5,5-Dimethyl-3-(5-methyl­isoxazol-3-yl)cyclo­hex-2-enone

The X-ray crystal structure of the title compound, C₁₂H₁₆N₂O₂, has been determined and its structure correlated with its anti­convulsant activity in mice and rats. In each of the two molecules of the asymmetric unit, the two rings are linked by an intramolecular C—H...N hydrogen bond.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.059
• wR factor = 0.148
• Data-to-parameter ratio = 11.3

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............      58.93 Deg.

Author Response: see _publ_section_exptl_refinement see _publ_section_exptl_refinement

Alert level B
THETM01_ALERT_3_B  The value of sine(theta_max)/wavelength is less than 0.575
            Calculated sin(theta_max)/wavelength =    0.5556
PLAT023_ALERT_3_B Resolution (too) Low [sin(th)/Lambda < 0.6].....      58.93 Deg.

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C5A
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C5B
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.08
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.16
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety       C12A
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         24

   1 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Our research on the anticonvulsant activity of the enaminones has been augmented by X-ray analysis (Kubicki & Codding, 1993; Laws et al., 1998; Foster et al., 1999; Kubicki et al., 2000; Eddington et al., 2002; Anderson et al., 2006; Hanson et al., 2006). Recently, our investigation has led to the evaluation of various isoxazoles, from which 5-methyl-3-(5-methylisoxazol-3-yl)cyclohex-2-enone, (I) (Hanson et al., 2006), and the title compound, (II), have emerged. Although structurally similar to (I) (Hanson et al., 2006), compound (II) was exclusively MES (maximal electroshock seizure evaluation) active and more toxic (3/7 animals protected at 100 mg kg⁻¹ at 30 min, 4/5 animals protected at 300 mg kg⁻¹ at 30 min and at 4 h; toxicity evaluation: 2/8 toxic at 100 mg kg⁻¹ at 30 min, 3/4 toxic at 300 mg kg⁻¹ at 30 min and 1/2 toxic at 300 mg kg⁻¹ at 4 h). Single-crystal X-ray analyses carried out on (I) (Hanson et al., 2006) and (II) (this work) point to the importance of intramolecular hydrogen bonding.

The structure of (II) is shown in Fig. 1. There are two structurally similar molecules, A and B, in the asymmetric unit. In agreement with our previous studies, hydrogen bonding occurs between the vinyl H atom and the aromatic/heterocyclic ring system (Fig. 2). In (II), this bonding occurs between the H atoms on atoms C2A and C2B and the lone pairs on atoms N2A and N2B on the isoxazole rings. Geometric parameters for this compound are similar to those observed in other related enaminones (Kubicki & Codding, 1993; Laws et al., 1998; Foster et al., 1999; Kubicki et al., 2002 Or 2000?; Eddington et al., 2002; Anderson et al., 2006; Hanson et al., 2006).

Compared with the packing arrangement in (I) (Hanson et al., 2006), a more complicated structural configuration occurs in the dimethyl analogue, (II). This compound is assembled as a head-to-tail dimer, exhibiting both intramolecular hydrogen bonding (C2B···N2B and N2A···C2A) and intermolecular hydrogen bonding with the carbonyl O atom (atom O1B and the isoxazole H atom on atom C10A, and the H atom on the secondary amine atom N1A), producing a pocket between these molecules. Furthermore, this clathrate conformation effectively blocks access to the proposed active site by virtue of the dimethyl substituents at both ends of the pocket. Pauling (1961, 1964a,b) proposed a molecular theory of general anesthesia, which involved the formation of minute hydrate crystals of the clathrate type that would interfere with nerve impulses. In the structure of (II), a clathrate has, in fact, been shown to occur which, if present in solution, could explain the toxicity of (II).

S2. Experimental

Following the procedure used in the synthesis of 5-methyl-3-(5-methylisoxazol-3-yl)cyclohex-2-enone (Hanson et al., 2006), 5,5-dimethylcyclohexane-1,3-dione (27 mmol) and 3-amino-5-methylisoxazole (33 mmol) produced light-yellow crystals of (II) (yield 3.1 g, 51%; m.p. 477–480 K). Spectroscopic analysis: ¹H NMR (DMSO-d₆, δ, p.p.m.): 1.0 (6H, s, gem CH₃), 2.0 (2H, s, C₄ CH₂), 2.5 (2H, s, C₆ CH₂), 3.3 (3H, s, isoxazole CH₃), 6.0 (1H, s, ═CH), 6.2 (1H, s, isoxazole CH═), 9.4 (1H, br s, NH). ¹³C NMR (DMSO-d₆, δ, p.p.m.): 5.0, 27.3, 42.0, 41.9, 43.4, 45.5, 47.2, 97.1, 102.3, 105.3, 155.3, 197.1; IR (KBr, ν, cm⁻¹): 3340.5 (NH), 3143.7 (5-methylisoxazole stretch), 1678.6 (C═O).

S3. Refinement

Diffraction data were collected out to d = 0.8. However, data for d < 0.9 were very weak (less than 1σ) and were thus omitted from the refinement. In view of the importance of this compound in comparison and in contrast with that in the previous paper (Hanson et al., 2006), it was felt that it warranted publication in spite of these limitations. All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry, with C—H distances of 0.98 Å and U_iso(H) = 1.5U_eq(C), but each group was allowed to rotate freely about its C—C bond. The position of the amine H atom was idealized, with an N—H distance of 0.86 Å and U_iso(H) = 1.2U_eq(N). All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.95–1.00 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The two independent molecules (suffixes A and B) of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 20% probability level and H atoms are represented by circles of arbitrary size. Dashed lines indicate hydrogen bonds.
	Fig. 2. The molecular packing of (II), viewed down the a axis. Dashed lines indicate hydrogen bonds.

5,5-Dimethyl-3-(5-methylisoxazol-3-yl)cyclohex-2-enone

Crystal data

C12H16N2O2	Z = 4
Mr = 220.27	F(000) = 472
Triclinic, P1	Dx = 1.210 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 6.2647 (4) Å	Cell parameters from 36 reflections
b = 12.2138 (10) Å	θ = 4.2–30.6°
c = 16.459 (2) Å	µ = 0.68 mm^−1
α = 101.137 (12)°	T = 294 K
β = 93.566 (9)°	Lath, colourless
γ = 100.306 (7)°	0.50 × 0.12 × 0.08 mm
V = 1209.6 (2) Å^3

Data collection

Bruker P4 diffractometer	Rint = 0.043
Radiation source: fine-focus sealed tube	θmax = 58.9°, θmin = 2.8°
Graphite monochromator	h = −6→1
2θ/ω scans	k = −13→13
4192 measured reflections	l = −18→17
3342 independent reflections	3 standard reflections every 97 reflections
2017 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0588P)^2] where P = (Fo^2 + 2Fc^2)/3
3342 reflections	(Δ/σ)max = 0.001
295 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1A	0.9358 (4)	0.6454 (2)	0.34741 (17)	0.0779 (9)
O2A	0.0714 (4)	0.57646 (19)	0.13600 (16)	0.0635 (7)
O1B	0.0544 (5)	0.1584 (2)	0.16727 (18)	0.0903 (10)
O2B	0.6299 (4)	−0.0220 (2)	0.40106 (16)	0.0746 (8)
N1A	0.3314 (4)	0.3734 (2)	0.20183 (17)	0.0537 (8)
H1AA	0.2853	0.3009	0.1888	0.064*
N2A	0.2521 (5)	0.5483 (2)	0.1781 (2)	0.0649 (9)
N1B	0.1230 (5)	−0.1531 (2)	0.29288 (18)	0.0602 (9)
H1BA	0.0532	−0.2200	0.2943	0.072*
N2B	0.4456 (5)	−0.0190 (2)	0.3476 (2)	0.0731 (10)
C1A	0.5233 (5)	0.4092 (3)	0.2528 (2)	0.0449 (9)
C2A	0.6292 (5)	0.5178 (3)	0.2765 (2)	0.0497 (9)
H2AA	0.5708	0.5750	0.2586	0.060*
C3A	0.8311 (6)	0.5468 (3)	0.3290 (2)	0.0544 (10)
C4A	0.9177 (6)	0.4549 (3)	0.3609 (2)	0.0577 (10)
H4AA	0.9896	0.4863	0.4165	0.069*
H4AB	1.0269	0.4311	0.3258	0.069*
C5A	0.7460 (6)	0.3502 (3)	0.3638 (2)	0.0561 (10)
C6A	0.6109 (6)	0.3138 (3)	0.2795 (2)	0.0549 (10)
H6AA	0.7005	0.2839	0.2379	0.066*
H6AB	0.4899	0.2531	0.2821	0.066*
C7A	0.5984 (7)	0.3792 (4)	0.4320 (3)	0.0909 (15)
H7AA	0.6839	0.4023	0.4850	0.136*
H7AB	0.4886	0.3135	0.4322	0.136*
H7AC	0.5299	0.4401	0.4215	0.136*
C8A	0.8595 (7)	0.2552 (3)	0.3808 (3)	0.0965 (17)
H8AA	0.9408	0.2783	0.4348	0.145*
H8AB	0.9569	0.2397	0.3392	0.145*
H8AC	0.7523	0.1878	0.3793	0.145*
C9A	0.2015 (5)	0.4381 (3)	0.1684 (2)	0.0454 (9)
C10A	−0.0008 (5)	0.3910 (3)	0.1215 (2)	0.0502 (9)
H10A	−0.0677	0.3147	0.1064	0.060*
C11A	−0.0754 (6)	0.4798 (3)	0.1034 (2)	0.0492 (9)
C12A	−0.2771 (6)	0.4935 (3)	0.0585 (2)	0.0626 (11)
H12A	−0.3685	0.4202	0.0377	0.094*
H12B	−0.2408	0.5295	0.0129	0.094*
H12C	−0.3531	0.5398	0.0958	0.094*
C1B	0.0214 (6)	−0.0961 (3)	0.2438 (2)	0.0503 (9)
C2B	0.1014 (6)	0.0093 (3)	0.2320 (2)	0.0583 (10)
H2BA	0.2380	0.0473	0.2579	0.070*
C3B	−0.0181 (6)	0.0635 (3)	0.1812 (2)	0.0617 (11)
C4B	−0.2466 (6)	0.0040 (3)	0.1453 (2)	0.0655 (11)
H4BA	−0.2831	0.0300	0.0950	0.079*
H4BB	−0.3481	0.0252	0.1849	0.079*
C5B	−0.2748 (6)	−0.1243 (3)	0.1247 (2)	0.0548 (10)
C6B	−0.1969 (6)	−0.1619 (3)	0.2024 (2)	0.0566 (10)
H6BA	−0.3041	−0.1544	0.2421	0.068*
H6BB	−0.1891	−0.2418	0.1875	0.068*
C7B	−0.1446 (7)	−0.1622 (4)	0.0526 (3)	0.0824 (13)
H7BA	−0.1978	−0.1391	0.0039	0.124*
H7BB	−0.1609	−0.2436	0.0414	0.124*
H7BC	0.0066	−0.1280	0.0670	0.124*
C8B	−0.5160 (6)	−0.1777 (3)	0.0998 (3)	0.0806 (13)
H8BA	−0.5621	−0.1594	0.0481	0.121*
H8BB	−0.6013	−0.1483	0.1423	0.121*
H8BC	−0.5359	−0.2588	0.0933	0.121*
C9B	0.3223 (6)	−0.1193 (3)	0.3409 (2)	0.0534 (10)
C10B	0.4146 (6)	−0.1879 (3)	0.3867 (2)	0.0619 (11)
H10B	0.3562	−0.2620	0.3906	0.074*
C11B	0.6029 (6)	−0.1244 (3)	0.4231 (2)	0.0616 (11)
C12B	0.7823 (6)	−0.1417 (3)	0.4793 (2)	0.0774 (13)
H12D	0.7750	−0.2217	0.4758	0.116*
H12E	0.7684	−0.1059	0.5355	0.116*
H12F	0.9199	−0.1087	0.4631	0.116*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0716 (19)	0.0522 (16)	0.099 (2)	−0.0191 (14)	−0.0265 (16)	0.0294 (14)
O2A	0.0549 (16)	0.0486 (14)	0.0872 (19)	0.0089 (13)	−0.0170 (15)	0.0228 (13)
O1B	0.095 (2)	0.0466 (15)	0.121 (2)	−0.0166 (15)	−0.0359 (19)	0.0419 (16)
O2B	0.0630 (18)	0.0604 (16)	0.094 (2)	−0.0093 (14)	−0.0262 (16)	0.0313 (15)
N1A	0.0477 (18)	0.0378 (15)	0.070 (2)	−0.0042 (14)	−0.0161 (16)	0.0173 (14)
N2A	0.055 (2)	0.0491 (18)	0.088 (2)	0.0024 (15)	−0.0224 (18)	0.0247 (17)
N1B	0.059 (2)	0.0408 (16)	0.077 (2)	−0.0074 (15)	−0.0093 (18)	0.0261 (15)
N2B	0.059 (2)	0.059 (2)	0.096 (3)	−0.0069 (17)	−0.021 (2)	0.0276 (18)
C1A	0.042 (2)	0.0407 (19)	0.051 (2)	0.0020 (16)	−0.0065 (18)	0.0142 (16)
C2A	0.049 (2)	0.0406 (19)	0.059 (2)	0.0035 (17)	−0.0063 (19)	0.0179 (17)
C3A	0.051 (2)	0.048 (2)	0.060 (2)	−0.0074 (18)	−0.002 (2)	0.0188 (18)
C4A	0.050 (2)	0.056 (2)	0.062 (2)	−0.0058 (18)	−0.015 (2)	0.0210 (19)
C5A	0.052 (2)	0.053 (2)	0.060 (2)	−0.0059 (18)	−0.015 (2)	0.0243 (18)
C6A	0.055 (2)	0.0423 (19)	0.063 (2)	0.0023 (17)	−0.015 (2)	0.0143 (17)
C7A	0.087 (3)	0.113 (4)	0.070 (3)	−0.009 (3)	0.002 (3)	0.043 (3)
C8A	0.100 (4)	0.058 (3)	0.127 (4)	0.005 (2)	−0.053 (3)	0.041 (3)
C9A	0.040 (2)	0.043 (2)	0.054 (2)	0.0066 (16)	−0.0028 (18)	0.0173 (16)
C10A	0.047 (2)	0.047 (2)	0.054 (2)	−0.0005 (17)	−0.0064 (19)	0.0156 (17)
C11A	0.045 (2)	0.052 (2)	0.051 (2)	0.0056 (18)	−0.0025 (18)	0.0166 (18)
C12A	0.055 (2)	0.073 (3)	0.064 (2)	0.020 (2)	−0.009 (2)	0.021 (2)
C1B	0.047 (2)	0.0400 (19)	0.062 (2)	0.0006 (17)	−0.0024 (19)	0.0164 (17)
C2B	0.055 (2)	0.042 (2)	0.076 (3)	−0.0007 (18)	−0.008 (2)	0.0193 (19)
C3B	0.063 (3)	0.042 (2)	0.077 (3)	0.0015 (19)	−0.011 (2)	0.0172 (19)
C4B	0.057 (3)	0.050 (2)	0.088 (3)	0.0080 (19)	−0.011 (2)	0.019 (2)
C5B	0.049 (2)	0.0424 (19)	0.069 (3)	0.0024 (17)	−0.006 (2)	0.0110 (18)
C6B	0.050 (2)	0.044 (2)	0.071 (3)	−0.0047 (17)	0.000 (2)	0.0157 (18)
C7B	0.082 (3)	0.082 (3)	0.076 (3)	0.010 (3)	0.001 (3)	0.008 (2)
C8B	0.056 (3)	0.071 (3)	0.106 (3)	−0.004 (2)	−0.019 (3)	0.021 (2)
C9B	0.054 (2)	0.043 (2)	0.058 (2)	−0.0051 (18)	−0.006 (2)	0.0149 (17)
C10B	0.060 (3)	0.049 (2)	0.075 (3)	−0.0047 (19)	−0.006 (2)	0.0271 (19)
C11B	0.063 (3)	0.056 (2)	0.067 (3)	0.004 (2)	−0.005 (2)	0.027 (2)
C12B	0.069 (3)	0.080 (3)	0.082 (3)	0.003 (2)	−0.012 (2)	0.032 (2)

Geometric parameters (Å, º)

O1A—C3A	1.235 (4)	C9A—C10A	1.407 (4)
O2A—C11A	1.354 (4)	C10A—C11A	1.331 (4)
O2A—N2A	1.419 (3)	C10A—H10A	0.9300
O1B—C3B	1.236 (4)	C11A—C12A	1.475 (4)
O2B—C11B	1.353 (4)	C12A—H12A	0.9600
O2B—N2B	1.418 (4)	C12A—H12B	0.9600
N1A—C1A	1.373 (4)	C12A—H12C	0.9600
N1A—C9A	1.391 (4)	C1B—C2B	1.351 (4)
N1A—H1AA	0.8600	C1B—C6B	1.503 (4)
N2A—C9A	1.302 (4)	C2B—C3B	1.418 (5)
N1B—C1B	1.362 (4)	C2B—H2BA	0.9300
N1B—C9B	1.386 (4)	C3B—C4B	1.512 (5)
N1B—H1BA	0.8600	C4B—C5B	1.513 (4)
N2B—C9B	1.306 (4)	C4B—H4BA	0.9700
C1A—C2A	1.344 (4)	C4B—H4BB	0.9700
C1A—C6A	1.499 (4)	C5B—C6B	1.520 (4)
C2A—C3A	1.435 (4)	C5B—C7B	1.528 (5)
C2A—H2AA	0.9300	C5B—C8B	1.531 (5)
C3A—C4A	1.496 (4)	C6B—H6BA	0.9700
C4A—C5A	1.527 (4)	C6B—H6BB	0.9700
C4A—H4AA	0.9700	C7B—H7BA	0.9600
C4A—H4AB	0.9700	C7B—H7BB	0.9600
C5A—C6A	1.524 (4)	C7B—H7BC	0.9600
C5A—C8A	1.526 (5)	C8B—H8BA	0.9600
C5A—C7A	1.527 (5)	C8B—H8BB	0.9600
C6A—H6AA	0.9700	C8B—H8BC	0.9600
C6A—H6AB	0.9700	C9B—C10B	1.403 (5)
C7A—H7AA	0.9600	C10B—C11B	1.326 (5)
C7A—H7AB	0.9600	C10B—H10B	0.9300
C7A—H7AC	0.9600	C11B—C12B	1.482 (5)
C8A—H8AA	0.9600	C12B—H12D	0.9600
C8A—H8AB	0.9600	C12B—H12E	0.9600
C8A—H8AC	0.9600	C12B—H12F	0.9600
C11A—O2A—N2A	109.0 (2)	C11A—C12A—H12B	109.5
C11B—O2B—N2B	109.0 (3)	H12A—C12A—H12B	109.5
C1A—N1A—C9A	128.9 (3)	C11A—C12A—H12C	109.5
C1A—N1A—H1AA	115.5	H12A—C12A—H12C	109.5
C9A—N1A—H1AA	115.5	H12B—C12A—H12C	109.5
C9A—N2A—O2A	103.8 (3)	C2B—C1B—N1B	125.3 (3)
C1B—N1B—C9B	129.6 (3)	C2B—C1B—C6B	121.3 (3)
C1B—N1B—H1BA	115.2	N1B—C1B—C6B	113.4 (3)
C9B—N1B—H1BA	115.2	C1B—C2B—C3B	121.6 (3)
C9B—N2B—O2B	103.7 (3)	C1B—C2B—H2BA	119.2
C2A—C1A—N1A	124.9 (3)	C3B—C2B—H2BA	119.2
C2A—C1A—C6A	121.7 (3)	O1B—C3B—C2B	122.8 (3)
N1A—C1A—C6A	113.3 (3)	O1B—C3B—C4B	118.9 (3)
C1A—C2A—C3A	120.8 (3)	C2B—C3B—C4B	118.2 (3)
C1A—C2A—H2AA	119.6	C3B—C4B—C5B	113.3 (3)
C3A—C2A—H2AA	119.6	C3B—C4B—H4BA	108.9
O1A—C3A—C2A	121.4 (3)	C5B—C4B—H4BA	108.9
O1A—C3A—C4A	119.5 (3)	C3B—C4B—H4BB	108.9
C2A—C3A—C4A	119.1 (3)	C5B—C4B—H4BB	108.9
C3A—C4A—C5A	114.8 (3)	H4BA—C4B—H4BB	107.7
C3A—C4A—H4AA	108.6	C4B—C5B—C6B	107.8 (3)
C5A—C4A—H4AA	108.6	C4B—C5B—C7B	110.6 (3)
C3A—C4A—H4AB	108.6	C6B—C5B—C7B	110.6 (3)
C5A—C4A—H4AB	108.6	C4B—C5B—C8B	109.7 (3)
H4AA—C4A—H4AB	107.5	C6B—C5B—C8B	109.4 (3)
C6A—C5A—C8A	110.2 (3)	C7B—C5B—C8B	108.7 (3)
C6A—C5A—C7A	109.6 (3)	C1B—C6B—C5B	114.4 (3)
C8A—C5A—C7A	109.9 (3)	C1B—C6B—H6BA	108.6
C6A—C5A—C4A	107.6 (3)	C5B—C6B—H6BA	108.6
C8A—C5A—C4A	109.3 (3)	C1B—C6B—H6BB	108.6
C7A—C5A—C4A	110.2 (3)	C5B—C6B—H6BB	108.6
C1A—C6A—C5A	113.0 (3)	H6BA—C6B—H6BB	107.6
C1A—C6A—H6AA	109.0	C5B—C7B—H7BA	109.5
C5A—C6A—H6AA	109.0	C5B—C7B—H7BB	109.5
C1A—C6A—H6AB	109.0	H7BA—C7B—H7BB	109.5
C5A—C6A—H6AB	109.0	C5B—C7B—H7BC	109.5
H6AA—C6A—H6AB	107.8	H7BA—C7B—H7BC	109.5
C5A—C7A—H7AA	109.5	H7BB—C7B—H7BC	109.5
C5A—C7A—H7AB	109.5	C5B—C8B—H8BA	109.5
H7AA—C7A—H7AB	109.5	C5B—C8B—H8BB	109.5
C5A—C7A—H7AC	109.5	H8BA—C8B—H8BB	109.5
H7AA—C7A—H7AC	109.5	C5B—C8B—H8BC	109.5
H7AB—C7A—H7AC	109.5	H8BA—C8B—H8BC	109.5
C5A—C8A—H8AA	109.5	H8BB—C8B—H8BC	109.5
C5A—C8A—H8AB	109.5	N2B—C9B—N1B	122.9 (3)
H8AA—C8A—H8AB	109.5	N2B—C9B—C10B	112.7 (3)
C5A—C8A—H8AC	109.5	N1B—C9B—C10B	124.3 (3)
H8AA—C8A—H8AC	109.5	C11B—C10B—C9B	105.2 (3)
H8AB—C8A—H8AC	109.5	C11B—C10B—H10B	127.4
N2A—C9A—N1A	123.8 (3)	C9B—C10B—H10B	127.4
N2A—C9A—C10A	113.0 (3)	C10B—C11B—O2B	109.4 (3)
N1A—C9A—C10A	123.2 (3)	C10B—C11B—C12B	134.7 (3)
C11A—C10A—C9A	104.8 (3)	O2B—C11B—C12B	116.0 (3)
C11A—C10A—H10A	127.6	C11B—C12B—H12D	109.5
C9A—C10A—H10A	127.6	C11B—C12B—H12E	109.5
C10A—C11A—O2A	109.4 (3)	H12D—C12B—H12E	109.5
C10A—C11A—C12A	134.2 (3)	C11B—C12B—H12F	109.5
O2A—C11A—C12A	116.4 (3)	H12D—C12B—H12F	109.5
C11A—C12A—H12A	109.5	H12E—C12B—H12F	109.5
C11A—O2A—N2A—C9A	−0.3 (4)	N2A—O2A—C11A—C12A	178.8 (3)
C11B—O2B—N2B—C9B	−0.3 (4)	C9B—N1B—C1B—C2B	0.3 (6)
C9A—N1A—C1A—C2A	−4.1 (6)	C9B—N1B—C1B—C6B	−179.1 (3)
C9A—N1A—C1A—C6A	177.3 (3)	N1B—C1B—C2B—C3B	−178.5 (4)
N1A—C1A—C2A—C3A	−178.9 (3)	C6B—C1B—C2B—C3B	0.9 (6)
C6A—C1A—C2A—C3A	−0.4 (5)	C1B—C2B—C3B—O1B	−177.5 (4)
C1A—C2A—C3A—O1A	176.0 (4)	C1B—C2B—C3B—C4B	4.6 (6)
C1A—C2A—C3A—C4A	−3.1 (5)	O1B—C3B—C4B—C5B	148.6 (4)
O1A—C3A—C4A—C5A	157.6 (4)	C2B—C3B—C4B—C5B	−33.5 (5)
C2A—C3A—C4A—C5A	−23.3 (5)	C3B—C4B—C5B—C6B	53.5 (4)
C3A—C4A—C5A—C6A	49.3 (4)	C3B—C4B—C5B—C7B	−67.6 (4)
C3A—C4A—C5A—C8A	169.0 (3)	C3B—C4B—C5B—C8B	172.5 (3)
C3A—C4A—C5A—C7A	−70.1 (4)	C2B—C1B—C6B—C5B	22.5 (5)
C2A—C1A—C6A—C5A	29.8 (5)	N1B—C1B—C6B—C5B	−158.0 (3)
N1A—C1A—C6A—C5A	−151.5 (3)	C4B—C5B—C6B—C1B	−48.2 (4)
C8A—C5A—C6A—C1A	−171.0 (3)	C7B—C5B—C6B—C1B	72.8 (4)
C7A—C5A—C6A—C1A	67.9 (4)	C8B—C5B—C6B—C1B	−167.4 (3)
C4A—C5A—C6A—C1A	−51.9 (4)	O2B—N2B—C9B—N1B	−179.5 (3)
O2A—N2A—C9A—N1A	−178.3 (3)	O2B—N2B—C9B—C10B	−0.1 (4)
O2A—N2A—C9A—C10A	0.7 (4)	C1B—N1B—C9B—N2B	2.1 (6)
C1A—N1A—C9A—N2A	3.6 (6)	C1B—N1B—C9B—C10B	−177.3 (4)
C1A—N1A—C9A—C10A	−175.3 (3)	N2B—C9B—C10B—C11B	0.4 (5)
N2A—C9A—C10A—C11A	−0.9 (4)	N1B—C9B—C10B—C11B	179.9 (4)
N1A—C9A—C10A—C11A	178.1 (3)	C9B—C10B—C11B—O2B	−0.6 (5)
C9A—C10A—C11A—O2A	0.6 (4)	C9B—C10B—C11B—C12B	−179.8 (4)
C9A—C10A—C11A—C12A	−178.2 (4)	N2B—O2B—C11B—C10B	0.6 (4)
N2A—O2A—C11A—C10A	−0.2 (4)	N2B—O2B—C11B—C12B	−180.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O1B	0.86	2.01	2.811 (3)	154
N1B—H1BA···O1A^i	0.86	2.05	2.862 (3)	157
C2A—H2AA···N2A	0.93	2.26	2.900 (4)	125
C2B—H2BA···N2B	0.93	2.26	2.898 (5)	125
C10A—H10A···O1B	0.93	2.53	3.148 (4)	124

Symmetry code: (i) x−1, y−1, z.