4-Ethynyl-4-hydroxycyclohexan-1-one and 4-ethynyl-4-hydroxy-2,3,5,6-tetramethylcyclohexa-2,5-dien-1-one

The title compounds, C₈H₁₀O₂, (I), and C₁₂H₁₄O₂, (II), occurred as by-products in the controlled synthesis of a series of bis­(gem-alkynols), prepared as part of an extensive study of synthon formation in simple gem-alkynol derivatives. The two 4-(gem-alkynol)-1-ones crystallize in space group P2₁/c, (I) with Z′ = 1 and (II) with Z′ = 2. Both structures are dominated by O—H...O=C hydrogen bonds, which form simple chains in the cyclo­hexane derivative, (I), and centrosymmetric dimers, of both symmetry-independent mol­ecules, in the cyclo­hexa-2,5-diene, (II). These strong synthons are further stabilized by C[triple bond]C—H...O=C, C_methylene—H...O(H) and C_methyl—H...O(H) interactions. The direct intermolecular interactions between donors and acceptors in the gem-alkynol group, which characterize the bis­(gem-alkynol) analogues of (I) and (II), are not present in the ketone derivatives studied here.

Computing details

For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

(I) 4-ethynyl-4-hydroxycyclohexan-1-one

Crystal data

C8H10O2	F(000) = 296
Mr = 138.16	Dx = 1.280 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.550 (1) Å	Cell parameters from 508 reflections
b = 16.931 (3) Å	θ = 6.7–21.2°
c = 6.493 (1) Å	µ = 0.09 mm^−1
β = 95.42 (3)°	T = 150 K
V = 716.9 (2) Å^3	Plate, colourless
Z = 4	0.40 × 0.10 × 0.05 mm

Data collection

Bruker SMART CCD diffractometer	1074 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.060
Graphite monochromator	θmax = 27.5°, θmin = 2.4°
Detector resolution: not relevant pixels mm^-1	h = −8→8
ω scans	k = −21→16
5018 measured reflections	l = −8→8
1657 independent reflections

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)] = 0.055	Hydrogen site location: difference Fourier map
wR(F^2) = 0.122	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0376P)^2 + 0.2197P] where P = (Fo^2 + 2Fc^2)/3
1657 reflections	(Δ/σ)max = 0.001
131 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.24 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
O1	0.4972 (2)	0.38506 (9)	−0.5079 (2)	0.0274 (4)
O2	0.2961 (2)	0.45098 (9)	0.1289 (2)	0.0216 (4)
HA	0.360 (5)	0.4335 (18)	0.237 (5)	0.059 (10)*
C1	0.0925 (3)	0.41199 (14)	−0.1794 (3)	0.0215 (5)
H1A	−0.013 (3)	0.4514 (13)	−0.157 (3)	0.026 (6)*
H1B	0.021 (3)	0.3653 (13)	−0.246 (3)	0.024 (6)*
C2	0.2469 (3)	0.44804 (14)	−0.3163 (3)	0.0228 (5)
H2A	0.184 (4)	0.4621 (15)	−0.460 (4)	0.045 (7)*
H2B	0.304 (4)	0.4972 (15)	−0.251 (4)	0.033 (7)*
C3	0.4263 (3)	0.39445 (12)	−0.3407 (3)	0.0191 (5)
C4	0.5206 (3)	0.35429 (14)	−0.1475 (3)	0.0208 (5)
H4A	0.617 (4)	0.3136 (14)	−0.187 (3)	0.029 (6)*
H4B	0.598 (3)	0.3968 (13)	−0.075 (3)	0.025 (6)*
C5	0.3612 (3)	0.32087 (13)	−0.0117 (3)	0.0199 (5)
H5A	0.433 (4)	0.3040 (14)	0.127 (4)	0.033 (6)*
H5B	0.289 (3)	0.2733 (13)	−0.077 (3)	0.020 (6)*
C6	0.1996 (3)	0.38333 (12)	0.0280 (3)	0.0183 (5)
C7	0.0450 (3)	0.35136 (13)	0.1602 (3)	0.0228 (5)
C8	−0.0786 (4)	0.33061 (15)	0.2714 (4)	0.0307 (6)
H8	−0.178 (4)	0.3135 (17)	0.364 (4)	0.056 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0269 (8)	0.0399 (10)	0.0158 (8)	0.0013 (7)	0.0050 (6)	−0.0005 (7)
O2	0.0262 (8)	0.0234 (8)	0.0149 (8)	−0.0020 (6)	0.0006 (6)	−0.0030 (6)
C1	0.0207 (11)	0.0266 (12)	0.0169 (10)	0.0034 (9)	0.0005 (9)	−0.0008 (9)
C2	0.0265 (12)	0.0276 (13)	0.0143 (10)	0.0037 (10)	0.0025 (9)	0.0033 (9)
C3	0.0211 (10)	0.0204 (11)	0.0161 (11)	−0.0041 (8)	0.0040 (8)	−0.0023 (8)
C4	0.0210 (11)	0.0254 (12)	0.0160 (10)	0.0041 (9)	0.0010 (9)	0.0008 (9)
C5	0.0250 (11)	0.0191 (11)	0.0153 (10)	0.0009 (9)	0.0009 (9)	0.0014 (9)
C6	0.0202 (10)	0.0200 (11)	0.0147 (10)	−0.0013 (8)	0.0025 (8)	−0.0008 (8)
C7	0.0239 (11)	0.0275 (12)	0.0167 (10)	0.0003 (9)	0.0004 (9)	−0.0004 (9)
C8	0.0285 (13)	0.0405 (14)	0.0234 (11)	−0.0053 (11)	0.0039 (10)	0.0012 (11)

Geometric parameters (Å, º)

O1—C3	1.231 (2)	C3—C4	1.507 (3)
O2—C6	1.436 (2)	C4—C5	1.537 (3)
O2—HA	0.84 (3)	C4—H4A	0.99 (2)
C1—C2	1.535 (3)	C4—H4B	0.98 (2)
C1—C6	1.537 (3)	C5—C6	1.535 (3)
C1—H1A	0.98 (2)	C5—H5A	1.02 (2)
C1—H1B	1.00 (2)	C5—H5B	1.01 (2)
C2—C3	1.505 (3)	C6—C7	1.490 (3)
C2—H2A	1.01 (3)	C7—C8	1.188 (3)
C2—H2B	0.99 (2)	C8—H8	0.97 (3)
C6—O2—HA	105 (2)	C5—C4—H4A	112.4 (13)
C2—C1—C6	111.21 (17)	C3—C4—H4B	102.9 (13)
C2—C1—H1A	109.0 (13)	C5—C4—H4B	110.2 (12)
C6—C1—H1A	110.9 (13)	H4A—C4—H4B	109.0 (19)
C2—C1—H1B	111.8 (12)	C6—C5—C4	111.07 (17)
C6—C1—H1B	106.7 (13)	C6—C5—H5A	108.2 (13)
H1A—C1—H1B	107.2 (19)	C4—C5—H5A	109.2 (13)
C3—C2—C1	112.66 (18)	C6—C5—H5B	108.6 (12)
C3—C2—H2A	107.5 (15)	C4—C5—H5B	111.7 (11)
C1—C2—H2A	113.0 (14)	H5A—C5—H5B	108.0 (17)
C3—C2—H2B	106.6 (14)	O2—C6—C7	108.69 (16)
C1—C2—H2B	109.2 (13)	O2—C6—C5	110.21 (17)
H2A—C2—H2B	107 (2)	C7—C6—C5	111.31 (17)
O1—C3—C2	122.32 (19)	O2—C6—C1	107.02 (17)
O1—C3—C4	121.10 (19)	C7—C6—C1	109.92 (17)
C2—C3—C4	116.55 (17)	C5—C6—C1	109.59 (17)
C3—C4—C5	113.34 (18)	C8—C7—C6	175.7 (2)
C3—C4—H4A	108.6 (13)	C7—C8—H8	179.2 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—HA···O1^i	0.84 (3)	1.99 (3)	2.820 (2)	175 (3)
C1—H1A···O2^ii	0.98 (2)	2.51 (2)	3.482 (3)	175.4 (18)
C8—H8···O1^iii	0.97 (3)	2.65 (3)	3.373 (3)	132 (2)

Symmetry codes: (i) x, y, z+1; (ii) −x, −y+1, −z; (iii) x−1, y, z+1.

(II) 4-ethynyl-4-hydroxy-2,3,4,5-tetramethylcyclohexa-2,5-diene-1-one

Crystal data

C12H14O2	F(000) = 816
Mr = 190.23	Dx = 1.206 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.020 (2) Å	Cell parameters from 999 reflections
b = 14.010 (3) Å	θ = 5.1–24.0°
c = 16.612 (3) Å	µ = 0.08 mm^−1
β = 93.56 (3)°	T = 150 K
V = 2095.2 (7) Å^3	Block, colourless
Z = 8	0.35 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer	4796 independent reflections
Radiation source: fine-focus sealed tube	3037 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: not relevant pixels mm^-1	θmax = 27.5°, θmin = 1.9°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −18→17
Tmin = 0.802, Tmax = 1.000	l = −21→21
14728 measured reflections

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)] = 0.052	Hydrogen site location: difference Fourier map
wR(F^2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0752P)^2 + 0.3548P] where P = (Fo^2 + 2Fc^2)/3
4796 reflections	(Δ/σ)max < 0.001
329 parameters	Δρmax = 0.29 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
C1	0.4469 (3)	0.18776 (17)	0.29582 (14)	0.0412 (6)
H1	0.447 (3)	0.214 (2)	0.3473 (19)	0.077 (9)*
C2	0.4521 (2)	0.15847 (14)	0.22992 (12)	0.0315 (5)
C3	0.4614 (2)	0.12292 (12)	0.14593 (11)	0.0245 (4)
O1	0.45510 (16)	0.20655 (9)	0.09553 (9)	0.0315 (3)
H1A	0.470 (3)	0.190 (2)	0.0491 (18)	0.062 (9)*
C4	0.3264 (2)	0.06088 (14)	0.12465 (11)	0.0275 (4)
C5	0.1791 (3)	0.10929 (19)	0.13290 (16)	0.0393 (5)
H5A	0.115 (3)	0.096 (2)	0.0844 (18)	0.067 (9)*
H5B	0.126 (3)	0.085 (2)	0.180 (2)	0.083 (10)*
H5C	0.190 (3)	0.179 (2)	0.1393 (17)	0.066 (8)*
C6	0.3409 (2)	−0.02932 (14)	0.09933 (11)	0.0277 (4)
C7	0.2113 (3)	−0.09396 (18)	0.07707 (16)	0.0472 (6)
H7A	0.2235	−0.1531	0.1059	0.094 (11)*
H7B	0.2069	−0.1062	0.0201	0.103 (12)*
H7C	0.1209	−0.0637	0.0910	0.114 (13)*
C8	0.4884 (2)	−0.07056 (13)	0.09038 (11)	0.0264 (4)
O2	0.50047 (17)	−0.15168 (9)	0.06234 (8)	0.0347 (4)
C9	0.6232 (2)	−0.01494 (13)	0.11358 (11)	0.0267 (4)
C10	0.7680 (3)	−0.06559 (19)	0.10501 (17)	0.0414 (6)
H10A	0.780 (4)	−0.083 (2)	0.050 (2)	0.087 (10)*
H10B	0.845 (4)	−0.034 (2)	0.1294 (19)	0.080 (10)*
H10C	0.765 (4)	−0.130 (3)	0.128 (2)	0.097 (12)*
C11	0.6119 (2)	0.07511 (13)	0.13995 (11)	0.0267 (4)
C12	0.7428 (2)	0.13775 (16)	0.16262 (15)	0.0417 (6)
H12A	0.7087	0.1972	0.1835	0.101 (12)*
H12B	0.7973	0.1497	0.1158	0.143 (17)*
H12C	0.8061	0.1065	0.2031	0.136 (16)*
C21	−0.0034 (2)	0.27725 (15)	0.27480 (13)	0.0341 (5)
H21	−0.007 (3)	0.2317 (17)	0.3176 (15)	0.049 (7)*
C22	−0.0059 (2)	0.33843 (13)	0.22580 (11)	0.0262 (4)
C23	−0.0118 (2)	0.41234 (12)	0.16210 (11)	0.0233 (4)
O21	0.00239 (16)	0.50329 (9)	0.20260 (8)	0.0297 (3)
H21A	0.013 (3)	0.544 (2)	0.1624 (17)	0.063 (8)*
C24	−0.1634 (2)	0.40601 (13)	0.11764 (11)	0.0249 (4)
C25	−0.2928 (3)	0.42295 (18)	0.16894 (15)	0.0359 (5)
H25A	−0.347 (3)	0.478 (2)	0.1522 (19)	0.077 (9)*
H25B	−0.364 (4)	0.367 (2)	0.160 (2)	0.091 (11)*
H25C	−0.263 (3)	0.428 (2)	0.222 (2)	0.072 (9)*
C26	−0.1790 (2)	0.38688 (12)	0.03851 (11)	0.0254 (4)
C27	−0.3273 (2)	0.37967 (17)	−0.00778 (14)	0.0387 (5)
H27A	−0.3825	0.4374	−0.0009	0.134 (16)*
H27B	−0.3816	0.3266	0.0120	0.17 (2)*
H27C	−0.3126	0.3705	−0.0640	0.157 (18)*
C28	−0.0462 (2)	0.37392 (12)	−0.00783 (11)	0.0250 (4)
O22	−0.06202 (17)	0.36239 (9)	−0.08191 (8)	0.0338 (4)
C29	0.1033 (2)	0.37620 (12)	0.03273 (11)	0.0252 (4)
C30	0.2294 (3)	0.35622 (17)	−0.02003 (14)	0.0350 (5)
H30A	0.229 (3)	0.291 (2)	−0.0441 (19)	0.087 (10)*
H30B	0.322 (4)	0.359 (2)	0.008 (2)	0.076 (10)*
H30C	0.225 (3)	0.395 (2)	−0.0673 (18)	0.065 (8)*
C31	0.1215 (2)	0.39679 (12)	0.11152 (11)	0.0236 (4)
C32	0.2695 (2)	0.40597 (16)	0.15749 (13)	0.0338 (5)
H32A	0.3022	0.4711	0.1560	0.122 (14)*
H32B	0.3405	0.3657	0.1334	0.138 (16)*
H32C	0.2602	0.3870	0.2125	0.150 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0584 (15)	0.0385 (13)	0.0272 (11)	−0.0011 (11)	0.0055 (11)	−0.0050 (9)
C2	0.0390 (12)	0.0254 (10)	0.0301 (11)	0.0007 (9)	0.0033 (9)	0.0004 (8)
C3	0.0316 (10)	0.0197 (9)	0.0224 (9)	0.0021 (8)	0.0024 (8)	0.0010 (7)
O1	0.0456 (9)	0.0230 (7)	0.0262 (8)	0.0056 (6)	0.0050 (7)	0.0029 (6)
C4	0.0291 (10)	0.0324 (10)	0.0213 (9)	0.0004 (8)	0.0038 (8)	0.0014 (8)
C5	0.0288 (12)	0.0474 (15)	0.0424 (14)	0.0064 (10)	0.0074 (10)	−0.0049 (11)
C6	0.0310 (10)	0.0301 (10)	0.0223 (9)	−0.0051 (8)	0.0038 (8)	0.0013 (8)
C7	0.0486 (14)	0.0454 (14)	0.0484 (15)	−0.0196 (12)	0.0100 (12)	−0.0075 (12)
C8	0.0415 (11)	0.0212 (9)	0.0166 (8)	0.0003 (8)	0.0035 (8)	0.0045 (7)
O2	0.0567 (9)	0.0217 (7)	0.0263 (7)	0.0019 (6)	0.0064 (7)	−0.0008 (6)
C9	0.0314 (10)	0.0282 (10)	0.0203 (9)	0.0060 (8)	0.0003 (8)	0.0034 (7)
C10	0.0382 (13)	0.0413 (14)	0.0439 (14)	0.0159 (11)	−0.0052 (11)	−0.0045 (11)
C11	0.0303 (10)	0.0265 (10)	0.0229 (9)	0.0017 (8)	−0.0011 (8)	0.0021 (7)
C12	0.0330 (12)	0.0379 (13)	0.0533 (15)	−0.0053 (10)	−0.0034 (11)	−0.0078 (11)
C21	0.0465 (13)	0.0291 (11)	0.0265 (10)	−0.0066 (9)	0.0007 (9)	0.0036 (9)
C22	0.0301 (10)	0.0273 (10)	0.0212 (9)	−0.0018 (8)	0.0015 (8)	−0.0027 (8)
C23	0.0295 (10)	0.0203 (9)	0.0202 (9)	−0.0010 (7)	0.0029 (8)	−0.0017 (7)
O21	0.0433 (8)	0.0217 (7)	0.0247 (7)	−0.0025 (6)	0.0061 (6)	−0.0038 (6)
C24	0.0267 (10)	0.0213 (9)	0.0270 (10)	0.0018 (7)	0.0045 (8)	0.0022 (7)
C25	0.0324 (12)	0.0406 (13)	0.0357 (12)	0.0024 (10)	0.0096 (10)	0.0012 (10)
C26	0.0289 (10)	0.0194 (9)	0.0277 (10)	−0.0020 (7)	−0.0013 (8)	0.0007 (7)
C27	0.0346 (12)	0.0428 (13)	0.0376 (13)	−0.0048 (10)	−0.0056 (10)	0.0015 (10)
C28	0.0397 (11)	0.0128 (8)	0.0227 (9)	−0.0003 (7)	0.0037 (8)	−0.0005 (7)
O22	0.0515 (9)	0.0278 (7)	0.0222 (7)	−0.0012 (6)	0.0020 (6)	−0.0036 (6)
C29	0.0331 (10)	0.0166 (9)	0.0265 (10)	0.0034 (7)	0.0072 (8)	0.0014 (7)
C30	0.0386 (13)	0.0350 (12)	0.0328 (12)	0.0093 (10)	0.0140 (10)	0.0011 (10)
C31	0.0282 (10)	0.0171 (9)	0.0255 (9)	0.0007 (7)	0.0027 (8)	0.0033 (7)
C32	0.0280 (11)	0.0363 (12)	0.0369 (12)	0.0008 (9)	0.0001 (9)	0.0014 (9)

Geometric parameters (Å, º)

C1—C2	1.173 (3)	C21—C22	1.181 (3)
C1—H1	0.93 (3)	C21—H21	0.96 (3)
C2—C3	1.489 (3)	C22—C23	1.479 (3)
C3—O1	1.439 (2)	C23—O21	1.443 (2)
C3—C4	1.520 (3)	C23—C24	1.516 (3)
C3—C11	1.523 (3)	C23—C31	1.524 (3)
O1—H1A	0.82 (3)	O21—H21A	0.89 (3)
C4—C6	1.341 (3)	C24—C26	1.340 (3)
C4—C5	1.505 (3)	C24—C25	1.507 (3)
C5—H5A	0.98 (3)	C25—H25A	0.95 (3)
C5—H5B	1.00 (3)	C25—H25B	1.02 (4)
C5—H5C	0.99 (3)	C25—H25C	0.91 (3)
C6—C8	1.467 (3)	C26—C28	1.475 (3)
C6—C7	1.507 (3)	C26—C27	1.504 (3)
C7—H7A	0.9600	C27—H27A	0.9600
C7—H7B	0.9600	C27—H27B	0.9600
C7—H7C	0.9600	C27—H27C	0.9600
C8—O2	1.236 (2)	C28—O22	1.241 (2)
C8—C9	1.475 (3)	C28—C29	1.470 (3)
C9—C11	1.341 (3)	C29—C31	1.340 (3)
C9—C10	1.501 (3)	C29—C30	1.504 (3)
C10—H10A	0.96 (4)	C30—H30A	1.00 (3)
C10—H10B	0.90 (3)	C30—H30B	0.93 (3)
C10—H10C	0.98 (4)	C30—H30C	0.96 (3)
C11—C12	1.500 (3)	C31—C32	1.502 (3)
C12—H12A	0.9600	C32—H32A	0.9600
C12—H12B	0.9600	C32—H32B	0.9600
C12—H12C	0.9600	C32—H32C	0.9600
C2—C1—H1	176.5 (19)	C22—C21—H21	174.5 (15)
C1—C2—C3	178.7 (2)	C21—C22—C23	177.7 (2)
O1—C3—C2	105.69 (14)	O21—C23—C22	106.64 (14)
O1—C3—C4	109.15 (15)	O21—C23—C24	109.26 (15)
C2—C3—C4	108.55 (16)	C22—C23—C24	107.37 (15)
O1—C3—C11	108.86 (15)	O21—C23—C31	109.47 (14)
C2—C3—C11	108.10 (16)	C22—C23—C31	107.46 (15)
C4—C3—C11	115.99 (15)	C24—C23—C31	116.20 (15)
C3—O1—H1A	108 (2)	C23—O21—H21A	103.4 (18)
C6—C4—C5	123.88 (19)	C26—C24—C25	123.24 (19)
C6—C4—C3	121.27 (17)	C26—C24—C23	121.76 (17)
C5—C4—C3	114.84 (18)	C25—C24—C23	115.01 (17)
C4—C5—H5A	108.7 (16)	C24—C25—H25A	111.3 (18)
C4—C5—H5B	112.3 (18)	C24—C25—H25B	107.4 (19)
H5A—C5—H5B	107 (2)	H25A—C25—H25B	106 (3)
C4—C5—H5C	111.8 (16)	C24—C25—H25C	111.8 (19)
H5A—C5—H5C	109 (2)	H25A—C25—H25C	110 (3)
H5B—C5—H5C	108 (2)	H25B—C25—H25C	110 (3)
C4—C6—C8	120.69 (18)	C24—C26—C28	119.80 (17)
C4—C6—C7	123.61 (19)	C24—C26—C27	123.42 (18)
C8—C6—C7	115.69 (18)	C28—C26—C27	116.76 (17)
C6—C7—H7A	109.5	C26—C27—H27A	109.5
C6—C7—H7B	109.5	C26—C27—H27B	109.5
H7A—C7—H7B	109.5	H27A—C27—H27B	109.5
C6—C7—H7C	109.5	C26—C27—H27C	109.5
H7A—C7—H7C	109.5	H27A—C27—H27C	109.5
H7B—C7—H7C	109.5	H27B—C27—H27C	109.5
O2—C8—C6	120.14 (18)	O22—C28—C29	120.22 (17)
O2—C8—C9	119.62 (18)	O22—C28—C26	119.12 (18)
C6—C8—C9	120.24 (16)	C29—C28—C26	120.66 (16)
C11—C9—C8	120.28 (17)	C31—C29—C28	120.34 (17)
C11—C9—C10	124.0 (2)	C31—C29—C30	123.93 (19)
C8—C9—C10	115.68 (18)	C28—C29—C30	115.72 (17)
C9—C10—H10A	111 (2)	C29—C30—H30A	114.7 (18)
C9—C10—H10B	112 (2)	C29—C30—H30B	113 (2)
H10A—C10—H10B	115 (3)	H30A—C30—H30B	103 (2)
C9—C10—H10C	111 (2)	C29—C30—H30C	112.3 (17)
H10A—C10—H10C	98 (3)	H30A—C30—H30C	101 (2)
H10B—C10—H10C	108 (3)	H30B—C30—H30C	112 (2)
C9—C11—C12	123.91 (18)	C29—C31—C32	124.46 (18)
C9—C11—C3	121.40 (17)	C29—C31—C23	121.09 (17)
C12—C11—C3	114.65 (17)	C32—C31—C23	114.45 (16)
C11—C12—H12A	109.5	C31—C32—H32A	109.5
C11—C12—H12B	109.5	C31—C32—H32B	109.5
H12A—C12—H12B	109.5	H32A—C32—H32B	109.5
C11—C12—H12C	109.5	C31—C32—H32C	109.5
H12A—C12—H12C	109.5	H32A—C32—H32C	109.5
H12B—C12—H12C	109.5	H32B—C32—H32C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2^i	0.82 (3)	1.96 (3)	2.786 (2)	179 (3)
O21—H21A···O22^ii	0.89 (3)	1.94 (3)	2.826 (2)	172 (2)
C1—H1···O2^iii	0.93 (3)	2.44 (3)	3.271 (3)	149 (2)
C21—H21···O22^iv	0.96 (3)	2.21 (3)	3.151 (3)	168 (2)
C12—H12C···O21^v	0.96	2.68	3.634 (3)	171
C32—H32B···O1	0.96	2.55	3.447 (3)	155

Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+1/2, z+1/2; (v) −x+1, y−1/2, −z+1/2.