research communications
Quaternary tryptammonium salts: N,N-dimethyl-N-n-propyltryptammonium (DMPT) iodide and N-allyl-N,N-dimethyltryptammonium (DMALT) iodide
aCaaMTech, LLC, 58 East Sunset Way, Suite 209, Issaquah, WA 98027, USA, and bUniversity of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
*Correspondence e-mail: dmanke@umassd.edu
The solid-state structures of two quaternary trytpammonium salts, namely, N,N-dimethyl-N-n-propyltryptammonium (DMPT) iodide [systematic name: 2-(1H-indol-3-yl)-N,N-dimethyl-N-propylazanium iodide], C15H23N2+·I−, and N-allyl-N,N-dimethyltryptammonium (DMALT) iodide, [systematic name: 2-(1H-indol-3-yl)-N,N-dimethyl-N-(prop-2-en-1-yl)azanium iodide], C15H21N2+·I−, are reported. Both salts possess a trialkyltryptammonium cation and an iodide anion in the which are joined together through N—H⋯I interactions. The DMALT structure was refined as an and the allyl group is disordered over two orientations with a 0.70 (4):0.30 (4) ratio.
Keywords: crystal structure; tryptamines; indoles; hydrogen bonding.
1. Chemical context
Quaternary tryptammonium salts have been observed in nature going back to 1934 when bufotenidine, the N-trimethyl analogue of serotonin, was discovered in the excretions of toads (Wieland et al., 1934). The unsubstituted N,N,N-trimethyltryptammonium iodide was studied in 1936 and demonstrated nicotine-stimulating action (Lee et al., 1936). In 1987, Gartz first identified a quaternary tryptammonium in `magic mushrooms' when he isolated aeruginascin, N,N,N-trimethyl-4-phosphoryloxytryptamine (Gartz, 1987). The tryptamines of `magic mushrooms' have garnered a great deal of interest of late as their psychotropic activity is being explored for the treatment of mental disorders including depression and anxiety (Johnson & Griffiths, 2017; Daniel & Haberman, 2017). Aeruginascin, in particular, has been featured in popular media for its potential to modulate the activity of psilocybin through an entourage effect (Farah, 2018), as well as its possible involvement in wood-lovers paralysis (Revell, 2020). The recent synthesis of aeruginascin (Sherwood, et al. 2020) and its active metabolite, 4-hydroxy-N,N,N-trimethyltryptamine (Chadeayne, Pham, Reid et al., 2020), as well as the biosynthetic production of both (Milne et al., 2020) further demonstrate the attention that these molecules have received. To this end, we sought to explore new quaternary tryptammonium salts, and the syntheses and structures of N,N-dimethyl-N-n-propyltryptammonium (DMPT) iodide and N-allyl-N,N-dimethyltryptammonium (DMALT) iodide are reported.
2. Structural commentary
The molecular structure of DMPT iodide is shown on the left of Fig. 1. The contains one N,N-dimethyl-N-n-propyltryptammonium (C15H23N2+) cation and one iodide anion. The indole ring of the cation is near planar, with a mean deviation from planarity of 0.011 Å. The ethylammonium arm is turned away from the plane with a C7—C8—C9—C10 torsion angle of 89.1 (4)°. The molecular structure of DMALT iodide is shown on the right of Fig. 1. The contains one N-allyl-N,N-dimethyltryptammonium (C15H21N2+) cation and one iodide anion. The indole ring of the cation is near planar, with a mean deviation from planarity of 0.013 Å. The ethylammonium arm is turned away from the plane with a C7—C8—C9—C10 torsion angle of 101.8 (10)°. The allyl group is disordered over two orientations with a 0.30 (4) to 0.70 (4) occupancy ratio for C14, C15 and C14A, C15A, respectively.
3. Supramolecular features
The DMPT cation and the iodide anion are held together in the via N1—H1⋯I1 hydrogen bonds, between the indole nitrogen and the iodide (Table 1). The packing of DMPT iodide is shown at the left of Fig. 2. The DMALT structure is very similar to that of DMPT, possessing a very similar with half of the volume. The cation and anion are held together in the through N1—H1⋯I1 hydrogen bonds (Table 2). The packing of DMALT iodide is shown on the right of Fig. 2
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4. Database survey
Only two other quaternary tryptammonium structures have been reported, and are those of 4-hydroxy-N,N,N-trimethyltryptammonium (4-HO-TMT) iodide and 4-acetoxy-N,N,N-trimethyltryptammonium (4-AcO-TMT) iodide, whose structures demonstrate different packing including the oxygen atoms of the compounds (XUXFAA and XUXDUS: Chadeayne, Pham, Reid et al., 2020). The other most closely related structures reported are of the N,N,N-trimethyl derivative of tryptophan – hypaphorine. This includes the zwitterionic hypaphorine (IZUTUU: Arderne & Ndinteh, 2016), its hydroiodide salt (PAMRUQ: Jones & Tiekink, 1997), and its 6-bromo derivative (BHYPUR: Raverty et al., 1977). DMPT iodide is synthesized from the freebase of N-methyl-N-propyltryptamine (MPT), whose structure has been reported (WOHYAW: Chadeayne et al., 2019). DMALT iodide is synthesized from N-allyl-N-methyltryptamine (MALT), whose structure has been reported as its fumarate salt (GUPBOL; Chadeayne, Pham, Golen & Manke, 2020).
5. Synthesis and crystallization
N,N-dimethyl-N-propyltryptammonium iodide was prepared by mixing 101 mg of a commercial sample of N-methyl-N-propyltryptamine (The Indole Shop) and 4 mL of methyl iodide in 4 mL of methanol. The mixture was refluxed for twelve hours under an atmosphere of nitrogen. The solvent was removed in vacuo, and the remaining residue was recrystallized from ethanol to yield colourless single crystals suitable for X-ray diffraction studies. The product was also characterized by nuclear magnetic resonance. 1H NMR (400 MHz, D2O): δ 7.69 (d, J = 8.0 Hz, 1 H, ArH), 7.55 (d, J = 8.2 Hz, 1 H, ArH), 7.33–7.28 (m, 2 H, ArH), 7.22 (t, J = 7.0 Hz, 1 H, ArH), 3.60 (m, 2 H, CH2), 3.36 (m, 4 H, CH2), 3.17 (s, 6 H, CH3), 1.82 (m, 2 H, CH2), 0.97 (t, J = 7.0 Hz, 3 H, CH3).
N-allyl-N,N-dimethyltryptammonium iodide was prepared by mixing 101 mg of a commercial sample of N-allyl-N-methyltryptamine (The Indole Shop) with 4 mL of methyl iodide in 4 mL of methanol. The mixture was refluxed for twelve hours under an atmosphere of nitrogen. The solvent was removed in vacuo, and the remaining residue was recrystallized from acetone to yield coloruless crystals suitable for X-ray diffraction studies. The product was also characterized by nuclear magnetic resonance. 1H NMR (400 MHz, D2O): δ 7.69 (d, J = 7.8 Hz, 1 H, ArH), 7.55 (d, J = 8.2 Hz, 1 H, ArH), 7.32–7.28 (m, 2 H, ArH), 7.22 (t, J = 7.2 Hz, 1 H, ArH), 6.13–6.03 (m, 1 H, CH), 5.77–5.71 (m, 2 H, CH2), 4.04 (d, J = 7.3 Hz, 2 H, CH2), 3.61–3.56 (m, 2 H, CH2), 3.37–3.32 (m, 2 H, CH2), 3.17 (s, 6 H, CH3).
6. Refinement
Crystal data, data collection and structure .
details are summarized in Table 3Supporting information
https://doi.org/10.1107/S2056989020010014/zq2255sup1.cif
contains datablocks DMPT, DMALT. DOI:Structure factors: contains datablock DMPT. DOI: https://doi.org/10.1107/S2056989020010014/zq2255DMPTsup2.hkl
Structure factors: contains datablock DMALT. DOI: https://doi.org/10.1107/S2056989020010014/zq2255DMALTsup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989020010014/zq2255DMPTsup4.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989020010014/zq2255DMALTsup5.cml
For both structures, data collection: APEX3 (Bruker, 2018); cell
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).C15H23N2+·I− | F(000) = 720 |
Mr = 358.25 | Dx = 1.467 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.4471 (6) Å | Cell parameters from 9256 reflections |
b = 9.9016 (9) Å | θ = 3.2–25.6° |
c = 22.052 (2) Å | µ = 1.96 mm−1 |
β = 94.184 (3)° | T = 303 K |
V = 1621.8 (2) Å3 | Block, colourless |
Z = 4 | 0.40 × 0.14 × 0.12 mm |
Bruker D8 Venture CMOS diffractometer | 2362 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.036 |
Absorption correction: multi-scan (SADABS; Bruker, 2018) | θmax = 25.7°, θmin = 3.2° |
Tmin = 0.470, Tmax = 0.562 | h = −9→8 |
44530 measured reflections | k = −12→12 |
3071 independent reflections | l = −26→26 |
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)] = 0.028 | w = 1/[σ2(Fo2) + (0.0068P)2 + 2.2525P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.054 | (Δ/σ)max < 0.001 |
S = 1.13 | Δρmax = 0.53 e Å−3 |
3071 reflections | Δρmin = −0.47 e Å−3 |
170 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0054 (2) |
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. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.71085 (3) | 0.75133 (2) | 0.06875 (2) | 0.04767 (10) | |
N1 | 0.5983 (4) | 0.7145 (3) | 0.23013 (12) | 0.0567 (8) | |
H1 | 0.618 (5) | 0.743 (4) | 0.1943 (8) | 0.068* | |
N2 | 0.1783 (3) | 0.7602 (3) | 0.44696 (10) | 0.0399 (6) | |
C1 | 0.4437 (5) | 0.7359 (4) | 0.25813 (14) | 0.0527 (8) | |
H1A | 0.351233 | 0.793238 | 0.243768 | 0.063* | |
C2 | 0.7010 (4) | 0.6220 (3) | 0.26291 (13) | 0.0428 (8) | |
C3 | 0.8656 (5) | 0.5669 (4) | 0.25282 (17) | 0.0576 (10) | |
H3 | 0.926911 | 0.592411 | 0.219393 | 0.069* | |
C4 | 0.9359 (5) | 0.4738 (4) | 0.2933 (2) | 0.0648 (11) | |
H4 | 1.045983 | 0.433742 | 0.286964 | 0.078* | |
C5 | 0.8457 (5) | 0.4376 (4) | 0.34402 (18) | 0.0614 (10) | |
H5 | 0.897326 | 0.374036 | 0.371038 | 0.074* | |
C6 | 0.6836 (4) | 0.4930 (3) | 0.35502 (14) | 0.0461 (8) | |
H6 | 0.625171 | 0.468037 | 0.389164 | 0.055* | |
C7 | 0.6070 (4) | 0.5878 (3) | 0.31407 (12) | 0.0359 (7) | |
C8 | 0.4436 (4) | 0.6624 (3) | 0.30961 (13) | 0.0411 (7) | |
C9 | 0.2957 (4) | 0.6588 (4) | 0.35230 (15) | 0.0499 (8) | |
H9A | 0.289023 | 0.569011 | 0.369594 | 0.060* | |
H9B | 0.181686 | 0.677469 | 0.329775 | 0.060* | |
C10 | 0.3259 (4) | 0.7604 (3) | 0.40295 (13) | 0.0409 (7) | |
H10A | 0.333745 | 0.849867 | 0.385399 | 0.049* | |
H10B | 0.440113 | 0.741329 | 0.425294 | 0.049* | |
C11 | −0.0058 (4) | 0.7839 (3) | 0.41756 (15) | 0.0465 (8) | |
H11A | −0.089932 | 0.788522 | 0.449056 | 0.056* | |
H11B | −0.039201 | 0.706873 | 0.392006 | 0.056* | |
C12 | −0.0254 (5) | 0.9091 (4) | 0.37978 (16) | 0.0557 (9) | |
H12A | 0.040947 | 0.898425 | 0.343839 | 0.067* | |
H12B | 0.026122 | 0.984880 | 0.402879 | 0.067* | |
C13 | −0.2223 (5) | 0.9394 (4) | 0.36047 (19) | 0.0702 (11) | |
H13A | −0.230110 | 1.022272 | 0.337814 | 0.105* | |
H13B | −0.288996 | 0.947971 | 0.395921 | 0.105* | |
H13C | −0.271725 | 0.867081 | 0.335514 | 0.105* | |
C14 | 0.1764 (6) | 0.6260 (4) | 0.47924 (17) | 0.0642 (11) | |
H14A | 0.144475 | 0.555988 | 0.450328 | 0.096* | |
H14B | 0.089724 | 0.628635 | 0.509391 | 0.096* | |
H14C | 0.293626 | 0.607988 | 0.498556 | 0.096* | |
C15 | 0.2247 (5) | 0.8653 (4) | 0.49425 (15) | 0.0533 (9) | |
H15A | 0.234238 | 0.951763 | 0.475042 | 0.080* | |
H15B | 0.337490 | 0.842968 | 0.515770 | 0.080* | |
H15C | 0.132085 | 0.868672 | 0.522304 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.05122 (14) | 0.04717 (14) | 0.04582 (14) | −0.00087 (11) | 0.01182 (8) | −0.00478 (11) |
N1 | 0.073 (2) | 0.064 (2) | 0.0345 (14) | 0.0053 (16) | 0.0152 (14) | 0.0093 (14) |
N2 | 0.0471 (14) | 0.0354 (13) | 0.0387 (13) | −0.0045 (13) | 0.0129 (10) | −0.0017 (12) |
C1 | 0.055 (2) | 0.056 (2) | 0.0470 (18) | 0.0115 (18) | 0.0010 (15) | 0.0021 (18) |
C2 | 0.0478 (18) | 0.0453 (19) | 0.0359 (17) | −0.0042 (15) | 0.0081 (14) | −0.0101 (14) |
C3 | 0.051 (2) | 0.061 (2) | 0.063 (2) | −0.0079 (19) | 0.0175 (18) | −0.022 (2) |
C4 | 0.039 (2) | 0.064 (3) | 0.090 (3) | 0.0038 (18) | −0.002 (2) | −0.035 (2) |
C5 | 0.062 (2) | 0.051 (2) | 0.066 (2) | 0.0092 (19) | −0.025 (2) | −0.0099 (19) |
C6 | 0.053 (2) | 0.0460 (19) | 0.0373 (17) | −0.0026 (16) | −0.0063 (14) | −0.0037 (15) |
C7 | 0.0400 (16) | 0.0390 (17) | 0.0286 (15) | −0.0042 (14) | 0.0010 (12) | −0.0052 (13) |
C8 | 0.0430 (17) | 0.0449 (18) | 0.0357 (17) | 0.0011 (14) | 0.0057 (13) | −0.0051 (14) |
C9 | 0.0435 (18) | 0.052 (2) | 0.055 (2) | −0.0039 (16) | 0.0125 (15) | −0.0113 (16) |
C10 | 0.0378 (15) | 0.0432 (17) | 0.0430 (16) | −0.0048 (15) | 0.0106 (12) | −0.0006 (15) |
C11 | 0.0450 (18) | 0.049 (2) | 0.0469 (18) | −0.0047 (14) | 0.0119 (14) | −0.0026 (15) |
C12 | 0.053 (2) | 0.052 (2) | 0.061 (2) | −0.0003 (17) | 0.0026 (17) | 0.0053 (18) |
C13 | 0.061 (2) | 0.074 (3) | 0.074 (3) | 0.000 (2) | −0.013 (2) | −0.004 (2) |
C14 | 0.083 (3) | 0.050 (2) | 0.062 (2) | 0.004 (2) | 0.024 (2) | 0.0159 (18) |
C15 | 0.061 (2) | 0.056 (2) | 0.0422 (19) | −0.0003 (18) | 0.0015 (16) | −0.0097 (17) |
N1—H1 | 0.861 (10) | C9—H9A | 0.9700 |
N1—C1 | 1.362 (4) | C9—H9B | 0.9700 |
N1—C2 | 1.366 (4) | C9—C10 | 1.508 (4) |
N2—C10 | 1.518 (3) | C10—H10A | 0.9700 |
N2—C11 | 1.492 (4) | C10—H10B | 0.9700 |
N2—C14 | 1.508 (4) | C11—H11A | 0.9700 |
N2—C15 | 1.496 (4) | C11—H11B | 0.9700 |
C1—H1A | 0.9300 | C11—C12 | 1.495 (4) |
C1—C8 | 1.349 (4) | C12—H12A | 0.9700 |
C2—C3 | 1.375 (5) | C12—H12B | 0.9700 |
C2—C7 | 1.411 (4) | C12—C13 | 1.527 (5) |
C3—H3 | 0.9300 | C13—H13A | 0.9600 |
C3—C4 | 1.361 (5) | C13—H13B | 0.9600 |
C4—H4 | 0.9300 | C13—H13C | 0.9600 |
C4—C5 | 1.394 (6) | C14—H14A | 0.9600 |
C5—H5 | 0.9300 | C14—H14B | 0.9600 |
C5—C6 | 1.364 (5) | C14—H14C | 0.9600 |
C6—H6 | 0.9300 | C15—H15A | 0.9600 |
C6—C7 | 1.395 (4) | C15—H15B | 0.9600 |
C7—C8 | 1.420 (4) | C15—H15C | 0.9600 |
C8—C9 | 1.501 (4) | ||
C1—N1—H1 | 125 (3) | C10—C9—H9B | 109.2 |
C1—N1—C2 | 108.9 (3) | N2—C10—H10A | 108.9 |
C2—N1—H1 | 126 (3) | N2—C10—H10B | 108.9 |
C11—N2—C10 | 114.0 (2) | C9—C10—N2 | 113.4 (2) |
C11—N2—C14 | 107.7 (3) | C9—C10—H10A | 108.9 |
C11—N2—C15 | 110.6 (2) | C9—C10—H10B | 108.9 |
C14—N2—C10 | 109.6 (2) | H10A—C10—H10B | 107.7 |
C15—N2—C10 | 107.7 (2) | N2—C11—H11A | 108.5 |
C15—N2—C14 | 107.1 (3) | N2—C11—H11B | 108.5 |
N1—C1—H1A | 124.8 | N2—C11—C12 | 115.0 (3) |
C8—C1—N1 | 110.5 (3) | H11A—C11—H11B | 107.5 |
C8—C1—H1A | 124.8 | C12—C11—H11A | 108.5 |
N1—C2—C3 | 130.7 (3) | C12—C11—H11B | 108.5 |
N1—C2—C7 | 107.0 (3) | C11—C12—H12A | 109.3 |
C3—C2—C7 | 122.3 (3) | C11—C12—H12B | 109.3 |
C2—C3—H3 | 121.1 | C11—C12—C13 | 111.8 (3) |
C4—C3—C2 | 117.9 (3) | H12A—C12—H12B | 107.9 |
C4—C3—H3 | 121.1 | C13—C12—H12A | 109.3 |
C3—C4—H4 | 119.5 | C13—C12—H12B | 109.3 |
C3—C4—C5 | 121.0 (3) | C12—C13—H13A | 109.5 |
C5—C4—H4 | 119.5 | C12—C13—H13B | 109.5 |
C4—C5—H5 | 119.2 | C12—C13—H13C | 109.5 |
C6—C5—C4 | 121.6 (3) | H13A—C13—H13B | 109.5 |
C6—C5—H5 | 119.2 | H13A—C13—H13C | 109.5 |
C5—C6—H6 | 120.6 | H13B—C13—H13C | 109.5 |
C5—C6—C7 | 118.7 (3) | N2—C14—H14A | 109.5 |
C7—C6—H6 | 120.6 | N2—C14—H14B | 109.5 |
C2—C7—C8 | 107.0 (3) | N2—C14—H14C | 109.5 |
C6—C7—C2 | 118.4 (3) | H14A—C14—H14B | 109.5 |
C6—C7—C8 | 134.6 (3) | H14A—C14—H14C | 109.5 |
C1—C8—C7 | 106.6 (3) | H14B—C14—H14C | 109.5 |
C1—C8—C9 | 125.9 (3) | N2—C15—H15A | 109.5 |
C7—C8—C9 | 127.5 (3) | N2—C15—H15B | 109.5 |
C8—C9—H9A | 109.2 | N2—C15—H15C | 109.5 |
C8—C9—H9B | 109.2 | H15A—C15—H15B | 109.5 |
C8—C9—C10 | 111.9 (3) | H15A—C15—H15C | 109.5 |
H9A—C9—H9B | 107.9 | H15B—C15—H15C | 109.5 |
C10—C9—H9A | 109.2 | ||
N1—C1—C8—C7 | −1.0 (4) | C3—C4—C5—C6 | 0.4 (5) |
N1—C1—C8—C9 | −179.5 (3) | C4—C5—C6—C7 | 0.2 (5) |
N1—C2—C3—C4 | −179.0 (3) | C5—C6—C7—C2 | 0.1 (4) |
N1—C2—C7—C6 | 179.4 (3) | C5—C6—C7—C8 | 178.2 (3) |
N1—C2—C7—C8 | 0.9 (3) | C6—C7—C8—C1 | −178.1 (3) |
N2—C11—C12—C13 | −170.0 (3) | C6—C7—C8—C9 | 0.3 (6) |
C1—N1—C2—C3 | 179.1 (3) | C7—C2—C3—C4 | 1.7 (5) |
C1—N1—C2—C7 | −1.5 (4) | C7—C8—C9—C10 | 89.1 (4) |
C1—C8—C9—C10 | −92.7 (4) | C8—C9—C10—N2 | 179.7 (3) |
C2—N1—C1—C8 | 1.6 (4) | C10—N2—C11—C12 | −54.3 (4) |
C2—C3—C4—C5 | −1.3 (5) | C11—N2—C10—C9 | −56.6 (4) |
C2—C7—C8—C1 | 0.1 (3) | C14—N2—C10—C9 | 64.1 (3) |
C2—C7—C8—C9 | 178.6 (3) | C14—N2—C11—C12 | −176.1 (3) |
C3—C2—C7—C6 | −1.1 (5) | C15—N2—C10—C9 | −179.7 (3) |
C3—C2—C7—C8 | −179.7 (3) | C15—N2—C11—C12 | 67.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···I1 | 0.86 (1) | 2.91 (2) | 3.733 (3) | 162 (3) |
0.5C15H21N2+·0.5I− | F(000) = 356 |
Mr = 178.12 | Dx = 1.480 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3471 (8) Å | Cell parameters from 9625 reflections |
b = 9.9672 (9) Å | θ = 3.2–25.7° |
c = 10.9499 (11) Å | µ = 1.99 mm−1 |
β = 94.671 (3)° | T = 303 K |
V = 799.20 (14) Å3 | Block, colourless |
Z = 4 | 0.39 × 0.22 × 0.15 mm |
Bruker D8 Venture CMOS diffractometer | 2868 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.031 |
Absorption correction: multi-scan (SADABS; Bruker, 2018) | θmax = 25.7°, θmin = 3.2° |
Tmin = 0.608, Tmax = 0.745 | h = −8→8 |
26314 measured reflections | k = −12→12 |
3038 independent reflections | l = −13→13 |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0345P)2 + 0.614P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.027 | (Δ/σ)max = 0.001 |
wR(F2) = 0.071 | Δρmax = 0.46 e Å−3 |
S = 1.13 | Δρmin = −0.48 e Å−3 |
3038 reflections | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
174 parameters | Extinction coefficient: 0.056 (3) |
5 restraints | Absolute structure: Refined as an inversion twin |
Hydrogen site location: inferred from neighbouring sites | Absolute structure parameter: 0.29 (5) |
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. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
I1 | 0.30017 (4) | 0.61487 (8) | 0.86560 (3) | 0.05386 (18) | |
N1 | 0.3947 (9) | 0.5802 (8) | 0.5378 (5) | 0.080 (3) | |
H1 | 0.366598 | 0.619421 | 0.603678 | 0.096* | |
N2 | 0.8350 (6) | 0.6202 (10) | 0.1131 (4) | 0.0491 (11) | |
C1 | 0.5456 (9) | 0.6076 (16) | 0.4777 (6) | 0.077 (2) | |
H1A | 0.633090 | 0.672620 | 0.499495 | 0.093* | |
C2 | 0.2924 (9) | 0.4792 (7) | 0.4766 (5) | 0.0498 (14) | |
C3 | 0.1281 (10) | 0.4191 (8) | 0.5025 (7) | 0.0669 (19) | |
H3 | 0.068939 | 0.443978 | 0.570894 | 0.080* | |
C4 | 0.0577 (10) | 0.3229 (9) | 0.4240 (9) | 0.076 (2) | |
H4 | −0.051395 | 0.281303 | 0.439444 | 0.091* | |
C5 | 0.1458 (11) | 0.2850 (8) | 0.3203 (8) | 0.074 (2) | |
H5 | 0.094346 | 0.219554 | 0.267657 | 0.089* | |
C6 | 0.3082 (10) | 0.3444 (7) | 0.2962 (6) | 0.0589 (16) | |
H6 | 0.366647 | 0.318328 | 0.227823 | 0.071* | |
C7 | 0.3847 (8) | 0.4426 (6) | 0.3731 (5) | 0.0445 (12) | |
C8 | 0.5458 (9) | 0.5203 (7) | 0.3770 (6) | 0.0576 (16) | |
C9 | 0.6952 (11) | 0.5117 (9) | 0.2917 (8) | 0.074 (2) | |
H9A | 0.812499 | 0.516278 | 0.339083 | 0.089* | |
H9B | 0.687847 | 0.425695 | 0.250073 | 0.089* | |
C10 | 0.6846 (8) | 0.6175 (13) | 0.2017 (5) | 0.0589 (15) | |
H10A | 0.685969 | 0.702654 | 0.244613 | 0.071* | |
H10B | 0.567847 | 0.610421 | 0.153994 | 0.071* | |
C13 | 1.0232 (7) | 0.6147 (14) | 0.1727 (5) | 0.0670 (14) | |
H13A | 1.106539 | 0.583631 | 0.114432 | 0.080* | 0.30 (4) |
H13B | 1.028342 | 0.552140 | 0.240738 | 0.080* | 0.30 (4) |
H13C | 1.108633 | 0.616136 | 0.109644 | 0.080* | 0.70 (4) |
H13D | 1.039323 | 0.530235 | 0.216237 | 0.080* | 0.70 (4) |
C12 | 0.8059 (14) | 0.7411 (10) | 0.0302 (8) | 0.055 (2) | |
H12A | 0.822133 | 0.821611 | 0.078022 | 0.083* | |
H12B | 0.684335 | 0.739046 | −0.009237 | 0.083* | |
H12C | 0.892702 | 0.739452 | −0.030715 | 0.083* | |
C14 | 1.080 (7) | 0.755 (3) | 0.219 (4) | 0.084 (5) | 0.30 (4) |
H14 | 0.995335 | 0.818264 | 0.189308 | 0.101* | 0.30 (4) |
C15 | 1.216 (7) | 0.813 (8) | 0.290 (4) | 0.090 (5) | 0.30 (4) |
H15A | 1.311433 | 0.761751 | 0.326014 | 0.108* | 0.30 (4) |
H15B | 1.215032 | 0.905645 | 0.302622 | 0.108* | 0.30 (4) |
C14A | 1.070 (2) | 0.7277 (18) | 0.2611 (18) | 0.084 (5) | 0.70 (4) |
H14A | 1.001641 | 0.742461 | 0.327829 | 0.101* | 0.70 (4) |
C15A | 1.211 (3) | 0.806 (3) | 0.241 (2) | 0.090 (5) | 0.70 (4) |
H15C | 1.277982 | 0.789671 | 0.173504 | 0.108* | 0.70 (4) |
H15D | 1.243546 | 0.876433 | 0.293577 | 0.108* | 0.70 (4) |
C11 | 0.811 (2) | 0.5005 (13) | 0.0358 (14) | 0.094 (5) | |
H11A | 0.689549 | 0.499355 | −0.003742 | 0.140* | |
H11B | 0.830123 | 0.421667 | 0.085540 | 0.140* | |
H11C | 0.897905 | 0.502045 | −0.025164 | 0.140* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0558 (2) | 0.0573 (2) | 0.0503 (2) | −0.0009 (3) | 0.01514 (13) | 0.0030 (3) |
N1 | 0.074 (4) | 0.120 (8) | 0.048 (3) | −0.014 (4) | 0.020 (3) | −0.026 (3) |
N2 | 0.053 (2) | 0.046 (2) | 0.050 (2) | 0.020 (4) | 0.0160 (17) | 0.011 (4) |
C1 | 0.064 (4) | 0.100 (6) | 0.068 (4) | −0.029 (7) | 0.012 (3) | −0.033 (7) |
C2 | 0.053 (3) | 0.057 (4) | 0.042 (3) | 0.000 (3) | 0.014 (3) | 0.003 (3) |
C3 | 0.058 (4) | 0.074 (5) | 0.072 (5) | 0.005 (4) | 0.023 (3) | 0.018 (4) |
C4 | 0.045 (4) | 0.078 (5) | 0.101 (6) | −0.009 (3) | −0.004 (4) | 0.031 (5) |
C5 | 0.071 (5) | 0.065 (4) | 0.080 (5) | −0.015 (4) | −0.027 (4) | 0.014 (4) |
C6 | 0.071 (4) | 0.056 (4) | 0.048 (4) | 0.008 (3) | −0.007 (3) | 0.000 (3) |
C7 | 0.047 (3) | 0.050 (3) | 0.036 (3) | 0.002 (2) | 0.002 (2) | 0.000 (2) |
C8 | 0.052 (4) | 0.067 (4) | 0.056 (4) | −0.002 (3) | 0.018 (3) | 0.000 (3) |
C9 | 0.065 (4) | 0.077 (5) | 0.086 (5) | 0.012 (4) | 0.034 (4) | 0.017 (4) |
C10 | 0.055 (3) | 0.065 (3) | 0.059 (3) | 0.029 (6) | 0.019 (2) | 0.004 (6) |
C13 | 0.053 (3) | 0.089 (4) | 0.062 (3) | 0.008 (8) | 0.019 (2) | 0.010 (8) |
C12 | 0.066 (6) | 0.057 (5) | 0.042 (4) | 0.000 (4) | −0.001 (4) | 0.017 (4) |
C14 | 0.072 (6) | 0.144 (11) | 0.040 (9) | −0.009 (7) | 0.025 (7) | −0.014 (9) |
C15 | 0.072 (6) | 0.115 (9) | 0.081 (14) | 0.009 (6) | 0.001 (11) | 0.006 (14) |
C14A | 0.072 (6) | 0.144 (11) | 0.040 (9) | −0.009 (7) | 0.025 (7) | −0.014 (9) |
C15A | 0.072 (6) | 0.115 (9) | 0.081 (14) | 0.009 (6) | 0.001 (11) | 0.006 (14) |
C11 | 0.110 (10) | 0.058 (6) | 0.121 (11) | −0.015 (6) | 0.062 (8) | −0.027 (6) |
N1—H1 | 0.8600 | C9—C10 | 1.441 (12) |
N1—C1 | 1.363 (9) | C10—H10A | 0.9700 |
N1—C2 | 1.396 (10) | C10—H10B | 0.9700 |
N2—C10 | 1.529 (6) | C13—H13A | 0.9700 |
N2—C13 | 1.482 (7) | C13—H13B | 0.9700 |
N2—C12 | 1.513 (13) | C13—H13C | 0.9700 |
N2—C11 | 1.465 (16) | C13—H13D | 0.9700 |
C1—H1A | 0.9300 | C13—C14 | 1.530 (14) |
C1—C8 | 1.405 (11) | C13—C14A | 1.506 (12) |
C2—C3 | 1.397 (10) | C12—H12A | 0.9600 |
C2—C7 | 1.415 (8) | C12—H12B | 0.9600 |
C3—H3 | 0.9300 | C12—H12C | 0.9600 |
C3—C4 | 1.361 (13) | C14—H14 | 0.9300 |
C4—H4 | 0.9300 | C14—C15 | 1.349 (14) |
C4—C5 | 1.404 (13) | C15—H15A | 0.9300 |
C5—H5 | 0.9300 | C15—H15B | 0.9300 |
C5—C6 | 1.377 (11) | C14A—H14A | 0.9300 |
C6—H6 | 0.9300 | C14A—C15A | 1.334 (12) |
C6—C7 | 1.380 (9) | C15A—H15C | 0.9300 |
C7—C8 | 1.412 (9) | C15A—H15D | 0.9300 |
C8—C9 | 1.501 (9) | C11—H11A | 0.9600 |
C9—H9A | 0.9700 | C11—H11B | 0.9600 |
C9—H9B | 0.9700 | C11—H11C | 0.9600 |
C1—N1—H1 | 125.1 | C9—C10—N2 | 116.4 (6) |
C1—N1—C2 | 109.9 (6) | C9—C10—H10A | 108.2 |
C2—N1—H1 | 125.1 | C9—C10—H10B | 108.2 |
C13—N2—C10 | 114.6 (4) | H10A—C10—H10B | 107.3 |
C13—N2—C12 | 112.0 (8) | N2—C13—H13A | 109.8 |
C12—N2—C10 | 108.7 (7) | N2—C13—H13B | 109.8 |
C11—N2—C10 | 107.1 (9) | N2—C13—H13C | 108.7 |
C11—N2—C13 | 106.7 (9) | N2—C13—H13D | 108.7 |
C11—N2—C12 | 107.3 (6) | N2—C13—C14 | 109 (2) |
N1—C1—H1A | 126.0 | N2—C13—C14A | 114.2 (11) |
N1—C1—C8 | 107.9 (8) | H13A—C13—H13B | 108.2 |
C8—C1—H1A | 126.0 | H13C—C13—H13D | 107.6 |
N1—C2—C3 | 130.7 (6) | C14—C13—H13A | 109.8 |
N1—C2—C7 | 107.2 (5) | C14—C13—H13B | 109.8 |
C3—C2—C7 | 122.1 (6) | C14A—C13—H13C | 108.7 |
C2—C3—H3 | 121.2 | C14A—C13—H13D | 108.7 |
C4—C3—C2 | 117.6 (7) | N2—C12—H12A | 109.5 |
C4—C3—H3 | 121.2 | N2—C12—H12B | 109.5 |
C3—C4—H4 | 119.2 | N2—C12—H12C | 109.5 |
C3—C4—C5 | 121.6 (7) | H12A—C12—H12B | 109.5 |
C5—C4—H4 | 119.2 | H12A—C12—H12C | 109.5 |
C4—C5—H5 | 119.9 | H12B—C12—H12C | 109.5 |
C6—C5—C4 | 120.2 (7) | C13—C14—H14 | 110.4 |
C6—C5—H5 | 119.9 | C15—C14—C13 | 139 (5) |
C5—C6—H6 | 119.8 | C15—C14—H14 | 110.4 |
C5—C6—C7 | 120.3 (7) | C14—C15—H15A | 120.0 |
C7—C6—H6 | 119.8 | C14—C15—H15B | 120.0 |
C6—C7—C2 | 118.2 (6) | H15A—C15—H15B | 120.0 |
C6—C7—C8 | 134.9 (6) | C13—C14A—H14A | 121.1 |
C8—C7—C2 | 106.9 (5) | C15A—C14A—C13 | 118 (2) |
C1—C8—C7 | 108.0 (6) | C15A—C14A—H14A | 121.1 |
C1—C8—C9 | 124.9 (7) | C14A—C15A—H15C | 120.0 |
C7—C8—C9 | 127.1 (7) | C14A—C15A—H15D | 120.0 |
C8—C9—H9A | 109.1 | H15C—C15A—H15D | 120.0 |
C8—C9—H9B | 109.1 | N2—C11—H11A | 109.5 |
H9A—C9—H9B | 107.8 | N2—C11—H11B | 109.5 |
C10—C9—C8 | 112.5 (6) | N2—C11—H11C | 109.5 |
C10—C9—H9A | 109.1 | H11A—C11—H11B | 109.5 |
C10—C9—H9B | 109.1 | H11A—C11—H11C | 109.5 |
N2—C10—H10A | 108.2 | H11B—C11—H11C | 109.5 |
N2—C10—H10B | 108.2 | ||
N1—C1—C8—C7 | 3.0 (12) | C4—C5—C6—C7 | −0.6 (11) |
N1—C1—C8—C9 | −175.9 (8) | C5—C6—C7—C2 | 0.4 (9) |
N1—C2—C3—C4 | 178.9 (7) | C5—C6—C7—C8 | 178.6 (7) |
N1—C2—C7—C6 | −179.2 (6) | C6—C7—C8—C1 | 178.5 (9) |
N1—C2—C7—C8 | 2.1 (7) | C6—C7—C8—C9 | −2.6 (13) |
N2—C13—C14—C15 | 170 (6) | C7—C2—C3—C4 | −0.1 (11) |
N2—C13—C14A—C15A | −121.9 (19) | C7—C8—C9—C10 | 101.8 (10) |
C1—N1—C2—C3 | −179.4 (9) | C8—C9—C10—N2 | 178.0 (7) |
C1—N1—C2—C7 | −0.2 (10) | C10—N2—C13—C14 | −80.6 (19) |
C1—C8—C9—C10 | −79.5 (12) | C10—N2—C13—C14A | −58.9 (14) |
C2—N1—C1—C8 | −1.8 (12) | C13—N2—C10—C9 | −51.2 (12) |
C2—C3—C4—C5 | −0.2 (11) | C12—N2—C10—C9 | −177.3 (8) |
C2—C7—C8—C1 | −3.1 (9) | C12—N2—C13—C14 | 43.9 (18) |
C2—C7—C8—C9 | 175.8 (7) | C12—N2—C13—C14A | 65.5 (12) |
C3—C2—C7—C6 | 0.0 (9) | C11—N2—C10—C9 | 67.0 (11) |
C3—C2—C7—C8 | −178.7 (7) | C11—N2—C13—C14 | 161.1 (18) |
C3—C4—C5—C6 | 0.6 (12) | C11—N2—C13—C14A | −177.3 (12) |
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
Arderne, C. & Ndinteh, D. T. (2016). CSD Communication (refcode IZUTUU). CCDC, Cambridge, England. 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. (2019). IUCrData, 4, x190962. Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2020). Acta Cryst. E76, 1201–1205. CSD CrossRef IUCr Journals Google Scholar
Chadeayne, A. R., Pham, D. N. K., Reid, B. G., Golen, J. A. & Manke, D. R. (2020). ACS Omega, https://doi. org/10.1021/acsomega.0c02208 Google Scholar
Daniel, J. & Haberman, M. (2017). Ment. Heal. Clin. 7, 24–28. CrossRef 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
Farah, T. (2018). Discover, https://discovermagazine.com/health/beyond-psilocybin-mushrooms-have-lots-of-cool-compounds-scientists-should-study (accessed July, 2020). Google Scholar
Gartz, J. (1987). Planta Med. 53, 539–541. CrossRef PubMed CAS Google Scholar
Johnson, M. W. & Griffiths, R. R. (2017). Neurotherapeutics, 14, 734–740. Web of Science CrossRef CAS PubMed Google Scholar
Jones, G. P. & Tiekink, E. R. T. (1997). Z. Krystallogr. 212, 881–883. CAS Google Scholar
Lee, H. M., VanArenkonk, A. M. & Chen, K. K. (1936). J. Pharmacol. Exp. Ther. 56, 446–472. Google Scholar
Milne, N., Thomsen, P., Mølgaard Knudsen, N., Rubaszka, P., Kristensen, M. & Borodina, I. (2020). Metab. Eng. 60, 25–36. CrossRef CAS PubMed Google Scholar
Raverty, W. D., Thomson, R. H. & King, T. J. (1977). J. Chem. Soc. Perkin Trans. 1, pp. 1204–1211. CSD CrossRef Google Scholar
Revell, J. (2020). Vice, https://vice. com/en_in/article-y3zp35/magic-mushroom-paralysis-heres-what-we-know (accessed July, 2020). 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., Halberstadt, A. L., Klein, A. K., McCorvy, J. D., Kaylo, K. W., Kargbo, R. B. & Meisenheimer, P. J. (2020). J. Nat. Prod. 83, 461–467. CrossRef CAS PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wieland, H., Konz, W. & Mittasch, H. (1934). Justus Liebigs Ann. Chem. 513, 1–25. CrossRef CAS Google Scholar
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