research communications
The methanol and ethanol solvates of 4-glutarato-N,N-diisopropyltryptamine
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
The solid-state structures of two solvated forms of 4-glutarato-N,N-diisopropyltryptamine were determined by single-crystal X-ray diffraction, namely, 5-[(3-{2-[bis(propan-2-yl)azaniumyl]ethyl}-1H-indol-4-yl)oxy]-5-oxopentanoate methanol monosolvate, C21H30N2O4·CH3OH, and the analogous ethanol monosolvate, C21H30N2O4·C2H6O. In both compounds, the 4-glutarato-N,N-diisopropyltryptamine exists as a zwitterion with a protonated tertiary ammonium and a deprotonated glutarato carboxylate. The tryptamine and alcohol solvates in both structures combine to produce near identical hydrogen-bonding networks, with N—H⋯O and O—H⋯O hydrogen bonds joining the molecules together in two-dimensional networks parallel to the (100) plane.
Keywords: crystal structure; tryptamines; indoles; zwitterions; hydrogen bonds.
1. Chemical context
Psychedelic compounds continue to be a major research focus for treating conditions including depression, post-traumatic stress disorder (PTSD), Alzheimer's disease, and chronic pain (Carhart-Harris & Goodwin, 2017; Krediet et al., 2020; Vann Jones & O'Kelly, 2020; Ramaekers et al., 2021). Tryptamine compounds with chemical structures resembling that of the active product of magic mushrooms, psilocin (4-hydroxy-N,N-dimethyltryptamine; 4-HO-DMT), are of particular interest. This is due not just to their structural similarities to the neurotransmitter serotonin (5-hydroxytryptamine; 5-HT), but because many have desirable drug characteristics including oral availability, lowered susceptibility to monoamine oxidase (MAO) degradation, and short duration of action (Kuypers et al., 2019). The synthesis of prodrugs that undergo hydrolysis to produce 4-hydroxy derivatives of dialkyltryptamines are of increasing interest (Klein et al., 2021; Chadeayne et al., 2019a; Chadeayne, Pham, Reid et al., 2020; Naeem et al., 2022).
4-Hydroxy-N,N-diisopropyltryptamine (4-HO-DiPT) is one example of a psilocin analog, first synthesized in 1977, in which both methyl groups on the ethylamino moiety of psilocin are replaced with isopropyl groups (Repke et al., 1977). In early 2022, 4-HO-DiPT along with four other psychedelics were part of a proposal issued by the US Drug Enforcement Administration (DEA), requesting comments on reclassifying these compounds to Schedule I of the Controlled Substance Act. Due to a strong public response, the DEA withdrew the proposal before the hearing, which was scheduled for August (US DEA, January 14 & July 6, 2022a,b).
4-HO-DiPT is a serotonin-2A (5-HT2A) receptor agonist that, like psilocin, produces a head-twitch response (HTR) in mice, indicating its competence in producing psychedelic effects (Halberstadt et al., 2020). 4-HO-DiPT also interacts with the serotonin transporter (SERT) with IC50 values in the low micromolar range, similar to 3,4-methylenedioxymethamphetamine (MDMA) (Rickli et al., 2016). 4-HO-DiPT has been reported as orally active at a 15–20 mg dose, with its profound psychedelic effects beginning within 15 minutes and lasting about 2–3 h (Shulgin & Shulgin, 2017).
4-HO-DiPT glutarate, a `hemiester' prodrug of 4-HO-DiPT has been reported in the patent literature (Bryson, 2022). We have previously published work characterizing tryptamine compounds, highlighting the importance of single-crystal X-ray diffraction studies when characterizing tryptamine salts because they can occur in a variety of forms that are often not appreciated by other means of characterization (Chadeayne et al., 2019a,b; Chadeayne, Pham, Golen et al., 2020; Sammeta et al., 2020; Pham et al., 2021; Naeem et al., 2022). To this end, we synthesized 4-glutarato-N,N-diisopropyltrypamine and report herein two crystalline forms of the compound as both its methanol and ethanol solvates.
2. Structural commentary
In the solid state, the compound exists as a zwitterion, with a protonated tertiary ammonium group and a deprotonated carboxylate of the glutarato group. Both of the solvate structures possess one zwitterionic molecule and one alcohol molecule in the ). In the ethanol solvate, the alcohol molecule is disordered over two orientations in a 0.531 (11):0.469 (11) ratio. Both solvates have near planar indole units with r.m.s. deviations from planarity of 0.009 and 0.016 Å for the methanol and ethanol solvates, respectively. The glutarato units are also close to planar with r.m.s. deviations of only 0.061 and 0.071 Å. In both cases, the glutarato unit is nearly orthogonal to the indole plane, showing plane-to-plane twists of 90.99 (6) and 94.21 (8)°. Likewise, the ethylamino arms are nearly orthogonal to the indole plane with C7—C8—C9—C10 angles of 90.2 (2) and 86.1 (3)°. Both ethylamino arms demonstrate anti configurations, with C8—C9—C10—N2 angles of 179.92 (14) and 180.0 (2)°. In both structures, the glutarato and ethylamino arms are turned to opposite sides of the indole. This differs from the structures observed in other zwitterionic indoles where intramolecular hydrogen bonding leads to two groups being on the same side of the aromatic rings (Naeem et al., 2022). The nature of the groups in this compound only allows for intermolecular interactions (vide infra) and having the groups on opposite sides of the indole is sterically preferred.
(Fig. 13. Supramolecular features
In both crystals, the zwitterionic molecules and alcohol solvents are held together by N+—H⋯O− and O—H⋯O hydrogen bonds that produce infinite two-dimensional networks parallel to the (100) plane. The most significant hydrogen bonds are N2—H2⋯O4 bonds between the diisopropyltryptammonium cation and the carboxylate anion of another zwitterionic molecule. These interactions form centrosymmetrical dimers, which form rings with graph-set notation of R22(28) (Etter et al., 1990). These dimers are shown in Fig. 2. The dimers are joined together through N1—H1⋯O3 hydrogen bonds between the indole nitrogen and the other carboxylate oxygen. The alcohol oxygens also hydrogen bond to the carboxylate anion through O5—H5⋯O4 bonds (Tables 1 and 2). The two structures demonstrate near identical hydrogen-bonding networks in the solid state, which can be seen in their packing diagrams (Fig. 3).
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4. Database survey
There are three reported tryptamine structures possessing isopropyl groups on the ethylamino arm, all of which are N-methyl-N-isopropyl derivatives: N-methyl-N-isopropyltryptammonium hydrofumarate (Chadeayne, Pham, Golen et al., 2019: RONSOF) as well as the hydrofumarate (Chadeayne, Pham, Golen et al., 2019: RONSUL) and fumarate (Chadeayne, Pham, Golen et al., 2020: TUFQAP) of 4-hydroxy-N-methyl-N-isopropyltryptamine. There are six structures of 4-substituted of tryptamines in the literature, all of which are 4-acetoxy derivatives: the hydrofumarate (Chadeayne et al., 2019a: HOCJUH) and fumarate (Chadeayne et al., 2019b: XOFDOO) of psilacetin (4-acetoxy-N,N-dimethyltryptamine), 4-acetoxy-N-methyl-N-ethyltryptammonium hydrofumarate (Pham et al., 2021: OJIQIK), 4-acetoxy-N-methyl-N-allyltryptammonium hydrofumarate (Pham et al., 2021: OJIQOQ), 4-acetoxy-N,N-diallyltryptammonium fumarate fumaric acid (Pham et al., 2021: OJIQUW), and 4-acetoxy-N,N,N-trimethyltryptammonium iodide (Chadeayne, Pham, Reid et al., 2020: XUXDUS). There are two tryptamine reported in the literature, those being the natural products baeocystin, 4-phosphoryloxy-N-methyltryptamine (Naeem et al., 2022), and psilocybin, 4-phosphoryloxy-N,N-dimethyltryptamine (Weber & Petcher, 1974; PSILOC; Sherwood et al., 2022: TAVZID, TAVZID01; Greenan et al., 2020; OKOKAD).
5. Synthesis and crystallization
112 mg of 4-hydroxy-N,N-diisopropyltryptamine (1 mmol) were dissolved in 5 mL of chloroform. 0.3 mL of triethylamine (5 mmol) followed by 490 mg of glutaric anhydride (10 mmol) were then added to the solution. The mixture was stirred at room temperature for 30 minutes, resulting in a precipitate which was isolated via filtration. The precipitate was triturated with tetrahydrofuran and washed with chloroform to obtain 73 mg of white powder (65% yield).
1H NMR (400 MHz, DMSO-d6): δ 11.02 (s, 1H, NH), 7.22 (d, J = 8.1 Hz, 1H, ArH), 7.16 (d, J = 2.3 Hz, 1H, ArH), 7.02 (t, J = 7.9 Hz, 1H, ArH), 6.64 (d, J = 7.5 Hz, 1H, ArH), 3.10 (sept, J = 6.5 Hz, 2H, CH), 2.77–2.63 (m, 6H, CH2), 2.31 (t, J = 7.2 Hz, 2H, CH2), 1.88 (t, J = 7.2 Hz, 2H, CH2), 1.00 (d, J = 6.6 Hz, 12H, CH3).
The powder was recrystallized from boiling methanol to yield single crystals of the methanol solvate suitable for X-ray
Slow evaporation of an ethanol solution of the powder produced single crystals of the ethanol solvate suitable for X-ray diffraction analysis.6. Refinement
Crystal data, data collection and structure . In the methanol solvate, hydrogen atoms H1, H2 and H5A were found in a difference-Fourier map and in the ethanol solvate, hydrogen atoms H1 and H2 were found in a difference-Fourier map. These hydrogens were refined isotropically, using DFIX restraints with N—H(indole) distances of 0.87 (1) Å, N—H(ammonium) distances of 0.90 (1) Å, and O—H distances of 0.99 (1) Å. Isotropic displacement parameters were set to 1.2Ueq of the parent nitrogen atoms and 1.5Ueq of the parent oxygen atom. All other hydrogens were placed in calculated positions [C—H = 0.93 Å (sp2), 0.97 Å (CH2), 0.96 Å (CH3)]. The hydrogen atoms in the disordered ethanol molecule were placed in calculated positions [O—H = 0.82 Å]. Isotropic displacement parameters were set to 1.2Ueq of the parent carbon atoms and 1.5Ueq of the parent oxygen atoms.
details are summarized in Table 3Supporting information
https://doi.org/10.1107/S2056989022009094/zn2023sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022009094/zn2023Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989022009094/zn2023IIsup3.hkl
For both structures, data collection: APEX4 (Bruker, 2021); cell
SAINT (Bruker, 2021); data reduction: SAINT (Bruker, 2021); 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).C21H30N2O4·CH4O | F(000) = 880 |
Mr = 406.51 | Dx = 1.194 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9531 (5) Å | Cell parameters from 9859 reflections |
b = 13.4224 (7) Å | θ = 3.0–25.6° |
c = 21.2015 (11) Å | µ = 0.08 mm−1 |
β = 92.484 (2)° | T = 297 K |
V = 2261.1 (2) Å3 | Block, colourless |
Z = 4 | 0.22 × 0.21 × 0.20 mm |
Bruker D8 Venture CMOS diffractometer | 3531 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.039 |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | θmax = 25.7°, θmin = 3.0° |
Tmin = 0.718, Tmax = 0.745 | h = −9→9 |
61210 measured reflections | k = −16→16 |
4304 independent reflections | l = −25→25 |
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)] = 0.050 | w = 1/[σ2(Fo2) + (0.0677P)2 + 1.0658P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.143 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.46 e Å−3 |
4304 reflections | Δρmin = −0.39 e Å−3 |
279 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
3 restraints | Extinction coefficient: 0.0049 (16) |
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 | ||
O1 | 0.17552 (17) | 0.35382 (9) | 0.29846 (5) | 0.0421 (3) | |
O2 | 0.2385 (2) | 0.51443 (11) | 0.28621 (6) | 0.0675 (5) | |
O3 | 0.3521 (2) | 0.72404 (12) | 0.48361 (7) | 0.0730 (5) | |
O4 | 0.2931 (2) | 0.66404 (11) | 0.57648 (6) | 0.0621 (4) | |
N1 | 0.4481 (2) | 0.26115 (12) | 0.11776 (7) | 0.0454 (4) | |
N2 | 0.61740 (18) | 0.15461 (10) | 0.37628 (6) | 0.0362 (3) | |
C1 | 0.5573 (2) | 0.25778 (14) | 0.16893 (9) | 0.0446 (4) | |
H1A | 0.669647 | 0.238884 | 0.167694 | 0.053* | |
C2 | 0.2940 (2) | 0.29148 (13) | 0.13645 (8) | 0.0386 (4) | |
C3 | 0.1426 (3) | 0.30411 (15) | 0.10225 (8) | 0.0481 (5) | |
H3 | 0.134321 | 0.291932 | 0.059041 | 0.058* | |
C4 | 0.0058 (3) | 0.33510 (17) | 0.13421 (9) | 0.0539 (5) | |
H4 | −0.096839 | 0.343720 | 0.112189 | 0.065* | |
C5 | 0.0169 (2) | 0.35412 (15) | 0.19936 (9) | 0.0489 (5) | |
H5 | −0.077222 | 0.375904 | 0.219944 | 0.059* | |
C6 | 0.1662 (2) | 0.34057 (12) | 0.23242 (8) | 0.0375 (4) | |
C7 | 0.3099 (2) | 0.30850 (12) | 0.20252 (7) | 0.0348 (4) | |
C8 | 0.4801 (2) | 0.28580 (12) | 0.22217 (8) | 0.0381 (4) | |
C9 | 0.5583 (2) | 0.27857 (13) | 0.28772 (8) | 0.0410 (4) | |
H9A | 0.501378 | 0.323224 | 0.315755 | 0.049* | |
H9B | 0.675960 | 0.297597 | 0.287599 | 0.049* | |
C10 | 0.5426 (2) | 0.17173 (13) | 0.31047 (8) | 0.0387 (4) | |
H10A | 0.424472 | 0.153645 | 0.309562 | 0.046* | |
H10B | 0.598183 | 0.128085 | 0.281434 | 0.046* | |
C11 | 0.4906 (2) | 0.10852 (14) | 0.41929 (9) | 0.0452 (4) | |
H11 | 0.547211 | 0.100130 | 0.460941 | 0.054* | |
C13 | 0.3444 (3) | 0.17846 (17) | 0.42725 (11) | 0.0581 (5) | |
H13A | 0.385521 | 0.241480 | 0.442784 | 0.087* | |
H13B | 0.269327 | 0.150484 | 0.456783 | 0.087* | |
H13C | 0.285274 | 0.187901 | 0.387253 | 0.087* | |
C12 | 0.4347 (4) | 0.00616 (17) | 0.39679 (13) | 0.0723 (7) | |
H12A | 0.530499 | −0.037275 | 0.396077 | 0.108* | |
H12B | 0.383512 | 0.011193 | 0.355068 | 0.108* | |
H12C | 0.354637 | −0.020317 | 0.424972 | 0.108* | |
C14 | 0.7823 (2) | 0.09675 (15) | 0.37460 (9) | 0.0471 (5) | |
H14 | 0.759363 | 0.032539 | 0.353974 | 0.057* | |
C15 | 0.8546 (3) | 0.0769 (2) | 0.44071 (11) | 0.0712 (7) | |
H15A | 0.783385 | 0.030922 | 0.461678 | 0.107* | |
H15B | 0.861037 | 0.138280 | 0.463944 | 0.107* | |
H15C | 0.965311 | 0.048954 | 0.438396 | 0.107* | |
C16 | 0.9078 (3) | 0.15321 (19) | 0.33620 (12) | 0.0632 (6) | |
H16A | 0.862701 | 0.161671 | 0.293803 | 0.095* | |
H16B | 1.011172 | 0.116333 | 0.335554 | 0.095* | |
H16C | 0.929013 | 0.217350 | 0.354941 | 0.095* | |
C17 | 0.2114 (2) | 0.44694 (13) | 0.32012 (8) | 0.0409 (4) | |
C18 | 0.2177 (3) | 0.44943 (14) | 0.39084 (8) | 0.0483 (5) | |
H18A | 0.306025 | 0.404959 | 0.406611 | 0.058* | |
H18B | 0.111785 | 0.424768 | 0.405632 | 0.058* | |
C19 | 0.2497 (3) | 0.55192 (15) | 0.41772 (9) | 0.0522 (5) | |
H19A | 0.162315 | 0.596552 | 0.401363 | 0.063* | |
H19B | 0.356367 | 0.576115 | 0.403349 | 0.063* | |
C20 | 0.2538 (3) | 0.55546 (15) | 0.48899 (9) | 0.0536 (5) | |
H20A | 0.332027 | 0.505235 | 0.505171 | 0.064* | |
H20B | 0.143059 | 0.538020 | 0.502980 | 0.064* | |
C21 | 0.3041 (3) | 0.65529 (15) | 0.51767 (9) | 0.0474 (5) | |
O5 | 0.1577 (3) | 0.53742 (16) | 0.66260 (11) | 0.0928 (6) | |
H5A | 0.224 (4) | 0.563 (2) | 0.6271 (11) | 0.111* | |
C22 | 0.2529 (6) | 0.4611 (3) | 0.6828 (2) | 0.1272 (15) | |
H22A | 0.184260 | 0.413329 | 0.703499 | 0.191* | |
H22B | 0.339437 | 0.484832 | 0.712036 | 0.191* | |
H22C | 0.303585 | 0.430125 | 0.647521 | 0.191* | |
H2 | 0.644 (2) | 0.2153 (9) | 0.3923 (9) | 0.045 (5)* | |
H1 | 0.475 (3) | 0.2488 (16) | 0.0796 (6) | 0.057 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0613 (8) | 0.0378 (6) | 0.0278 (6) | −0.0046 (6) | 0.0104 (5) | −0.0059 (5) |
O2 | 0.1172 (14) | 0.0483 (8) | 0.0375 (7) | −0.0279 (9) | 0.0073 (8) | 0.0011 (6) |
O3 | 0.1127 (14) | 0.0647 (10) | 0.0436 (8) | −0.0400 (9) | 0.0275 (8) | −0.0135 (7) |
O4 | 0.1033 (12) | 0.0526 (8) | 0.0311 (7) | −0.0267 (8) | 0.0110 (7) | −0.0100 (6) |
N1 | 0.0607 (10) | 0.0477 (9) | 0.0289 (7) | 0.0035 (7) | 0.0133 (7) | −0.0045 (6) |
N2 | 0.0427 (8) | 0.0336 (7) | 0.0321 (7) | −0.0030 (6) | −0.0009 (6) | −0.0024 (6) |
C1 | 0.0484 (10) | 0.0436 (10) | 0.0421 (10) | 0.0040 (8) | 0.0068 (8) | −0.0017 (8) |
C2 | 0.0537 (10) | 0.0338 (8) | 0.0286 (8) | −0.0027 (7) | 0.0058 (7) | −0.0025 (6) |
C3 | 0.0624 (12) | 0.0538 (11) | 0.0278 (8) | −0.0041 (9) | −0.0028 (8) | −0.0026 (8) |
C4 | 0.0502 (11) | 0.0655 (13) | 0.0452 (11) | −0.0023 (10) | −0.0074 (9) | 0.0017 (9) |
C5 | 0.0455 (10) | 0.0558 (11) | 0.0460 (11) | 0.0010 (9) | 0.0075 (8) | −0.0030 (9) |
C6 | 0.0500 (10) | 0.0347 (8) | 0.0283 (8) | −0.0044 (7) | 0.0073 (7) | −0.0033 (6) |
C7 | 0.0476 (9) | 0.0301 (8) | 0.0266 (8) | −0.0030 (7) | 0.0026 (7) | −0.0017 (6) |
C8 | 0.0480 (10) | 0.0333 (8) | 0.0331 (8) | −0.0006 (7) | 0.0028 (7) | −0.0002 (7) |
C9 | 0.0477 (10) | 0.0379 (9) | 0.0370 (9) | −0.0015 (7) | −0.0027 (7) | −0.0032 (7) |
C10 | 0.0440 (9) | 0.0398 (9) | 0.0318 (8) | −0.0042 (7) | −0.0027 (7) | −0.0033 (7) |
C11 | 0.0531 (11) | 0.0423 (10) | 0.0404 (9) | −0.0060 (8) | 0.0054 (8) | 0.0046 (8) |
C13 | 0.0523 (12) | 0.0638 (13) | 0.0592 (13) | −0.0052 (10) | 0.0121 (10) | −0.0035 (10) |
C12 | 0.0905 (18) | 0.0434 (12) | 0.0845 (17) | −0.0185 (12) | 0.0207 (14) | 0.0013 (11) |
C14 | 0.0463 (10) | 0.0472 (10) | 0.0475 (10) | 0.0064 (8) | −0.0030 (8) | −0.0041 (8) |
C15 | 0.0655 (15) | 0.0859 (17) | 0.0609 (14) | 0.0185 (13) | −0.0131 (11) | 0.0064 (12) |
C16 | 0.0448 (11) | 0.0772 (16) | 0.0678 (14) | 0.0022 (10) | 0.0058 (10) | −0.0027 (12) |
C17 | 0.0503 (10) | 0.0382 (9) | 0.0349 (9) | −0.0052 (8) | 0.0075 (7) | −0.0045 (7) |
C18 | 0.0719 (13) | 0.0414 (10) | 0.0319 (9) | −0.0056 (9) | 0.0054 (8) | −0.0059 (7) |
C19 | 0.0747 (14) | 0.0454 (11) | 0.0367 (10) | −0.0082 (9) | 0.0036 (9) | −0.0102 (8) |
C20 | 0.0731 (14) | 0.0505 (11) | 0.0380 (10) | −0.0169 (10) | 0.0104 (9) | −0.0105 (8) |
C21 | 0.0573 (11) | 0.0509 (11) | 0.0349 (9) | −0.0159 (9) | 0.0107 (8) | −0.0100 (8) |
O5 | 0.0849 (13) | 0.0864 (14) | 0.1090 (16) | 0.0042 (11) | 0.0245 (11) | 0.0304 (12) |
C22 | 0.152 (4) | 0.073 (2) | 0.159 (4) | 0.045 (2) | 0.036 (3) | 0.038 (2) |
O1—C6 | 1.4100 (19) | C11—C12 | 1.515 (3) |
O1—C17 | 1.358 (2) | C13—H13A | 0.9600 |
O2—C17 | 1.182 (2) | C13—H13B | 0.9600 |
O3—C21 | 1.242 (2) | C13—H13C | 0.9600 |
O4—C21 | 1.259 (2) | C12—H12A | 0.9600 |
N1—C1 | 1.361 (2) | C12—H12B | 0.9600 |
N1—C2 | 1.366 (2) | C12—H12C | 0.9600 |
N1—H1 | 0.862 (9) | C14—H14 | 0.9800 |
N2—C10 | 1.510 (2) | C14—C15 | 1.515 (3) |
N2—C11 | 1.520 (2) | C14—C16 | 1.518 (3) |
N2—C14 | 1.526 (2) | C15—H15A | 0.9600 |
N2—H2 | 0.903 (9) | C15—H15B | 0.9600 |
C1—H1A | 0.9300 | C15—H15C | 0.9600 |
C1—C8 | 1.361 (2) | C16—H16A | 0.9600 |
C2—C3 | 1.389 (3) | C16—H16B | 0.9600 |
C2—C7 | 1.420 (2) | C16—H16C | 0.9600 |
C3—H3 | 0.9300 | C17—C18 | 1.498 (2) |
C3—C4 | 1.371 (3) | C18—H18A | 0.9700 |
C4—H4 | 0.9300 | C18—H18B | 0.9700 |
C4—C5 | 1.404 (3) | C18—C19 | 1.506 (3) |
C5—H5 | 0.9300 | C19—H19A | 0.9700 |
C5—C6 | 1.364 (3) | C19—H19B | 0.9700 |
C6—C7 | 1.399 (2) | C19—C20 | 1.511 (3) |
C7—C8 | 1.431 (3) | C20—H20A | 0.9700 |
C8—C9 | 1.501 (2) | C20—H20B | 0.9700 |
C9—H9A | 0.9700 | C20—C21 | 1.518 (3) |
C9—H9B | 0.9700 | O5—H5A | 0.998 (10) |
C9—C10 | 1.520 (2) | O5—C22 | 1.334 (4) |
C10—H10A | 0.9700 | C22—H22A | 0.9600 |
C10—H10B | 0.9700 | C22—H22B | 0.9600 |
C11—H11 | 0.9800 | C22—H22C | 0.9600 |
C11—C13 | 1.510 (3) | ||
C17—O1—C6 | 116.95 (13) | H13B—C13—H13C | 109.5 |
C1—N1—C2 | 109.15 (14) | C11—C12—H12A | 109.5 |
C1—N1—H1 | 124.4 (15) | C11—C12—H12B | 109.5 |
C2—N1—H1 | 126.4 (15) | C11—C12—H12C | 109.5 |
C10—N2—C11 | 111.80 (14) | H12A—C12—H12B | 109.5 |
C10—N2—C14 | 111.11 (13) | H12A—C12—H12C | 109.5 |
C10—N2—H2 | 106.6 (13) | H12B—C12—H12C | 109.5 |
C11—N2—C14 | 113.58 (14) | N2—C14—H14 | 108.3 |
C11—N2—H2 | 106.8 (13) | C15—C14—N2 | 111.09 (16) |
C14—N2—H2 | 106.4 (13) | C15—C14—H14 | 108.3 |
N1—C1—H1A | 124.6 | C15—C14—C16 | 110.61 (19) |
N1—C1—C8 | 110.89 (17) | C16—C14—N2 | 110.14 (16) |
C8—C1—H1A | 124.6 | C16—C14—H14 | 108.3 |
N1—C2—C3 | 130.79 (16) | C14—C15—H15A | 109.5 |
N1—C2—C7 | 106.95 (15) | C14—C15—H15B | 109.5 |
C3—C2—C7 | 122.25 (17) | C14—C15—H15C | 109.5 |
C2—C3—H3 | 121.1 | H15A—C15—H15B | 109.5 |
C4—C3—C2 | 117.88 (17) | H15A—C15—H15C | 109.5 |
C4—C3—H3 | 121.1 | H15B—C15—H15C | 109.5 |
C3—C4—H4 | 119.2 | C14—C16—H16A | 109.5 |
C3—C4—C5 | 121.60 (18) | C14—C16—H16B | 109.5 |
C5—C4—H4 | 119.2 | C14—C16—H16C | 109.5 |
C4—C5—H5 | 120.1 | H16A—C16—H16B | 109.5 |
C6—C5—C4 | 119.84 (18) | H16A—C16—H16C | 109.5 |
C6—C5—H5 | 120.1 | H16B—C16—H16C | 109.5 |
C5—C6—O1 | 120.02 (16) | O1—C17—C18 | 110.89 (14) |
C5—C6—C7 | 121.21 (16) | O2—C17—O1 | 122.74 (16) |
C7—C6—O1 | 118.69 (15) | O2—C17—C18 | 126.32 (17) |
C2—C7—C8 | 107.19 (15) | C17—C18—H18A | 108.9 |
C6—C7—C2 | 117.21 (16) | C17—C18—H18B | 108.9 |
C6—C7—C8 | 135.60 (15) | C17—C18—C19 | 113.38 (16) |
C1—C8—C7 | 105.81 (15) | H18A—C18—H18B | 107.7 |
C1—C8—C9 | 124.48 (17) | C19—C18—H18A | 108.9 |
C7—C8—C9 | 129.19 (15) | C19—C18—H18B | 108.9 |
C8—C9—H9A | 110.0 | C18—C19—H19A | 108.8 |
C8—C9—H9B | 110.0 | C18—C19—H19B | 108.8 |
C8—C9—C10 | 108.57 (14) | C18—C19—C20 | 113.78 (16) |
H9A—C9—H9B | 108.4 | H19A—C19—H19B | 107.7 |
C10—C9—H9A | 110.0 | C20—C19—H19A | 108.8 |
C10—C9—H9B | 110.0 | C20—C19—H19B | 108.8 |
N2—C10—C9 | 113.72 (13) | C19—C20—H20A | 108.5 |
N2—C10—H10A | 108.8 | C19—C20—H20B | 108.5 |
N2—C10—H10B | 108.8 | C19—C20—C21 | 114.98 (16) |
C9—C10—H10A | 108.8 | H20A—C20—H20B | 107.5 |
C9—C10—H10B | 108.8 | C21—C20—H20A | 108.5 |
H10A—C10—H10B | 107.7 | C21—C20—H20B | 108.5 |
N2—C11—H11 | 107.3 | O3—C21—O4 | 122.88 (17) |
C13—C11—N2 | 110.38 (15) | O3—C21—C20 | 120.35 (16) |
C13—C11—H11 | 107.3 | O4—C21—C20 | 116.77 (17) |
C13—C11—C12 | 112.46 (19) | C22—O5—H5A | 101 (2) |
C12—C11—N2 | 111.93 (16) | O5—C22—H22A | 109.5 |
C12—C11—H11 | 107.3 | O5—C22—H22B | 109.5 |
C11—C13—H13A | 109.5 | O5—C22—H22C | 109.5 |
C11—C13—H13B | 109.5 | H22A—C22—H22B | 109.5 |
C11—C13—H13C | 109.5 | H22A—C22—H22C | 109.5 |
H13A—C13—H13B | 109.5 | H22B—C22—H22C | 109.5 |
H13A—C13—H13C | 109.5 | ||
O1—C6—C7—C2 | 177.15 (14) | C6—O1—C17—O2 | −2.0 (3) |
O1—C6—C7—C8 | −2.1 (3) | C6—O1—C17—C18 | −179.77 (15) |
O1—C17—C18—C19 | −177.50 (17) | C6—C7—C8—C1 | 179.74 (19) |
O2—C17—C18—C19 | 4.8 (3) | C6—C7—C8—C9 | 7.9 (3) |
N1—C1—C8—C7 | −0.1 (2) | C7—C2—C3—C4 | 0.7 (3) |
N1—C1—C8—C9 | 172.23 (16) | C7—C8—C9—C10 | 90.2 (2) |
N1—C2—C3—C4 | 179.42 (19) | C8—C9—C10—N2 | 179.92 (14) |
N1—C2—C7—C6 | 179.94 (15) | C10—N2—C11—C13 | −63.01 (19) |
N1—C2—C7—C8 | −0.61 (19) | C10—N2—C11—C12 | 63.1 (2) |
C1—N1—C2—C3 | −178.34 (19) | C10—N2—C14—C15 | −178.31 (17) |
C1—N1—C2—C7 | 0.5 (2) | C10—N2—C14—C16 | 58.79 (19) |
C1—C8—C9—C10 | −80.3 (2) | C11—N2—C10—C9 | 125.26 (16) |
C2—N1—C1—C8 | −0.3 (2) | C11—N2—C14—C15 | −51.2 (2) |
C2—C3—C4—C5 | 0.3 (3) | C11—N2—C14—C16 | −174.13 (16) |
C2—C7—C8—C1 | 0.45 (19) | C14—N2—C10—C9 | −106.70 (17) |
C2—C7—C8—C9 | −171.42 (16) | C14—N2—C11—C13 | 170.27 (16) |
C3—C2—C7—C6 | −1.1 (2) | C14—N2—C11—C12 | −63.6 (2) |
C3—C2—C7—C8 | 178.39 (16) | C17—O1—C6—C5 | −89.2 (2) |
C3—C4—C5—C6 | −0.8 (3) | C17—O1—C6—C7 | 94.06 (19) |
C4—C5—C6—O1 | −176.20 (17) | C17—C18—C19—C20 | 179.16 (18) |
C4—C5—C6—C7 | 0.4 (3) | C18—C19—C20—C21 | 173.75 (19) |
C5—C6—C7—C2 | 0.5 (2) | C19—C20—C21—O3 | −6.2 (3) |
C5—C6—C7—C8 | −178.76 (19) | C19—C20—C21—O4 | 173.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O4 | 1.00 (1) | 1.83 (2) | 2.748 (2) | 151 (3) |
N2—H2···O4i | 0.90 (1) | 1.81 (1) | 2.7154 (19) | 177 (2) |
N1—H1···O3ii | 0.86 (1) | 1.99 (1) | 2.773 (2) | 151 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2. |
C21H30N2O4·C2H6O | F(000) = 912 |
Mr = 420.54 | Dx = 1.156 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0087 (12) Å | Cell parameters from 7678 reflections |
b = 13.7968 (17) Å | θ = 2.5–24.9° |
c = 21.878 (3) Å | µ = 0.08 mm−1 |
β = 90.749 (4)° | T = 297 K |
V = 2417.2 (5) Å3 | Block, colourless |
Z = 4 | 0.30 × 0.27 × 0.22 mm |
Bruker D8 Venture CMOS diffractometer | 3038 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.055 |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | θmax = 25.4°, θmin = 2.5° |
Tmin = 0.692, Tmax = 0.745 | h = −9→9 |
37412 measured reflections | k = −16→16 |
4461 independent reflections | l = −26→26 |
Refinement on F2 | 46 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.060 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.176 | w = 1/[σ2(Fo2) + (0.0772P)2 + 1.2353P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
4461 reflections | Δρmax = 0.35 e Å−3 |
313 parameters | Δρmin = −0.46 e Å−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 | 0.2092 (2) | 0.36531 (11) | 0.30305 (7) | 0.0553 (5) | |
O2 | 0.2584 (3) | 0.52278 (14) | 0.28903 (8) | 0.0832 (7) | |
O3 | 0.3563 (3) | 0.73209 (16) | 0.48029 (8) | 0.0872 (7) | |
O4 | 0.2945 (3) | 0.67092 (14) | 0.56965 (8) | 0.0787 (7) | |
N1 | 0.4952 (3) | 0.27474 (16) | 0.12915 (9) | 0.0595 (6) | |
N2 | 0.6135 (3) | 0.16000 (15) | 0.37926 (9) | 0.0508 (5) | |
C1 | 0.5975 (4) | 0.26944 (19) | 0.17914 (11) | 0.0583 (7) | |
H1A | 0.708687 | 0.250056 | 0.178280 | 0.070* | |
C2 | 0.3413 (4) | 0.30442 (17) | 0.14673 (10) | 0.0513 (6) | |
C3 | 0.1947 (4) | 0.31751 (19) | 0.11340 (12) | 0.0630 (7) | |
H3 | 0.191217 | 0.307090 | 0.071410 | 0.076* | |
C4 | 0.0551 (4) | 0.3462 (2) | 0.14408 (13) | 0.0701 (8) | |
H4 | −0.044828 | 0.354362 | 0.122584 | 0.084* | |
C5 | 0.0599 (4) | 0.3635 (2) | 0.20711 (12) | 0.0628 (7) | |
H5 | −0.035912 | 0.383807 | 0.226972 | 0.075* | |
C6 | 0.2045 (3) | 0.35080 (17) | 0.23928 (10) | 0.0504 (6) | |
C7 | 0.3503 (3) | 0.31992 (15) | 0.21087 (10) | 0.0461 (6) | |
C8 | 0.5159 (3) | 0.29619 (16) | 0.23053 (10) | 0.0492 (6) | |
C9 | 0.5832 (3) | 0.28496 (17) | 0.29440 (11) | 0.0532 (6) | |
H9A | 0.528225 | 0.330228 | 0.321445 | 0.064* | |
H9B | 0.702044 | 0.298597 | 0.295389 | 0.064* | |
C10 | 0.5518 (3) | 0.18157 (17) | 0.31541 (10) | 0.0513 (6) | |
H10A | 0.432721 | 0.168963 | 0.313271 | 0.062* | |
H10B | 0.605720 | 0.137478 | 0.287333 | 0.062* | |
C11 | 0.7716 (4) | 0.0990 (2) | 0.37851 (13) | 0.0689 (8) | |
H11 | 0.745795 | 0.037954 | 0.357516 | 0.083* | |
C12 | 0.8324 (5) | 0.0750 (3) | 0.44274 (16) | 0.0990 (12) | |
H12A | 0.753581 | 0.032798 | 0.461969 | 0.148* | |
H12B | 0.843001 | 0.133711 | 0.466050 | 0.148* | |
H12C | 0.938971 | 0.043428 | 0.440839 | 0.148* | |
C13 | 0.9059 (4) | 0.1506 (3) | 0.34291 (17) | 0.0903 (11) | |
H13A | 0.866622 | 0.162243 | 0.301912 | 0.135* | |
H13B | 1.004393 | 0.111058 | 0.341935 | 0.135* | |
H13C | 0.931685 | 0.211311 | 0.362305 | 0.135* | |
C14 | 0.4773 (4) | 0.11792 (19) | 0.41877 (12) | 0.0615 (7) | |
H14 | 0.526311 | 0.106134 | 0.459368 | 0.074* | |
C15 | 0.4148 (5) | 0.0211 (2) | 0.39449 (17) | 0.0947 (12) | |
H15A | 0.505966 | −0.023937 | 0.393021 | 0.142* | |
H15B | 0.368656 | 0.029758 | 0.354130 | 0.142* | |
H15C | 0.330151 | −0.003624 | 0.420973 | 0.142* | |
C16 | 0.3377 (4) | 0.1903 (2) | 0.42646 (14) | 0.0753 (9) | |
H16A | 0.255515 | 0.164077 | 0.453397 | 0.113* | |
H16B | 0.286909 | 0.203677 | 0.387375 | 0.113* | |
H16C | 0.381923 | 0.249228 | 0.443505 | 0.113* | |
C17 | 0.2386 (3) | 0.45697 (18) | 0.32284 (11) | 0.0538 (6) | |
C18 | 0.2450 (4) | 0.46119 (18) | 0.39101 (11) | 0.0596 (7) | |
H18A | 0.336436 | 0.420965 | 0.405661 | 0.072* | |
H18B | 0.142255 | 0.434400 | 0.406826 | 0.072* | |
C19 | 0.2678 (4) | 0.56242 (19) | 0.41582 (11) | 0.0625 (7) | |
H19A | 0.373719 | 0.587837 | 0.402005 | 0.075* | |
H19B | 0.179984 | 0.603603 | 0.399319 | 0.075* | |
C20 | 0.2642 (4) | 0.5668 (2) | 0.48422 (11) | 0.0690 (8) | |
H20A | 0.341419 | 0.518749 | 0.500346 | 0.083* | |
H20B | 0.153216 | 0.548829 | 0.497359 | 0.083* | |
C21 | 0.3081 (4) | 0.6643 (2) | 0.51231 (11) | 0.0627 (7) | |
H2 | 0.640 (3) | 0.217 (2) | 0.3959 (12) | 0.064 (8)* | |
H1 | 0.526 (3) | 0.261 (2) | 0.0929 (6) | 0.068 (8)* | |
O5 | −0.1278 (12) | 0.4643 (7) | 0.3667 (5) | 0.123 (3) | 0.531 (11) |
H5A | −0.165922 | 0.438097 | 0.397138 | 0.184* | 0.531 (11) |
C22 | −0.2489 (13) | 0.5309 (7) | 0.3417 (5) | 0.106 (3) | 0.531 (11) |
H22A | −0.281815 | 0.577081 | 0.372735 | 0.127* | 0.531 (11) |
H22B | −0.347635 | 0.495888 | 0.328047 | 0.127* | 0.531 (11) |
C23 | −0.1720 (13) | 0.5827 (6) | 0.2891 (3) | 0.106 (3) | 0.531 (11) |
H23A | −0.251356 | 0.627541 | 0.271841 | 0.159* | 0.531 (11) |
H23B | −0.074882 | 0.617423 | 0.303038 | 0.159* | 0.531 (11) |
H23C | −0.140469 | 0.536518 | 0.258509 | 0.159* | 0.531 (11) |
O5A | −0.1337 (9) | 0.4474 (4) | 0.3501 (3) | 0.0655 (18) | 0.469 (11) |
H5AA | −0.198660 | 0.410977 | 0.367474 | 0.098* | 0.469 (11) |
C22A | −0.1963 (16) | 0.5437 (6) | 0.3520 (4) | 0.098 (3) | 0.469 (11) |
H22C | −0.106576 | 0.590542 | 0.356016 | 0.117* | 0.469 (11) |
H22D | −0.273691 | 0.552244 | 0.385271 | 0.117* | 0.469 (11) |
C23A | −0.2814 (13) | 0.5518 (7) | 0.2923 (4) | 0.097 (3) | 0.469 (11) |
H23D | −0.329689 | 0.615146 | 0.288185 | 0.146* | 0.469 (11) |
H23E | −0.202252 | 0.541673 | 0.260303 | 0.146* | 0.469 (11) |
H23F | −0.367862 | 0.503720 | 0.289294 | 0.146* | 0.469 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0813 (13) | 0.0451 (9) | 0.0399 (9) | −0.0016 (8) | 0.0149 (8) | −0.0089 (7) |
O2 | 0.142 (2) | 0.0566 (12) | 0.0510 (11) | −0.0251 (12) | 0.0040 (12) | 0.0006 (9) |
O3 | 0.142 (2) | 0.0749 (13) | 0.0456 (10) | −0.0433 (13) | 0.0284 (11) | −0.0115 (10) |
O4 | 0.1303 (19) | 0.0686 (12) | 0.0376 (9) | −0.0367 (12) | 0.0170 (10) | −0.0126 (8) |
N1 | 0.0858 (17) | 0.0567 (13) | 0.0364 (11) | 0.0033 (11) | 0.0155 (11) | −0.0061 (9) |
N2 | 0.0669 (14) | 0.0427 (11) | 0.0428 (11) | −0.0010 (10) | 0.0009 (9) | −0.0050 (9) |
C1 | 0.0704 (18) | 0.0556 (15) | 0.0491 (14) | 0.0020 (13) | 0.0113 (12) | −0.0018 (11) |
C2 | 0.0757 (18) | 0.0403 (12) | 0.0382 (12) | −0.0019 (12) | 0.0086 (12) | −0.0034 (10) |
C3 | 0.090 (2) | 0.0592 (16) | 0.0391 (13) | −0.0040 (15) | −0.0046 (14) | −0.0045 (11) |
C4 | 0.075 (2) | 0.0740 (19) | 0.0604 (17) | −0.0038 (16) | −0.0109 (15) | −0.0013 (14) |
C5 | 0.0634 (18) | 0.0629 (17) | 0.0621 (16) | 0.0023 (13) | 0.0069 (14) | −0.0077 (13) |
C6 | 0.0693 (17) | 0.0428 (13) | 0.0392 (12) | −0.0041 (11) | 0.0078 (11) | −0.0071 (10) |
C7 | 0.0662 (16) | 0.0360 (11) | 0.0360 (11) | −0.0054 (10) | 0.0050 (10) | −0.0042 (9) |
C8 | 0.0650 (16) | 0.0410 (12) | 0.0417 (12) | −0.0040 (11) | 0.0050 (11) | −0.0024 (10) |
C9 | 0.0671 (17) | 0.0480 (14) | 0.0444 (13) | −0.0043 (12) | 0.0013 (11) | −0.0063 (10) |
C10 | 0.0649 (16) | 0.0482 (14) | 0.0407 (12) | −0.0041 (12) | −0.0010 (11) | −0.0045 (10) |
C11 | 0.078 (2) | 0.0663 (18) | 0.0619 (16) | 0.0174 (15) | −0.0067 (14) | −0.0074 (14) |
C12 | 0.103 (3) | 0.113 (3) | 0.080 (2) | 0.033 (2) | −0.021 (2) | 0.003 (2) |
C13 | 0.066 (2) | 0.112 (3) | 0.094 (2) | 0.0162 (19) | 0.0070 (18) | −0.011 (2) |
C14 | 0.081 (2) | 0.0516 (14) | 0.0520 (14) | −0.0085 (14) | 0.0075 (13) | 0.0042 (12) |
C15 | 0.126 (3) | 0.0562 (18) | 0.102 (3) | −0.0246 (19) | 0.022 (2) | 0.0006 (17) |
C16 | 0.078 (2) | 0.076 (2) | 0.0728 (19) | −0.0069 (16) | 0.0166 (16) | −0.0036 (15) |
C17 | 0.0651 (17) | 0.0494 (14) | 0.0470 (13) | −0.0051 (12) | 0.0068 (11) | −0.0079 (11) |
C18 | 0.0809 (19) | 0.0515 (14) | 0.0466 (14) | −0.0031 (13) | 0.0096 (13) | −0.0091 (11) |
C19 | 0.083 (2) | 0.0556 (15) | 0.0487 (14) | −0.0081 (14) | 0.0050 (13) | −0.0121 (12) |
C20 | 0.098 (2) | 0.0628 (17) | 0.0465 (14) | −0.0181 (15) | 0.0105 (14) | −0.0130 (12) |
C21 | 0.084 (2) | 0.0624 (16) | 0.0420 (13) | −0.0190 (14) | 0.0143 (13) | −0.0109 (12) |
O5 | 0.125 (4) | 0.120 (4) | 0.123 (4) | 0.0016 (19) | 0.0008 (19) | 0.0101 (19) |
C22 | 0.106 (3) | 0.105 (3) | 0.107 (3) | 0.0010 (10) | 0.0003 (10) | −0.0001 (10) |
C23 | 0.107 (3) | 0.104 (3) | 0.106 (3) | 0.0061 (19) | 0.0028 (19) | 0.0021 (19) |
O5A | 0.070 (2) | 0.060 (2) | 0.067 (2) | −0.0011 (15) | 0.0075 (16) | 0.0087 (16) |
C22A | 0.098 (3) | 0.096 (3) | 0.099 (3) | 0.0021 (10) | 0.0001 (10) | 0.0004 (10) |
C23A | 0.098 (4) | 0.094 (3) | 0.100 (3) | 0.0024 (19) | −0.0061 (19) | 0.0016 (19) |
O1—C6 | 1.409 (3) | C13—H13B | 0.9600 |
O1—C17 | 1.356 (3) | C13—H13C | 0.9600 |
O2—C17 | 1.183 (3) | C14—H14 | 0.9800 |
O3—C21 | 1.234 (3) | C14—C15 | 1.520 (4) |
O4—C21 | 1.264 (3) | C14—C16 | 1.510 (4) |
N1—C1 | 1.360 (4) | C15—H15A | 0.9600 |
N1—C2 | 1.359 (3) | C15—H15B | 0.9600 |
N1—H1 | 0.853 (10) | C15—H15C | 0.9600 |
N2—C10 | 1.505 (3) | C16—H16A | 0.9600 |
N2—C11 | 1.521 (4) | C16—H16B | 0.9600 |
N2—C14 | 1.517 (3) | C16—H16C | 0.9600 |
N2—H2 | 0.90 (3) | C17—C18 | 1.493 (3) |
C1—H1A | 0.9300 | C18—H18A | 0.9700 |
C1—C8 | 1.359 (3) | C18—H18B | 0.9700 |
C2—C3 | 1.386 (4) | C18—C19 | 1.509 (3) |
C2—C7 | 1.420 (3) | C19—H19A | 0.9700 |
C3—H3 | 0.9300 | C19—H19B | 0.9700 |
C3—C4 | 1.370 (4) | C19—C20 | 1.498 (3) |
C4—H4 | 0.9300 | C20—H20A | 0.9700 |
C4—C5 | 1.400 (4) | C20—H20B | 0.9700 |
C5—H5 | 0.9300 | C20—C21 | 1.518 (4) |
C5—C6 | 1.358 (4) | O5—H5A | 0.8200 |
C6—C7 | 1.397 (3) | O5—C22 | 1.439 (8) |
C7—C8 | 1.427 (4) | C22—H22A | 0.9700 |
C8—C9 | 1.499 (3) | C22—H22B | 0.9700 |
C9—H9A | 0.9700 | C22—C23 | 1.496 (8) |
C9—H9B | 0.9700 | C23—H23A | 0.9600 |
C9—C10 | 1.521 (3) | C23—H23B | 0.9600 |
C10—H10A | 0.9700 | C23—H23C | 0.9600 |
C10—H10B | 0.9700 | O5A—H5AA | 0.8200 |
C11—H11 | 0.9800 | O5A—C22A | 1.420 (8) |
C11—C12 | 1.517 (4) | C22A—H22C | 0.9700 |
C11—C13 | 1.514 (5) | C22A—H22D | 0.9700 |
C12—H12A | 0.9600 | C22A—C23A | 1.470 (8) |
C12—H12B | 0.9600 | C23A—H23D | 0.9600 |
C12—H12C | 0.9600 | C23A—H23E | 0.9600 |
C13—H13A | 0.9600 | C23A—H23F | 0.9600 |
C17—O1—C6 | 116.79 (18) | C15—C14—H14 | 107.3 |
C1—N1—H1 | 124 (2) | C16—C14—N2 | 110.5 (2) |
C2—N1—C1 | 109.1 (2) | C16—C14—H14 | 107.3 |
C2—N1—H1 | 127 (2) | C16—C14—C15 | 112.3 (3) |
C10—N2—C11 | 111.28 (19) | C14—C15—H15A | 109.5 |
C10—N2—C14 | 112.0 (2) | C14—C15—H15B | 109.5 |
C10—N2—H2 | 106.1 (17) | C14—C15—H15C | 109.5 |
C11—N2—H2 | 107.4 (18) | H15A—C15—H15B | 109.5 |
C14—N2—C11 | 113.6 (2) | H15A—C15—H15C | 109.5 |
C14—N2—H2 | 106.0 (17) | H15B—C15—H15C | 109.5 |
N1—C1—H1A | 124.5 | C14—C16—H16A | 109.5 |
C8—C1—N1 | 111.1 (3) | C14—C16—H16B | 109.5 |
C8—C1—H1A | 124.5 | C14—C16—H16C | 109.5 |
N1—C2—C3 | 131.0 (2) | H16A—C16—H16B | 109.5 |
N1—C2—C7 | 106.9 (2) | H16A—C16—H16C | 109.5 |
C3—C2—C7 | 122.1 (2) | H16B—C16—H16C | 109.5 |
C2—C3—H3 | 120.9 | O1—C17—C18 | 111.0 (2) |
C4—C3—C2 | 118.1 (2) | O2—C17—O1 | 122.7 (2) |
C4—C3—H3 | 120.9 | O2—C17—C18 | 126.3 (2) |
C3—C4—H4 | 119.3 | C17—C18—H18A | 108.9 |
C3—C4—C5 | 121.3 (3) | C17—C18—H18B | 108.9 |
C5—C4—H4 | 119.3 | C17—C18—C19 | 113.5 (2) |
C4—C5—H5 | 120.0 | H18A—C18—H18B | 107.7 |
C6—C5—C4 | 120.0 (3) | C19—C18—H18A | 108.9 |
C6—C5—H5 | 120.0 | C19—C18—H18B | 108.9 |
C5—C6—O1 | 120.4 (2) | C18—C19—H19A | 109.0 |
C5—C6—C7 | 121.4 (2) | C18—C19—H19B | 109.0 |
C7—C6—O1 | 118.2 (2) | H19A—C19—H19B | 107.8 |
C2—C7—C8 | 107.4 (2) | C20—C19—C18 | 113.1 (2) |
C6—C7—C2 | 117.0 (2) | C20—C19—H19A | 109.0 |
C6—C7—C8 | 135.6 (2) | C20—C19—H19B | 109.0 |
C1—C8—C7 | 105.6 (2) | C19—C20—H20A | 108.4 |
C1—C8—C9 | 124.9 (2) | C19—C20—H20B | 108.4 |
C7—C8—C9 | 128.8 (2) | C19—C20—C21 | 115.7 (2) |
C8—C9—H9A | 110.0 | H20A—C20—H20B | 107.4 |
C8—C9—H9B | 110.0 | C21—C20—H20A | 108.4 |
C8—C9—C10 | 108.65 (19) | C21—C20—H20B | 108.4 |
H9A—C9—H9B | 108.3 | O3—C21—O4 | 122.7 (2) |
C10—C9—H9A | 110.0 | O3—C21—C20 | 121.0 (2) |
C10—C9—H9B | 110.0 | O4—C21—C20 | 116.3 (2) |
N2—C10—C9 | 114.35 (19) | C22—O5—H5A | 109.5 |
N2—C10—H10A | 108.7 | O5—C22—H22A | 110.0 |
N2—C10—H10B | 108.7 | O5—C22—H22B | 110.0 |
C9—C10—H10A | 108.7 | O5—C22—C23 | 108.4 (8) |
C9—C10—H10B | 108.7 | H22A—C22—H22B | 108.4 |
H10A—C10—H10B | 107.6 | C23—C22—H22A | 110.0 |
N2—C11—H11 | 108.1 | C23—C22—H22B | 110.0 |
C12—C11—N2 | 111.6 (2) | C22—C23—H23A | 109.5 |
C12—C11—H11 | 108.1 | C22—C23—H23B | 109.5 |
C13—C11—N2 | 110.0 (2) | C22—C23—H23C | 109.5 |
C13—C11—H11 | 108.1 | H23A—C23—H23B | 109.5 |
C13—C11—C12 | 111.0 (3) | H23A—C23—H23C | 109.5 |
C11—C12—H12A | 109.5 | H23B—C23—H23C | 109.5 |
C11—C12—H12B | 109.5 | C22A—O5A—H5AA | 109.5 |
C11—C12—H12C | 109.5 | O5A—C22A—H22C | 111.4 |
H12A—C12—H12B | 109.5 | O5A—C22A—H22D | 111.4 |
H12A—C12—H12C | 109.5 | O5A—C22A—C23A | 101.9 (7) |
H12B—C12—H12C | 109.5 | H22C—C22A—H22D | 109.3 |
C11—C13—H13A | 109.5 | C23A—C22A—H22C | 111.4 |
C11—C13—H13B | 109.5 | C23A—C22A—H22D | 111.4 |
C11—C13—H13C | 109.5 | C22A—C23A—H23D | 109.5 |
H13A—C13—H13B | 109.5 | C22A—C23A—H23E | 109.5 |
H13A—C13—H13C | 109.5 | C22A—C23A—H23F | 109.5 |
H13B—C13—H13C | 109.5 | H23D—C23A—H23E | 109.5 |
N2—C14—H14 | 107.3 | H23D—C23A—H23F | 109.5 |
N2—C14—C15 | 111.9 (2) | H23E—C23A—H23F | 109.5 |
O1—C6—C7—C2 | 179.04 (19) | C6—O1—C17—O2 | 0.6 (4) |
O1—C6—C7—C8 | 0.8 (4) | C6—O1—C17—C18 | −178.4 (2) |
O1—C17—C18—C19 | −176.7 (2) | C6—C7—C8—C1 | 179.0 (3) |
O2—C17—C18—C19 | 4.3 (5) | C6—C7—C8—C9 | 8.9 (4) |
N1—C1—C8—C7 | 0.0 (3) | C7—C2—C3—C4 | −0.1 (4) |
N1—C1—C8—C9 | 170.6 (2) | C7—C8—C9—C10 | 86.1 (3) |
N1—C2—C3—C4 | 178.3 (3) | C8—C9—C10—N2 | 180.0 (2) |
N1—C2—C7—C6 | −179.8 (2) | C10—N2—C11—C12 | −178.7 (3) |
N1—C2—C7—C8 | −1.1 (3) | C10—N2—C11—C13 | 57.7 (3) |
C1—N1—C2—C3 | −177.5 (3) | C10—N2—C14—C15 | 62.8 (3) |
C1—N1—C2—C7 | 1.1 (3) | C10—N2—C14—C16 | −63.1 (3) |
C1—C8—C9—C10 | −82.3 (3) | C11—N2—C10—C9 | −105.4 (3) |
C2—N1—C1—C8 | −0.7 (3) | C11—N2—C14—C15 | −64.3 (3) |
C2—C3—C4—C5 | 1.0 (4) | C11—N2—C14—C16 | 169.8 (2) |
C2—C7—C8—C1 | 0.7 (3) | C14—N2—C10—C9 | 126.3 (2) |
C2—C7—C8—C9 | −169.4 (2) | C14—N2—C11—C12 | −51.2 (3) |
C3—C2—C7—C6 | −1.0 (3) | C14—N2—C11—C13 | −174.8 (2) |
C3—C2—C7—C8 | 177.7 (2) | C17—O1—C6—C5 | −87.0 (3) |
C3—C4—C5—C6 | −0.8 (4) | C17—O1—C6—C7 | 95.2 (3) |
C4—C5—C6—O1 | −178.1 (2) | C17—C18—C19—C20 | 176.7 (3) |
C4—C5—C6—C7 | −0.4 (4) | C18—C19—C20—C21 | 172.6 (3) |
C5—C6—C7—C2 | 1.2 (3) | C19—C20—C21—O3 | −5.6 (5) |
C5—C6—C7—C8 | −177.0 (3) | C19—C20—C21—O4 | 175.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O4i | 0.90 (3) | 1.79 (3) | 2.686 (3) | 177 (3) |
N1—H1···O3ii | 0.85 (1) | 1.91 (1) | 2.751 (3) | 167 (3) |
O5—H5A···O4iii | 0.82 | 1.97 | 2.692 (10) | 147 |
O5A—H5AA···O4iii | 0.82 | 1.95 | 2.732 (6) | 160 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) −x, −y+1, −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 (award No. CHE-1429086).
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