108.8
C4—C5—C6	118.05 (14)	O1—C17—H17A	109.5
C6—C5—H5	121.0	O1—C17—H17B	109.5
N1—C6—C1	107.68 (13)	O1—C17—H17C	109.5
N1—C6—C5	130.91 (14)	H17A—C17—H17B	109.5
C5—C6—C1	121.41 (14)	H17A—C17—H17C	109.5
N1—C7—H7	124.8	H17B—C17—H17C	109.5
C8—C7—N1	110.47 (14)	C14—C15—H15	118.1
C8—C7—H7	124.8	C16—C15—C14	123.87 (18)
C1—C8—C9	125.93 (13)	C16—C15—H15	118.1
C7—C8—C1	106.20 (13)	C15—C16—H16A	120.0
C7—C8—C9	127.88 (14)	C15—C16—H16B	120.0
C8—C9—H9A	109.2	H16A—C16—H16B	120.0
C8—C9—H9B	109.2	C19ⁱ—C19—H19	118.0
C8—C9—C10	112.05 (12)	C19ⁱ—C19—C18	124.09 (18)
H9A—C9—H9B	107.9	C18—C19—H19	118.0
C10—C9—H9A	109.2	O3—C18—C19	116.27 (13)
C10—C9—H9B	109.2	O2—C18—O3	125.12 (14)
N2—C10—C9	114.87 (11)	O2—C18—C19	118.62 (15)

O1—C3—C4—C5	−179.30 (16)	C6—C1—C8—C9	178.77 (14)
N1—C7—C8—C1	0.28 (18)	C7—N1—C6—C1	−1.02 (18)
N1—C7—C8—C9	−179.37 (14)	C7—N1—C6—C5	179.81 (17)
N2—C11—C12—C13	−128.3 (2)	C7—C8—C9—C10	−103.93 (18)
N2—C14—C15—C16	−130.4 (2)	C8—C1—C2—C3	−179.20 (15)
C1—C2—C3—O1	179.27 (15)	C8—C1—C6—N1	1.18 (17)
C1—C2—C3—C4	−1.5 (2)	C8—C1—C6—C5	−179.56 (14)
C1—C8—C9—C10	76.48 (19)	C8—C9—C10—N2	179.04 (12)
C2—C1—C6—N1	−178.59 (13)	C10—N2—C11—C12	61.28 (17)
C2—C1—C6—C5	0.7 (2)	C10—N2—C14—C15	−164.89 (14)
C2—C1—C8—C7	178.83 (16)	C11—N2—C10—C9	65.56 (16)
C2—C1—C8—C9	−1.5 (3)	C11—N2—C14—C15	65.76 (18)
C2—C3—C4—C5	1.4 (3)	C14—N2—C10—C9	−63.11 (17)
C3—C4—C5—C6	−0.2 (3)	C14—N2—C11—C12	−170.43 (13)
C4—C5—C6—N1	178.27 (16)	C17—O1—C3—C2	−13.9 (2)
C4—C5—C6—C1	−0.8 (2)	C17—O1—C3—C4	166.81 (16)
C6—N1—C7—C8	0.46 (19)	C19ⁱ—C19—C18—O3	14.9 (3)
C6—C1—C2—C3	0.5 (2)	C19ⁱ—C19—C18—O2	−165.31 (18)
C6—C1—C8—C7	−0.89 (17)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱⁱ	0.87 (1)	1.91 (1)	2.7729 (17)	175 (2)
N2—H2···O3	0.90 (1)	1.68 (1)	2.5669 (16)	171 (2)

Symmetry code: (ii) −x+1, −y+2, −z+1.

Acknowledgements

Financial statements and conflict of interest: This study was funded by CaaMTech, Inc. ARC reports an ownership interest in CaaMTech, Inc., which owns US and worldwide patent applications, covering new tryptamine compounds, compositions, formulations, novel crystalline forms, and methods of making and using the same.

Funding information

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

References

Bergin, R., Carlström, D., Falkenberg, G. & Ringertz, H. (1968). Acta Cryst. B24, 882. CSD CrossRef IUCr Journals Web of Science Google Scholar
Bruker (2018). APEX3, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chadeayne, A. R., Golen, J. A. & Manke, D. R. (2019a). Acta Cryst. E75, 900–902. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chadeayne, A. R., Golen, J. A. & Manke, D. R. (2019b). Psychedelic Science Review, https://psychedelicreview.com/the-crystal-structure-of-4-aco-dmt-fumarate/ Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2019a). Acta Cryst. E75, 1316–1320. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2019b). IUCrData, 4, x191469. Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2020a). Acta Cryst. E76, 514–517. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2020b). Acta Cryst. E76, 589–593. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2020c). Acta Cryst. E76, 1201–1205. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2020d). IUCrData, 5, x200498. Google Scholar
Corkery, J. M., Durkin, E., Elliott, S., Schifano, F. & Ghodse, A. H. (2012). Prog. Neuropsychopharmacol. Biol. Psychiatry, 39, 259–262. Web of Science CrossRef CAS PubMed Google Scholar
Cozzi, N. V. & Daley, P. F. (2016). Bioorg. Med. Chem. Lett. 26, 959–964. Web of Science CrossRef CAS PubMed Google Scholar
Davis, A. K., Barsuglia, J. P., Lancelotta, R., Grant, R. M. & Renn, E. (2018). J. Psychopharmacol. 32, 779–792. CrossRef CAS PubMed Google Scholar
Desiraju, G. R. & Steiner, T. (2001). The Weak Hydrogen Bond in Structural Chemistry and Biology. Oxford University Press. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Falkenberg, G. (1972). Acta Cryst. B28, 3075–3083. CSD CrossRef IUCr Journals Web of Science Google Scholar
Falkenberg, G. & Carlström, D. (1971). Acta Cryst. B27, 411–418. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Nichols, C. D. & Hendricks, P. S. (2020). Handb. Behav. Neurosci, 31, 959–966. CrossRef Google Scholar
Pham, D. N. K., Chadeayne, A. R., Golen, J. A. & Manke, D. R. (2021). Acta Cryst. E77, 190–194. CSD CrossRef IUCr Journals Google Scholar
Quarles, W. G., Templeton, D. H. & Zalkin, A. (1974). Acta Cryst. B30, 95–98. CSD CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sherwood, A. M., Claveau, R., Lancelotta, R., Kaylo, K. W. & Lenoch, K. (2020). ACS Omega, 5, 32067–32075. CrossRef CAS PubMed Google Scholar
Shulgin, A. T. & Shulgin, A. (2016). TiKHAL: The Continuation. Isomerdesign. Available at: https://isomerdesign.com/PiHKAL/read.php?domain=tk&id=56. Accessed 25 December 2020. Google Scholar
Weil, A. T. & Davis, W. (1994). J. Ethnopharmacol. 41, 1–8. CrossRef CAS PubMed Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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