research communications
Synthesis and structure of 4-hydroxy-N-isopropyltryptamine (4-HO-NiPT) and its precursors
aCaaMTech, Inc., 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 title compound, 4-hydroxy-N-isopropyltryptamine (4) or 4-HO-NiPT (systematic name: 3-{2-[(propan-2-yl)amino]ethyl}-1H-indol-4-ol), C13H18N2O, was synthesized in three steps from 4-benzyloxyindole (1) (systematic name: 4-phenoxy-1H-indole), C15H13NO. (1) was treated with oxalyl chloride and isopropylamine to produce N-isopropyl-4-benzyloxy-3-indoleglyoxylamide (2) {systematic name: 2-[4-(benzyloxy)-1H-indol-3-yl]-2-oxo-N-(propan-2-yl)acetamide}, C20H20N2O3. (2) was reduced to generate 4-benzyloxy-N-isopropyltryptamine (3) or 4-HO-NiPT, which was characterized as its chloride salt 4-benzyloxy-N-isopropyltryptammonium chloride (3a) (systematic name: {2-[4-(benzyloxy)-1H-indol-3-yl]ethyl}(propan-2-yl)azanium chloride), C20H25N2O·Cl. Finally the benzyl group of (3) was removed via hydrogenation to generate 4-HO-NiPT. The crystal structures of the title compound and all three synthetic precursors are presented.
Keywords: crystal structure; tryptamines; indoles; hydrogen bonding.
1. Chemical context
Psilocybin (C12H17N2O4P, 4-phosphoryloxy-N,N-dimethyltryptamine) has recently garnered a great deal of interest due to its potential to ameliorate a number of treatment resistant mood disorders (Carhart-Harris & Goodwin, 2017; Nichols et al., 2017). Upon administration, psilocybin is enzymatically metabolized via hydrolysis of its 4-phosphoryloxy group, producing psilocin (C12H16N2O, 4-hydroxy-N,N-dimethyltryptamine) as the active metabolite. Psilocin is an agonist of the serotonin 2A (5-HT2A) receptor; this activity is believed to be responsible for producing a head-twitch response (HTR) in murine models, as well as subjective `psychedelic' effects in human subjects as well as other potentially beneficial biological and clinical results (Halberstadt et al., 2020).
Psilocybin and psilocin are both natural products, found in over 200 species of `magic mushrooms' (Stamets, 1996). However, psilocybin and psilocin are not the only tryptamines present in these fungi. Other structurally similar molecules have been observed in significant quantities. (Leung & Paul, 1968; Jensen et al., 2006; Lenz et al., 2017). Such structural analogs include baeocystin (C11H15N2O4P, 4-phosphoryloxy-N-methyltryptamine), the monomethyl derivative of psilocybin, and aerugeniscin (C13H20N2O4P, 4-phosphoryloxy-N,N,N-trimethyltryptamine), its trimethyl variant. Like psilocybin, both baeocystin and aeruginascin are 4-phosphoryloxytryptamines, which are hydrolized to their analogous 4-hydroxytryptamines: norpsilocin (C11H14N2O) and 4-hydroxy-N,N,N-trimethyltryptamine respectively.
In the case of baeocystin, its active metabolite norpsilocin (4-hydroxy-N-methyltryptamine) has been examined and shown to be a full agonist of the 5-HT2A receptor (Sherwood et al., 2020; Glatfelter et al., 2022b). Notably, despite this activity, norpsilocin does not show a head-twitch response (HTR) in mice, the standard animal test to indicate a psychedelic-like response. Unlike dialkyl tryptamines (e.g., psilocybin and psilocin) the pharmacology of analogous monoalkyl tryptamines (e.g., baeocystin and norpsilocin) is relatively unknown. Accordingly, the importance of these compounds within the context of the overall polypharmacological `magic mushroom' experience is not understood. In an effort to explore the proprieties of monoalkyltryptamines, we previously reported the structural characterization, cellular, and behavioral data for baeocystin and norpsilocin (Naeem et al., 2022; Chadeayne et al., 2020b).
Herein, we expand our exploration to include other 4-hydroxy monoalkyl tryptamines in an effort to examine how the steric variation impacts serotonergic activity. Our first target, 4-hydroxy-N-isopropyltryptamine (4-HO-NiPT), replaces the methyl group of norpsilocin with an isopropyl group. The only previous literature report of this molecule is as a metabolite of the new psychoactive substance (NPS) 4-acetoxy-N,N-diisoproptyltryptamine (4-AcO-DiPT) from 2022 (Malaca et al., 2022). The synthesis of the title compound, 4-HO-NiPT, follows a procedure modified from the psilocin synthesis put forward by Albert Hofmann in 1959 (Troxler et al., 1959). The structure of 4-HO-NiPT and those of its three synthetic precursors are reported herein.
2. Structural commentary
The 15H13NO (1) contains a single molecule (Fig. 1). The indole ring system of the tryptamine grouping is almost planar with an r.m.s. deviation from planarity of 0.013 Å. The benzyloxy group has an anti conformation with a C6—O1—C9—C10 torsion angle of −179.00 (13)°. The benzene ring of the benzyloxy group is near perpendicular from the indole ring with a plane to plane twist of 89.73 (6)°.
of 4-benzyloxyindole, CThe N-2-propyl-α-oxo-4-(phenylmethoxy)-1H-indole-3-acetamide, C20H20N2O3 (2) contains two molecules of the indole-amide (Fig. 1). The indole rings of both molecules are near planar, with r.m.s. deviations from planarity of 0.021 Å and 0.011 Å for the N1 and N3 molecules, respectively. The benzyloxy groups both have anti conformations with a C6—O3—C14—C15 torsion angle of 179.6 (4)° and a C26—O6—C34—C35 angle of −178.2 (4)°. The benzene rings of the benzyloxy groups are slightly twisted from the indole rings with plane-to-plane (dihedral) twists of 19.98 (16) and 21.45 (16)°, respectively. The amide arms are slightly turned away from the indole rings with a C7—C8—C9—C10 angle of 157.3 (4)° and a C27—C28—C29—C30 angle of −160.8 (4)°. The amine groups are in anti conformations with C8—C9—C10—N2 = 165.2 (4)° and C28—C29—C30—N4 = 174.3 (4)°. The isopropyl groups are also in anti conformations with a C9—C10—N2—C11 angle of −178.1 (4)° and a C29—C30—N4—C31 angle of 178.5 (4)°. In the the indole–amide molecules are linked by an N—H⋯O hydrogen bond between the indole nitrogen and the carbonyl oxygen of the amide group.
ofThe N-isopropyltryptammonium chloride, C20H25N2O+·Cl− (3a) contains two tryptammonium cations (identified by atoms N1 and N3) and two chloride anions (Fig. 1). The indole rings of both cations are close to planar, with r.m.s. deviations of 0.004 Å and 0.010 Å for the N1 and N3 cations, respectively. The benzyloxy group of the N1 cation shows an anti conformation with a C6—O1—C14—C15 angle of −173.52 (17)°; in the N3 cation, the benzyloxy group is turned nearly perpendicular to the indole ring with a C26—O2—C34—C35 angle of 85.8 (2)°. In both cations, the ethylamino arms are turned away from the indole rings, with a C7—C8—C9—C10 angle of 73.5 (2)° and a C27—C28—C29—C30 angle of 72.3 (2)°. The amine groups of the arm are both in anti conformations with C8—C9—C10—N2 = −153.55 (16)° and C28—C29—C30—N4 = −172.94 (14)°. On the contrary, the isopropyl groups are in syn conformations with a C9—C10—N2—C11 angle of −59.7 (2)° and a C29—C30—N4—C31 angle of −54.9 (2)°. In the the tryptammonium cations and chloride anions are linked by N—H⋯Cl hydrogen bonds arising from the indole nitrogen atoms.
of 4-benzyloxy-The N-isopropyltryptamine C13H18N2O (4) contains a single tryptamine molecule (Fig. 1). The indole ring system is almost planar with an r.m.s. deviation of 0.006 Å. The ethylamine arm of the tryptamine is turned away from the indole ring, with a C7—C8—C9—C10 torsion angle of 75.2 (2)° whereas the C8—C9—C10—N2 torsion angle of −72.6 (2)° turns the amine group back toward the hydroxide substituent on the 4-position of the indole ring system. The turn of the ethylamine arm is due to an intramolecular O—H⋯N hydrogen bond between the hydroxide group and the amine N atom.
of 4-hydroxy-3. Supramolecular features
There are no significant intermolecular interactions in (1) beyond normal van der Waals contacts. The molecules of (2) are linked by N—H⋯O hydrogen bonds, generating infinite chains along the [100] direction between indole N atoms and the O atoms of the amide carbonyl groups (Table 1). The tryptammonium cations and chloride anions of (3a) are linked into infinite chains propagating along [010] by N—H⋯Cl hydrogen bonds between the indole nitrogen atoms and the chloride anions and the ammonium N atoms and the Cl− ions (Table 2). The tryptamine molecules of (4) are held together in infinite chains along the [010] direction by N—H⋯O hydrogen bonds between the indole NH groupings and the hydroxide O atoms (Table 3). The crystal packing of compounds (1)–(4) are shown in Fig. 2.
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4. Database survey
The most closely related structure to the title compound is norpsilocin, 4-hydroxy-N-methyltryptamine, which has been reported as its free base and its fumarate salt [Cambridge Structural Database (Groom et al., 2016) refcodes MULXAV and MULXEZ: Chadeayne et al., 2020a]. Norpsilocin free base has its ethylamino arm in an anti conformation, with O—H⋯N hydrogen bonds being intermolecular rather than intramolecular like compound (4). There are three other monoalkyltryptamines reported in the literature, the natural product baeocystin (FEJBAB: Naeem et al., 2022), 4-acetoxy-N-methyltryptamine (Glatfelter et al., 2022b) and 5-methoxy-N-methyltryptamine (QQQAHA: Bergin et al., 1968). There are nine other 4-hydroxytryptamines reported in the literature, the natural product psilocin (PSILIN: Petcher & Weber, 1974), 4-hydroxy-N-methyl-N-isopropyltryptamine as its fumarate (TUFQAP: Chadeayne et al., 2020a) and hydrofumarate (RONSUL: Chadeayne et al., 2019a) salts, 4-hydroxy-N,N-di-n-propyltryptamine as its chloride (WAMGEA: Sammeta et al., 2020) and fumarate (WUCGAF: Chadeayne et al., 2019b) salts, and the four quaternary tryptamines 4-hydroxy-N,N,N-trimethyltryptamine (XUXFAA: Chadeayne et al., 2020c), 4-hydroxy-N,N-dimethyl-N-ethyltryptamine, 4-hydroxy-N,N-dimethylisopropyltryptamine, and 4-hydroxy-N,N-di-n-propyltryptamine (EDOYIJ, EDOYUV and EDOZIK: Glatfelter et al., 2022a). The reported structures most closely related to compound (2) are indole-3-yl-N-isopropylglyoxalylamide (HUNCID: Mansell et al., 2009), 4-benzyloxyindole-3-yl-N,N-diisopropylglyoxalylamide (RUHYEY: Spaeth et al., 1997) and 4-acetoxyindole-3-yl-N,N-diethylglyoxalylamide (AVUMOT: Wu et al., 2004).
5. Synthesis and crystallization
4-Benzyloxyindole (1): Single crystals of (1) were grown from the vapor diffusion of diethyl ether into a methylene chloride solution of a commercial sample (Biosynth).
N-isopropyl-4-benzyloxy-3-indoleglyoxylamide (2): to a solution of (1) (2.0 g, 8.96 mmol) in diethylether (50 ml) was added oxalylchloride (2.3 g, 17.93 mmol) dropwise at 273 K. The resulting mixture was stirred for 6 h at 273 K, and 2-propylamine (4.24 g, 71.68 mmol) was added dropwise. The mixture was warmed to room temperature and stirred overnight. Solvent was removed in vacuo, and the resulting residue was purified on a silica gel column (methylene chloride/methanol) to afford the product as a yellow oil (2.9 g, 96% yield). Single crystals of (2) suitable for X-ray diffraction studies were grown by vapor diffusion of diethyl ether into a methylene chloride solution.
4-Benzyloxy-N-isopropyltryptamine (3): To a suspension of (2) (900 mg, 2.68 mmol) in tetrahydrofuran (12 ml) was added borane–tetrahydrofuran complex (1.0 M, 8.0 ml, 8.0 mmol) dropwise at 273 K. The reaction was then heated at reflux overnight. The resulting yellow solution was cooled to room temperature and quenched with hydrochloric acid (2.0 M), then heated at 273 K for 2 h. The mixture was cooled to room temperature and ammonium hydroxide was added until the pH exceeded 8. The mixture was extracted with methylene chloride and the organic layer was washed with water and brine, dried over sodium sulfate, and solvent was removed in vacuo. The residue was purified by silica gel (methylene chloride/ammonia-methanol solution) to afford (3) as a yellow solid (190 mg, 23% yield). The compound was treated with hydrochloric acid (1.0 M in diethylether) and filtered to yield the chloride salt (3a). Single crystals of (3a) suitable for X-ray diffraction studies were grown from the vapour diffusion of diethylether into a methanol solution.1H NMR (400 MHz, CDCl3): δ 8.11 (br s, 1H, NH), 7.49 (d, J = 7.2 Hz, 2H, ArH), 7.41 (t, J = 7.2 Hz, 2H, ArH), 7.35 (d, J = 7.2 Hz, 1H, ArH), 7.08 (t, J = 8.0 Hz, 1H, ArH), 6.99 (d, J = 8.0 Hz, 1H, ArH), 6.96 (s, 1H, ArH), 6.57 (d, J = 8.0 Hz, 1H, ArH), 3.11 (t, J = 7.2 Hz, 2H, CH2), 2.93 (t, J = 7.2 Hz, 2H, CH2), 2.77–2.71 (m, 1H, CH), 0.99 (d, J = 6.4 Hz, 6H, CH3).
4-Hydroxy-N-isopropyltryptamine (4): To a solution of (3) (190 mg, 0.62 mmol) in methanol (4.0 ml) was added palladium on carbon (30 mg) and palladium hydroxide on carbon (30 mg). The mixture was stirred for 3 h under an atmosphere of hydrogen. The resulting black suspension was filtered and washed with methanol. Solvent was removed in vacuo and the resulting residue was purified by silica gel (methylene chloride/ammonia methanol solution) to afford (4) as an off-white solid (87 mg, 64% yield). Single crystals of (4) suitable for X-ray diffraction studies were grown from the slow evaporation of an acetone solution. 1H NMR (400 MHz, CDCl3): δ 7.88 (s, 1H, NH), 7.05 (t, J = 7.9 Hz, 1H, ArH), 6.90–6.79 (m, 2H, ArH), 6.59 (d, 1H, ArH), 3.02 (t, 2H, CH2), 2.96 (t, 2H, CH2), 2.91–2.83 (m, 1H, CH), 1.12 (d, J = 6.4 Hz, 6H, CH3). 13C NMR (101 MHz, CDCl3): δ 151.9 (ArC), 138.7 (ArC), 123.5 (ArC), 120.8 (ArC), 118.5 (ArC), 114.0 (ArC), 107.0 (ArC), 102.7 (ArC), 49.5 (AkC), 48.0 (AkC), 27.6 (AkC), 22.1 (AkC). MS (ESI) calculated for C13H16N2O: 218.1; found: 218.9 [M + 1].
6. Refinement
Crystal data, data collection and structure . Hydrogen atoms H1 in compound (1), H1, H2, H3A and H4A in compound (2), H1, H2A, H2B, H3A, H4A and H4B in compound (3a) and H1, H1A and H2 in compound (4) were found from difference-Fourier maps and were refined isotropically. DFIX restraints were used on all of these hydrogen atoms [except H1 in compound (1), which was refined freely] with N—H distances of 0.87 (1) Å for the indole N atoms, 0.90 (1) Å for the ethylamino N atoms, 0.95 (1) Å for ethylammonium N atoms, and 1.00 (1) Å for the O–H distance. Isotropic displacement parameters were set to 1.2 Ueq of the indole N atoms and 1.5 Ueq of the parent ethylamino N atoms and the parent oxygen atom. All other hydrogen atoms were placed in calculated positions (C—H = 0.93–0.98 Å). Isotropic displacement parameters were set to 1.2 Ueq (C) or 1.5 Ueq (C-methyl).
details are summarized in Table 4
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Supporting information
https://doi.org/10.1107/S2056989023002098/hb8057sup1.cif
contains datablocks 1, 2, 3a, 4, global. DOI:Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989023002098/hb80571sup2.hkl
Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989023002098/hb80572sup3.hkl
Structure factors: contains datablock 3a. DOI: https://doi.org/10.1107/S2056989023002098/hb80573asup4.hkl
Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S2056989023002098/hb80574sup5.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989023002098/hb80571sup6.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989023002098/hb80572sup7.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989023002098/hb80573sup8.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989023002098/hb80574sup9.cml
For all structures, data collection: APEX4 (Bruker, 2021); cell
SAINT (Bruker, 2021); data reduction: SAINT (Bruker, 2021). Program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a) for (1), (2), (4); SHELXS2014 (Sheldrick, 2015a) for (3a). For all structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C15H13NO | Dx = 1.242 Mg m−3 |
Mr = 223.26 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 9827 reflections |
a = 9.8201 (9) Å | θ = 2.6–26.3° |
b = 9.0067 (7) Å | µ = 0.08 mm−1 |
c = 26.995 (2) Å | T = 300 K |
V = 2387.6 (4) Å3 | Block, colourless |
Z = 8 | 0.40 × 0.22 × 0.12 mm |
F(000) = 944 |
Bruker D8 Venture CMOS diffractometer | 2098 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.039 |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | θmax = 26.4°, θmin = 3.0° |
Tmin = 0.697, Tmax = 0.745 | h = −12→12 |
56335 measured reflections | k = −11→10 |
2451 independent reflections | l = −33→33 |
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)] = 0.045 | w = 1/[σ2(Fo2) + (0.0359P)2 + 0.787P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.110 | (Δ/σ)max < 0.001 |
S = 1.11 | Δρmax = 0.16 e Å−3 |
2451 reflections | Δρmin = −0.12 e Å−3 |
159 parameters | Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0078 (11) |
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 | 0.45181 (11) | 0.35485 (11) | 0.37604 (4) | 0.0502 (3) | |
N1 | 0.64192 (16) | −0.06802 (16) | 0.31310 (6) | 0.0608 (4) | |
H1 | 0.659 (2) | −0.148 (2) | 0.2961 (8) | 0.081 (6)* | |
C1 | 0.71754 (19) | −0.01437 (19) | 0.35146 (7) | 0.0602 (5) | |
H1A | 0.796959 | −0.057322 | 0.363578 | 0.072* | |
C2 | 0.53303 (16) | 0.02425 (16) | 0.30472 (6) | 0.0494 (4) | |
C3 | 0.43121 (19) | 0.01880 (19) | 0.26876 (6) | 0.0599 (5) | |
H3 | 0.428870 | −0.056114 | 0.245062 | 0.072* | |
C4 | 0.33512 (18) | 0.1283 (2) | 0.26987 (6) | 0.0600 (5) | |
H4 | 0.266037 | 0.127455 | 0.246312 | 0.072* | |
C5 | 0.33709 (16) | 0.24214 (18) | 0.30539 (6) | 0.0511 (4) | |
H5 | 0.269033 | 0.313937 | 0.305279 | 0.061* | |
C6 | 0.43895 (15) | 0.24842 (15) | 0.34041 (5) | 0.0430 (3) | |
C7 | 0.54041 (15) | 0.13840 (15) | 0.34020 (5) | 0.0428 (3) | |
C8 | 0.65916 (17) | 0.11138 (17) | 0.36927 (6) | 0.0506 (4) | |
H8 | 0.690629 | 0.169017 | 0.395459 | 0.061* | |
C9 | 0.34925 (19) | 0.4685 (2) | 0.37747 (7) | 0.0668 (5) | |
H9A | 0.260551 | 0.424643 | 0.383434 | 0.080* | |
H9B | 0.346282 | 0.520817 | 0.346073 | 0.080* | |
C10 | 0.38433 (16) | 0.57386 (17) | 0.41830 (6) | 0.0523 (4) | |
C11 | 0.3366 (2) | 0.5527 (2) | 0.46590 (7) | 0.0689 (5) | |
H11 | 0.278860 | 0.473301 | 0.472565 | 0.083* | |
C12 | 0.3732 (2) | 0.6474 (3) | 0.50358 (8) | 0.0809 (6) | |
H12 | 0.340519 | 0.631075 | 0.535449 | 0.097* | |
C13 | 0.4566 (2) | 0.7645 (2) | 0.49464 (8) | 0.0759 (6) | |
H13 | 0.481679 | 0.827876 | 0.520269 | 0.091* | |
C14 | 0.5032 (2) | 0.7883 (2) | 0.44799 (9) | 0.0790 (6) | |
H14 | 0.559340 | 0.869157 | 0.441610 | 0.095* | |
C15 | 0.4679 (2) | 0.6935 (2) | 0.40992 (7) | 0.0669 (5) | |
H15 | 0.501146 | 0.710903 | 0.378193 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0511 (6) | 0.0444 (6) | 0.0550 (6) | 0.0090 (5) | −0.0092 (5) | −0.0083 (5) |
N1 | 0.0713 (10) | 0.0414 (7) | 0.0696 (9) | 0.0005 (7) | 0.0253 (8) | −0.0041 (7) |
C1 | 0.0624 (11) | 0.0513 (9) | 0.0669 (10) | 0.0107 (8) | 0.0129 (9) | 0.0111 (8) |
C2 | 0.0548 (9) | 0.0420 (8) | 0.0514 (8) | −0.0100 (7) | 0.0189 (7) | 0.0003 (7) |
C3 | 0.0697 (11) | 0.0574 (10) | 0.0526 (9) | −0.0223 (9) | 0.0118 (8) | −0.0129 (8) |
C4 | 0.0618 (10) | 0.0669 (11) | 0.0513 (9) | −0.0211 (9) | −0.0041 (8) | −0.0027 (8) |
C5 | 0.0496 (9) | 0.0509 (9) | 0.0528 (9) | −0.0062 (7) | −0.0035 (7) | 0.0030 (7) |
C6 | 0.0475 (8) | 0.0387 (7) | 0.0429 (7) | −0.0056 (6) | 0.0029 (6) | 0.0016 (6) |
C7 | 0.0478 (8) | 0.0381 (7) | 0.0426 (7) | −0.0050 (6) | 0.0080 (6) | 0.0037 (6) |
C8 | 0.0556 (9) | 0.0444 (8) | 0.0519 (9) | 0.0039 (7) | 0.0035 (7) | 0.0052 (7) |
C9 | 0.0596 (11) | 0.0601 (10) | 0.0808 (12) | 0.0192 (9) | −0.0176 (9) | −0.0165 (9) |
C10 | 0.0465 (8) | 0.0466 (8) | 0.0636 (10) | 0.0119 (7) | −0.0016 (7) | −0.0060 (7) |
C11 | 0.0643 (11) | 0.0618 (11) | 0.0806 (12) | −0.0071 (9) | 0.0135 (10) | −0.0012 (10) |
C12 | 0.0892 (15) | 0.0908 (15) | 0.0627 (11) | 0.0035 (13) | 0.0165 (11) | −0.0105 (11) |
C13 | 0.0741 (13) | 0.0727 (13) | 0.0809 (13) | 0.0049 (11) | −0.0008 (11) | −0.0264 (11) |
C14 | 0.0742 (13) | 0.0569 (11) | 0.1059 (16) | −0.0140 (10) | 0.0105 (12) | −0.0099 (11) |
C15 | 0.0702 (12) | 0.0633 (11) | 0.0673 (11) | −0.0006 (9) | 0.0149 (9) | 0.0001 (9) |
O1—C6 | 1.3636 (17) | C7—C8 | 1.426 (2) |
O1—C9 | 1.4368 (19) | C8—H8 | 0.9300 |
N1—H1 | 0.87 (2) | C9—H9A | 0.9700 |
N1—C1 | 1.363 (2) | C9—H9B | 0.9700 |
N1—C2 | 1.373 (2) | C9—C10 | 1.494 (2) |
C1—H1A | 0.9300 | C10—C11 | 1.381 (2) |
C1—C8 | 1.357 (2) | C10—C15 | 1.373 (2) |
C2—C3 | 1.394 (2) | C11—H11 | 0.9300 |
C2—C7 | 1.407 (2) | C11—C12 | 1.375 (3) |
C3—H3 | 0.9300 | C12—H12 | 0.9300 |
C3—C4 | 1.365 (3) | C12—C13 | 1.357 (3) |
C4—H4 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.404 (2) | C13—C14 | 1.357 (3) |
C5—H5 | 0.9300 | C14—H14 | 0.9300 |
C5—C6 | 1.377 (2) | C14—C15 | 1.380 (3) |
C6—C7 | 1.405 (2) | C15—H15 | 0.9300 |
C6—O1—C9 | 117.07 (12) | C1—C8—H8 | 126.5 |
C1—N1—H1 | 125.9 (14) | C7—C8—H8 | 126.5 |
C1—N1—C2 | 109.56 (14) | O1—C9—H9A | 110.1 |
C2—N1—H1 | 124.5 (14) | O1—C9—H9B | 110.1 |
N1—C1—H1A | 125.2 | O1—C9—C10 | 108.10 (13) |
C8—C1—N1 | 109.56 (16) | H9A—C9—H9B | 108.4 |
C8—C1—H1A | 125.2 | C10—C9—H9A | 110.1 |
N1—C2—C3 | 130.67 (15) | C10—C9—H9B | 110.1 |
N1—C2—C7 | 106.86 (14) | C11—C10—C9 | 121.35 (17) |
C3—C2—C7 | 122.45 (15) | C15—C10—C9 | 120.96 (16) |
C2—C3—H3 | 121.5 | C15—C10—C11 | 117.68 (16) |
C4—C3—C2 | 117.05 (15) | C10—C11—H11 | 119.5 |
C4—C3—H3 | 121.5 | C12—C11—C10 | 120.90 (18) |
C3—C4—H4 | 118.9 | C12—C11—H11 | 119.5 |
C3—C4—C5 | 122.22 (16) | C11—C12—H12 | 119.7 |
C5—C4—H4 | 118.9 | C13—C12—C11 | 120.56 (19) |
C4—C5—H5 | 119.7 | C13—C12—H12 | 119.7 |
C6—C5—C4 | 120.58 (16) | C12—C13—H13 | 120.3 |
C6—C5—H5 | 119.7 | C14—C13—C12 | 119.40 (19) |
O1—C6—C5 | 125.45 (14) | C14—C13—H13 | 120.3 |
O1—C6—C7 | 115.65 (13) | C13—C14—H14 | 119.7 |
C5—C6—C7 | 118.89 (14) | C13—C14—C15 | 120.61 (19) |
C2—C7—C8 | 106.97 (14) | C15—C14—H14 | 119.7 |
C6—C7—C2 | 118.78 (14) | C10—C15—C14 | 120.84 (17) |
C6—C7—C8 | 134.25 (14) | C10—C15—H15 | 119.6 |
C1—C8—C7 | 107.03 (15) | C14—C15—H15 | 119.6 |
O1—C6—C7—C2 | 179.47 (12) | C4—C5—C6—C7 | −0.4 (2) |
O1—C6—C7—C8 | −0.8 (2) | C5—C6—C7—C2 | −1.1 (2) |
O1—C9—C10—C11 | −90.2 (2) | C5—C6—C7—C8 | 178.69 (15) |
O1—C9—C10—C15 | 88.3 (2) | C6—O1—C9—C10 | −179.00 (13) |
N1—C1—C8—C7 | −0.28 (18) | C6—C7—C8—C1 | 179.77 (16) |
N1—C2—C3—C4 | −179.92 (15) | C7—C2—C3—C4 | −1.5 (2) |
N1—C2—C7—C6 | −179.18 (12) | C9—O1—C6—C5 | 0.9 (2) |
N1—C2—C7—C8 | 1.00 (15) | C9—O1—C6—C7 | −179.63 (14) |
C1—N1—C2—C3 | 177.39 (15) | C9—C10—C11—C12 | 177.77 (18) |
C1—N1—C2—C7 | −1.20 (17) | C9—C10—C15—C14 | −178.20 (17) |
C2—N1—C1—C8 | 0.94 (18) | C10—C11—C12—C13 | 0.4 (3) |
C2—C3—C4—C5 | 0.0 (2) | C11—C10—C15—C14 | 0.4 (3) |
C2—C7—C8—C1 | −0.45 (16) | C11—C12—C13—C14 | 0.5 (3) |
C3—C2—C7—C6 | 2.1 (2) | C12—C13—C14—C15 | −0.9 (3) |
C3—C2—C7—C8 | −177.73 (14) | C13—C14—C15—C10 | 0.5 (3) |
C3—C4—C5—C6 | 1.0 (2) | C15—C10—C11—C12 | −0.8 (3) |
C4—C5—C6—O1 | 179.00 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O1i | 0.93 | 2.61 | 3.517 (2) | 164 |
Symmetry code: (i) −x+3/2, y−1/2, z. |
C20H20N2O3 | Dx = 1.239 Mg m−3 |
Mr = 336.38 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 9851 reflections |
a = 16.4230 (13) Å | θ = 2.6–23.9° |
b = 6.5609 (4) Å | µ = 0.08 mm−1 |
c = 33.469 (2) Å | T = 300 K |
V = 3606.2 (4) Å3 | Block, brown |
Z = 8 | 0.34 × 0.30 × 0.08 mm |
F(000) = 1424 |
Bruker D8 Venture CMOS diffractometer | 5295 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.037 |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | θmax = 25.4°, θmin = 2.6° |
Tmin = 0.694, Tmax = 0.745 | h = −19→19 |
48212 measured reflections | k = −7→7 |
6584 independent reflections | l = −40→40 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(Fo2) + (0.0416P)2 + 1.3827P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.117 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.17 e Å−3 |
6584 reflections | Δρmin = −0.15 e Å−3 |
468 parameters | Absolute structure: Refined as an inversion twin |
4 restraints | Absolute structure parameter: 0.1 (18) |
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 | ||
O1 | 0.5240 (2) | 0.4291 (5) | 0.63818 (8) | 0.0793 (10) | |
O2 | 0.4162 (2) | 0.2561 (6) | 0.55613 (9) | 0.0768 (10) | |
O3 | 0.58588 (18) | 0.8372 (5) | 0.63145 (7) | 0.0597 (8) | |
N1 | 0.6357 (2) | 0.4857 (7) | 0.51462 (11) | 0.0679 (11) | |
H1 | 0.654322 | 0.447962 | 0.491765 | 0.081* | |
N2 | 0.4109 (2) | 0.1572 (6) | 0.62014 (11) | 0.0657 (10) | |
C1 | 0.5799 (3) | 0.3846 (8) | 0.53570 (13) | 0.0636 (11) | |
H1A | 0.554698 | 0.264721 | 0.527535 | 0.076* | |
C2 | 0.6597 (3) | 0.6615 (8) | 0.53495 (12) | 0.0589 (11) | |
C3 | 0.7126 (3) | 0.8123 (10) | 0.52259 (15) | 0.0748 (15) | |
H3 | 0.739396 | 0.805187 | 0.498151 | 0.090* | |
C4 | 0.7236 (3) | 0.9720 (9) | 0.54802 (14) | 0.0741 (14) | |
H4 | 0.758745 | 1.076869 | 0.540825 | 0.089* | |
C5 | 0.6830 (3) | 0.9818 (8) | 0.58479 (12) | 0.0612 (11) | |
H5 | 0.692192 | 1.092406 | 0.601560 | 0.073* | |
C6 | 0.6296 (2) | 0.8310 (6) | 0.59669 (11) | 0.0492 (10) | |
C7 | 0.6170 (2) | 0.6621 (6) | 0.57142 (11) | 0.0487 (9) | |
C8 | 0.5648 (3) | 0.4837 (6) | 0.57149 (11) | 0.0502 (9) | |
C9 | 0.5135 (3) | 0.4002 (6) | 0.60271 (11) | 0.0523 (10) | |
C10 | 0.4423 (3) | 0.2625 (6) | 0.59046 (12) | 0.0538 (10) | |
C11 | 0.3443 (3) | 0.0112 (7) | 0.61586 (14) | 0.0683 (12) | |
H11 | 0.310596 | 0.052903 | 0.593100 | 0.082* | |
C12 | 0.2927 (4) | 0.0139 (12) | 0.6525 (2) | 0.120 (3) | |
H12A | 0.246303 | −0.072908 | 0.648646 | 0.180* | |
H12B | 0.274682 | 0.150566 | 0.657642 | 0.180* | |
H12C | 0.323935 | −0.034373 | 0.674832 | 0.180* | |
C13 | 0.3778 (4) | −0.1934 (10) | 0.6075 (3) | 0.137 (3) | |
H13A | 0.333875 | −0.287603 | 0.603218 | 0.205* | |
H13B | 0.409957 | −0.237864 | 0.629772 | 0.205* | |
H13C | 0.411226 | −0.187746 | 0.583979 | 0.205* | |
C14 | 0.6120 (3) | 0.9724 (7) | 0.66161 (12) | 0.0606 (11) | |
H14A | 0.611897 | 1.110978 | 0.651536 | 0.073* | |
H14B | 0.667060 | 0.938485 | 0.669739 | 0.073* | |
C15 | 0.5556 (3) | 0.9555 (7) | 0.69666 (12) | 0.0569 (10) | |
C16 | 0.5345 (3) | 1.1282 (8) | 0.71718 (14) | 0.0739 (13) | |
H16 | 0.554437 | 1.254255 | 0.709074 | 0.089* | |
C17 | 0.4829 (4) | 1.1146 (11) | 0.75046 (16) | 0.0929 (19) | |
H17 | 0.468398 | 1.231677 | 0.764431 | 0.112* | |
C18 | 0.4540 (4) | 0.9305 (12) | 0.76219 (16) | 0.0919 (18) | |
H18 | 0.420685 | 0.921799 | 0.784579 | 0.110* | |
C19 | 0.4728 (4) | 0.7627 (11) | 0.74217 (16) | 0.0945 (19) | |
H19 | 0.452191 | 0.637347 | 0.750308 | 0.113* | |
C20 | 0.5232 (4) | 0.7744 (9) | 0.70914 (17) | 0.0851 (16) | |
H20 | 0.535284 | 0.656109 | 0.695042 | 0.102* | |
O4 | 0.2897 (2) | 0.4332 (5) | 0.36366 (8) | 0.0784 (10) | |
O5 | 0.1974 (2) | 0.2158 (6) | 0.44698 (10) | 0.0901 (11) | |
O6 | 0.35700 (18) | 0.8328 (5) | 0.36871 (8) | 0.0625 (8) | |
N3 | 0.4045 (3) | 0.4959 (7) | 0.48712 (12) | 0.0727 (12) | |
N4 | 0.1780 (3) | 0.1631 (6) | 0.38136 (12) | 0.0727 (11) | |
C21 | 0.3495 (3) | 0.3903 (8) | 0.46630 (13) | 0.0644 (12) | |
H21 | 0.324853 | 0.270395 | 0.474817 | 0.077* | |
C22 | 0.4279 (3) | 0.6671 (8) | 0.46657 (13) | 0.0617 (12) | |
C23 | 0.4817 (3) | 0.8206 (10) | 0.47795 (14) | 0.0741 (14) | |
H23 | 0.507633 | 0.817635 | 0.502655 | 0.089* | |
C24 | 0.4950 (3) | 0.9755 (9) | 0.45151 (15) | 0.0779 (14) | |
H24 | 0.531739 | 1.078188 | 0.458057 | 0.093* | |
C25 | 0.4543 (3) | 0.9828 (8) | 0.41458 (13) | 0.0658 (12) | |
H25 | 0.464119 | 1.090643 | 0.397189 | 0.079* | |
C26 | 0.4000 (3) | 0.8317 (7) | 0.40384 (12) | 0.0537 (10) | |
C27 | 0.3857 (2) | 0.6662 (7) | 0.42979 (11) | 0.0521 (10) | |
C28 | 0.3347 (3) | 0.4858 (7) | 0.43015 (11) | 0.0557 (11) | |
C29 | 0.2838 (3) | 0.3987 (7) | 0.39941 (12) | 0.0602 (11) | |
C30 | 0.2157 (3) | 0.2463 (7) | 0.41220 (13) | 0.0630 (12) | |
C31 | 0.1127 (3) | 0.0105 (8) | 0.38476 (16) | 0.0762 (14) | |
H31 | 0.079731 | 0.044781 | 0.408215 | 0.091* | |
C32 | 0.1477 (4) | −0.1950 (10) | 0.3911 (3) | 0.132 (3) | |
H32A | 0.105164 | −0.288177 | 0.398326 | 0.198* | |
H32B | 0.187428 | −0.189390 | 0.412091 | 0.198* | |
H32C | 0.173287 | −0.240602 | 0.366869 | 0.198* | |
C33 | 0.0584 (4) | 0.0240 (12) | 0.3481 (2) | 0.118 (2) | |
H33A | 0.014535 | −0.071859 | 0.350550 | 0.176* | |
H33B | 0.089728 | −0.007008 | 0.324646 | 0.176* | |
H33C | 0.036669 | 0.159366 | 0.345916 | 0.176* | |
C34 | 0.3794 (3) | 0.9784 (7) | 0.33933 (13) | 0.0627 (11) | |
H34A | 0.435266 | 0.955549 | 0.331010 | 0.075* | |
H34B | 0.375553 | 1.114783 | 0.350360 | 0.075* | |
C35 | 0.3235 (3) | 0.9582 (7) | 0.30415 (12) | 0.0569 (10) | |
C36 | 0.2928 (4) | 0.7746 (8) | 0.29169 (16) | 0.0822 (16) | |
H36 | 0.305948 | 0.656060 | 0.305515 | 0.099* | |
C37 | 0.2430 (4) | 0.7651 (11) | 0.25894 (19) | 0.102 (2) | |
H37 | 0.223112 | 0.639073 | 0.250766 | 0.122* | |
C38 | 0.2219 (4) | 0.9337 (13) | 0.23815 (16) | 0.0936 (19) | |
H38 | 0.188330 | 0.924009 | 0.215841 | 0.112* | |
C39 | 0.2504 (4) | 1.1171 (10) | 0.25040 (16) | 0.0881 (17) | |
H39 | 0.235846 | 1.234867 | 0.236685 | 0.106* | |
C40 | 0.3017 (3) | 1.1296 (8) | 0.28350 (14) | 0.0709 (13) | |
H40 | 0.321249 | 1.255985 | 0.291639 | 0.085* | |
H2 | 0.433 (2) | 0.187 (7) | 0.6439 (7) | 0.057 (12)* | |
H4A | 0.199 (3) | 0.184 (8) | 0.3569 (8) | 0.091 (17)* | |
H3A | 0.420 (3) | 0.448 (7) | 0.5101 (8) | 0.086 (16)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.131 (3) | 0.071 (2) | 0.0366 (16) | −0.029 (2) | −0.0051 (17) | 0.0044 (14) |
O2 | 0.091 (2) | 0.097 (2) | 0.0430 (17) | −0.019 (2) | −0.0148 (16) | 0.0155 (16) |
O3 | 0.0653 (17) | 0.0731 (19) | 0.0406 (15) | −0.0187 (15) | 0.0093 (13) | −0.0113 (14) |
N1 | 0.065 (2) | 0.094 (3) | 0.045 (2) | 0.013 (2) | 0.0100 (18) | −0.014 (2) |
N2 | 0.082 (3) | 0.070 (2) | 0.046 (2) | −0.016 (2) | −0.0082 (19) | 0.0055 (18) |
C1 | 0.067 (3) | 0.072 (3) | 0.051 (2) | 0.011 (2) | 0.000 (2) | −0.010 (2) |
C2 | 0.049 (2) | 0.084 (3) | 0.043 (2) | 0.013 (2) | 0.0008 (19) | −0.002 (2) |
C3 | 0.056 (3) | 0.115 (4) | 0.054 (3) | −0.001 (3) | 0.017 (2) | 0.001 (3) |
C4 | 0.059 (3) | 0.101 (4) | 0.063 (3) | −0.012 (3) | 0.015 (2) | 0.008 (3) |
C5 | 0.058 (3) | 0.071 (3) | 0.055 (3) | −0.004 (2) | 0.009 (2) | 0.002 (2) |
C6 | 0.044 (2) | 0.064 (3) | 0.040 (2) | 0.0053 (19) | 0.0027 (17) | 0.0007 (19) |
C7 | 0.045 (2) | 0.066 (3) | 0.035 (2) | 0.0082 (19) | −0.0007 (16) | 0.0049 (18) |
C8 | 0.057 (2) | 0.059 (2) | 0.0351 (18) | 0.010 (2) | −0.0030 (17) | −0.0009 (18) |
C9 | 0.078 (3) | 0.044 (2) | 0.035 (2) | 0.002 (2) | −0.0022 (19) | 0.0018 (17) |
C10 | 0.069 (3) | 0.050 (2) | 0.043 (2) | 0.006 (2) | −0.0006 (19) | 0.0052 (17) |
C11 | 0.071 (3) | 0.076 (3) | 0.058 (3) | −0.013 (2) | −0.005 (2) | 0.006 (2) |
C12 | 0.119 (5) | 0.144 (6) | 0.096 (5) | −0.051 (5) | 0.019 (4) | −0.003 (4) |
C13 | 0.097 (5) | 0.082 (4) | 0.232 (10) | −0.016 (4) | −0.025 (6) | −0.044 (5) |
C14 | 0.060 (3) | 0.069 (3) | 0.052 (3) | −0.004 (2) | 0.004 (2) | −0.009 (2) |
C15 | 0.056 (2) | 0.070 (3) | 0.045 (2) | 0.000 (2) | −0.0023 (19) | −0.006 (2) |
C16 | 0.099 (4) | 0.074 (3) | 0.049 (3) | 0.012 (3) | −0.003 (2) | −0.001 (2) |
C17 | 0.116 (5) | 0.109 (5) | 0.053 (3) | 0.048 (4) | 0.005 (3) | −0.015 (3) |
C18 | 0.083 (4) | 0.137 (6) | 0.056 (3) | 0.000 (4) | 0.013 (3) | 0.006 (4) |
C19 | 0.125 (5) | 0.104 (5) | 0.054 (3) | −0.039 (4) | 0.016 (3) | −0.003 (3) |
C20 | 0.106 (4) | 0.082 (4) | 0.068 (3) | −0.022 (3) | 0.014 (3) | −0.017 (3) |
O4 | 0.129 (3) | 0.0681 (19) | 0.0376 (16) | −0.025 (2) | 0.0117 (17) | 0.0062 (15) |
O5 | 0.102 (3) | 0.117 (3) | 0.051 (2) | −0.014 (2) | 0.0224 (18) | 0.0188 (19) |
O6 | 0.0669 (19) | 0.0725 (19) | 0.0483 (17) | −0.0109 (15) | −0.0070 (13) | 0.0182 (14) |
N3 | 0.070 (2) | 0.102 (3) | 0.046 (2) | 0.028 (2) | 0.005 (2) | 0.016 (2) |
N4 | 0.093 (3) | 0.073 (3) | 0.051 (2) | −0.010 (2) | 0.015 (2) | 0.009 (2) |
C21 | 0.068 (3) | 0.078 (3) | 0.048 (2) | 0.019 (2) | 0.012 (2) | 0.014 (2) |
C22 | 0.058 (3) | 0.085 (3) | 0.042 (2) | 0.023 (2) | 0.008 (2) | 0.007 (2) |
C23 | 0.069 (3) | 0.109 (4) | 0.045 (2) | 0.011 (3) | −0.009 (2) | −0.009 (3) |
C24 | 0.078 (3) | 0.093 (4) | 0.064 (3) | 0.002 (3) | −0.010 (3) | −0.014 (3) |
C25 | 0.068 (3) | 0.072 (3) | 0.058 (3) | 0.001 (2) | 0.000 (2) | −0.004 (2) |
C26 | 0.055 (2) | 0.063 (3) | 0.043 (2) | 0.009 (2) | 0.0028 (18) | −0.0016 (19) |
C27 | 0.052 (2) | 0.066 (3) | 0.039 (2) | 0.017 (2) | 0.0084 (17) | 0.0039 (19) |
C28 | 0.061 (3) | 0.066 (3) | 0.040 (2) | 0.017 (2) | 0.0141 (19) | 0.0084 (19) |
C29 | 0.081 (3) | 0.055 (2) | 0.044 (2) | 0.013 (2) | 0.017 (2) | 0.007 (2) |
C30 | 0.082 (3) | 0.066 (3) | 0.041 (2) | 0.012 (3) | 0.013 (2) | 0.012 (2) |
C31 | 0.073 (3) | 0.084 (3) | 0.071 (3) | −0.009 (3) | 0.018 (3) | 0.013 (3) |
C32 | 0.101 (5) | 0.079 (4) | 0.215 (9) | −0.015 (4) | 0.027 (5) | 0.038 (5) |
C33 | 0.115 (5) | 0.131 (6) | 0.107 (5) | −0.024 (5) | −0.019 (4) | 0.013 (4) |
C34 | 0.071 (3) | 0.064 (3) | 0.053 (3) | −0.005 (2) | 0.003 (2) | 0.012 (2) |
C35 | 0.060 (3) | 0.067 (3) | 0.043 (2) | −0.003 (2) | 0.0055 (19) | 0.012 (2) |
C36 | 0.113 (4) | 0.076 (3) | 0.058 (3) | −0.023 (3) | −0.012 (3) | 0.016 (3) |
C37 | 0.115 (5) | 0.110 (5) | 0.080 (4) | −0.043 (4) | −0.022 (4) | 0.006 (3) |
C38 | 0.085 (4) | 0.142 (6) | 0.054 (3) | 0.006 (4) | −0.007 (3) | 0.004 (4) |
C39 | 0.112 (4) | 0.095 (4) | 0.058 (3) | 0.037 (4) | −0.006 (3) | 0.012 (3) |
C40 | 0.094 (4) | 0.065 (3) | 0.054 (3) | 0.014 (3) | 0.002 (2) | 0.004 (2) |
O1—C9 | 1.215 (4) | O4—C29 | 1.222 (5) |
O2—C10 | 1.227 (5) | O5—C30 | 1.219 (5) |
O3—C6 | 1.368 (4) | O6—C26 | 1.372 (5) |
O3—C14 | 1.411 (5) | O6—C34 | 1.420 (5) |
N1—H1 | 0.8600 | N3—C21 | 1.334 (6) |
N1—C1 | 1.333 (6) | N3—C22 | 1.372 (7) |
N1—C2 | 1.396 (6) | N3—H3A | 0.871 (15) |
N2—C10 | 1.315 (5) | N4—C30 | 1.322 (6) |
N2—C11 | 1.461 (6) | N4—C31 | 1.471 (6) |
N2—H2 | 0.894 (14) | N4—H4A | 0.897 (15) |
C1—H1A | 0.9300 | C21—H21 | 0.9300 |
C1—C8 | 1.385 (6) | C21—C28 | 1.384 (6) |
C2—C3 | 1.381 (7) | C22—C23 | 1.394 (8) |
C2—C7 | 1.408 (5) | C22—C27 | 1.412 (6) |
C3—H3 | 0.9300 | C23—H23 | 0.9300 |
C3—C4 | 1.362 (8) | C23—C24 | 1.365 (8) |
C4—H4 | 0.9300 | C24—H24 | 0.9300 |
C4—C5 | 1.401 (6) | C24—C25 | 1.406 (6) |
C5—H5 | 0.9300 | C25—H25 | 0.9300 |
C5—C6 | 1.380 (6) | C25—C26 | 1.381 (7) |
C6—C7 | 1.410 (6) | C26—C27 | 1.410 (6) |
C7—C8 | 1.451 (6) | C27—C28 | 1.450 (6) |
C8—C9 | 1.450 (6) | C28—C29 | 1.444 (6) |
C9—C10 | 1.533 (6) | C29—C30 | 1.560 (6) |
C11—H11 | 0.9800 | C31—H31 | 0.9800 |
C11—C12 | 1.491 (8) | C31—C32 | 1.481 (8) |
C11—C13 | 1.478 (8) | C31—C33 | 1.520 (8) |
C12—H12A | 0.9600 | C32—H32A | 0.9600 |
C12—H12B | 0.9600 | C32—H32B | 0.9600 |
C12—H12C | 0.9600 | C32—H32C | 0.9600 |
C13—H13A | 0.9600 | C33—H33A | 0.9600 |
C13—H13B | 0.9600 | C33—H33B | 0.9600 |
C13—H13C | 0.9600 | C33—H33C | 0.9600 |
C14—H14A | 0.9700 | C34—H34A | 0.9700 |
C14—H14B | 0.9700 | C34—H34B | 0.9700 |
C14—C15 | 1.499 (6) | C34—C35 | 1.499 (6) |
C15—C16 | 1.369 (7) | C35—C36 | 1.371 (7) |
C15—C20 | 1.367 (7) | C35—C40 | 1.368 (6) |
C16—H16 | 0.9300 | C36—H36 | 0.9300 |
C16—C17 | 1.403 (8) | C36—C37 | 1.369 (8) |
C17—H17 | 0.9300 | C37—H37 | 0.9300 |
C17—C18 | 1.356 (9) | C37—C38 | 1.352 (9) |
C18—H18 | 0.9300 | C38—H38 | 0.9300 |
C18—C19 | 1.325 (9) | C38—C39 | 1.355 (9) |
C19—H19 | 0.9300 | C39—H39 | 0.9300 |
C19—C20 | 1.382 (8) | C39—C40 | 1.393 (7) |
C20—H20 | 0.9300 | C40—H40 | 0.9300 |
C6—O3—C14 | 117.9 (3) | C26—O6—C34 | 117.6 (3) |
C1—N1—H1 | 124.9 | C21—N3—C22 | 110.6 (4) |
C1—N1—C2 | 110.3 (4) | C21—N3—H3A | 119 (3) |
C2—N1—H1 | 124.9 | C22—N3—H3A | 131 (3) |
C10—N2—C11 | 124.3 (4) | C30—N4—C31 | 124.2 (4) |
C10—N2—H2 | 113 (3) | C30—N4—H4A | 118 (4) |
C11—N2—H2 | 122 (3) | C31—N4—H4A | 117 (4) |
N1—C1—H1A | 124.8 | N3—C21—H21 | 125.0 |
N1—C1—C8 | 110.3 (4) | N3—C21—C28 | 109.9 (5) |
C8—C1—H1A | 124.8 | C28—C21—H21 | 125.0 |
N1—C2—C7 | 106.6 (4) | N3—C22—C23 | 129.2 (5) |
C3—C2—N1 | 128.6 (4) | N3—C22—C27 | 107.2 (4) |
C3—C2—C7 | 124.8 (5) | C23—C22—C27 | 123.5 (4) |
C2—C3—H3 | 121.7 | C22—C23—H23 | 121.2 |
C4—C3—C2 | 116.6 (4) | C24—C23—C22 | 117.5 (4) |
C4—C3—H3 | 121.7 | C24—C23—H23 | 121.2 |
C3—C4—H4 | 119.3 | C23—C24—H24 | 119.4 |
C3—C4—C5 | 121.4 (5) | C23—C24—C25 | 121.3 (5) |
C5—C4—H4 | 119.3 | C25—C24—H24 | 119.4 |
C4—C5—H5 | 119.2 | C24—C25—H25 | 119.6 |
C6—C5—C4 | 121.5 (4) | C26—C25—C24 | 120.8 (5) |
C6—C5—H5 | 119.2 | C26—C25—H25 | 119.6 |
O3—C6—C5 | 123.9 (4) | O6—C26—C25 | 123.5 (4) |
O3—C6—C7 | 117.1 (4) | O6—C26—C27 | 116.5 (4) |
C5—C6—C7 | 118.9 (4) | C25—C26—C27 | 120.0 (4) |
C2—C7—C6 | 116.7 (4) | C22—C27—C28 | 106.2 (4) |
C2—C7—C8 | 107.0 (4) | C26—C27—C22 | 116.9 (4) |
C6—C7—C8 | 136.1 (3) | C26—C27—C28 | 136.9 (4) |
C1—C8—C7 | 105.8 (4) | C21—C28—C27 | 106.0 (4) |
C1—C8—C9 | 123.4 (4) | C21—C28—C29 | 123.1 (4) |
C9—C8—C7 | 130.5 (3) | C29—C28—C27 | 130.7 (4) |
O1—C9—C8 | 124.3 (4) | O4—C29—C28 | 125.4 (4) |
O1—C9—C10 | 117.5 (4) | O4—C29—C30 | 116.4 (4) |
C8—C9—C10 | 118.2 (3) | C28—C29—C30 | 118.3 (3) |
O2—C10—N2 | 123.5 (4) | O5—C30—N4 | 124.2 (5) |
O2—C10—C9 | 122.5 (4) | O5—C30—C29 | 123.0 (4) |
N2—C10—C9 | 114.0 (4) | N4—C30—C29 | 112.7 (4) |
N2—C11—H11 | 108.4 | N4—C31—H31 | 108.0 |
N2—C11—C12 | 109.7 (4) | N4—C31—C32 | 110.3 (5) |
N2—C11—C13 | 109.6 (4) | N4—C31—C33 | 109.0 (4) |
C12—C11—H11 | 108.4 | C32—C31—H31 | 108.0 |
C13—C11—H11 | 108.4 | C32—C31—C33 | 113.3 (6) |
C13—C11—C12 | 112.2 (6) | C33—C31—H31 | 108.0 |
C11—C12—H12A | 109.5 | C31—C32—H32A | 109.5 |
C11—C12—H12B | 109.5 | C31—C32—H32B | 109.5 |
C11—C12—H12C | 109.5 | C31—C32—H32C | 109.5 |
H12A—C12—H12B | 109.5 | H32A—C32—H32B | 109.5 |
H12A—C12—H12C | 109.5 | H32A—C32—H32C | 109.5 |
H12B—C12—H12C | 109.5 | H32B—C32—H32C | 109.5 |
C11—C13—H13A | 109.5 | C31—C33—H33A | 109.5 |
C11—C13—H13B | 109.5 | C31—C33—H33B | 109.5 |
C11—C13—H13C | 109.5 | C31—C33—H33C | 109.5 |
H13A—C13—H13B | 109.5 | H33A—C33—H33B | 109.5 |
H13A—C13—H13C | 109.5 | H33A—C33—H33C | 109.5 |
H13B—C13—H13C | 109.5 | H33B—C33—H33C | 109.5 |
O3—C14—H14A | 109.9 | O6—C34—H34A | 109.9 |
O3—C14—H14B | 109.9 | O6—C34—H34B | 109.9 |
O3—C14—C15 | 109.0 (3) | O6—C34—C35 | 109.0 (3) |
H14A—C14—H14B | 108.3 | H34A—C34—H34B | 108.3 |
C15—C14—H14A | 109.9 | C35—C34—H34A | 109.9 |
C15—C14—H14B | 109.9 | C35—C34—H34B | 109.9 |
C16—C15—C14 | 119.2 (4) | C36—C35—C34 | 122.8 (4) |
C20—C15—C14 | 122.9 (4) | C40—C35—C34 | 119.0 (4) |
C20—C15—C16 | 117.9 (4) | C40—C35—C36 | 118.2 (4) |
C15—C16—H16 | 120.1 | C35—C36—H36 | 119.9 |
C15—C16—C17 | 119.9 (5) | C37—C36—C35 | 120.2 (5) |
C17—C16—H16 | 120.1 | C37—C36—H36 | 119.9 |
C16—C17—H17 | 120.1 | C36—C37—H37 | 119.1 |
C18—C17—C16 | 119.8 (5) | C38—C37—C36 | 121.9 (6) |
C18—C17—H17 | 120.1 | C38—C37—H37 | 119.1 |
C17—C18—H18 | 119.6 | C37—C38—H38 | 120.6 |
C19—C18—C17 | 120.8 (5) | C37—C38—C39 | 118.8 (5) |
C19—C18—H18 | 119.6 | C39—C38—H38 | 120.6 |
C18—C19—H19 | 120.1 | C38—C39—H39 | 119.9 |
C18—C19—C20 | 119.8 (6) | C38—C39—C40 | 120.1 (5) |
C20—C19—H19 | 120.1 | C40—C39—H39 | 119.9 |
C15—C20—C19 | 121.7 (5) | C35—C40—C39 | 120.8 (5) |
C15—C20—H20 | 119.1 | C35—C40—H40 | 119.6 |
C19—C20—H20 | 119.1 | C39—C40—H40 | 119.6 |
O1—C9—C10—O2 | 164.9 (5) | O4—C29—C30—O5 | −171.7 (5) |
O1—C9—C10—N2 | −13.5 (6) | O4—C29—C30—N4 | 5.2 (6) |
O3—C6—C7—C2 | 177.4 (3) | O6—C26—C27—C22 | −178.1 (3) |
O3—C6—C7—C8 | 2.7 (7) | O6—C26—C27—C28 | −0.7 (7) |
O3—C14—C15—C16 | −141.2 (4) | O6—C34—C35—C36 | −34.8 (6) |
O3—C14—C15—C20 | 38.2 (6) | O6—C34—C35—C40 | 145.0 (4) |
N1—C1—C8—C7 | 0.2 (5) | N3—C21—C28—C27 | −0.4 (5) |
N1—C1—C8—C9 | −173.3 (4) | N3—C21—C28—C29 | 174.1 (4) |
N1—C2—C3—C4 | 178.1 (5) | N3—C22—C23—C24 | 179.5 (5) |
N1—C2—C7—C6 | −178.0 (3) | N3—C22—C27—C26 | 179.2 (4) |
N1—C2—C7—C8 | −1.8 (4) | N3—C22—C27—C28 | 1.0 (4) |
C1—N1—C2—C3 | −176.3 (5) | C21—N3—C22—C23 | 178.0 (5) |
C1—N1—C2—C7 | 2.0 (5) | C21—N3—C22—C27 | −1.3 (5) |
C1—C8—C9—O1 | 147.7 (5) | C21—C28—C29—O4 | −153.3 (5) |
C1—C8—C9—C10 | −30.9 (6) | C21—C28—C29—C30 | 26.2 (6) |
C2—N1—C1—C8 | −1.4 (5) | C22—N3—C21—C28 | 1.1 (5) |
C2—C3—C4—C5 | 0.0 (8) | C22—C23—C24—C25 | 1.6 (8) |
C2—C7—C8—C1 | 1.0 (4) | C22—C27—C28—C21 | −0.4 (4) |
C2—C7—C8—C9 | 173.9 (4) | C22—C27—C28—C29 | −174.3 (4) |
C3—C2—C7—C6 | 0.4 (6) | C23—C22—C27—C26 | −0.1 (6) |
C3—C2—C7—C8 | 176.6 (4) | C23—C22—C27—C28 | −178.3 (4) |
C3—C4—C5—C6 | −0.6 (8) | C23—C24—C25—C26 | −0.6 (8) |
C4—C5—C6—O3 | −177.2 (4) | C24—C25—C26—O6 | 178.4 (4) |
C4—C5—C6—C7 | 1.1 (6) | C24—C25—C26—C27 | −0.9 (7) |
C5—C6—C7—C2 | −1.0 (5) | C25—C26—C27—C22 | 1.2 (6) |
C5—C6—C7—C8 | −175.7 (4) | C25—C26—C27—C28 | 178.6 (4) |
C6—O3—C14—C15 | 179.6 (4) | C26—O6—C34—C35 | −178.2 (4) |
C6—C7—C8—C1 | 176.1 (4) | C26—C27—C28—C21 | −178.0 (5) |
C6—C7—C8—C9 | −11.0 (8) | C26—C27—C28—C29 | 8.1 (8) |
C7—C2—C3—C4 | 0.1 (7) | C27—C22—C23—C24 | −1.3 (7) |
C7—C8—C9—O1 | −24.1 (7) | C27—C28—C29—O4 | 19.7 (7) |
C7—C8—C9—C10 | 157.3 (4) | C27—C28—C29—C30 | −160.8 (4) |
C8—C9—C10—O2 | −16.4 (6) | C28—C29—C30—O5 | 8.8 (6) |
C8—C9—C10—N2 | 165.2 (4) | C28—C29—C30—N4 | −174.3 (4) |
C10—N2—C11—C12 | −146.4 (5) | C30—N4—C31—C32 | −81.7 (7) |
C10—N2—C11—C13 | 90.0 (6) | C30—N4—C31—C33 | 153.3 (5) |
C11—N2—C10—O2 | 3.5 (7) | C31—N4—C30—O5 | −4.7 (8) |
C11—N2—C10—C9 | −178.1 (4) | C31—N4—C30—C29 | 178.5 (4) |
C14—O3—C6—C5 | −18.0 (6) | C34—O6—C26—C25 | 10.6 (6) |
C14—O3—C6—C7 | 163.8 (4) | C34—O6—C26—C27 | −170.1 (4) |
C14—C15—C16—C17 | −178.9 (4) | C34—C35—C36—C37 | −179.0 (5) |
C14—C15—C20—C19 | 178.4 (5) | C34—C35—C40—C39 | 179.4 (4) |
C15—C16—C17—C18 | 0.1 (8) | C35—C36—C37—C38 | −0.5 (10) |
C16—C15—C20—C19 | −2.1 (8) | C36—C35—C40—C39 | −0.8 (7) |
C16—C17—C18—C19 | −1.3 (9) | C36—C37—C38—C39 | −0.6 (10) |
C17—C18—C19—C20 | 0.7 (10) | C37—C38—C39—C40 | 1.0 (9) |
C18—C19—C20—C15 | 1.0 (10) | C38—C39—C40—C35 | −0.3 (8) |
C20—C15—C16—C17 | 1.6 (7) | C40—C35—C36—C37 | 1.2 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5i | 0.86 | 1.98 | 2.810 (5) | 164 |
N3—H3A···O2 | 0.87 (2) | 1.99 (3) | 2.801 (5) | 154 (5) |
Symmetry code: (i) x+1/2, −y+1/2, z. |
C20H25N2O+·Cl− | Z = 4 |
Mr = 344.87 | F(000) = 736 |
Triclinic, P1 | Dx = 1.188 Mg m−3 |
a = 10.1895 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.9117 (7) Å | Cell parameters from 9870 reflections |
c = 17.6887 (14) Å | θ = 2.8–25.6° |
α = 86.798 (3)° | µ = 0.21 mm−1 |
β = 79.340 (3)° | T = 300 K |
γ = 87.587 (3)° | Blcok, colourless |
V = 1928.7 (3) Å3 | 0.30 × 0.27 × 0.20 mm |
Bruker D8 Venture CMOS diffractometer | 5589 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.033 |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | θmax = 25.8°, θmin = 2.7° |
Tmin = 0.658, Tmax = 0.745 | h = −12→12 |
42151 measured reflections | k = −13→13 |
7362 independent reflections | l = −21→21 |
Refinement on F2 | 6 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.7204P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
7362 reflections | Δρmax = 0.26 e Å−3 |
461 parameters | Δρmin = −0.29 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 | ||
Cl1 | 0.92323 (5) | 0.67300 (4) | 0.44633 (3) | 0.05824 (14) | |
Cl2 | 0.34634 (5) | 0.14033 (4) | −0.04745 (3) | 0.05806 (14) | |
O1 | 0.96246 (14) | 0.75588 (11) | 0.81683 (7) | 0.0543 (3) | |
O2 | 0.58220 (15) | 0.24805 (12) | 0.28702 (8) | 0.0599 (4) | |
N1 | 1.00390 (18) | 1.05554 (15) | 0.62139 (10) | 0.0569 (4) | |
N2 | 0.88071 (16) | 0.54312 (14) | 0.61023 (9) | 0.0472 (4) | |
N3 | 0.55205 (18) | 0.60081 (15) | 0.13621 (10) | 0.0571 (4) | |
N4 | 0.44895 (16) | 0.07170 (13) | 0.10585 (8) | 0.0447 (3) | |
C1 | 0.9363 (2) | 0.95917 (17) | 0.60396 (11) | 0.0522 (4) | |
H1A | 0.902311 | 0.955148 | 0.558905 | 0.063* | |
C2 | 1.03828 (19) | 1.03071 (16) | 0.69185 (11) | 0.0493 (4) | |
C3 | 1.1079 (2) | 1.10215 (18) | 0.73283 (13) | 0.0618 (5) | |
H3 | 1.138537 | 1.178820 | 0.713479 | 0.074* | |
C4 | 1.1292 (2) | 1.05469 (19) | 0.80252 (13) | 0.0685 (6) | |
H4 | 1.176174 | 1.099975 | 0.831038 | 0.082* | |
C5 | 1.0825 (2) | 0.93968 (19) | 0.83272 (12) | 0.0622 (5) | |
H5 | 1.098189 | 0.910655 | 0.880799 | 0.075* | |
C6 | 1.01364 (19) | 0.86924 (16) | 0.79188 (10) | 0.0488 (4) | |
C7 | 0.99032 (17) | 0.91381 (15) | 0.71935 (10) | 0.0422 (4) | |
C8 | 0.92513 (17) | 0.86917 (15) | 0.66134 (10) | 0.0429 (4) | |
C9 | 0.85418 (17) | 0.75285 (16) | 0.65954 (11) | 0.0478 (4) | |
H9A | 0.801952 | 0.761737 | 0.618827 | 0.057* | |
H9B | 0.792351 | 0.740893 | 0.707906 | 0.057* | |
C10 | 0.94459 (19) | 0.63883 (16) | 0.64680 (11) | 0.0504 (4) | |
H10A | 1.028450 | 0.660588 | 0.614039 | 0.060* | |
H10B | 0.963891 | 0.606101 | 0.695828 | 0.060* | |
C11 | 0.7499 (2) | 0.4955 (2) | 0.65233 (14) | 0.0660 (6) | |
H11 | 0.692227 | 0.565425 | 0.671627 | 0.079* | |
C12 | 0.6860 (3) | 0.4335 (3) | 0.5953 (2) | 0.1251 (13) | |
H12A | 0.600112 | 0.405005 | 0.620140 | 0.188* | |
H12B | 0.741760 | 0.365091 | 0.575636 | 0.188* | |
H12C | 0.675264 | 0.490939 | 0.553517 | 0.188* | |
C13 | 0.7723 (3) | 0.4133 (3) | 0.71931 (19) | 0.1196 (12) | |
H13A | 0.688711 | 0.380818 | 0.745018 | 0.179* | |
H13B | 0.809615 | 0.459136 | 0.754522 | 0.179* | |
H13C | 0.832962 | 0.346907 | 0.701486 | 0.179* | |
C14 | 0.9880 (3) | 0.70915 (19) | 0.89042 (12) | 0.0694 (6) | |
H14A | 0.941757 | 0.760771 | 0.930509 | 0.083* | |
H14B | 1.083012 | 0.710211 | 0.890900 | 0.083* | |
C15 | 0.9408 (2) | 0.58056 (17) | 0.90557 (11) | 0.0529 (5) | |
C16 | 1.0015 (3) | 0.4873 (2) | 0.86211 (13) | 0.0793 (7) | |
H16 | 1.069007 | 0.504242 | 0.820162 | 0.095* | |
C17 | 0.9628 (4) | 0.3679 (2) | 0.88032 (17) | 0.0979 (10) | |
H17 | 1.003586 | 0.304756 | 0.850290 | 0.117* | |
C18 | 0.8641 (3) | 0.3422 (2) | 0.94272 (17) | 0.0867 (8) | |
H18 | 0.838464 | 0.261697 | 0.955274 | 0.104* | |
C19 | 0.8042 (2) | 0.4345 (2) | 0.98584 (15) | 0.0744 (7) | |
H19 | 0.737486 | 0.417467 | 1.028176 | 0.089* | |
C20 | 0.8420 (2) | 0.55345 (19) | 0.96718 (12) | 0.0604 (5) | |
H20 | 0.799728 | 0.616432 | 0.996864 | 0.072* | |
C21 | 0.4874 (2) | 0.50805 (17) | 0.11145 (11) | 0.0540 (5) | |
H21 | 0.443699 | 0.515233 | 0.069597 | 0.065* | |
C22 | 0.60418 (18) | 0.55794 (16) | 0.19888 (11) | 0.0492 (4) | |
C23 | 0.6753 (2) | 0.6196 (2) | 0.24423 (13) | 0.0636 (5) | |
H23 | 0.695515 | 0.701766 | 0.233628 | 0.076* | |
C24 | 0.7138 (2) | 0.5547 (2) | 0.30457 (14) | 0.0701 (6) | |
H24 | 0.760723 | 0.593864 | 0.336106 | 0.084* | |
C25 | 0.6851 (2) | 0.4307 (2) | 0.32078 (12) | 0.0630 (5) | |
H25 | 0.713598 | 0.389018 | 0.362452 | 0.076* | |
C26 | 0.61511 (19) | 0.36954 (17) | 0.27569 (10) | 0.0492 (4) | |
C27 | 0.57152 (17) | 0.43356 (15) | 0.21327 (9) | 0.0423 (4) | |
C28 | 0.49560 (18) | 0.40345 (15) | 0.15642 (9) | 0.0438 (4) | |
C29 | 0.42841 (18) | 0.28675 (16) | 0.14869 (10) | 0.0483 (4) | |
H29A | 0.367867 | 0.302283 | 0.112632 | 0.058* | |
H29B | 0.375132 | 0.262903 | 0.198241 | 0.058* | |
C30 | 0.52222 (18) | 0.18076 (16) | 0.12175 (10) | 0.0469 (4) | |
H30A | 0.582922 | 0.206845 | 0.075240 | 0.056* | |
H30B | 0.575094 | 0.157353 | 0.160871 | 0.056* | |
C31 | 0.3427 (2) | 0.02117 (18) | 0.16887 (11) | 0.0548 (5) | |
H31 | 0.275339 | 0.086446 | 0.183618 | 0.066* | |
C32 | 0.4012 (3) | −0.0205 (2) | 0.23822 (13) | 0.0850 (8) | |
H32A | 0.436550 | 0.048546 | 0.258190 | 0.128* | |
H32B | 0.471660 | −0.080659 | 0.223843 | 0.128* | |
H32C | 0.332963 | −0.056095 | 0.276988 | 0.128* | |
C33 | 0.2771 (2) | −0.0812 (2) | 0.13661 (15) | 0.0756 (7) | |
H33A | 0.204093 | −0.111016 | 0.174616 | 0.113* | |
H33B | 0.341352 | −0.147018 | 0.123327 | 0.113* | |
H33C | 0.244225 | −0.050541 | 0.091469 | 0.113* | |
C34 | 0.6554 (2) | 0.1705 (2) | 0.33397 (12) | 0.0656 (6) | |
H34A | 0.747301 | 0.196068 | 0.324815 | 0.079* | |
H34B | 0.655949 | 0.086874 | 0.318031 | 0.079* | |
C35 | 0.60064 (19) | 0.17215 (17) | 0.41881 (11) | 0.0516 (4) | |
C36 | 0.4761 (2) | 0.2165 (3) | 0.44842 (15) | 0.0865 (8) | |
H36 | 0.422403 | 0.251246 | 0.415227 | 0.104* | |
C37 | 0.4278 (3) | 0.2110 (3) | 0.52678 (16) | 0.0948 (9) | |
H37 | 0.342522 | 0.242462 | 0.545606 | 0.114* | |
C38 | 0.5026 (3) | 0.1608 (2) | 0.57590 (14) | 0.0775 (7) | |
H38 | 0.469508 | 0.155762 | 0.628582 | 0.093* | |
C39 | 0.6263 (3) | 0.1178 (3) | 0.54767 (14) | 0.0979 (9) | |
H39 | 0.679341 | 0.083373 | 0.581328 | 0.117* | |
C40 | 0.6759 (3) | 0.1238 (3) | 0.46979 (13) | 0.0837 (8) | |
H40 | 0.762384 | 0.094324 | 0.451731 | 0.100* | |
H1 | 1.015 (2) | 1.1243 (12) | 0.5942 (11) | 0.067 (6)* | |
H2A | 0.9443 (16) | 0.4778 (14) | 0.6006 (11) | 0.063 (6)* | |
H2B | 0.868 (2) | 0.5789 (17) | 0.5622 (7) | 0.064 (6)* | |
H3A | 0.567 (2) | 0.6707 (13) | 0.1113 (12) | 0.082 (8)* | |
H4A | 0.5134 (15) | 0.0084 (13) | 0.0920 (10) | 0.053 (5)* | |
H4B | 0.4086 (19) | 0.0901 (18) | 0.0626 (8) | 0.061 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0705 (3) | 0.0464 (3) | 0.0552 (3) | 0.0067 (2) | −0.0081 (2) | 0.0021 (2) |
Cl2 | 0.0782 (4) | 0.0465 (3) | 0.0504 (3) | 0.0089 (2) | −0.0167 (2) | −0.00195 (19) |
O1 | 0.0714 (9) | 0.0488 (7) | 0.0461 (7) | −0.0095 (6) | −0.0207 (6) | 0.0075 (5) |
O2 | 0.0800 (10) | 0.0513 (8) | 0.0553 (8) | −0.0016 (7) | −0.0317 (7) | 0.0025 (6) |
N1 | 0.0722 (11) | 0.0430 (9) | 0.0551 (10) | −0.0021 (8) | −0.0136 (8) | 0.0085 (7) |
N2 | 0.0496 (9) | 0.0416 (8) | 0.0488 (9) | −0.0019 (7) | −0.0038 (7) | −0.0059 (7) |
N3 | 0.0707 (11) | 0.0428 (9) | 0.0561 (10) | −0.0033 (8) | −0.0077 (8) | 0.0020 (7) |
N4 | 0.0547 (9) | 0.0424 (8) | 0.0372 (8) | −0.0007 (7) | −0.0072 (7) | −0.0075 (6) |
C1 | 0.0586 (12) | 0.0526 (11) | 0.0454 (10) | 0.0041 (9) | −0.0110 (9) | −0.0011 (8) |
C2 | 0.0543 (11) | 0.0406 (9) | 0.0521 (10) | 0.0001 (8) | −0.0082 (8) | −0.0017 (8) |
C3 | 0.0728 (14) | 0.0436 (11) | 0.0716 (13) | −0.0110 (9) | −0.0179 (11) | −0.0015 (9) |
C4 | 0.0830 (16) | 0.0544 (12) | 0.0760 (15) | −0.0141 (11) | −0.0301 (12) | −0.0107 (10) |
C5 | 0.0782 (15) | 0.0588 (12) | 0.0558 (12) | −0.0073 (10) | −0.0279 (11) | −0.0006 (9) |
C6 | 0.0560 (11) | 0.0430 (10) | 0.0483 (10) | −0.0014 (8) | −0.0119 (8) | −0.0013 (8) |
C7 | 0.0439 (9) | 0.0380 (9) | 0.0443 (9) | 0.0011 (7) | −0.0066 (7) | −0.0037 (7) |
C8 | 0.0424 (9) | 0.0435 (9) | 0.0421 (9) | 0.0039 (7) | −0.0060 (7) | −0.0053 (7) |
C9 | 0.0411 (10) | 0.0505 (10) | 0.0506 (10) | 0.0004 (8) | −0.0034 (8) | −0.0118 (8) |
C10 | 0.0492 (11) | 0.0479 (10) | 0.0556 (11) | −0.0003 (8) | −0.0127 (8) | −0.0059 (8) |
C11 | 0.0536 (12) | 0.0550 (12) | 0.0834 (15) | −0.0090 (9) | 0.0065 (11) | −0.0087 (10) |
C12 | 0.085 (2) | 0.125 (3) | 0.171 (3) | −0.0436 (19) | −0.014 (2) | −0.052 (2) |
C13 | 0.101 (2) | 0.113 (2) | 0.116 (2) | 0.0037 (18) | 0.0356 (19) | 0.049 (2) |
C14 | 0.0998 (18) | 0.0593 (13) | 0.0554 (12) | −0.0121 (12) | −0.0327 (12) | 0.0105 (10) |
C15 | 0.0661 (13) | 0.0496 (11) | 0.0453 (10) | 0.0032 (9) | −0.0192 (9) | 0.0041 (8) |
C16 | 0.103 (2) | 0.0744 (16) | 0.0540 (13) | 0.0122 (13) | −0.0007 (12) | −0.0045 (11) |
C17 | 0.158 (3) | 0.0610 (16) | 0.0798 (18) | 0.0265 (17) | −0.0355 (19) | −0.0222 (13) |
C18 | 0.125 (2) | 0.0573 (15) | 0.0916 (19) | −0.0223 (15) | −0.0574 (18) | 0.0139 (13) |
C19 | 0.0616 (14) | 0.0821 (17) | 0.0806 (16) | −0.0122 (12) | −0.0211 (12) | 0.0216 (13) |
C20 | 0.0604 (13) | 0.0627 (13) | 0.0576 (12) | 0.0125 (10) | −0.0146 (10) | 0.0020 (9) |
C21 | 0.0631 (12) | 0.0541 (11) | 0.0453 (10) | 0.0054 (9) | −0.0124 (9) | −0.0035 (8) |
C22 | 0.0472 (10) | 0.0475 (10) | 0.0503 (10) | −0.0033 (8) | −0.0007 (8) | −0.0071 (8) |
C23 | 0.0623 (13) | 0.0569 (12) | 0.0718 (14) | −0.0165 (10) | −0.0057 (11) | −0.0160 (10) |
C24 | 0.0637 (14) | 0.0817 (16) | 0.0701 (14) | −0.0203 (12) | −0.0157 (11) | −0.0232 (12) |
C25 | 0.0601 (13) | 0.0785 (15) | 0.0554 (12) | −0.0076 (11) | −0.0213 (10) | −0.0064 (10) |
C26 | 0.0492 (11) | 0.0525 (11) | 0.0468 (10) | −0.0026 (8) | −0.0100 (8) | −0.0061 (8) |
C27 | 0.0417 (9) | 0.0441 (9) | 0.0404 (9) | −0.0010 (7) | −0.0043 (7) | −0.0080 (7) |
C28 | 0.0475 (10) | 0.0447 (9) | 0.0389 (9) | 0.0024 (7) | −0.0060 (7) | −0.0073 (7) |
C29 | 0.0484 (10) | 0.0508 (10) | 0.0467 (10) | 0.0001 (8) | −0.0091 (8) | −0.0108 (8) |
C30 | 0.0484 (10) | 0.0483 (10) | 0.0436 (9) | −0.0032 (8) | −0.0046 (8) | −0.0105 (7) |
C31 | 0.0597 (12) | 0.0527 (11) | 0.0489 (10) | −0.0084 (9) | 0.0001 (9) | −0.0048 (8) |
C32 | 0.108 (2) | 0.0951 (18) | 0.0491 (12) | −0.0190 (15) | −0.0087 (13) | 0.0137 (12) |
C33 | 0.0767 (16) | 0.0639 (14) | 0.0851 (16) | −0.0214 (12) | −0.0064 (13) | −0.0075 (12) |
C34 | 0.0764 (15) | 0.0659 (13) | 0.0562 (12) | 0.0195 (11) | −0.0217 (11) | −0.0027 (10) |
C35 | 0.0540 (11) | 0.0476 (10) | 0.0555 (11) | 0.0055 (8) | −0.0187 (9) | −0.0005 (8) |
C36 | 0.0594 (14) | 0.128 (2) | 0.0729 (16) | 0.0244 (14) | −0.0234 (12) | 0.0059 (15) |
C37 | 0.0599 (15) | 0.134 (3) | 0.0820 (18) | 0.0177 (15) | 0.0019 (13) | 0.0025 (17) |
C38 | 0.0893 (18) | 0.0795 (16) | 0.0592 (13) | 0.0041 (13) | −0.0058 (13) | 0.0061 (11) |
C39 | 0.107 (2) | 0.128 (2) | 0.0575 (14) | 0.0461 (19) | −0.0248 (14) | 0.0058 (14) |
C40 | 0.0757 (16) | 0.112 (2) | 0.0617 (14) | 0.0441 (14) | −0.0193 (12) | −0.0026 (13) |
O1—C6 | 1.380 (2) | C16—H16 | 0.9300 |
O1—C14 | 1.436 (2) | C16—C17 | 1.380 (4) |
O2—C26 | 1.376 (2) | C17—H17 | 0.9300 |
O2—C34 | 1.435 (2) | C17—C18 | 1.374 (4) |
N1—C1 | 1.360 (3) | C18—H18 | 0.9300 |
N1—C2 | 1.366 (2) | C18—C19 | 1.353 (4) |
N1—H1 | 0.868 (9) | C19—H19 | 0.9300 |
N2—C10 | 1.490 (2) | C19—C20 | 1.374 (3) |
N2—C11 | 1.500 (2) | C20—H20 | 0.9300 |
N2—H2A | 0.944 (9) | C21—H21 | 0.9300 |
N2—H2B | 0.945 (9) | C21—C28 | 1.363 (2) |
N3—C21 | 1.365 (3) | C22—C23 | 1.392 (3) |
N3—C22 | 1.367 (2) | C22—C27 | 1.409 (2) |
N3—H3A | 0.863 (10) | C23—H23 | 0.9300 |
N4—C30 | 1.498 (2) | C23—C24 | 1.357 (3) |
N4—C31 | 1.501 (2) | C24—H24 | 0.9300 |
N4—H4A | 0.943 (9) | C24—C25 | 1.399 (3) |
N4—H4B | 0.941 (9) | C25—H25 | 0.9300 |
C1—H1A | 0.9300 | C25—C26 | 1.378 (3) |
C1—C8 | 1.365 (2) | C26—C27 | 1.405 (2) |
C2—C3 | 1.392 (3) | C27—C28 | 1.437 (2) |
C2—C7 | 1.413 (2) | C28—C29 | 1.495 (2) |
C3—H3 | 0.9300 | C29—H29A | 0.9700 |
C3—C4 | 1.361 (3) | C29—H29B | 0.9700 |
C4—H4 | 0.9300 | C29—C30 | 1.509 (2) |
C4—C5 | 1.403 (3) | C30—H30A | 0.9700 |
C5—H5 | 0.9300 | C30—H30B | 0.9700 |
C5—C6 | 1.378 (3) | C31—H31 | 0.9800 |
C6—C7 | 1.405 (2) | C31—C32 | 1.501 (3) |
C7—C8 | 1.438 (2) | C31—C33 | 1.516 (3) |
C8—C9 | 1.492 (2) | C32—H32A | 0.9600 |
C9—H9A | 0.9700 | C32—H32B | 0.9600 |
C9—H9B | 0.9700 | C32—H32C | 0.9600 |
C9—C10 | 1.518 (2) | C33—H33A | 0.9600 |
C10—H10A | 0.9700 | C33—H33B | 0.9600 |
C10—H10B | 0.9700 | C33—H33C | 0.9600 |
C11—H11 | 0.9800 | C34—H34A | 0.9700 |
C11—C12 | 1.503 (4) | C34—H34B | 0.9700 |
C11—C13 | 1.492 (4) | C34—C35 | 1.502 (3) |
C12—H12A | 0.9600 | C35—C36 | 1.360 (3) |
C12—H12B | 0.9600 | C35—C40 | 1.360 (3) |
C12—H12C | 0.9600 | C36—H36 | 0.9300 |
C13—H13A | 0.9600 | C36—C37 | 1.381 (4) |
C13—H13B | 0.9600 | C37—H37 | 0.9300 |
C13—H13C | 0.9600 | C37—C38 | 1.339 (3) |
C14—H14A | 0.9700 | C38—H38 | 0.9300 |
C14—H14B | 0.9700 | C38—C39 | 1.342 (4) |
C14—C15 | 1.497 (3) | C39—H39 | 0.9300 |
C15—C16 | 1.367 (3) | C39—C40 | 1.376 (3) |
C15—C20 | 1.368 (3) | C40—H40 | 0.9300 |
C6—O1—C14 | 115.71 (14) | C18—C17—H17 | 119.9 |
C26—O2—C34 | 117.54 (16) | C17—C18—H18 | 120.2 |
C1—N1—C2 | 108.70 (15) | C19—C18—C17 | 119.7 (2) |
C1—N1—H1 | 124.7 (15) | C19—C18—H18 | 120.2 |
C2—N1—H1 | 126.2 (15) | C18—C19—H19 | 119.9 |
C10—N2—C11 | 117.90 (15) | C18—C19—C20 | 120.1 (2) |
C10—N2—H2A | 106.6 (13) | C20—C19—H19 | 119.9 |
C10—N2—H2B | 105.5 (13) | C15—C20—C19 | 120.9 (2) |
C11—N2—H2A | 110.2 (13) | C15—C20—H20 | 119.5 |
C11—N2—H2B | 108.4 (13) | C19—C20—H20 | 119.5 |
H2A—N2—H2B | 107.8 (18) | N3—C21—H21 | 124.6 |
C21—N3—C22 | 108.79 (15) | C28—C21—N3 | 110.75 (17) |
C21—N3—H3A | 123.8 (17) | C28—C21—H21 | 124.6 |
C22—N3—H3A | 126.8 (17) | N3—C22—C23 | 129.43 (18) |
C30—N4—C31 | 118.11 (13) | N3—C22—C27 | 107.60 (16) |
C30—N4—H4A | 107.1 (12) | C23—C22—C27 | 122.96 (19) |
C30—N4—H4B | 109.6 (12) | C22—C23—H23 | 121.4 |
C31—N4—H4A | 108.1 (12) | C24—C23—C22 | 117.2 (2) |
C31—N4—H4B | 107.0 (13) | C24—C23—H23 | 121.4 |
H4A—N4—H4B | 106.4 (17) | C23—C24—H24 | 119.0 |
N1—C1—H1A | 124.5 | C23—C24—C25 | 122.00 (19) |
N1—C1—C8 | 111.04 (17) | C25—C24—H24 | 119.0 |
C8—C1—H1A | 124.5 | C24—C25—H25 | 119.6 |
N1—C2—C3 | 129.08 (18) | C26—C25—C24 | 120.8 (2) |
N1—C2—C7 | 107.80 (16) | C26—C25—H25 | 119.6 |
C3—C2—C7 | 123.13 (18) | O2—C26—C25 | 124.99 (18) |
C2—C3—H3 | 121.5 | O2—C26—C27 | 115.83 (15) |
C4—C3—C2 | 116.96 (18) | C25—C26—C27 | 119.19 (18) |
C4—C3—H3 | 121.5 | C22—C27—C28 | 107.04 (15) |
C3—C4—H4 | 118.9 | C26—C27—C22 | 117.85 (16) |
C3—C4—C5 | 122.12 (19) | C26—C27—C28 | 135.10 (16) |
C5—C4—H4 | 118.9 | C21—C28—C27 | 105.81 (16) |
C4—C5—H5 | 119.7 | C21—C28—C29 | 124.87 (17) |
C6—C5—C4 | 120.69 (19) | C27—C28—C29 | 129.18 (16) |
C6—C5—H5 | 119.7 | C28—C29—H29A | 108.6 |
O1—C6—C7 | 115.58 (15) | C28—C29—H29B | 108.6 |
C5—C6—O1 | 125.13 (17) | C28—C29—C30 | 114.73 (15) |
C5—C6—C7 | 119.28 (17) | H29A—C29—H29B | 107.6 |
C2—C7—C8 | 106.75 (15) | C30—C29—H29A | 108.6 |
C6—C7—C2 | 117.81 (16) | C30—C29—H29B | 108.6 |
C6—C7—C8 | 135.44 (16) | N4—C30—C29 | 112.12 (15) |
C1—C8—C7 | 105.72 (16) | N4—C30—H30A | 109.2 |
C1—C8—C9 | 123.63 (17) | N4—C30—H30B | 109.2 |
C7—C8—C9 | 130.62 (16) | C29—C30—H30A | 109.2 |
C8—C9—H9A | 108.6 | C29—C30—H30B | 109.2 |
C8—C9—H9B | 108.6 | H30A—C30—H30B | 107.9 |
C8—C9—C10 | 114.85 (15) | N4—C31—H31 | 108.5 |
H9A—C9—H9B | 107.5 | N4—C31—C33 | 107.79 (16) |
C10—C9—H9A | 108.6 | C32—C31—N4 | 110.56 (18) |
C10—C9—H9B | 108.6 | C32—C31—H31 | 108.5 |
N2—C10—C9 | 111.09 (15) | C32—C31—C33 | 112.83 (19) |
N2—C10—H10A | 109.4 | C33—C31—H31 | 108.5 |
N2—C10—H10B | 109.4 | C31—C32—H32A | 109.5 |
C9—C10—H10A | 109.4 | C31—C32—H32B | 109.5 |
C9—C10—H10B | 109.4 | C31—C32—H32C | 109.5 |
H10A—C10—H10B | 108.0 | H32A—C32—H32B | 109.5 |
N2—C11—H11 | 108.6 | H32A—C32—H32C | 109.5 |
N2—C11—C12 | 107.6 (2) | H32B—C32—H32C | 109.5 |
C12—C11—H11 | 108.6 | C31—C33—H33A | 109.5 |
C13—C11—N2 | 109.8 (2) | C31—C33—H33B | 109.5 |
C13—C11—H11 | 108.6 | C31—C33—H33C | 109.5 |
C13—C11—C12 | 113.6 (3) | H33A—C33—H33B | 109.5 |
C11—C12—H12A | 109.5 | H33A—C33—H33C | 109.5 |
C11—C12—H12B | 109.5 | H33B—C33—H33C | 109.5 |
C11—C12—H12C | 109.5 | O2—C34—H34A | 108.7 |
H12A—C12—H12B | 109.5 | O2—C34—H34B | 108.7 |
H12A—C12—H12C | 109.5 | O2—C34—C35 | 114.29 (17) |
H12B—C12—H12C | 109.5 | H34A—C34—H34B | 107.6 |
C11—C13—H13A | 109.5 | C35—C34—H34A | 108.7 |
C11—C13—H13B | 109.5 | C35—C34—H34B | 108.7 |
C11—C13—H13C | 109.5 | C36—C35—C34 | 123.43 (19) |
H13A—C13—H13B | 109.5 | C36—C35—C40 | 117.1 (2) |
H13A—C13—H13C | 109.5 | C40—C35—C34 | 119.48 (19) |
H13B—C13—H13C | 109.5 | C35—C36—H36 | 119.3 |
O1—C14—H14A | 109.7 | C35—C36—C37 | 121.4 (2) |
O1—C14—H14B | 109.8 | C37—C36—H36 | 119.3 |
O1—C14—C15 | 109.60 (16) | C36—C37—H37 | 119.7 |
H14A—C14—H14B | 108.2 | C38—C37—C36 | 120.6 (2) |
C15—C14—H14A | 109.7 | C38—C37—H37 | 119.7 |
C15—C14—H14B | 109.8 | C37—C38—H38 | 120.6 |
C16—C15—C14 | 121.0 (2) | C37—C38—C39 | 118.7 (2) |
C16—C15—C20 | 119.0 (2) | C39—C38—H38 | 120.6 |
C20—C15—C14 | 119.89 (19) | C38—C39—H39 | 119.4 |
C15—C16—H16 | 119.9 | C38—C39—C40 | 121.1 (2) |
C15—C16—C17 | 120.2 (2) | C40—C39—H39 | 119.4 |
C17—C16—H16 | 119.9 | C35—C40—C39 | 121.0 (2) |
C16—C17—H17 | 119.9 | C35—C40—H40 | 119.5 |
C18—C17—C16 | 120.1 (2) | C39—C40—H40 | 119.5 |
O1—C6—C7—C2 | 178.71 (16) | C14—O1—C6—C7 | 179.02 (18) |
O1—C6—C7—C8 | −0.9 (3) | C14—C15—C16—C17 | 175.4 (2) |
O1—C14—C15—C16 | 66.8 (3) | C14—C15—C20—C19 | −174.8 (2) |
O1—C14—C15—C20 | −118.0 (2) | C15—C16—C17—C18 | −0.7 (4) |
O2—C26—C27—C22 | −179.31 (15) | C16—C15—C20—C19 | 0.4 (3) |
O2—C26—C27—C28 | 1.4 (3) | C16—C17—C18—C19 | 0.5 (4) |
O2—C34—C35—C36 | 15.9 (3) | C17—C18—C19—C20 | 0.1 (4) |
O2—C34—C35—C40 | −166.3 (2) | C18—C19—C20—C15 | −0.6 (3) |
N1—C1—C8—C7 | 0.4 (2) | C20—C15—C16—C17 | 0.2 (4) |
N1—C1—C8—C9 | 178.92 (16) | C21—N3—C22—C23 | −178.5 (2) |
N1—C2—C3—C4 | −179.8 (2) | C21—N3—C22—C27 | 0.4 (2) |
N1—C2—C7—C6 | −179.56 (16) | C21—C28—C29—C30 | 112.7 (2) |
N1—C2—C7—C8 | 0.1 (2) | C22—N3—C21—C28 | −0.2 (2) |
N3—C21—C28—C27 | −0.2 (2) | C22—C23—C24—C25 | 0.6 (3) |
N3—C21—C28—C29 | 175.82 (16) | C22—C27—C28—C21 | 0.45 (19) |
N3—C22—C23—C24 | 178.9 (2) | C22—C27—C28—C29 | −175.33 (17) |
N3—C22—C27—C26 | −179.99 (16) | C23—C22—C27—C26 | −1.0 (3) |
N3—C22—C27—C28 | −0.54 (19) | C23—C22—C27—C28 | 178.44 (17) |
C1—N1—C2—C3 | 179.9 (2) | C23—C24—C25—C26 | −0.4 (3) |
C1—N1—C2—C7 | 0.1 (2) | C24—C25—C26—O2 | −179.99 (19) |
C1—C8—C9—C10 | 108.3 (2) | C24—C25—C26—C27 | −0.5 (3) |
C2—N1—C1—C8 | −0.3 (2) | C25—C26—C27—C22 | 1.2 (3) |
C2—C3—C4—C5 | −0.6 (3) | C25—C26—C27—C28 | −178.05 (19) |
C2—C7—C8—C1 | −0.32 (19) | C26—O2—C34—C35 | 85.8 (2) |
C2—C7—C8—C9 | −178.69 (17) | C26—C27—C28—C21 | 179.8 (2) |
C3—C2—C7—C6 | 0.6 (3) | C26—C27—C28—C29 | 4.0 (3) |
C3—C2—C7—C8 | −179.69 (18) | C27—C22—C23—C24 | 0.1 (3) |
C3—C4—C5—C6 | 0.7 (4) | C27—C28—C29—C30 | −72.3 (2) |
C4—C5—C6—O1 | −179.2 (2) | C28—C29—C30—N4 | −172.94 (14) |
C4—C5—C6—C7 | 0.0 (3) | C30—N4—C31—C32 | −60.6 (2) |
C5—C6—C7—C2 | −0.6 (3) | C30—N4—C31—C33 | 175.65 (17) |
C5—C6—C7—C8 | 179.9 (2) | C31—N4—C30—C29 | −54.9 (2) |
C6—O1—C14—C15 | −173.52 (17) | C34—O2—C26—C25 | −18.4 (3) |
C6—C7—C8—C1 | 179.3 (2) | C34—O2—C26—C27 | 162.13 (16) |
C6—C7—C8—C9 | 0.9 (3) | C34—C35—C36—C37 | 177.0 (3) |
C7—C2—C3—C4 | 0.0 (3) | C34—C35—C40—C39 | −176.5 (3) |
C7—C8—C9—C10 | −73.5 (2) | C35—C36—C37—C38 | −0.4 (5) |
C8—C9—C10—N2 | −153.55 (15) | C36—C35—C40—C39 | 1.5 (4) |
C10—N2—C11—C12 | 162.3 (2) | C36—C37—C38—C39 | 1.1 (5) |
C10—N2—C11—C13 | −73.6 (3) | C37—C38—C39—C40 | −0.5 (5) |
C11—N2—C10—C9 | −59.7 (2) | C38—C39—C40—C35 | −0.8 (5) |
C14—O1—C6—C5 | −1.8 (3) | C40—C35—C36—C37 | −0.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1i | 0.87 (1) | 2.36 (1) | 3.1969 (17) | 162 (2) |
N2—H2A···Cl1ii | 0.94 (1) | 2.18 (1) | 3.1114 (16) | 167 (2) |
N2—H2B···Cl1 | 0.95 (1) | 2.23 (1) | 3.1191 (16) | 157 (2) |
N3—H3A···Cl2iii | 0.86 (1) | 2.42 (1) | 3.2657 (17) | 168 (2) |
N4—H4A···Cl2iv | 0.94 (1) | 2.20 (1) | 3.1360 (16) | 173 (2) |
N4—H4B···Cl2 | 0.94 (1) | 2.19 (1) | 3.1247 (16) | 171 (2) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) −x+1, −y, −z. |
C13H18N2O | Dx = 1.207 Mg m−3 |
Mr = 218.29 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 9906 reflections |
a = 8.4065 (5) Å | θ = 2.8–25.6° |
b = 14.3944 (9) Å | µ = 0.08 mm−1 |
c = 19.8501 (10) Å | T = 300 K |
V = 2402.0 (2) Å3 | Block, colourless |
Z = 8 | 0.33 × 0.25 × 0.20 mm |
F(000) = 944 |
Bruker D8 Venture CMOS diffractometer | 2121 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.050 |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | θmax = 26.4°, θmin = 2.8° |
Tmin = 0.715, Tmax = 0.745 | h = −10→10 |
61022 measured reflections | k = −18→18 |
2461 independent reflections | l = −24→24 |
Refinement on F2 | 3 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0509P)2 + 0.7218P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2461 reflections | Δρmax = 0.18 e Å−3 |
159 parameters | Δρmin = −0.15 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 | ||
O1 | 0.61118 (12) | 0.61010 (6) | 0.38334 (6) | 0.0478 (3) | |
N1 | 0.77344 (18) | 0.91907 (9) | 0.37395 (8) | 0.0551 (4) | |
N2 | 0.32230 (14) | 0.67852 (8) | 0.37951 (6) | 0.0397 (3) | |
C1 | 0.6437 (2) | 0.90682 (11) | 0.33371 (9) | 0.0522 (4) | |
H1B | 0.595323 | 0.953994 | 0.309107 | 0.063* | |
C2 | 0.81228 (17) | 0.83572 (10) | 0.40260 (7) | 0.0406 (3) | |
C3 | 0.93477 (18) | 0.81377 (11) | 0.44719 (8) | 0.0496 (4) | |
H3 | 1.006571 | 0.858574 | 0.461856 | 0.059* | |
C4 | 0.94493 (19) | 0.72347 (12) | 0.46850 (8) | 0.0496 (4) | |
H4 | 1.025759 | 0.706585 | 0.498049 | 0.060* | |
C5 | 0.83653 (18) | 0.65601 (11) | 0.44684 (8) | 0.0439 (4) | |
H5 | 0.846425 | 0.595429 | 0.462570 | 0.053* | |
C6 | 0.71540 (16) | 0.67743 (9) | 0.40270 (7) | 0.0350 (3) | |
C7 | 0.70144 (15) | 0.76948 (9) | 0.37899 (6) | 0.0332 (3) | |
C8 | 0.59388 (17) | 0.81690 (10) | 0.33409 (7) | 0.0400 (3) | |
C9 | 0.45501 (19) | 0.78061 (12) | 0.29482 (8) | 0.0496 (4) | |
H9A | 0.486563 | 0.723433 | 0.272682 | 0.060* | |
H9B | 0.428623 | 0.825257 | 0.259960 | 0.060* | |
C10 | 0.30611 (18) | 0.76164 (12) | 0.33657 (9) | 0.0516 (4) | |
H10A | 0.284311 | 0.815124 | 0.364830 | 0.062* | |
H10B | 0.216237 | 0.753324 | 0.306528 | 0.062* | |
C11 | 0.21361 (17) | 0.60121 (11) | 0.36284 (8) | 0.0458 (4) | |
H11 | 0.105392 | 0.625769 | 0.358403 | 0.055* | |
C12 | 0.2167 (2) | 0.53158 (12) | 0.41978 (10) | 0.0643 (5) | |
H12A | 0.143267 | 0.482209 | 0.410295 | 0.096* | |
H12B | 0.186765 | 0.561735 | 0.461012 | 0.096* | |
H12C | 0.322036 | 0.506555 | 0.424211 | 0.096* | |
C13 | 0.2623 (2) | 0.55756 (15) | 0.29654 (10) | 0.0741 (6) | |
H13A | 0.190508 | 0.507916 | 0.285706 | 0.111* | |
H13B | 0.368466 | 0.533495 | 0.300308 | 0.111* | |
H13C | 0.258916 | 0.603620 | 0.261593 | 0.111* | |
H2 | 0.304 (2) | 0.6938 (12) | 0.4226 (5) | 0.054 (5)* | |
H1A | 0.822 (2) | 0.9726 (9) | 0.3790 (9) | 0.071 (6)* | |
H1 | 0.5026 (15) | 0.6380 (13) | 0.3800 (10) | 0.077 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0387 (6) | 0.0262 (5) | 0.0784 (8) | 0.0011 (4) | −0.0065 (5) | −0.0003 (5) |
N1 | 0.0535 (9) | 0.0306 (7) | 0.0813 (10) | −0.0091 (6) | 0.0127 (7) | 0.0033 (6) |
N2 | 0.0369 (6) | 0.0376 (6) | 0.0445 (7) | −0.0001 (5) | −0.0022 (5) | −0.0035 (5) |
C1 | 0.0510 (9) | 0.0372 (8) | 0.0684 (10) | 0.0040 (7) | 0.0142 (8) | 0.0191 (7) |
C2 | 0.0405 (7) | 0.0342 (7) | 0.0470 (8) | −0.0044 (6) | 0.0132 (6) | −0.0054 (6) |
C3 | 0.0405 (8) | 0.0546 (9) | 0.0537 (9) | −0.0082 (7) | 0.0042 (7) | −0.0176 (7) |
C4 | 0.0404 (8) | 0.0643 (10) | 0.0441 (8) | 0.0062 (7) | −0.0037 (6) | −0.0081 (7) |
C5 | 0.0419 (8) | 0.0418 (8) | 0.0479 (8) | 0.0068 (6) | 0.0002 (6) | 0.0052 (6) |
C6 | 0.0340 (7) | 0.0289 (6) | 0.0421 (7) | 0.0026 (5) | 0.0042 (6) | −0.0007 (5) |
C7 | 0.0336 (7) | 0.0304 (7) | 0.0357 (6) | 0.0009 (5) | 0.0090 (5) | −0.0012 (5) |
C8 | 0.0394 (7) | 0.0367 (7) | 0.0439 (7) | 0.0035 (6) | 0.0094 (6) | 0.0085 (6) |
C9 | 0.0478 (9) | 0.0538 (9) | 0.0473 (8) | 0.0050 (7) | −0.0025 (7) | 0.0134 (7) |
C10 | 0.0369 (8) | 0.0482 (9) | 0.0697 (10) | 0.0063 (7) | −0.0036 (7) | 0.0084 (8) |
C11 | 0.0350 (7) | 0.0475 (8) | 0.0548 (9) | −0.0042 (6) | 0.0007 (6) | −0.0105 (7) |
C12 | 0.0593 (11) | 0.0459 (9) | 0.0876 (13) | −0.0085 (8) | −0.0020 (10) | 0.0046 (9) |
C13 | 0.0622 (11) | 0.0869 (14) | 0.0731 (12) | −0.0139 (10) | 0.0048 (10) | −0.0392 (11) |
O1—C6 | 1.3618 (17) | C6—C7 | 1.4110 (18) |
O1—H1 | 0.999 (9) | C7—C8 | 1.4415 (19) |
N1—C1 | 1.363 (2) | C8—C9 | 1.498 (2) |
N1—C2 | 1.367 (2) | C9—H9A | 0.9700 |
N1—H1A | 0.877 (9) | C9—H9B | 0.9700 |
N2—C10 | 1.475 (2) | C9—C10 | 1.526 (2) |
N2—C11 | 1.4774 (19) | C10—H10A | 0.9700 |
N2—H2 | 0.897 (9) | C10—H10B | 0.9700 |
C1—H1B | 0.9300 | C11—H11 | 0.9800 |
C1—C8 | 1.360 (2) | C11—C12 | 1.511 (2) |
C2—C3 | 1.394 (2) | C11—C13 | 1.515 (2) |
C2—C7 | 1.4131 (19) | C12—H12A | 0.9600 |
C3—H3 | 0.9300 | C12—H12B | 0.9600 |
C3—C4 | 1.370 (2) | C12—H12C | 0.9600 |
C4—H4 | 0.9300 | C13—H13A | 0.9600 |
C4—C5 | 1.399 (2) | C13—H13B | 0.9600 |
C5—H5 | 0.9300 | C13—H13C | 0.9600 |
C5—C6 | 1.378 (2) | ||
C6—O1—H1 | 108.7 (12) | C8—C9—H9A | 108.6 |
C1—N1—C2 | 108.74 (13) | C8—C9—H9B | 108.6 |
C1—N1—H1A | 123.5 (13) | C8—C9—C10 | 114.77 (13) |
C2—N1—H1A | 127.8 (14) | H9A—C9—H9B | 107.6 |
C10—N2—C11 | 115.11 (12) | C10—C9—H9A | 108.6 |
C10—N2—H2 | 109.6 (11) | C10—C9—H9B | 108.6 |
C11—N2—H2 | 106.9 (11) | N2—C10—C9 | 112.54 (12) |
N1—C1—H1B | 124.3 | N2—C10—H10A | 109.1 |
C8—C1—N1 | 111.47 (14) | N2—C10—H10B | 109.1 |
C8—C1—H1B | 124.3 | C9—C10—H10A | 109.1 |
N1—C2—C3 | 129.74 (14) | C9—C10—H10B | 109.1 |
N1—C2—C7 | 107.26 (13) | H10A—C10—H10B | 107.8 |
C3—C2—C7 | 123.00 (13) | N2—C11—H11 | 108.8 |
C2—C3—H3 | 121.4 | N2—C11—C12 | 108.75 (13) |
C4—C3—C2 | 117.20 (14) | N2—C11—C13 | 109.86 (13) |
C4—C3—H3 | 121.4 | C12—C11—H11 | 108.8 |
C3—C4—H4 | 119.2 | C12—C11—C13 | 111.73 (15) |
C3—C4—C5 | 121.54 (15) | C13—C11—H11 | 108.8 |
C5—C4—H4 | 119.2 | C11—C12—H12A | 109.5 |
C4—C5—H5 | 119.3 | C11—C12—H12B | 109.5 |
C6—C5—C4 | 121.41 (14) | C11—C12—H12C | 109.5 |
C6—C5—H5 | 119.3 | H12A—C12—H12B | 109.5 |
O1—C6—C5 | 119.70 (12) | H12A—C12—H12C | 109.5 |
O1—C6—C7 | 121.38 (12) | H12B—C12—H12C | 109.5 |
C5—C6—C7 | 118.92 (13) | C11—C13—H13A | 109.5 |
C2—C7—C8 | 107.41 (12) | C11—C13—H13B | 109.5 |
C6—C7—C2 | 117.91 (13) | C11—C13—H13C | 109.5 |
C6—C7—C8 | 134.67 (13) | H13A—C13—H13B | 109.5 |
C1—C8—C7 | 105.12 (14) | H13A—C13—H13C | 109.5 |
C1—C8—C9 | 124.66 (14) | H13B—C13—H13C | 109.5 |
C7—C8—C9 | 130.21 (13) | ||
O1—C6—C7—C2 | 178.65 (12) | C3—C2—C7—C8 | −179.83 (13) |
O1—C6—C7—C8 | −0.4 (2) | C3—C4—C5—C6 | 0.5 (2) |
N1—C1—C8—C7 | 0.54 (17) | C4—C5—C6—O1 | −179.29 (13) |
N1—C1—C8—C9 | −179.63 (14) | C4—C5—C6—C7 | 0.1 (2) |
N1—C2—C3—C4 | 179.42 (15) | C5—C6—C7—C2 | −0.74 (19) |
N1—C2—C7—C6 | −178.91 (12) | C5—C6—C7—C8 | −179.82 (14) |
N1—C2—C7—C8 | 0.40 (15) | C6—C7—C8—C1 | 178.58 (15) |
C1—N1—C2—C3 | −179.82 (15) | C6—C7—C8—C9 | −1.2 (3) |
C1—N1—C2—C7 | −0.08 (17) | C7—C2—C3—C4 | −0.3 (2) |
C1—C8—C9—C10 | −104.54 (17) | C7—C8—C9—C10 | 75.2 (2) |
C2—N1—C1—C8 | −0.30 (19) | C8—C9—C10—N2 | −72.62 (18) |
C2—C3—C4—C5 | −0.4 (2) | C10—N2—C11—C12 | −166.98 (14) |
C2—C7—C8—C1 | −0.57 (15) | C10—N2—C11—C13 | 70.45 (18) |
C2—C7—C8—C9 | 179.61 (14) | C11—N2—C10—C9 | −115.33 (15) |
C3—C2—C7—C6 | 0.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.88 (1) | 2.06 (1) | 2.9217 (16) | 167 (2) |
O1—H1···N2 | 1.00 (1) | 1.62 (1) | 2.6217 (15) | 176 (2) |
Symmetry code: (i) −x+3/2, y+1/2, z. |
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).
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