research communications
The fumarate salts of the N-isopropyl-N-methyl derivatives of DMT and psilocin
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
The solid-state structures of the salts of two substituted tryptamines, namely N-isopropyl-N-methyltryptaminium (MiPT) fumarate {systematic name: [2-(1H-indol-3-yl)ethyl](methyl)propan-2-ylazanium 3-carboxyprop-2-enoate}, C14H21N2+·C4H3O4−, and 4-hydroxy-N-isopropyl-N-methyltryptaminium (4-HO-MiPT) fumarate monohydrate {systematic name: [2-(4-hydroxy-1H-indol-3-yl)ethyl](methyl)propan-2-ylazanium 3-carboxyprop-2-enoate monohydrate}, C14H21N2O+·C4H3O4−·H2O, are reported. Both salts possess a protonated tryptammonium cation and a 3-carboxyacrylate (hydrogen fumarate) anion in the the 4-HO-MiPT structure also contains a water molecule of crystallization. Both cations feature disorder of the side chain over two orientations, in a 0.630 (3):0.370 (3) ratio for MiPT and a 0.775 (5):0.225 (5) ratio for 4-HO-MiPT. In both extended structures, N—H⋯O and O—H⋯O hydrogen bonds generate infinite two-dimensional networks.
Keywords: crystal structure; tryptamines; hydrogen bonding.
1. Chemical context
N,N-dimethyltryptamine (DMT) and its derivatives have been used by humans for centuries because of their psychoactive, entheogenic, or hallucinogenic effects, or combinations thereof (Cameron & Olson, 2018). Psilocybin, the 4-phosphate variant of DMT, is arguably its most studied derivative. Psilocybin is one of several naturally occurring psychoactive tryptamines found in `magic' mushrooms. When consumed by humans, psilocybin serves as a prodrug of psilocin. Upon digestion, psilocybin hydrolyses to generate psilocin, the 4-hydroxy derivative of DMT. Psilocin is a potent seratonin 2a-agonist, which is responsible for its psychoactive properties (Dinis-Oliveira, 2017; Nichols, 2012). Psychoactive tryptamines like DMT and psilocin have garnered significant interest recently because of their potential for treating mood disorders, including depression, anxiety, addiction, and post-traumatic stress disorder (PTSD) (Johnson & Griffiths, 2017; Carhart-Harris & Goodwin, 2017).
Altering the chemical structure within this class of compounds can dramatically influence the potency and action of the drugs. For example, merely changing the N,N-dialkyl groups on DMT can modify its psychoactive properties: increasing the chain length of the two of the tryptamine to larger than n-butyl dramatically reduces or eliminates the psychoactive effects (Bradley & Johnston, 1970).
The synthesis of N-methyl-N-isopropyltryptamine (MiPT) was reported in 1981 (Repke et al., 1981). In 1985, Repke and co-workers reported that of the compounds in the series of N,N-dialkyl-4-hydroxytryptamines, the N-methyl-N-isopropyl derivative (4-HO-MiPT) is the most potent based upon qualitative effects on humans (Repke et al., 1985). Later quantitative studies showed the N-methyl-N-isopropyl derivatives of DMT and psilocin to be more potent as seratonin-1A, −2A and −2B receptors compared to the analogous dimethyl compounds (McKenna et al., 1990).
Improving our understanding of how these drugs interact with particular biological receptors requires a complete understanding of their chemical structures. Given their therapeutic potential and the significant structure–activity relationship between them, further studies would benefit from better understanding of their chemical structures. Responding to this unmet need, we report the crystal structures of the fumarate salts of MiPT and 4-HO-MiPT herein.
2. Structural commentary
The molecular structure of MiPT fumarate is shown on the left of Fig. 1. The contains one N-methyl-N-isopropyltryptammonium (C14H21N2+) cation and one 3-carboxyacrylate (C4H3O4−) anion. The indole ring system of the cation is near planar with an r.m.s. deviation from planarity of 0.006 Å. The singly protonated fumarate anion is in the trans configuration and is slightly distorted from planarity with an r.m.s. deviation of 0.133 Å and a carboxylate twist angle of 18.370 (5)°. The N-methyl-N-isopropylammonium group is disordered over two orientations in a 0.630 (3):0.370 (3) ratio.
The molecular structure of 4-HO-MiPT fumarate monohydrate is shown on the right of Fig. 1. The contains one 4-hydroxy-N-methyl-N-isopropyltryptammonium (C14H21N2O+) cation, one 3-carboxyacrylate anion and one water molecule of crystallization. The indole ring system of the cation is close to planar with an r.m.s. deviation of 0.021 Å. The singly protonated fumarate anion is also near planar with an r.m.s. deviation of 0.049 Å. The N-methyl-N-isopropylammonium group shows a similar disorder to the MiPT structure over two orientations in a 0.775 (5):0.225 (5) ratio.
3. Supramolecular features
In the extended structure of MiPT fumarate, the N-methyl-N-isopropylamine and fumarate ions are linked into infinite two-dimensional networks lying parallel to the (010) plane through N—H⋯O and O—H⋯O hydrogen bonds (Table 1). The proton of the ammonium cation forms a hydrogen bond with one of the oxygen atoms of the deprotonated –CO2− group of the 3-carboxyacrylate ion. The carboxylic acid proton forms a hydrogen bond with an oxygen atom of an adjacent 3-carboxyacrylate anion. The N—H grouping of the indole ring also hydrogen bonds to one of the oxygen atoms of the 3-carboxyacrylate anion. The hydrogen bonding is shown on the left in Fig. 2, and the packing of MiPT fumarate is shown on the left in Fig. 3.
In the structure of 4-HO-MiPT fumarate, there are N—H⋯O and O—H⋯O hydrogen bonds that link together the cations and anions as well as the water molecules of crystallization (Table 2). The result is a two-dimensional network lying parallel to the (01) plane. The proton of the ammonium cation forms a bifurcated N—H⋯(O,O) hydrogen bond with the deprotonated –CO2− group of the 3-carboxyacrylate ion. The hydrogen of the hydroxy group also hydrogen bonds to the same oxygen atom of the anion. The carboxylic acid proton hydrogen bonds with a water molecule in the structure. Two other water molecules form hydrogen bonds with two different oxygen atoms of the anion. The hydrogen bonding is shown on the right in Fig. 2, and the packing of 4-HO-MiPT fumarate is shown on the right in Fig. 3.
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4. Database survey
The MiPT structure described above is a derivative of DMT (N,N-dimethyltryptamine), which has been structurally characterized (Falkenberg, 1972), as well as its close derivative MPT, N-methyl-N-propyltryptamine (Chadeayne et al. 2019b). In both cases, these were crystallized as free bases, while MiPT is the fumarate salt. In the case of 4-HO-MiPT, the most closely related molecule is psilocin, which has been structurally characterized (Petcher & Weber, 1974), as well as psilocybin (Weber & Petcher, 1974). Psilocin was reported as the free base and psilocybin was reported as a zwitterionic molecule, while the structure of 4-HO-MiPT reported here is the hydrated fumarate salt. Two different ionic structures of the 4-acetoxy derivative of DMT have been reported as fumarate salts (Chadeayne et al. 2019a,c). The metrical parameters of the tryptammonium cations for MiPT and 4-HO-MiPT are consistent with those of the other tryptammonium structures reported.
5. Synthesis and crystallization
Single crystals suitable for X-ray analysis were obtained from the slow evaporation of aqueous solutions of commercial samples of N-methyl-N-isopropyltryptammonium fumarate and 4-hydroxy-N-methyl-N-isopropyltryptammonium fumarate (The Indole Shop).
6. Refinement
Crystal data, data collection and structure . C-bound H atoms were placed in calculated positions (C—H = 0.95–1.00 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-methyl). The following restraints were applied: C—N = 1.54±0.01, N—H = 0.87±0.01, O—H = 0.86±0.01 Å. N- and O-bound H atoms were refined with Uiso(H) = 1.5Ueq(N,O). In the MiPT fumarate, the N-methyl-N-isopropylaminium group is disordered. It is modeled as two components: N2 and C11–C14 with an occupancy of 0.630 (3) and N2A and C11A–C14A with an occupancy of 0.370 (3). 4-HO MiPT fumarate exhibits a similar disorder of the N-methyl-N-isopropylaminium group that is modeled as two components: N2, C11--C14 with an occupancy of 0.775 (5) and N2A, C11A–C14A with an occupancy of 0.225 (5).
details are summarized in Table 3
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Supporting information
https://doi.org/10.1107/S2056989019011253/hb7844sup1.cif
contains datablocks MiPT, 4-HO-MiPT, I. DOI:Structure factors: contains datablock MiPT. DOI: https://doi.org/10.1107/S2056989019011253/hb7844MiPTsup2.hkl
Structure factors: contains datablock 4-HO-MiPT. DOI: https://doi.org/10.1107/S2056989019011253/hb78444-HO-MiPTsup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019011253/hb7844MiPTsup4.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989019011253/hb78444-HO-MiPTsup5.cml
For both structures, data collection: APEX3 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C14H21N2+·C4H3O4− | F(000) = 712 |
Mr = 332.39 | Dx = 1.231 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.852 (2) Å | Cell parameters from 9752 reflections |
b = 12.789 (2) Å | θ = 3.0–25.3° |
c = 14.875 (3) Å | µ = 0.09 mm−1 |
β = 106.932 (7)° | T = 200 K |
V = 1793.0 (6) Å3 | BLOCK, colourless |
Z = 4 | 0.20 × 0.18 × 0.05 mm |
Bruker D8 Venture CMOS diffractometer | 2605 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.052 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.4°, θmin = 3.0° |
Tmin = 0.687, Tmax = 0.745 | h = −11→11 |
36899 measured reflections | k = −15→15 |
3297 independent reflections | l = −17→17 |
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)] = 0.049 | w = 1/[σ2(Fo2) + (0.0488P)2 + 1.0971P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.127 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.26 e Å−3 |
3297 reflections | Δρmin = −0.25 e Å−3 |
240 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
8 restraints | Extinction coefficient: 0.039 (3) |
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 | Occ. (<1) | |
O1 | 0.17442 (15) | 0.78060 (11) | 0.58471 (8) | 0.0395 (4) | |
O2 | 0.21577 (18) | 0.61007 (12) | 0.58250 (9) | 0.0521 (4) | |
O3 | 0.19484 (17) | 0.72434 (11) | 0.25829 (9) | 0.0442 (4) | |
H3A | 0.184 (3) | 0.724 (2) | 0.1982 (8) | 0.066* | |
O4 | 0.1592 (2) | 0.55393 (12) | 0.24156 (11) | 0.0731 (6) | |
N1 | 0.88917 (17) | 0.64452 (13) | 1.00719 (12) | 0.0382 (4) | |
H1 | 0.9809 (11) | 0.6526 (17) | 1.0259 (15) | 0.046* | |
N2 | 0.3185 (3) | 0.5163 (2) | 0.74864 (18) | 0.0303 (7) | 0.630 (3) |
H2 | 0.281 (3) | 0.551 (2) | 0.6962 (14) | 0.036* | 0.630 (3) |
C11 | 0.3410 (4) | 0.4055 (3) | 0.7190 (2) | 0.0443 (4) | 0.630 (3) |
H11 | 0.3829 | 0.3640 | 0.7775 | 0.053* | 0.630 (3) |
C12 | 0.2020 (4) | 0.3543 (3) | 0.6666 (3) | 0.0443 (4) | 0.630 (3) |
H12A | 0.2210 | 0.2905 | 0.6359 | 0.066* | 0.630 (3) |
H12B | 0.1459 | 0.4027 | 0.6191 | 0.066* | 0.630 (3) |
H12C | 0.1490 | 0.3365 | 0.7110 | 0.066* | 0.630 (3) |
C13 | 0.4553 (5) | 0.4179 (4) | 0.6694 (3) | 0.0443 (4) | 0.630 (3) |
H13A | 0.5401 | 0.4493 | 0.7127 | 0.066* | 0.630 (3) |
H13B | 0.4200 | 0.4631 | 0.6143 | 0.066* | 0.630 (3) |
H13C | 0.4794 | 0.3491 | 0.6493 | 0.066* | 0.630 (3) |
C14 | 0.2176 (6) | 0.5221 (4) | 0.8107 (4) | 0.0443 (4) | 0.630 (3) |
H14A | 0.2112 | 0.5946 | 0.8304 | 0.066* | 0.630 (3) |
H14B | 0.2545 | 0.4779 | 0.8664 | 0.066* | 0.630 (3) |
H14C | 0.1232 | 0.4974 | 0.7749 | 0.066* | 0.630 (3) |
N2A | 0.3757 (5) | 0.4914 (4) | 0.7207 (3) | 0.0342 (11) | 0.370 (3) |
H2A | 0.336 (6) | 0.533 (4) | 0.674 (3) | 0.041* | 0.370 (3) |
C11A | 0.2757 (6) | 0.4302 (5) | 0.7616 (4) | 0.0443 (4) | 0.370 (3) |
H11A | 0.3302 | 0.3822 | 0.8124 | 0.053* | 0.370 (3) |
C12A | 0.1685 (8) | 0.3698 (6) | 0.6867 (5) | 0.0443 (4) | 0.370 (3) |
H12D | 0.2131 | 0.3066 | 0.6710 | 0.066* | 0.370 (3) |
H12E | 0.1341 | 0.4134 | 0.6305 | 0.066* | 0.370 (3) |
H12F | 0.0887 | 0.3500 | 0.7099 | 0.066* | 0.370 (3) |
C13A | 0.4250 (8) | 0.4028 (6) | 0.6507 (5) | 0.0443 (4) | 0.370 (3) |
H13D | 0.5166 | 0.4234 | 0.6426 | 0.066* | 0.370 (3) |
H13E | 0.3532 | 0.4006 | 0.5892 | 0.066* | 0.370 (3) |
H13F | 0.4336 | 0.3335 | 0.6800 | 0.066* | 0.370 (3) |
C14A | 0.1952 (10) | 0.5037 (7) | 0.7980 (7) | 0.0443 (4) | 0.370 (3) |
H14D | 0.1334 | 0.4659 | 0.8279 | 0.066* | 0.370 (3) |
H14E | 0.1373 | 0.5467 | 0.7465 | 0.066* | 0.370 (3) |
H14F | 0.2601 | 0.5487 | 0.8445 | 0.066* | 0.370 (3) |
C1 | 0.8135 (2) | 0.57049 (15) | 0.94651 (13) | 0.0380 (5) | |
H1A | 0.8536 | 0.5193 | 0.9156 | 0.046* | |
C2 | 0.7970 (2) | 0.70501 (14) | 1.03799 (13) | 0.0333 (4) | |
C3 | 0.8232 (2) | 0.78851 (15) | 1.10072 (14) | 0.0411 (5) | |
H3 | 0.9169 | 0.8130 | 1.1293 | 0.049* | |
C4 | 0.7083 (2) | 0.83418 (16) | 1.11972 (16) | 0.0475 (5) | |
H4 | 0.7230 | 0.8911 | 1.1625 | 0.057* | |
C5 | 0.5702 (2) | 0.79874 (17) | 1.07743 (16) | 0.0468 (5) | |
H5 | 0.4929 | 0.8323 | 1.0916 | 0.056* | |
C6 | 0.5444 (2) | 0.71618 (15) | 1.01564 (14) | 0.0392 (5) | |
H6 | 0.4501 | 0.6926 | 0.9874 | 0.047* | |
C7 | 0.6584 (2) | 0.66727 (14) | 0.99481 (12) | 0.0317 (4) | |
C8 | 0.6725 (2) | 0.58089 (14) | 0.93698 (12) | 0.0343 (4) | |
C9 | 0.5561 (2) | 0.51227 (15) | 0.87944 (13) | 0.0410 (5) | |
H9A | 0.4972 | 0.4877 | 0.9190 | 0.049* | |
H9B | 0.5982 | 0.4502 | 0.8581 | 0.049* | |
C10 | 0.4622 (2) | 0.56961 (15) | 0.79425 (13) | 0.0413 (5) | |
H10A | 0.5141 | 0.5759 | 0.7466 | 0.050* | 0.630 (3) |
H10B | 0.4446 | 0.6412 | 0.8135 | 0.050* | 0.630 (3) |
H10C | 0.5221 | 0.6129 | 0.7657 | 0.050* | 0.370 (3) |
H10D | 0.3967 | 0.6167 | 0.8143 | 0.050* | 0.370 (3) |
C15 | 0.19062 (19) | 0.69693 (15) | 0.54455 (12) | 0.0311 (4) | |
C16 | 0.17850 (19) | 0.70575 (15) | 0.44231 (12) | 0.0314 (4) | |
H16 | 0.1595 | 0.7725 | 0.4133 | 0.038* | |
C17 | 0.1928 (2) | 0.62619 (16) | 0.39115 (13) | 0.0379 (5) | |
H17 | 0.2124 | 0.5600 | 0.4212 | 0.045* | |
C18 | 0.1807 (2) | 0.63118 (15) | 0.28967 (13) | 0.0366 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0506 (8) | 0.0474 (8) | 0.0207 (6) | 0.0070 (6) | 0.0106 (6) | −0.0012 (6) |
O2 | 0.0820 (12) | 0.0477 (9) | 0.0241 (7) | 0.0098 (8) | 0.0117 (7) | 0.0083 (6) |
O3 | 0.0714 (10) | 0.0420 (8) | 0.0197 (7) | −0.0031 (7) | 0.0143 (7) | −0.0007 (6) |
O4 | 0.1495 (19) | 0.0411 (9) | 0.0324 (8) | −0.0018 (10) | 0.0323 (10) | −0.0061 (7) |
N1 | 0.0326 (9) | 0.0421 (9) | 0.0379 (9) | −0.0025 (7) | 0.0068 (7) | −0.0066 (7) |
N2 | 0.0357 (16) | 0.0298 (14) | 0.0220 (14) | −0.0031 (12) | 0.0034 (12) | −0.0004 (11) |
C11 | 0.0445 (12) | 0.0460 (10) | 0.0386 (10) | −0.0045 (7) | 0.0064 (7) | −0.0135 (8) |
C12 | 0.0445 (12) | 0.0460 (10) | 0.0386 (10) | −0.0045 (7) | 0.0064 (7) | −0.0135 (8) |
C13 | 0.0445 (12) | 0.0460 (10) | 0.0386 (10) | −0.0045 (7) | 0.0064 (7) | −0.0135 (8) |
C14 | 0.0445 (12) | 0.0460 (10) | 0.0386 (10) | −0.0045 (7) | 0.0064 (7) | −0.0135 (8) |
N2A | 0.040 (3) | 0.033 (3) | 0.025 (2) | −0.002 (2) | 0.002 (2) | 0.000 (2) |
C11A | 0.0445 (12) | 0.0460 (10) | 0.0386 (10) | −0.0045 (7) | 0.0064 (7) | −0.0135 (8) |
C12A | 0.0445 (12) | 0.0460 (10) | 0.0386 (10) | −0.0045 (7) | 0.0064 (7) | −0.0135 (8) |
C13A | 0.0445 (12) | 0.0460 (10) | 0.0386 (10) | −0.0045 (7) | 0.0064 (7) | −0.0135 (8) |
C14A | 0.0445 (12) | 0.0460 (10) | 0.0386 (10) | −0.0045 (7) | 0.0064 (7) | −0.0135 (8) |
C1 | 0.0453 (12) | 0.0365 (10) | 0.0305 (10) | 0.0001 (9) | 0.0084 (9) | −0.0056 (8) |
C2 | 0.0369 (10) | 0.0314 (9) | 0.0296 (9) | −0.0035 (8) | 0.0066 (8) | −0.0005 (7) |
C3 | 0.0431 (11) | 0.0376 (11) | 0.0385 (11) | −0.0104 (9) | 0.0055 (9) | −0.0081 (9) |
C4 | 0.0602 (14) | 0.0360 (11) | 0.0467 (12) | −0.0029 (10) | 0.0159 (11) | −0.0117 (9) |
C5 | 0.0477 (13) | 0.0433 (12) | 0.0514 (13) | 0.0043 (10) | 0.0175 (10) | −0.0052 (10) |
C6 | 0.0346 (10) | 0.0393 (11) | 0.0409 (11) | −0.0028 (8) | 0.0069 (9) | 0.0015 (9) |
C7 | 0.0360 (10) | 0.0288 (9) | 0.0264 (9) | −0.0031 (7) | 0.0029 (8) | 0.0020 (7) |
C8 | 0.0419 (11) | 0.0313 (9) | 0.0252 (9) | −0.0041 (8) | 0.0025 (8) | −0.0006 (7) |
C9 | 0.0505 (12) | 0.0342 (10) | 0.0288 (10) | −0.0102 (9) | −0.0033 (9) | 0.0004 (8) |
C10 | 0.0500 (12) | 0.0360 (10) | 0.0291 (10) | −0.0150 (9) | −0.0025 (9) | 0.0034 (8) |
C15 | 0.0283 (9) | 0.0436 (11) | 0.0201 (9) | 0.0028 (8) | 0.0049 (7) | 0.0025 (8) |
C16 | 0.0340 (10) | 0.0384 (10) | 0.0208 (9) | 0.0026 (8) | 0.0063 (7) | 0.0036 (7) |
C17 | 0.0505 (12) | 0.0392 (10) | 0.0237 (9) | 0.0066 (9) | 0.0104 (8) | 0.0038 (8) |
C18 | 0.0478 (12) | 0.0392 (11) | 0.0232 (9) | 0.0067 (9) | 0.0108 (8) | −0.0008 (8) |
O1—C15 | 1.258 (2) | C12A—H12F | 0.9800 |
O2—C15 | 1.238 (2) | C13A—H13D | 0.9800 |
O3—H3A | 0.869 (10) | C13A—H13E | 0.9800 |
O3—C18 | 1.302 (2) | C13A—H13F | 0.9800 |
O4—C18 | 1.202 (2) | C14A—H14D | 0.9800 |
N1—H1 | 0.870 (10) | C14A—H14E | 0.9800 |
N1—C1 | 1.369 (2) | C14A—H14F | 0.9800 |
N1—C2 | 1.369 (3) | C1—H1A | 0.9500 |
N2—H2 | 0.880 (10) | C1—C8 | 1.361 (3) |
N2—C11 | 1.518 (4) | C2—C3 | 1.392 (3) |
N2—C14 | 1.543 (7) | C2—C7 | 1.414 (3) |
N2—C10 | 1.540 (3) | C3—H3 | 0.9500 |
C11—H11 | 1.0000 | C3—C4 | 1.375 (3) |
C11—C12 | 1.513 (5) | C4—H4 | 0.9500 |
C11—C13 | 1.523 (6) | C4—C5 | 1.397 (3) |
C12—H12A | 0.9800 | C5—H5 | 0.9500 |
C12—H12B | 0.9800 | C5—C6 | 1.374 (3) |
C12—H12C | 0.9800 | C6—H6 | 0.9500 |
C13—H13A | 0.9800 | C6—C7 | 1.397 (3) |
C13—H13B | 0.9800 | C7—C8 | 1.432 (3) |
C13—H13C | 0.9800 | C8—C9 | 1.499 (3) |
C14—H14A | 0.9800 | C9—H9A | 0.9900 |
C14—H14B | 0.9800 | C9—H9B | 0.9900 |
C14—H14C | 0.9800 | C9—C10 | 1.522 (3) |
N2A—H2A | 0.876 (10) | C10—H10A | 0.9900 |
N2A—C11A | 1.518 (6) | C10—H10B | 0.9900 |
N2A—C13A | 1.702 (10) | C10—H10C | 0.9900 |
N2A—C10 | 1.543 (4) | C10—H10D | 0.9900 |
C11A—H11A | 1.0000 | C15—C16 | 1.495 (2) |
C11A—C12A | 1.506 (9) | C16—H16 | 0.9500 |
C11A—C14A | 1.433 (12) | C16—C17 | 1.303 (3) |
C12A—H12D | 0.9800 | C17—H17 | 0.9500 |
C12A—H12E | 0.9800 | C17—C18 | 1.481 (3) |
C18—O3—H3A | 111.8 (17) | C11A—C14A—H14E | 109.5 |
C1—N1—H1 | 127.4 (15) | C11A—C14A—H14F | 109.5 |
C2—N1—H1 | 123.6 (15) | H14D—C14A—H14E | 109.5 |
C2—N1—C1 | 108.93 (16) | H14D—C14A—H14F | 109.5 |
C11—N2—H2 | 106 (2) | H14E—C14A—H14F | 109.5 |
C11—N2—C14 | 113.1 (3) | N1—C1—H1A | 124.9 |
C11—N2—C10 | 110.3 (3) | C8—C1—N1 | 110.14 (17) |
C14—N2—H2 | 109 (2) | C8—C1—H1A | 124.9 |
C10—N2—H2 | 105 (2) | N1—C2—C3 | 130.27 (18) |
C10—N2—C14 | 112.6 (2) | N1—C2—C7 | 107.58 (16) |
N2—C11—H11 | 107.5 | C3—C2—C7 | 122.15 (18) |
N2—C11—C13 | 103.6 (3) | C2—C3—H3 | 121.3 |
C12—C11—N2 | 111.5 (3) | C4—C3—C2 | 117.45 (19) |
C12—C11—H11 | 107.5 | C4—C3—H3 | 121.3 |
C12—C11—C13 | 118.8 (3) | C3—C4—H4 | 119.3 |
C13—C11—H11 | 107.5 | C3—C4—C5 | 121.44 (19) |
C11—C12—H12A | 109.5 | C5—C4—H4 | 119.3 |
C11—C12—H12B | 109.5 | C4—C5—H5 | 119.4 |
C11—C12—H12C | 109.5 | C6—C5—C4 | 121.1 (2) |
H12A—C12—H12B | 109.5 | C6—C5—H5 | 119.4 |
H12A—C12—H12C | 109.5 | C5—C6—H6 | 120.4 |
H12B—C12—H12C | 109.5 | C5—C6—C7 | 119.22 (19) |
C11—C13—H13A | 109.5 | C7—C6—H6 | 120.4 |
C11—C13—H13B | 109.5 | C2—C7—C8 | 106.62 (17) |
C11—C13—H13C | 109.5 | C6—C7—C2 | 118.61 (17) |
H13A—C13—H13B | 109.5 | C6—C7—C8 | 134.76 (18) |
H13A—C13—H13C | 109.5 | C1—C8—C7 | 106.73 (16) |
H13B—C13—H13C | 109.5 | C1—C8—C9 | 126.19 (18) |
N2—C14—H14A | 109.5 | C7—C8—C9 | 127.05 (18) |
N2—C14—H14B | 109.5 | C8—C9—H9A | 109.3 |
N2—C14—H14C | 109.5 | C8—C9—H9B | 109.3 |
H14A—C14—H14B | 109.5 | C8—C9—C10 | 111.81 (16) |
H14A—C14—H14C | 109.5 | H9A—C9—H9B | 107.9 |
H14B—C14—H14C | 109.5 | C10—C9—H9A | 109.3 |
C11A—N2A—H2A | 116 (4) | C10—C9—H9B | 109.3 |
C11A—N2A—C13A | 103.7 (4) | N2—C10—H10A | 108.7 |
C11A—N2A—C10 | 109.8 (4) | N2—C10—H10B | 108.7 |
C13A—N2A—H2A | 94 (4) | N2A—C10—H10C | 109.5 |
C10—N2A—H2A | 101 (4) | N2A—C10—H10D | 109.5 |
C10—N2A—C13A | 131.9 (5) | C9—C10—N2 | 114.26 (17) |
N2A—C11A—H11A | 110.5 | C9—C10—N2A | 110.7 (2) |
C12A—C11A—N2A | 111.4 (5) | C9—C10—H10A | 108.7 |
C12A—C11A—H11A | 110.5 | C9—C10—H10B | 108.7 |
C14A—C11A—N2A | 107.9 (6) | C9—C10—H10C | 109.5 |
C14A—C11A—H11A | 110.5 | C9—C10—H10D | 109.5 |
C14A—C11A—C12A | 105.7 (5) | H10A—C10—H10B | 107.6 |
C11A—C12A—H12D | 109.5 | H10C—C10—H10D | 108.1 |
C11A—C12A—H12E | 109.5 | O1—C15—C16 | 115.80 (16) |
C11A—C12A—H12F | 109.5 | O2—C15—O1 | 125.66 (16) |
H12D—C12A—H12E | 109.5 | O2—C15—C16 | 118.53 (17) |
H12D—C12A—H12F | 109.5 | C15—C16—H16 | 118.5 |
H12E—C12A—H12F | 109.5 | C17—C16—C15 | 123.04 (17) |
N2A—C13A—H13D | 109.5 | C17—C16—H16 | 118.5 |
N2A—C13A—H13E | 109.5 | C16—C17—H17 | 117.6 |
N2A—C13A—H13F | 109.5 | C16—C17—C18 | 124.86 (18) |
H13D—C13A—H13E | 109.5 | C18—C17—H17 | 117.6 |
H13D—C13A—H13F | 109.5 | O3—C18—C17 | 114.82 (16) |
H13E—C13A—H13F | 109.5 | O4—C18—O3 | 123.88 (17) |
C11A—C14A—H14D | 109.5 | O4—C18—C17 | 121.30 (18) |
O1—C15—C16—C17 | 179.92 (19) | C2—C7—C8—C9 | 177.68 (18) |
O2—C15—C16—C17 | 0.2 (3) | C3—C2—C7—C6 | 0.4 (3) |
N1—C1—C8—C7 | 0.4 (2) | C3—C2—C7—C8 | −178.93 (18) |
N1—C1—C8—C9 | −177.70 (17) | C3—C4—C5—C6 | 0.5 (3) |
N1—C2—C3—C4 | −179.1 (2) | C4—C5—C6—C7 | −0.2 (3) |
N1—C2—C7—C6 | 179.60 (16) | C5—C6—C7—C2 | −0.3 (3) |
N1—C2—C7—C8 | 0.2 (2) | C5—C6—C7—C8 | 178.9 (2) |
C11—N2—C10—C9 | −57.8 (3) | C6—C7—C8—C1 | −179.6 (2) |
C14—N2—C11—C12 | 57.6 (4) | C6—C7—C8—C9 | −1.5 (3) |
C14—N2—C11—C13 | −173.6 (3) | C7—C2—C3—C4 | −0.1 (3) |
C14—N2—C10—C9 | 69.7 (3) | C7—C8—C9—C10 | 71.3 (3) |
C11A—N2A—C10—C9 | 63.3 (5) | C8—C9—C10—N2 | −163.3 (2) |
C13A—N2A—C11A—C12A | −47.0 (6) | C8—C9—C10—N2A | 162.0 (3) |
C13A—N2A—C11A—C14A | −162.6 (6) | C10—N2—C11—C12 | −175.2 (3) |
C13A—N2A—C10—C9 | −68.0 (6) | C10—N2—C11—C13 | −46.4 (3) |
C1—N1—C2—C3 | 179.1 (2) | C10—N2A—C11A—C12A | 168.1 (4) |
C1—N1—C2—C7 | 0.0 (2) | C10—N2A—C11A—C14A | 52.4 (6) |
C1—C8—C9—C10 | −111.0 (2) | C15—C16—C17—C18 | 179.57 (18) |
C2—N1—C1—C8 | −0.2 (2) | C16—C17—C18—O3 | 18.9 (3) |
C2—C3—C4—C5 | −0.3 (3) | C16—C17—C18—O4 | −160.9 (2) |
C2—C7—C8—C1 | −0.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O1i | 0.87 (1) | 1.66 (1) | 2.5316 (18) | 176 (3) |
N1—H1···O1ii | 0.87 (1) | 2.04 (1) | 2.874 (2) | 160 (2) |
N2—H2···O2 | 0.88 (1) | 1.79 (1) | 2.667 (3) | 173 (3) |
N2A—H2A···O2 | 0.88 (1) | 1.81 (2) | 2.670 (5) | 167 (6) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x+1, −y+3/2, z+1/2. |
C14H21N2O+·C4H3O4−·H2O | F(000) = 1568 |
Mr = 366.41 | Dx = 1.301 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 29.507 (3) Å | Cell parameters from 9718 reflections |
b = 8.7445 (8) Å | θ = 2.9–25.3° |
c = 17.3659 (18) Å | µ = 0.10 mm−1 |
β = 123.389 (3)° | T = 200 K |
V = 3741.2 (7) Å3 | BLOCK, colourless |
Z = 8 | 0.30 × 0.25 × 0.20 mm |
Bruker D8 Venture CMOS diffractometer | 2978 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.041 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.4°, θmin = 3.1° |
Tmin = 0.719, Tmax = 0.745 | h = −35→35 |
70395 measured reflections | k = −10→10 |
3458 independent reflections | l = −20→20 |
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)] = 0.041 | w = 1/[σ2(Fo2) + (0.0299P)2 + 3.9177P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.096 | (Δ/σ)max < 0.001 |
S = 1.08 | Δρmax = 0.22 e Å−3 |
3458 reflections | Δρmin = −0.20 e Å−3 |
320 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
12 restraints | Extinction coefficient: 0.0081 (4) |
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 | Occ. (<1) | |
O1 | 0.69858 (5) | 0.51214 (13) | 0.50306 (8) | 0.0369 (3) | |
O1W | 0.52724 (8) | 1.07404 (17) | 0.09877 (11) | 0.0664 (5) | |
O2 | 0.56158 (8) | 0.24517 (15) | 0.24314 (9) | 0.0786 (6) | |
O3 | 0.61162 (5) | 0.35608 (13) | 0.37801 (7) | 0.0421 (3) | |
O4 | 0.54759 (7) | 0.80247 (15) | 0.16809 (9) | 0.0621 (4) | |
O5 | 0.49277 (7) | 0.70299 (16) | 0.03041 (9) | 0.0718 (5) | |
N1 | 0.77812 (6) | 0.83838 (17) | 0.75125 (10) | 0.0411 (4) | |
C1 | 0.73684 (6) | 0.67519 (16) | 0.63265 (10) | 0.0277 (3) | |
C2 | 0.69254 (6) | 0.58832 (17) | 0.56519 (10) | 0.0304 (3) | |
C3 | 0.64541 (7) | 0.58566 (19) | 0.56435 (11) | 0.0376 (4) | |
H3 | 0.6153 | 0.5269 | 0.5191 | 0.045* | |
C4 | 0.64171 (7) | 0.6688 (2) | 0.62958 (12) | 0.0420 (4) | |
H4 | 0.6088 | 0.6650 | 0.6274 | 0.050* | |
C5 | 0.68368 (7) | 0.7552 (2) | 0.69635 (12) | 0.0410 (4) | |
H5 | 0.6807 | 0.8105 | 0.7405 | 0.049* | |
C6 | 0.73117 (7) | 0.75834 (18) | 0.69665 (10) | 0.0337 (4) | |
C7 | 0.81267 (7) | 0.81061 (19) | 0.72352 (11) | 0.0376 (4) | |
H7 | 0.8477 | 0.8547 | 0.7507 | 0.045* | |
C8 | 0.78980 (6) | 0.71090 (17) | 0.65144 (10) | 0.0303 (3) | |
C9 | 0.81461 (7) | 0.65950 (17) | 0.60004 (11) | 0.0327 (4) | |
H9A | 0.8449 | 0.7289 | 0.6150 | 0.039* | |
H9B | 0.7871 | 0.6673 | 0.5330 | 0.039* | |
C10 | 0.83576 (7) | 0.49632 (18) | 0.62290 (11) | 0.0319 (4) | |
H10A | 0.8586 | 0.4839 | 0.6907 | 0.038* | 0.775 (5) |
H10B | 0.8046 | 0.4253 | 0.5984 | 0.038* | 0.775 (5) |
H10C | 0.810 (3) | 0.427 (9) | 0.621 (5) | 0.038* | 0.225 (5) |
H10D | 0.868 (3) | 0.486 (9) | 0.684 (5) | 0.038* | 0.225 (5) |
N2 | 0.86881 (10) | 0.4538 (2) | 0.58322 (14) | 0.0299 (6) | 0.775 (5) |
H2 | 0.8759 (9) | 0.3557 (13) | 0.5963 (16) | 0.036* | 0.775 (5) |
C11 | 0.83717 (10) | 0.4648 (2) | 0.47872 (14) | 0.0347 (7) | 0.775 (5) |
H11 | 0.8309 | 0.5755 | 0.4615 | 0.042* | 0.775 (5) |
C12 | 0.8709 (2) | 0.3979 (9) | 0.4448 (4) | 0.0500 (13) | 0.775 (5) |
H12A | 0.9040 | 0.4584 | 0.4692 | 0.075* | 0.775 (5) |
H12B | 0.8497 | 0.4003 | 0.3772 | 0.075* | 0.775 (5) |
H12C | 0.8806 | 0.2919 | 0.4661 | 0.075* | 0.775 (5) |
C13 | 0.7823 (3) | 0.3875 (9) | 0.4349 (4) | 0.0421 (12) | 0.775 (5) |
H13A | 0.7633 | 0.3916 | 0.3676 | 0.063* | 0.775 (5) |
H13B | 0.7607 | 0.4403 | 0.4539 | 0.063* | 0.775 (5) |
H13C | 0.7874 | 0.2805 | 0.4549 | 0.063* | 0.775 (5) |
C14 | 0.92160 (18) | 0.5366 (7) | 0.6263 (3) | 0.0410 (10) | 0.775 (5) |
H14A | 0.9364 | 0.5538 | 0.6918 | 0.062* | 0.775 (5) |
H14B | 0.9158 | 0.6352 | 0.5954 | 0.062* | 0.775 (5) |
H14C | 0.9472 | 0.4752 | 0.6201 | 0.062* | 0.775 (5) |
N2A | 0.8395 (3) | 0.4167 (7) | 0.5478 (5) | 0.032 (2) | 0.225 (5) |
H2A | 0.855 (3) | 0.327 (4) | 0.567 (5) | 0.038* | 0.225 (5) |
C11A | 0.8776 (3) | 0.5046 (8) | 0.5319 (6) | 0.038 (2) | 0.225 (5) |
H11A | 0.8584 | 0.5998 | 0.4974 | 0.046* | 0.225 (5) |
C12A | 0.8893 (9) | 0.410 (3) | 0.4699 (16) | 0.063 (6) | 0.225 (5) |
H12D | 0.9164 | 0.4626 | 0.4635 | 0.094* | 0.225 (5) |
H12E | 0.8558 | 0.3970 | 0.4089 | 0.094* | 0.225 (5) |
H12F | 0.9033 | 0.3089 | 0.4978 | 0.094* | 0.225 (5) |
C13A | 0.9288 (7) | 0.554 (3) | 0.6248 (13) | 0.080 (8) | 0.225 (5) |
H13D | 0.9558 | 0.5949 | 0.6140 | 0.120* | 0.225 (5) |
H13E | 0.9440 | 0.4655 | 0.6660 | 0.120* | 0.225 (5) |
H13F | 0.9190 | 0.6331 | 0.6532 | 0.120* | 0.225 (5) |
C14A | 0.7888 (8) | 0.371 (3) | 0.4588 (10) | 0.041 (4) | 0.225 (5) |
H14D | 0.7606 | 0.3451 | 0.4699 | 0.061* | 0.225 (5) |
H14E | 0.7963 | 0.2819 | 0.4332 | 0.061* | 0.225 (5) |
H14F | 0.7764 | 0.4561 | 0.4150 | 0.061* | 0.225 (5) |
C15 | 0.57935 (7) | 0.36013 (18) | 0.29127 (11) | 0.0373 (4) | |
C16 | 0.56391 (6) | 0.51453 (18) | 0.24727 (11) | 0.0348 (4) | |
H16 | 0.5762 | 0.6017 | 0.2864 | 0.042* | |
C17 | 0.53429 (7) | 0.53709 (19) | 0.15761 (11) | 0.0380 (4) | |
H17 | 0.5193 | 0.4499 | 0.1188 | 0.046* | |
C18 | 0.52272 (7) | 0.68853 (19) | 0.11306 (11) | 0.0378 (4) | |
H1A | 0.7846 (8) | 0.902 (3) | 0.7946 (15) | 0.061 (6)* | |
H1WA | 0.5221 (10) | 1.123 (3) | 0.0534 (18) | 0.075 (8)* | |
H1WB | 0.5371 (10) | 1.140 (3) | 0.1427 (18) | 0.073 (7)* | |
H1 | 0.6684 (10) | 0.469 (3) | 0.4607 (17) | 0.076 (8)* | |
H4A | 0.5378 (13) | 0.894 (4) | 0.135 (2) | 0.125 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0456 (7) | 0.0314 (6) | 0.0333 (6) | −0.0030 (5) | 0.0214 (6) | −0.0072 (5) |
O1W | 0.1121 (14) | 0.0383 (8) | 0.0472 (9) | −0.0134 (8) | 0.0428 (9) | −0.0065 (7) |
O2 | 0.1293 (14) | 0.0301 (7) | 0.0322 (7) | 0.0008 (8) | 0.0165 (8) | −0.0033 (6) |
O3 | 0.0499 (7) | 0.0332 (6) | 0.0275 (6) | 0.0026 (5) | 0.0113 (5) | 0.0022 (5) |
O4 | 0.0913 (11) | 0.0326 (7) | 0.0362 (7) | −0.0040 (7) | 0.0184 (7) | 0.0013 (6) |
O5 | 0.0944 (11) | 0.0447 (8) | 0.0316 (7) | −0.0044 (8) | 0.0063 (7) | 0.0075 (6) |
N1 | 0.0512 (9) | 0.0411 (8) | 0.0336 (7) | −0.0029 (7) | 0.0251 (7) | −0.0114 (6) |
C1 | 0.0364 (8) | 0.0237 (7) | 0.0244 (7) | 0.0042 (6) | 0.0176 (6) | 0.0041 (6) |
C2 | 0.0403 (9) | 0.0228 (7) | 0.0280 (7) | 0.0045 (6) | 0.0188 (7) | 0.0062 (6) |
C3 | 0.0365 (9) | 0.0355 (9) | 0.0369 (9) | 0.0011 (7) | 0.0178 (7) | 0.0061 (7) |
C4 | 0.0406 (9) | 0.0463 (10) | 0.0458 (10) | 0.0100 (8) | 0.0281 (8) | 0.0130 (8) |
C5 | 0.0519 (10) | 0.0441 (10) | 0.0381 (9) | 0.0115 (8) | 0.0318 (9) | 0.0051 (8) |
C6 | 0.0442 (9) | 0.0309 (8) | 0.0281 (8) | 0.0057 (7) | 0.0212 (7) | 0.0028 (6) |
C7 | 0.0390 (9) | 0.0385 (9) | 0.0351 (8) | −0.0027 (7) | 0.0202 (7) | −0.0034 (7) |
C8 | 0.0371 (8) | 0.0264 (8) | 0.0282 (7) | 0.0030 (6) | 0.0183 (7) | 0.0022 (6) |
C9 | 0.0404 (9) | 0.0301 (8) | 0.0328 (8) | 0.0045 (7) | 0.0234 (7) | 0.0043 (6) |
C10 | 0.0418 (9) | 0.0312 (8) | 0.0288 (8) | 0.0047 (7) | 0.0233 (7) | 0.0045 (6) |
N2 | 0.0369 (13) | 0.0259 (10) | 0.0279 (11) | 0.0045 (9) | 0.0186 (10) | 0.0037 (8) |
C11 | 0.0512 (17) | 0.0285 (11) | 0.0276 (12) | 0.0075 (10) | 0.0237 (12) | 0.0049 (9) |
C12 | 0.070 (3) | 0.048 (2) | 0.048 (3) | 0.005 (2) | 0.043 (3) | 0.0000 (18) |
C13 | 0.045 (2) | 0.037 (2) | 0.029 (2) | 0.006 (2) | 0.0113 (18) | 0.001 (2) |
C14 | 0.043 (2) | 0.0354 (18) | 0.048 (2) | −0.0057 (17) | 0.0271 (19) | −0.0075 (14) |
N2A | 0.037 (4) | 0.026 (4) | 0.030 (4) | 0.010 (3) | 0.018 (4) | 0.005 (3) |
C11A | 0.045 (5) | 0.035 (4) | 0.039 (5) | 0.004 (4) | 0.027 (5) | 0.004 (3) |
C12A | 0.090 (15) | 0.071 (10) | 0.056 (12) | 0.002 (11) | 0.058 (12) | −0.009 (9) |
C13A | 0.039 (8) | 0.090 (14) | 0.068 (12) | −0.036 (7) | 0.002 (8) | 0.003 (10) |
C14A | 0.033 (6) | 0.046 (8) | 0.025 (8) | 0.016 (5) | 0.005 (5) | 0.014 (7) |
C15 | 0.0455 (9) | 0.0306 (8) | 0.0286 (8) | 0.0031 (7) | 0.0159 (7) | −0.0008 (7) |
C16 | 0.0399 (9) | 0.0279 (8) | 0.0311 (8) | −0.0002 (7) | 0.0161 (7) | −0.0021 (6) |
C17 | 0.0415 (9) | 0.0301 (8) | 0.0303 (8) | 0.0006 (7) | 0.0121 (7) | −0.0014 (7) |
C18 | 0.0395 (9) | 0.0344 (9) | 0.0293 (8) | 0.0016 (7) | 0.0125 (7) | 0.0008 (7) |
O1—C2 | 1.3606 (18) | N2—C11 | 1.520 (3) |
O1—H1 | 0.87 (2) | N2—C14 | 1.493 (5) |
O1W—H1WA | 0.84 (3) | C11—H11 | 1.0000 |
O1W—H1WB | 0.87 (3) | C11—C12 | 1.524 (5) |
O2—C15 | 1.225 (2) | C11—C13 | 1.518 (6) |
O3—C15 | 1.2642 (19) | C12—H12A | 0.9800 |
O4—C18 | 1.293 (2) | C12—H12B | 0.9800 |
O4—H4A | 0.93 (3) | C12—H12C | 0.9800 |
O5—C18 | 1.209 (2) | C13—H13A | 0.9800 |
N1—C6 | 1.365 (2) | C13—H13B | 0.9800 |
N1—C7 | 1.368 (2) | C13—H13C | 0.9800 |
N1—H1A | 0.87 (2) | C14—H14A | 0.9800 |
C1—C2 | 1.404 (2) | C14—H14B | 0.9800 |
C1—C6 | 1.413 (2) | C14—H14C | 0.9800 |
C1—C8 | 1.444 (2) | N2A—H2A | 0.872 (10) |
C2—C3 | 1.383 (2) | N2A—C11A | 1.507 (8) |
C3—H3 | 0.9500 | N2A—C14A | 1.497 (10) |
C3—C4 | 1.400 (2) | C11A—H11A | 1.0000 |
C4—H4 | 0.9500 | C11A—C12A | 1.543 (10) |
C4—C5 | 1.367 (3) | C11A—C13A | 1.545 (10) |
C5—H5 | 0.9500 | C12A—H12D | 0.9800 |
C5—C6 | 1.398 (2) | C12A—H12E | 0.9800 |
C7—H7 | 0.9500 | C12A—H12F | 0.9800 |
C7—C8 | 1.361 (2) | C13A—H13D | 0.9800 |
C8—C9 | 1.501 (2) | C13A—H13E | 0.9800 |
C9—H9A | 0.9900 | C13A—H13F | 0.9800 |
C9—H9B | 0.9900 | C14A—H14D | 0.9800 |
C9—C10 | 1.520 (2) | C14A—H14E | 0.9800 |
C10—H10A | 0.9900 | C14A—H14F | 0.9800 |
C10—H10B | 0.9900 | C15—C16 | 1.494 (2) |
C10—H10C | 0.97 (8) | C16—H16 | 0.9500 |
C10—H10D | 0.96 (8) | C16—C17 | 1.315 (2) |
C10—N2 | 1.518 (2) | C17—H17 | 0.9500 |
C10—N2A | 1.536 (6) | C17—C18 | 1.476 (2) |
N2—H2 | 0.882 (10) | ||
C2—O1—H1 | 111.3 (16) | C11—C12—H12A | 109.5 |
H1WA—O1W—H1WB | 106 (2) | C11—C12—H12B | 109.5 |
C18—O4—H4A | 110 (2) | C11—C12—H12C | 109.5 |
C6—N1—C7 | 109.43 (14) | H12A—C12—H12B | 109.5 |
C6—N1—H1A | 125.7 (14) | H12A—C12—H12C | 109.5 |
C7—N1—H1A | 124.7 (14) | H12B—C12—H12C | 109.5 |
C2—C1—C6 | 118.41 (14) | C11—C13—H13A | 109.5 |
C2—C1—C8 | 134.44 (14) | C11—C13—H13B | 109.5 |
C6—C1—C8 | 107.03 (13) | C11—C13—H13C | 109.5 |
O1—C2—C1 | 117.29 (14) | H13A—C13—H13B | 109.5 |
O1—C2—C3 | 123.58 (15) | H13A—C13—H13C | 109.5 |
C3—C2—C1 | 119.13 (14) | H13B—C13—H13C | 109.5 |
C2—C3—H3 | 119.7 | N2—C14—H14A | 109.5 |
C2—C3—C4 | 120.57 (16) | N2—C14—H14B | 109.5 |
C4—C3—H3 | 119.7 | N2—C14—H14C | 109.5 |
C3—C4—H4 | 118.8 | H14A—C14—H14B | 109.5 |
C5—C4—C3 | 122.39 (16) | H14A—C14—H14C | 109.5 |
C5—C4—H4 | 118.8 | H14B—C14—H14C | 109.5 |
C4—C5—H5 | 121.6 | C10—N2A—H2A | 110 (6) |
C4—C5—C6 | 116.89 (15) | C11A—N2A—C10 | 109.5 (6) |
C6—C5—H5 | 121.6 | C11A—N2A—H2A | 104 (6) |
N1—C6—C1 | 107.22 (14) | C14A—N2A—C10 | 120.0 (13) |
N1—C6—C5 | 130.14 (15) | C14A—N2A—H2A | 100 (5) |
C5—C6—C1 | 122.61 (15) | C14A—N2A—C11A | 111.7 (11) |
N1—C7—H7 | 124.8 | N2A—C11A—H11A | 107.5 |
C8—C7—N1 | 110.45 (15) | N2A—C11A—C12A | 109.2 (12) |
C8—C7—H7 | 124.8 | N2A—C11A—C13A | 110.6 (13) |
C1—C8—C9 | 128.47 (14) | C12A—C11A—H11A | 107.5 |
C7—C8—C1 | 105.86 (13) | C12A—C11A—C13A | 114.4 (14) |
C7—C8—C9 | 125.56 (15) | C13A—C11A—H11A | 107.5 |
C8—C9—H9A | 109.0 | C11A—C12A—H12D | 109.5 |
C8—C9—H9B | 109.0 | C11A—C12A—H12E | 109.5 |
C8—C9—C10 | 112.98 (12) | C11A—C12A—H12F | 109.5 |
H9A—C9—H9B | 107.8 | H12D—C12A—H12E | 109.5 |
C10—C9—H9A | 109.0 | H12D—C12A—H12F | 109.5 |
C10—C9—H9B | 109.0 | H12E—C12A—H12F | 109.5 |
C9—C10—H10A | 109.1 | C11A—C13A—H13D | 109.5 |
C9—C10—H10B | 109.1 | C11A—C13A—H13E | 109.5 |
C9—C10—H10C | 112 (4) | C11A—C13A—H13F | 109.5 |
C9—C10—H10D | 113 (5) | H13D—C13A—H13E | 109.5 |
C9—C10—N2A | 114.5 (3) | H13D—C13A—H13F | 109.5 |
H10A—C10—H10B | 107.8 | H13E—C13A—H13F | 109.5 |
H10C—C10—H10D | 105 (6) | N2A—C14A—H14D | 109.5 |
N2—C10—C9 | 112.69 (13) | N2A—C14A—H14E | 109.5 |
N2—C10—H10A | 109.1 | N2A—C14A—H14F | 109.5 |
N2—C10—H10B | 109.1 | H14D—C14A—H14E | 109.5 |
N2A—C10—H10C | 97 (4) | H14D—C14A—H14F | 109.5 |
N2A—C10—H10D | 114 (5) | H14E—C14A—H14F | 109.5 |
C10—N2—H2 | 104.1 (17) | O2—C15—O3 | 123.28 (15) |
C10—N2—C11 | 113.62 (18) | O2—C15—C16 | 119.80 (14) |
C11—N2—H2 | 105.8 (16) | O3—C15—C16 | 116.91 (14) |
C14—N2—C10 | 114.0 (2) | C15—C16—H16 | 118.0 |
C14—N2—H2 | 107.9 (16) | C17—C16—C15 | 123.93 (15) |
C14—N2—C11 | 110.7 (3) | C17—C16—H16 | 118.0 |
N2—C11—H11 | 108.0 | C16—C17—H17 | 117.7 |
N2—C11—C12 | 109.5 (3) | C16—C17—C18 | 124.51 (15) |
C12—C11—H11 | 108.0 | C18—C17—H17 | 117.7 |
C13—C11—N2 | 110.8 (3) | O4—C18—C17 | 115.49 (14) |
C13—C11—H11 | 108.0 | O5—C18—O4 | 122.93 (16) |
C13—C11—C12 | 112.2 (4) | O5—C18—C17 | 121.56 (15) |
O1—C2—C3—C4 | −178.98 (14) | C7—C8—C9—C10 | 106.26 (18) |
O2—C15—C16—C17 | −4.2 (3) | C8—C1—C2—O1 | 3.2 (2) |
O3—C15—C16—C17 | 174.39 (17) | C8—C1—C2—C3 | −176.09 (16) |
N1—C7—C8—C1 | 0.49 (18) | C8—C1—C6—N1 | −0.47 (17) |
N1—C7—C8—C9 | 176.96 (14) | C8—C1—C6—C5 | 177.70 (14) |
C1—C2—C3—C4 | 0.2 (2) | C8—C9—C10—N2 | −170.62 (16) |
C1—C8—C9—C10 | −78.1 (2) | C8—C9—C10—N2A | 156.1 (4) |
C2—C1—C6—N1 | −177.00 (13) | C9—C10—N2—C11 | −60.2 (2) |
C2—C1—C6—C5 | 1.2 (2) | C9—C10—N2—C14 | 67.9 (3) |
C2—C1—C8—C7 | 175.72 (16) | C9—C10—N2A—C11A | 60.3 (6) |
C2—C1—C8—C9 | −0.6 (3) | C9—C10—N2A—C14A | −70.7 (12) |
C2—C3—C4—C5 | −0.1 (3) | C10—N2—C11—C12 | −171.7 (4) |
C3—C4—C5—C6 | 0.4 (2) | C10—N2—C11—C13 | −47.3 (4) |
C4—C5—C6—N1 | 176.71 (17) | C10—N2A—C11A—C12A | 169.9 (12) |
C4—C5—C6—C1 | −1.0 (2) | C10—N2A—C11A—C13A | 43.1 (13) |
C6—N1—C7—C8 | −0.81 (19) | C14—N2—C11—C12 | 58.5 (4) |
C6—C1—C2—O1 | 178.51 (13) | C14—N2—C11—C13 | −177.2 (4) |
C6—C1—C2—C3 | −0.7 (2) | C14A—N2A—C11A—C12A | −54.8 (18) |
C6—C1—C8—C7 | −0.01 (17) | C14A—N2A—C11A—C13A | 178.4 (18) |
C6—C1—C8—C9 | −176.34 (14) | C15—C16—C17—C18 | −174.40 (16) |
C7—N1—C6—C1 | 0.78 (18) | C16—C17—C18—O4 | 5.5 (3) |
C7—N1—C6—C5 | −177.20 (16) | C16—C17—C18—O5 | −175.90 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2i | 0.88 (1) | 2.51 (2) | 3.085 (2) | 124 (2) |
N2—H2···O3i | 0.88 (1) | 1.89 (1) | 2.775 (2) | 178 (2) |
N2A—H2A···O3i | 0.87 (1) | 1.85 (2) | 2.717 (6) | 172 (8) |
O1—H1···O3 | 0.87 (2) | 1.79 (3) | 2.6512 (17) | 172 (2) |
O4—H4A···O1W | 0.93 (3) | 1.66 (3) | 2.579 (2) | 167 (3) |
O1W—H1WA···O5ii | 0.84 (3) | 1.98 (3) | 2.779 (2) | 160 (2) |
O1W—H1WB···O2iii | 0.87 (3) | 1.74 (3) | 2.599 (2) | 170 (2) |
Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+1, −y+2, −z; (iii) x, y+1, z. |
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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