(±)-(4bS,8aR,10aS)-10a-Ethynyl-4b,8,8-trimethyl-3,7-dioxo-3,4b,7,8,8a,9,10,10a-octa-hydro-phenanthrene-2,6-dicarbonitrile.

The anti-inflammatory and cytoprotective tricyclic title compound, C(21)H(18)N(2)O(2), also known as TBE-31, crystallizes with two nearly superimposable mol-ecules in the asymmetric unit. In both mol-ecules, the three ring systems conform to an envelope-chair-planar arrangement. The central ring, in a cyclohexane chair conformation, contains an axial ethynyl group that bends slightly off from a nearby axial methyl group because of the 1,3-diaxial repulsion between the two groups. In the crystal, weak C-H⋯N and C-H⋯O inter-actions form chains along [001].

Related literature

For anti-inflammatory, growth suppressive, and proapoptotic properties of TBE-31 and the structural assignment of racemic TBE-31 by NMR spectroscopy, see: Honda et al. (2007 ▶, 2011 ▶). For inducing NQO1 and GST in the liver, skin, and stomach in mice, see: Dinkova-Kostova et al. (2010 ▶). For TBE-31 activity against aflatoxin-induced liver cancer in rats, see: Liby et al. (2008 ▶). For reactivity of the non-enolizable cyano­enone in ring C of TBE-31 compared to that of MCE-1, see: Dinkova-Kostova et al. (2010 ▶). For the biological potency in bioassays for inhibition of inflammation and carcinogenesis and related biological potency, see: Zheng et al. (2012 ▶). For the synthesis of TBE-31, see: Honda et al. (2011 ▶). For literature on the number of chemical formula units per asymmetric unit, Z′, see: Steiner (2000 ▶); Steed (2003 ▶); Gavezzotti (2008 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶). For all-trans-perhydro­phenanthrene comparisons, see: Marcos et al. (2005 ▶). For a related structure, see: Bore et al. (2002 ▶).

Experimental

Crystal data

C21H18N2O2

M = 330.37

Triclinic,

a = 7.3012 (2) Å

b = 12.9843 (3) Å

c = 18.4254 (4) Å

α = 95.051 (2)°

β = 96.284 (2)°

γ = 92.338 (2)°

V = 1727.26 (7) Å3

Z = 4

Cu Kα radiation

μ = 0.66 mm−1

T = 299 K

0.71 × 0.46 × 0.29 mm

Data collection

Oxford Diffraction Xcalibur Atlas Gemini diffractometer

Absorption correction: Gaussian (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.745, T max = 0.897

33944 measured reflections

6478 independent reflections

5160 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.140

S = 1.03

6478 reflections

458 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.18 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2010 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: WinGX (Farrugia, 1999 ▶); software used to prepare material for publication: Mercury (Macrae et al., 2006 ▶), PLATON (Spek, 2009) ▶ and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536812041244/qk2041sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812041244/qk2041Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812041244/qk2041Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H18N2O2	Z = 4
Mr = 330.37	F(000) = 696
Triclinic, P1	Dx = 1.270 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 7.3012 (2) Å	Cell parameters from 16712 reflections
b = 12.9843 (3) Å	θ = 4.0–73.2°
c = 18.4254 (4) Å	µ = 0.66 mm−1
α = 95.051 (2)°	T = 299 K
β = 96.284 (2)°	Prism, colourless
γ = 92.338 (2)°	0.71 × 0.46 × 0.29 mm
V = 1727.26 (7) Å3

Oxford Diffraction Xcalibur Atlas Gemini diffractometer	6478 independent reflections
Radiation source: fine-focus sealed tube	5160 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 69.5°, θmin = 4.0°
Absorption correction: gaussian (CrysAlis RED; Oxford Diffraction, 2010)	h = −8→7
Tmin = 0.745, Tmax = 0.897	k = −15→15
33944 measured reflections	l = −22→22

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050	H-atom parameters constrained
wR(F2) = 0.140	w = 1/[σ2(Fo2) + (0.0731P)2 + 0.4667P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
6478 reflections	Δρmax = 0.22 e Å−3
458 parameters	Δρmin = −0.18 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0024 (4)

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.

	x	y	z	Uiso*/Ueq
O1A	0.7242 (2)	0.61192 (10)	0.49832 (8)	0.0625 (4)
O2A	0.6374 (2)	0.18345 (11)	0.77597 (7)	0.0649 (4)
N1A	0.6155 (3)	0.61182 (13)	0.31626 (10)	0.0667 (5)
N2A	0.8755 (3)	0.41471 (15)	0.84087 (9)	0.0693 (5)
C1A	0.6816 (3)	0.37153 (14)	0.38940 (10)	0.0486 (5)
H1A	0.6463	0.3461	0.3409	0.058*
C2A	0.6841 (3)	0.47338 (13)	0.40640 (9)	0.0441 (4)
C3A	0.7309 (3)	0.51902 (13)	0.48269 (10)	0.0423 (4)
C4A	0.7798 (3)	0.44778 (13)	0.53745 (9)	0.0414 (4)
H4A	0.8082	0.4750	0.5860	0.050*
C5A	0.7864 (2)	0.34548 (12)	0.52233 (9)	0.0370 (4)
C6A	0.8231 (2)	0.27223 (12)	0.58271 (9)	0.0387 (4)
C7A	0.8644 (3)	0.33248 (13)	0.65657 (9)	0.0419 (4)
H7A	0.9394	0.3928	0.6605	0.050*
C8A	0.7985 (3)	0.30344 (13)	0.71694 (9)	0.0407 (4)
C9A	0.6819 (3)	0.20774 (13)	0.71829 (9)	0.0429 (4)
C10A	0.6279 (3)	0.13976 (13)	0.64671 (9)	0.0413 (4)
C11A	0.6413 (2)	0.20507 (12)	0.58059 (9)	0.0373 (4)
H11A	0.5445	0.2549	0.5840	0.045*
C12A	0.5947 (3)	0.14469 (13)	0.50516 (9)	0.0458 (4)
H12A	0.6948	0.1006	0.4951	0.055*
H12B	0.4841	0.1007	0.5052	0.055*
C13A	0.5641 (3)	0.21787 (14)	0.44515 (9)	0.0472 (4)
H13A	0.4560	0.2567	0.4526	0.057*
H13B	0.5406	0.1775	0.3979	0.057*
C14A	0.7328 (3)	0.29491 (13)	0.44422 (9)	0.0430 (4)
C15A	0.6422 (3)	0.54746 (14)	0.35364 (10)	0.0505 (5)
C16A	0.8435 (3)	0.36536 (14)	0.78652 (10)	0.0493 (5)
C17A	0.8861 (3)	0.24025 (14)	0.41381 (10)	0.0516 (5)
C18A	1.0007 (4)	0.20171 (19)	0.38268 (13)	0.0751 (7)
H18A	1.0918	0.1711	0.3579	0.090*
C19A	0.9995 (3)	0.21202 (15)	0.57255 (11)	0.0500 (5)
H19A	1.0412	0.1835	0.6174	0.075*
H19B	1.0943	0.2583	0.5599	0.075*
H19C	0.9718	0.1570	0.5340	0.075*
C20A	0.4273 (3)	0.10060 (18)	0.64789 (12)	0.0628 (6)
H20A	0.3491	0.1583	0.6485	0.094*
H20B	0.4175	0.0650	0.6909	0.094*
H20C	0.3896	0.0540	0.6050	0.094*
C21A	0.7504 (3)	0.04632 (14)	0.64789 (11)	0.0549 (5)
H21A	0.7189	0.0041	0.6854	0.082*
H21B	0.8776	0.0702	0.6579	0.082*
H21C	0.7311	0.0063	0.6011	0.082*
O1B	0.2331 (2)	0.59090 (9)	−0.04320 (7)	0.0543 (4)
O2B	0.3443 (3)	0.18811 (12)	0.26554 (7)	0.0739 (5)
N1B	0.4173 (3)	0.59329 (14)	−0.20451 (10)	0.0731 (6)
N2B	0.0835 (4)	0.40614 (15)	0.29028 (11)	0.0835 (7)
C1B	0.3689 (3)	0.35541 (13)	−0.12918 (9)	0.0441 (4)
H1B	0.4221	0.3321	−0.1708	0.053*
C2B	0.3422 (3)	0.45595 (13)	−0.11789 (9)	0.0429 (4)
C3B	0.2610 (2)	0.49869 (13)	−0.05254 (9)	0.0406 (4)
C4B	0.2208 (2)	0.42658 (13)	0.00024 (9)	0.0407 (4)
H4B	0.1804	0.4531	0.0439	0.049*
C5B	0.2381 (2)	0.32459 (12)	−0.01003 (8)	0.0365 (4)
C6B	0.2005 (2)	0.25142 (13)	0.04851 (9)	0.0391 (4)
C7B	0.1386 (3)	0.31054 (14)	0.11468 (10)	0.0457 (4)
H7B	0.0566	0.3625	0.1072	0.055*
C8B	0.1951 (3)	0.29232 (13)	0.18311 (9)	0.0457 (4)
C9B	0.3180 (3)	0.20864 (14)	0.20232 (10)	0.0495 (5)
C10B	0.3991 (3)	0.14548 (14)	0.14088 (10)	0.0488 (5)
C11B	0.3891 (3)	0.20508 (12)	0.07121 (9)	0.0385 (4)
H11B	0.4752	0.2654	0.0846	0.046*
C12B	0.4612 (3)	0.14779 (13)	0.00498 (9)	0.0439 (4)
H12C	0.5753	0.1163	0.0207	0.053*
H12D	0.3720	0.0931	−0.0164	0.053*
C13B	0.4954 (3)	0.22156 (13)	−0.05243 (9)	0.0427 (4)
H13C	0.5381	0.1831	−0.0944	0.051*
H13D	0.5916	0.2730	−0.0321	0.051*
C14B	0.3177 (3)	0.27718 (12)	−0.07820 (9)	0.0394 (4)
C15B	0.3863 (3)	0.53055 (14)	−0.16767 (10)	0.0518 (5)
C16B	0.1314 (3)	0.35449 (15)	0.24348 (11)	0.0575 (5)
C17B	0.1887 (3)	0.20143 (14)	−0.12493 (10)	0.0484 (5)
C18B	0.1001 (4)	0.14161 (19)	−0.16700 (12)	0.0741 (7)
H18B	0.0296	0.0940	−0.2005	0.089*
C19B	0.0366 (3)	0.17316 (16)	0.01889 (11)	0.0563 (5)
H19D	−0.0096	0.1422	0.0591	0.085*
H19E	0.0782	0.1202	−0.0143	0.085*
H19F	−0.0599	0.2088	−0.0065	0.085*
C20B	0.6023 (4)	0.1310 (2)	0.16788 (13)	0.0761 (7)
H20D	0.6711	0.1960	0.1705	0.114*
H20E	0.6520	0.0816	0.1344	0.114*
H20F	0.6107	0.1062	0.2157	0.114*
C21B	0.2943 (4)	0.03946 (15)	0.13001 (12)	0.0746 (7)
H21D	0.3250	0.0023	0.1721	0.112*
H21E	0.3283	0.0009	0.0871	0.112*
H21F	0.1640	0.0489	0.1241	0.112*

	U11	U22	U33	U12	U13	U23
O1A	0.0943 (12)	0.0354 (7)	0.0570 (8)	0.0079 (7)	0.0032 (8)	0.0036 (6)
O2A	0.0980 (12)	0.0608 (9)	0.0384 (7)	−0.0080 (8)	0.0199 (7)	0.0098 (6)
N1A	0.0991 (15)	0.0513 (10)	0.0524 (10)	0.0162 (10)	0.0058 (10)	0.0175 (8)
N2A	0.0989 (16)	0.0633 (11)	0.0424 (9)	0.0044 (10)	0.0005 (9)	−0.0046 (8)
C1A	0.0721 (14)	0.0424 (10)	0.0319 (8)	0.0071 (9)	0.0039 (8)	0.0069 (7)
C2A	0.0551 (12)	0.0403 (9)	0.0391 (9)	0.0071 (8)	0.0071 (8)	0.0116 (7)
C3A	0.0467 (11)	0.0369 (9)	0.0446 (9)	0.0035 (7)	0.0086 (8)	0.0052 (7)
C4A	0.0505 (11)	0.0387 (9)	0.0348 (8)	0.0022 (8)	0.0056 (7)	0.0025 (7)
C5A	0.0411 (10)	0.0381 (8)	0.0327 (8)	0.0025 (7)	0.0054 (7)	0.0058 (7)
C6A	0.0462 (10)	0.0366 (8)	0.0338 (8)	0.0025 (7)	0.0040 (7)	0.0062 (7)
C7A	0.0477 (11)	0.0390 (9)	0.0379 (9)	−0.0004 (7)	−0.0008 (7)	0.0062 (7)
C8A	0.0487 (11)	0.0400 (9)	0.0331 (8)	0.0047 (7)	0.0016 (7)	0.0035 (7)
C9A	0.0516 (11)	0.0417 (9)	0.0374 (9)	0.0079 (8)	0.0072 (8)	0.0094 (7)
C10A	0.0498 (11)	0.0360 (8)	0.0387 (9)	−0.0003 (7)	0.0057 (7)	0.0073 (7)
C11A	0.0453 (10)	0.0319 (8)	0.0347 (8)	0.0039 (7)	0.0019 (7)	0.0052 (6)
C12A	0.0596 (12)	0.0370 (9)	0.0392 (9)	−0.0023 (8)	0.0005 (8)	0.0023 (7)
C13A	0.0631 (12)	0.0409 (9)	0.0352 (9)	0.0010 (8)	−0.0023 (8)	0.0013 (7)
C14A	0.0623 (12)	0.0346 (8)	0.0326 (8)	0.0073 (8)	0.0048 (8)	0.0043 (7)
C15A	0.0669 (13)	0.0424 (10)	0.0436 (10)	0.0095 (9)	0.0064 (9)	0.0086 (8)
C16A	0.0647 (13)	0.0444 (10)	0.0390 (10)	0.0049 (9)	0.0043 (9)	0.0070 (8)
C17A	0.0762 (15)	0.0426 (10)	0.0383 (9)	0.0085 (9)	0.0123 (9)	0.0061 (8)
C18A	0.102 (2)	0.0725 (15)	0.0586 (13)	0.0294 (14)	0.0306 (13)	0.0106 (11)
C19A	0.0501 (12)	0.0538 (11)	0.0492 (10)	0.0108 (9)	0.0073 (9)	0.0163 (9)
C20A	0.0626 (14)	0.0693 (14)	0.0571 (12)	−0.0130 (11)	0.0059 (10)	0.0174 (10)
C21A	0.0788 (15)	0.0401 (10)	0.0486 (11)	0.0117 (9)	0.0098 (10)	0.0128 (8)
O1B	0.0689 (9)	0.0358 (7)	0.0592 (8)	0.0092 (6)	0.0076 (7)	0.0065 (6)
O2B	0.1148 (14)	0.0751 (10)	0.0388 (8)	0.0313 (9)	0.0169 (8)	0.0212 (7)
N1B	0.1133 (17)	0.0531 (10)	0.0526 (10)	−0.0171 (10)	0.0080 (10)	0.0151 (8)
N2B	0.143 (2)	0.0590 (11)	0.0570 (11)	0.0193 (12)	0.0420 (12)	0.0056 (9)
C1B	0.0576 (12)	0.0432 (9)	0.0328 (8)	0.0024 (8)	0.0093 (8)	0.0053 (7)
C2B	0.0532 (11)	0.0392 (9)	0.0362 (9)	−0.0013 (8)	0.0029 (8)	0.0080 (7)
C3B	0.0422 (10)	0.0377 (9)	0.0406 (9)	0.0037 (7)	−0.0014 (7)	0.0037 (7)
C4B	0.0471 (11)	0.0405 (9)	0.0351 (8)	0.0075 (8)	0.0064 (7)	0.0028 (7)
C5B	0.0388 (9)	0.0399 (9)	0.0309 (8)	0.0031 (7)	0.0022 (7)	0.0056 (6)
C6B	0.0462 (10)	0.0375 (9)	0.0349 (8)	0.0040 (7)	0.0071 (7)	0.0062 (7)
C7B	0.0553 (12)	0.0436 (9)	0.0428 (10)	0.0114 (8)	0.0161 (8)	0.0127 (8)
C8B	0.0644 (13)	0.0384 (9)	0.0374 (9)	0.0053 (8)	0.0168 (8)	0.0066 (7)
C9B	0.0699 (13)	0.0432 (10)	0.0377 (9)	0.0058 (9)	0.0099 (9)	0.0105 (8)
C10B	0.0707 (13)	0.0396 (9)	0.0397 (9)	0.0147 (9)	0.0116 (9)	0.0120 (7)
C11B	0.0490 (11)	0.0337 (8)	0.0345 (8)	0.0056 (7)	0.0075 (7)	0.0068 (6)
C12B	0.0538 (11)	0.0386 (9)	0.0411 (9)	0.0116 (8)	0.0088 (8)	0.0056 (7)
C13B	0.0517 (11)	0.0411 (9)	0.0367 (9)	0.0064 (8)	0.0108 (8)	0.0028 (7)
C14B	0.0518 (11)	0.0340 (8)	0.0330 (8)	0.0033 (7)	0.0076 (7)	0.0032 (6)
C15B	0.0717 (14)	0.0416 (10)	0.0416 (10)	−0.0046 (9)	0.0055 (9)	0.0061 (8)
C16B	0.0911 (17)	0.0443 (10)	0.0419 (10)	0.0093 (10)	0.0219 (10)	0.0101 (8)
C17B	0.0637 (13)	0.0441 (10)	0.0374 (9)	0.0017 (9)	0.0035 (9)	0.0066 (8)
C18B	0.099 (2)	0.0655 (14)	0.0514 (12)	−0.0145 (13)	−0.0106 (12)	0.0025 (11)
C19B	0.0561 (13)	0.0623 (12)	0.0515 (11)	−0.0109 (10)	0.0088 (9)	0.0132 (9)
C20B	0.0853 (18)	0.0932 (18)	0.0565 (13)	0.0401 (14)	0.0086 (12)	0.0275 (12)
C21B	0.133 (2)	0.0385 (11)	0.0569 (13)	0.0057 (12)	0.0219 (14)	0.0154 (9)

O1A—C3A	1.219 (2)	O1B—C3B	1.223 (2)
O2A—C9A	1.208 (2)	O2B—C9B	1.214 (2)
N1A—C15A	1.138 (2)	N1B—C15B	1.136 (2)
N2A—C16A	1.137 (2)	N2B—C16B	1.139 (3)
C1A—C2A	1.331 (2)	C1B—C2B	1.329 (2)
C1A—C14A	1.508 (2)	C1B—C14B	1.506 (2)
C1A—H1A	0.9300	C1B—H1B	0.9300
C2A—C15A	1.445 (2)	C2B—C15B	1.442 (2)
C2A—C3A	1.475 (2)	C2B—C3B	1.475 (2)
C3A—C4A	1.454 (2)	C3B—C4B	1.452 (2)
C4A—C5A	1.337 (2)	C4B—C5B	1.334 (2)
C4A—H4A	0.9300	C4B—H4B	0.9300
C5A—C14A	1.531 (2)	C5B—C14B	1.532 (2)
C5A—C6A	1.535 (2)	C5B—C6B	1.538 (2)
C6A—C7A	1.503 (2)	C6B—C7B	1.505 (2)
C6A—C11A	1.553 (2)	C6B—C11B	1.555 (2)
C6A—C19A	1.553 (3)	C6B—C19B	1.556 (3)
C7A—C8A	1.337 (2)	C7B—C8B	1.327 (3)
C7A—H7A	0.9300	C7B—H7B	0.9300
C8A—C16A	1.450 (2)	C8B—C16B	1.446 (3)
C8A—C9A	1.481 (3)	C8B—C9B	1.480 (3)
C9A—C10A	1.525 (2)	C9B—C10B	1.526 (3)
C10A—C20A	1.534 (3)	C10B—C21B	1.534 (3)
C10A—C21A	1.536 (3)	C10B—C20B	1.537 (3)
C10A—C11A	1.554 (2)	C10B—C11B	1.553 (2)
C11A—C12A	1.531 (2)	C11B—C12B	1.527 (2)
C11A—H11A	0.9800	C11B—H11B	0.9800
C12A—C13A	1.524 (2)	C12B—C13B	1.522 (2)
C12A—H12A	0.9700	C12B—H12C	0.9700
C12A—H12B	0.9700	C12B—H12D	0.9700
C13A—C14A	1.557 (3)	C13B—C14B	1.559 (3)
C13A—H13A	0.9700	C13B—H13C	0.9700
C13A—H13B	0.9700	C13B—H13D	0.9700
C14A—C17A	1.484 (3)	C14B—C17B	1.481 (3)
C17A—C18A	1.170 (3)	C17B—C18B	1.169 (3)
C18A—H18A	0.9300	C18B—H18B	0.9300
C19A—H19A	0.9600	C19B—H19D	0.9600
C19A—H19B	0.9600	C19B—H19E	0.9600
C19A—H19C	0.9600	C19B—H19F	0.9600
C20A—H20A	0.9600	C20B—H20D	0.9600
C20A—H20B	0.9600	C20B—H20E	0.9600
C20A—H20C	0.9600	C20B—H20F	0.9600
C21A—H21A	0.9600	C21B—H21D	0.9600
C21A—H21B	0.9600	C21B—H21E	0.9600
C21A—H21C	0.9600	C21B—H21F	0.9600
C2A—C1A—C14A	123.82 (16)	C2B—C1B—C14B	123.56 (16)
C2A—C1A—H1A	118.1	C2B—C1B—H1B	118.2
C14A—C1A—H1A	118.1	C14B—C1B—H1B	118.2
C1A—C2A—C15A	124.07 (17)	C1B—C2B—C15B	123.65 (17)
C1A—C2A—C3A	121.19 (16)	C1B—C2B—C3B	121.25 (16)
C15A—C2A—C3A	114.74 (15)	C15B—C2B—C3B	115.09 (15)
O1A—C3A—C4A	122.47 (16)	O1B—C3B—C4B	122.28 (16)
O1A—C3A—C2A	120.75 (16)	O1B—C3B—C2B	120.98 (16)
C4A—C3A—C2A	116.76 (15)	C4B—C3B—C2B	116.73 (14)
C5A—C4A—C3A	124.00 (16)	C5B—C4B—C3B	124.08 (15)
C5A—C4A—H4A	118.0	C5B—C4B—H4B	118.0
C3A—C4A—H4A	118.0	C3B—C4B—H4B	118.0
C4A—C5A—C14A	120.71 (15)	C4B—C5B—C14B	120.39 (15)
C4A—C5A—C6A	122.14 (15)	C4B—C5B—C6B	122.36 (14)
C14A—C5A—C6A	116.69 (13)	C14B—C5B—C6B	116.92 (13)
C7A—C6A—C5A	110.68 (13)	C7B—C6B—C5B	110.75 (13)
C7A—C6A—C11A	109.43 (14)	C7B—C6B—C11B	108.83 (14)
C5A—C6A—C11A	105.41 (13)	C5B—C6B—C11B	105.36 (13)
C7A—C6A—C19A	104.61 (14)	C7B—C6B—C19B	105.03 (15)
C5A—C6A—C19A	110.83 (14)	C5B—C6B—C19B	110.11 (14)
C11A—C6A—C19A	115.95 (14)	C11B—C6B—C19B	116.80 (15)
C8A—C7A—C6A	123.10 (16)	C8B—C7B—C6B	123.41 (16)
C8A—C7A—H7A	118.5	C8B—C7B—H7B	118.3
C6A—C7A—H7A	118.5	C6B—C7B—H7B	118.3
C7A—C8A—C16A	120.27 (17)	C7B—C8B—C16B	119.65 (18)
C7A—C8A—C9A	123.61 (16)	C7B—C8B—C9B	123.64 (16)
C16A—C8A—C9A	116.11 (15)	C16B—C8B—C9B	116.69 (16)
O2A—C9A—C8A	119.60 (16)	O2B—C9B—C8B	119.72 (17)
O2A—C9A—C10A	121.65 (16)	O2B—C9B—C10B	121.47 (17)
C8A—C9A—C10A	118.69 (14)	C8B—C9B—C10B	118.69 (15)
C9A—C10A—C20A	106.60 (15)	C9B—C10B—C21B	106.79 (17)
C9A—C10A—C21A	107.22 (15)	C9B—C10B—C20B	107.19 (17)
C20A—C10A—C21A	108.35 (16)	C21B—C10B—C20B	109.00 (19)
C9A—C10A—C11A	109.79 (13)	C9B—C10B—C11B	110.05 (14)
C20A—C10A—C11A	109.59 (15)	C21B—C10B—C11B	114.39 (16)
C21A—C10A—C11A	114.95 (15)	C20B—C10B—C11B	109.17 (17)
C12A—C11A—C6A	110.22 (14)	C12B—C11B—C10B	114.85 (13)
C12A—C11A—C10A	114.83 (13)	C12B—C11B—C6B	110.69 (14)
C6A—C11A—C10A	115.50 (14)	C10B—C11B—C6B	115.74 (14)
C12A—C11A—H11A	105.0	C12B—C11B—H11B	104.7
C6A—C11A—H11A	105.0	C10B—C11B—H11B	104.7
C10A—C11A—H11A	105.0	C6B—C11B—H11B	104.7
C13A—C12A—C11A	111.05 (14)	C13B—C12B—C11B	110.78 (13)
C13A—C12A—H12A	109.4	C13B—C12B—H12C	109.5
C11A—C12A—H12A	109.4	C11B—C12B—H12C	109.5
C13A—C12A—H12B	109.4	C13B—C12B—H12D	109.5
C11A—C12A—H12B	109.4	C11B—C12B—H12D	109.5
H12A—C12A—H12B	108.0	H12C—C12B—H12D	108.1
C12A—C13A—C14A	112.38 (15)	C12B—C13B—C14B	111.87 (15)
C12A—C13A—H13A	109.1	C12B—C13B—H13C	109.2
C14A—C13A—H13A	109.1	C14B—C13B—H13C	109.2
C12A—C13A—H13B	109.1	C12B—C13B—H13D	109.2
C14A—C13A—H13B	109.1	C14B—C13B—H13D	109.2
H13A—C13A—H13B	107.9	H13C—C13B—H13D	107.9
C17A—C14A—C1A	103.64 (15)	C17B—C14B—C1B	104.38 (14)
C17A—C14A—C5A	112.85 (16)	C17B—C14B—C5B	113.64 (15)
C1A—C14A—C5A	113.42 (14)	C1B—C14B—C5B	113.76 (13)
C17A—C14A—C13A	110.09 (15)	C17B—C14B—C13B	108.64 (14)
C1A—C14A—C13A	108.47 (16)	C1B—C14B—C13B	108.01 (15)
C5A—C14A—C13A	108.25 (14)	C5B—C14B—C13B	108.18 (13)
N1A—C15A—C2A	174.5 (2)	N1B—C15B—C2B	176.3 (2)
N2A—C16A—C8A	178.7 (2)	N2B—C16B—C8B	177.9 (2)
C18A—C17A—C14A	172.5 (2)	C18B—C17B—C14B	173.0 (2)
C17A—C18A—H18A	180.0	C17B—C18B—H18B	180.0
C6A—C19A—H19A	109.5	C6B—C19B—H19D	109.5
C6A—C19A—H19B	109.5	C6B—C19B—H19E	109.5
H19A—C19A—H19B	109.5	H19D—C19B—H19E	109.5
C6A—C19A—H19C	109.5	C6B—C19B—H19F	109.5
H19A—C19A—H19C	109.5	H19D—C19B—H19F	109.5
H19B—C19A—H19C	109.5	H19E—C19B—H19F	109.5
C10A—C20A—H20A	109.5	C10B—C20B—H20D	109.5
C10A—C20A—H20B	109.5	C10B—C20B—H20E	109.5
H20A—C20A—H20B	109.5	H20D—C20B—H20E	109.5
C10A—C20A—H20C	109.5	C10B—C20B—H20F	109.5
H20A—C20A—H20C	109.5	H20D—C20B—H20F	109.5
H20B—C20A—H20C	109.5	H20E—C20B—H20F	109.5
C10A—C21A—H21A	109.5	C10B—C21B—H21D	109.5
C10A—C21A—H21B	109.5	C10B—C21B—H21E	109.5
H21A—C21A—H21B	109.5	H21D—C21B—H21E	109.5
C10A—C21A—H21C	109.5	C10B—C21B—H21F	109.5
H21A—C21A—H21C	109.5	H21D—C21B—H21F	109.5
H21B—C21A—H21C	109.5	H21E—C21B—H21F	109.5
C14A—C1A—C2A—C15A	177.48 (19)	C14B—C1B—C2B—C15B	−178.20 (18)
C14A—C1A—C2A—C3A	−2.6 (3)	C14B—C1B—C2B—C3B	0.9 (3)
C1A—C2A—C3A—O1A	−176.5 (2)	C1B—C2B—C3B—O1B	−178.44 (18)
C15A—C2A—C3A—O1A	3.4 (3)	C15B—C2B—C3B—O1B	0.7 (3)
C1A—C2A—C3A—C4A	2.0 (3)	C1B—C2B—C3B—C4B	3.0 (3)
C15A—C2A—C3A—C4A	−178.11 (17)	C15B—C2B—C3B—C4B	−177.85 (16)
O1A—C3A—C4A—C5A	179.23 (19)	O1B—C3B—C4B—C5B	175.56 (18)
C2A—C3A—C4A—C5A	0.8 (3)	C2B—C3B—C4B—C5B	−5.9 (3)
C3A—C4A—C5A—C14A	−2.8 (3)	C3B—C4B—C5B—C14B	4.6 (3)
C3A—C4A—C5A—C6A	−174.82 (16)	C3B—C4B—C5B—C6B	177.81 (16)
C4A—C5A—C6A—C7A	−4.8 (2)	C4B—C5B—C6B—C7B	1.7 (2)
C14A—C5A—C6A—C7A	−177.07 (15)	C14B—C5B—C6B—C7B	175.09 (15)
C4A—C5A—C6A—C11A	113.46 (18)	C4B—C5B—C6B—C11B	−115.85 (18)
C14A—C5A—C6A—C11A	−58.85 (19)	C14B—C5B—C6B—C11B	57.58 (18)
C4A—C5A—C6A—C19A	−120.35 (19)	C4B—C5B—C6B—C19B	117.39 (19)
C14A—C5A—C6A—C19A	67.3 (2)	C14B—C5B—C6B—C19B	−69.2 (2)
C5A—C6A—C7A—C8A	138.96 (18)	C5B—C6B—C7B—C8B	−139.05 (19)
C11A—C6A—C7A—C8A	23.2 (2)	C11B—C6B—C7B—C8B	−23.7 (2)
C19A—C6A—C7A—C8A	−101.6 (2)	C19B—C6B—C7B—C8B	102.1 (2)
C6A—C7A—C8A—C16A	−179.86 (16)	C6B—C7B—C8B—C16B	178.71 (18)
C6A—C7A—C8A—C9A	1.6 (3)	C6B—C7B—C8B—C9B	−3.1 (3)
C7A—C8A—C9A—O2A	175.28 (18)	C7B—C8B—C9B—O2B	−170.4 (2)
C16A—C8A—C9A—O2A	−3.3 (3)	C16B—C8B—C9B—O2B	7.8 (3)
C7A—C8A—C9A—C10A	−2.1 (3)	C7B—C8B—C9B—C10B	5.7 (3)
C16A—C8A—C9A—C10A	179.36 (16)	C16B—C8B—C9B—C10B	−176.02 (18)
O2A—C9A—C10A—C20A	41.6 (2)	O2B—C9B—C10B—C21B	70.5 (3)
C8A—C9A—C10A—C20A	−141.06 (17)	C8B—C9B—C10B—C21B	−105.6 (2)
O2A—C9A—C10A—C21A	−74.2 (2)	O2B—C9B—C10B—C20B	−46.2 (3)
C8A—C9A—C10A—C21A	103.07 (18)	C8B—C9B—C10B—C20B	137.69 (19)
O2A—C9A—C10A—C11A	160.26 (18)	O2B—C9B—C10B—C11B	−164.8 (2)
C8A—C9A—C10A—C11A	−22.4 (2)	C8B—C9B—C10B—C11B	19.1 (3)
C7A—C6A—C11A—C12A	178.85 (13)	C9B—C10B—C11B—C12B	−178.19 (17)
C5A—C6A—C11A—C12A	59.80 (17)	C21B—C10B—C11B—C12B	−58.0 (2)
C19A—C6A—C11A—C12A	−63.18 (18)	C20B—C10B—C11B—C12B	64.4 (2)
C7A—C6A—C11A—C10A	−48.96 (18)	C9B—C10B—C11B—C6B	−47.2 (2)
C5A—C6A—C11A—C10A	−168.01 (13)	C21B—C10B—C11B—C6B	73.0 (2)
C19A—C6A—C11A—C10A	69.01 (19)	C20B—C10B—C11B—C6B	−164.62 (16)
C9A—C10A—C11A—C12A	178.62 (15)	C7B—C6B—C11B—C12B	−177.78 (14)
C20A—C10A—C11A—C12A	−64.6 (2)	C5B—C6B—C11B—C12B	−58.97 (17)
C21A—C10A—C11A—C12A	57.7 (2)	C19B—C6B—C11B—C12B	63.59 (19)
C9A—C10A—C11A—C6A	48.63 (19)	C7B—C6B—C11B—C10B	49.32 (19)
C20A—C10A—C11A—C6A	165.39 (15)	C5B—C6B—C11B—C10B	168.12 (14)
C21A—C10A—C11A—C6A	−72.33 (19)	C19B—C6B—C11B—C10B	−69.31 (19)
C6A—C11A—C12A—C13A	−61.7 (2)	C10B—C11B—C12B—C13B	−164.38 (16)
C10A—C11A—C12A—C13A	165.77 (16)	C6B—C11B—C12B—C13B	62.27 (19)
C11A—C12A—C13A—C14A	56.2 (2)	C11B—C12B—C13B—C14B	−57.5 (2)
C2A—C1A—C14A—C17A	−122.1 (2)	C2B—C1B—C14B—C17B	122.2 (2)
C2A—C1A—C14A—C5A	0.6 (3)	C2B—C1B—C14B—C5B	−2.2 (3)
C2A—C1A—C14A—C13A	120.9 (2)	C2B—C1B—C14B—C13B	−122.32 (19)
C4A—C5A—C14A—C17A	119.57 (18)	C4B—C5B—C14B—C17B	−119.76 (18)
C6A—C5A—C14A—C17A	−68.0 (2)	C6B—C5B—C14B—C17B	66.67 (19)
C4A—C5A—C14A—C1A	2.1 (3)	C4B—C5B—C14B—C1B	−0.5 (2)
C6A—C5A—C14A—C1A	174.52 (16)	C6B—C5B—C14B—C1B	−174.06 (15)
C4A—C5A—C14A—C13A	−118.33 (18)	C4B—C5B—C14B—C13B	119.51 (17)
C6A—C5A—C14A—C13A	54.1 (2)	C6B—C5B—C14B—C13B	−54.06 (19)
C12A—C13A—C14A—C17A	73.72 (18)	C12B—C13B—C14B—C17B	−72.61 (17)
C12A—C13A—C14A—C1A	−173.52 (15)	C12B—C13B—C14B—C1B	174.72 (14)
C12A—C13A—C14A—C5A	−50.06 (19)	C12B—C13B—C14B—C5B	51.18 (18)

D—H···A	D—H	H···A	D···A	D—H···A
C4A—H4A···N2Bi	0.93	2.66	3.572 (3)	166
C4B—H4B···N2Ai	0.93	2.69	3.580 (2)	161
C7B—H7B···O1Bii	0.93	2.43	3.246 (2)	146
C13B—H13D···O1Biii	0.97	2.38	3.324 (2)	163
C13B—H13C···O2Aiv	0.97	2.57	3.435 (2)	148
C13A—H13A···O1Ai	0.97	2.37	3.295 (2)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4A—H4A⋯N2B i	0.93	2.66	3.572 (3)	166
C4B—H4B⋯N2A i	0.93	2.69	3.580 (2)	161
C7B—H7B⋯O1B ii	0.93	2.43	3.246 (2)	146
C13B—H13D⋯O1B iii	0.97	2.38	3.324 (2)	163
C13B—H13C⋯O2A iv	0.97	2.57	3.435 (2)	148
C13A—H13A⋯O1A i	0.97	2.37	3.295 (2)	159

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .