[(2R,5R,6S,9R)-6-Isopropyl-9-methyl-1,4-dioxaspiro-[4.5]decan-2-yl]methyl 4-bromo-benzoate.

The title compound, C(20)H(27)BrO(4), a 4-bromo-benzoyl derivative of a stereoisomer of glycerol menthonide, synthesized as part of a study of 3-carbon stereochemical moieties, crystallizes with two crystallographically independent mol-ecules in the asymmetric unit, the two mol-ecules differing only in one of the C-O-C-C torsion angles around the ester O atom [-106.5 (7) and 146.1 (6)°]. The two mol-ecules are crystallographically related by a pseudotranslation along the (011) diagonal of the unit cell, emulating a primitive monoclinic cell of half the volume. The translational symmetry is broken by the 4-bromo-benzoate groups. The crystallographic assignment of the absolute stereochemistry is consistent with having started with (-)-menthone, the acetal C atom is R and the secondary alcohol is R. This brings the bromo-benzoate into approximately the same plane as the menthyl ring and cis to the isopropyl group. The glycerol menthonide sections of the molecules interact with each other via C-H⋯O interactions, leading to the formation of chains either A or B molecules that stretch parallel to [010], forming column-shaped double chains. Interactions between neighboring columns are limited to van der Waals contacts.

Related literature

For the original synthesis of glycerol menthonides, see: Greenberg (1999 ▶). For general background to glycerol menthonides, see: Kiessling et al. (2009b ▶). For a related structure, see: Kiessling et al. (2009a ▶).

Experimental

Crystal data

C20H27BrO4

M = 411.33

Monoclinic,

a = 42.976 (7) Å

b = 5.5763 (9) Å

c = 16.072 (3) Å

β = 92.618 (2)°

V = 3847.5 (11) Å3

Z = 8

Mo Kα radiation

μ = 2.16 mm−1

T = 100 K

0.50 × 0.05 × 0.03 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.588, T max = 0.746

17537 measured reflections

9230 independent reflections

6765 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.148

S = 1.02

9230 reflections

457 parameters

1 restraint

H-atom parameters constrained

Δρmax = 4.00 e Å−3

Δρmin = −0.75 e Å−3

Absolute structure: Flack (1983 ▶), 3965 Friedel pairs

Flack parameter: 0.000 (13)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL and Mercury.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811006428/tk2718sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006428/tk2718Isup2.hkl

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

C20H27BrO4	F(000) = 1712
Mr = 411.33	Dx = 1.420 Mg m−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 3693 reflections
a = 42.976 (7) Å	θ = 2.5–27.6°
b = 5.5763 (9) Å	µ = 2.16 mm−1
c = 16.072 (3) Å	T = 100 K
β = 92.618 (2)°	Needle, colourless
V = 3847.5 (11) Å3	0.50 × 0.05 × 0.03 mm
Z = 8

Bruker SMART APEX CCD diffractometer	9230 independent reflections
Radiation source: fine-focus sealed tube	6765 reflections with I > 2σ(I)
graphite	Rint = 0.043
ω scans	θmax = 28.3°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −57→56
Tmin = 0.588, Tmax = 0.746	k = −7→7
17537 measured reflections	l = −21→21

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)] = 0.058	H-atom parameters constrained
wR(F2) = 0.148	w = 1/[σ2(Fo2) + (0.0759P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
9230 reflections	Δρmax = 4.00 e Å−3
457 parameters	Δρmin = −0.75 e Å−3
1 restraint	Absolute structure: Flack (1983), 3965 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.000 (13)

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
Br1A	0.677987 (16)	0.69491 (10)	0.98525 (5)	0.02577 (19)
Br1B	0.822411 (16)	0.57423 (10)	0.51465 (5)	0.02449 (18)
C1A	0.79543 (14)	0.4707 (12)	0.7970 (4)	0.0172 (14)
C2A	0.76758 (14)	0.5328 (11)	0.8445 (4)	0.0141 (12)
C3A	0.74302 (14)	0.3702 (11)	0.8413 (4)	0.0165 (13)
H3A	0.7448	0.2269	0.8099	0.020*
C4A	0.71634 (15)	0.4125 (12)	0.8826 (4)	0.0167 (13)
H4A	0.6998	0.2990	0.8814	0.020*
C5A	0.71416 (17)	0.6295 (9)	0.9266 (5)	0.0119 (18)
C6A	0.73825 (16)	0.7922 (11)	0.9304 (4)	0.0195 (14)
H6A	0.7365	0.9360	0.9615	0.023*
C7A	0.76521 (14)	0.7446 (12)	0.8881 (4)	0.0188 (14)
H7A	0.7818	0.8571	0.8894	0.023*
C8A	0.84603 (15)	0.6051 (12)	0.7615 (5)	0.0151 (15)
H8A1	0.8517	0.7596	0.7359	0.018*
H8A2	0.8419	0.4871	0.7163	0.018*
C9A	0.87254 (10)	0.5184 (8)	0.8185 (3)	0.0130 (9)
H9A	0.8746	0.6223	0.8691	0.016*
C10A	0.86975 (11)	0.2539 (9)	0.8437 (3)	0.0169 (10)
H10A	0.8786	0.2267	0.9009	0.020*
H10B	0.8478	0.2005	0.8404	0.020*
C11A	0.91262 (10)	0.2894 (9)	0.7673 (3)	0.0139 (9)
C12A	0.93969 (12)	0.2590 (10)	0.8319 (3)	0.0172 (11)
H12A	0.9557	0.3822	0.8221	0.021*
H12B	0.9320	0.2852	0.8883	0.021*
C13A	0.95462 (12)	0.0102 (10)	0.8282 (3)	0.0201 (11)
H13A	0.9388	−0.1127	0.8423	0.024*
C14A	0.96479 (11)	−0.0364 (10)	0.7392 (3)	0.0201 (11)
H14A	0.9817	0.0764	0.7263	0.024*
H14B	0.9731	−0.2014	0.7357	0.024*
C15A	0.93810 (12)	−0.0064 (10)	0.6753 (3)	0.0172 (11)
H15A	0.9220	−0.1289	0.6850	0.021*
H15B	0.9458	−0.0324	0.6189	0.021*
C16A	0.92351 (11)	0.2444 (9)	0.6798 (3)	0.0127 (10)
H16A	0.9408	0.3608	0.6715	0.015*
C17A	0.89885 (11)	0.2924 (9)	0.6090 (3)	0.0151 (9)
H17A	0.8856	0.4287	0.6270	0.018*
C18A	0.87701 (16)	0.0784 (15)	0.5892 (5)	0.0263 (15)
H18A	0.8662	0.0337	0.6394	0.039*
H18B	0.8893	−0.0582	0.5707	0.039*
H18C	0.8616	0.1237	0.5450	0.039*
C19A	0.91434 (13)	0.3708 (10)	0.5304 (3)	0.0234 (11)
H19A	0.8983	0.4080	0.4869	0.035*
H19B	0.9276	0.2411	0.5112	0.035*
H19C	0.9271	0.5137	0.5422	0.035*
C20A	0.98250 (12)	−0.0095 (12)	0.8913 (3)	0.0289 (13)
H20A	0.9986	0.1052	0.8766	0.043*
H20B	0.9910	−0.1725	0.8902	0.043*
H20C	0.9757	0.0265	0.9473	0.043*
C1B	0.70385 (15)	0.7839 (11)	0.6994 (4)	0.0161 (13)
C2B	0.73214 (14)	0.7265 (13)	0.6536 (4)	0.0182 (13)
C3B	0.75673 (15)	0.8902 (13)	0.6586 (4)	0.0199 (14)
H3B	0.7550	1.0339	0.6898	0.024*
C4B	0.78383 (15)	0.8412 (12)	0.6174 (4)	0.0174 (14)
H4B	0.8008	0.9506	0.6204	0.021*
C5B	0.78569 (19)	0.6330 (10)	0.5726 (5)	0.0149 (19)
C6B	0.76197 (14)	0.4659 (12)	0.5682 (4)	0.0163 (13)
H6B	0.7641	0.3207	0.5381	0.020*
C7B	0.73489 (14)	0.5156 (11)	0.6091 (4)	0.0142 (13)
H7B	0.7182	0.4042	0.6064	0.017*
C8B	0.65383 (17)	0.6320 (10)	0.7341 (5)	0.0187 (18)
H8B1	0.6496	0.8006	0.7493	0.022*
H8B2	0.6560	0.5358	0.7858	0.022*
C9B	0.62768 (10)	0.5353 (8)	0.6779 (3)	0.0136 (9)
H9B	0.6255	0.6337	0.6259	0.016*
C10B	0.63120 (11)	0.2705 (9)	0.6557 (3)	0.0163 (10)
H10C	0.6230	0.2379	0.5982	0.020*
H10D	0.6533	0.2198	0.6611	0.020*
C11B	0.58757 (10)	0.3063 (9)	0.7291 (3)	0.0137 (9)
C12B	0.56128 (12)	0.2708 (10)	0.6640 (3)	0.0168 (10)
H12C	0.5693	0.2956	0.6079	0.020*
H12D	0.5449	0.3919	0.6724	0.020*
C13B	0.54689 (11)	0.0148 (10)	0.6691 (3)	0.0157 (11)
H13B	0.5631	−0.1054	0.6551	0.019*
C14B	0.53697 (11)	−0.0327 (9)	0.7582 (3)	0.0175 (10)
H14C	0.5192	0.0726	0.7701	0.021*
H14D	0.5299	−0.2010	0.7625	0.021*
C15B	0.56317 (12)	0.0115 (10)	0.8228 (3)	0.0153 (11)
H15C	0.5800	−0.1063	0.8149	0.018*
H15D	0.5553	−0.0133	0.8791	0.018*
C16B	0.57645 (11)	0.2651 (9)	0.8171 (3)	0.0124 (10)
H16B	0.5584	0.3760	0.8231	0.015*
C17B	0.60009 (12)	0.3292 (9)	0.8881 (3)	0.0180 (10)
H17B	0.6117	0.4749	0.8707	0.022*
C18B	0.6239 (2)	0.1343 (11)	0.9093 (5)	0.028 (2)
H18D	0.6132	−0.0096	0.9282	0.042*
H18E	0.6385	0.1913	0.9537	0.042*
H18F	0.6354	0.0959	0.8598	0.042*
C19B	0.58304 (13)	0.3940 (11)	0.9663 (3)	0.0257 (12)
H19D	0.5983	0.4311	1.0117	0.039*
H19E	0.5701	0.2583	0.9824	0.039*
H19F	0.5698	0.5342	0.9550	0.039*
C20B	0.51938 (12)	−0.0086 (11)	0.6060 (3)	0.0262 (12)
H20D	0.5032	0.1069	0.6195	0.039*
H20E	0.5109	−0.1716	0.6082	0.039*
H20F	0.5264	0.0237	0.5500	0.039*
O1A	0.79755 (11)	0.2908 (9)	0.7548 (3)	0.0252 (11)
O2A	0.81834 (12)	0.6356 (6)	0.8087 (3)	0.0151 (13)
O3A	0.90037 (7)	0.5265 (6)	0.7737 (2)	0.0152 (7)
O4A	0.88748 (12)	0.1333 (6)	0.7838 (3)	0.0165 (13)
O1B	0.70079 (11)	0.9560 (8)	0.7431 (3)	0.0222 (10)
O2B	0.68186 (12)	0.6166 (8)	0.6883 (4)	0.0186 (13)
O3B	0.59946 (7)	0.5436 (6)	0.7213 (2)	0.0158 (7)
O4B	0.61311 (12)	0.1522 (7)	0.7151 (3)	0.0132 (12)

	U11	U22	U33	U12	U13	U23
Br1A	0.0183 (4)	0.0367 (4)	0.0226 (4)	0.0055 (4)	0.0042 (3)	−0.0042 (4)
Br1B	0.0170 (4)	0.0360 (4)	0.0207 (4)	0.0008 (4)	0.0030 (3)	−0.0012 (4)
C1A	0.013 (3)	0.023 (3)	0.015 (3)	0.002 (2)	0.000 (2)	0.004 (3)
C2A	0.022 (3)	0.009 (3)	0.012 (3)	0.003 (2)	−0.001 (2)	−0.002 (3)
C3A	0.021 (3)	0.008 (3)	0.020 (3)	−0.001 (2)	−0.001 (3)	−0.001 (2)
C4A	0.020 (3)	0.013 (3)	0.017 (3)	−0.005 (2)	−0.002 (3)	−0.002 (3)
C5A	0.009 (4)	0.017 (4)	0.009 (4)	0.0005 (19)	0.000 (3)	0.005 (2)
C6A	0.034 (4)	0.004 (3)	0.020 (3)	0.001 (3)	−0.002 (3)	0.000 (2)
C7A	0.015 (3)	0.015 (4)	0.026 (4)	−0.001 (3)	0.001 (3)	0.006 (3)
C8A	0.015 (3)	0.017 (3)	0.014 (3)	−0.001 (2)	0.005 (3)	0.002 (2)
C9A	0.015 (2)	0.014 (2)	0.010 (2)	−0.0014 (17)	0.0048 (17)	0.0005 (18)
C10A	0.017 (2)	0.017 (3)	0.016 (2)	0.0037 (18)	0.0025 (18)	0.0067 (19)
C11A	0.011 (2)	0.016 (2)	0.015 (2)	0.0002 (18)	−0.0002 (17)	0.0033 (19)
C12A	0.011 (2)	0.024 (3)	0.016 (2)	−0.002 (2)	−0.002 (2)	−0.002 (2)
C13A	0.015 (2)	0.031 (3)	0.014 (2)	−0.006 (2)	−0.008 (2)	0.007 (2)
C14A	0.014 (2)	0.029 (3)	0.018 (2)	0.009 (2)	0.0013 (19)	0.004 (2)
C15A	0.019 (3)	0.021 (3)	0.012 (2)	0.001 (2)	0.001 (2)	0.004 (2)
C16A	0.012 (2)	0.015 (3)	0.011 (2)	−0.002 (2)	0.0002 (19)	0.0048 (18)
C17A	0.018 (2)	0.015 (2)	0.012 (2)	−0.0008 (19)	−0.0034 (18)	0.0032 (19)
C18A	0.029 (4)	0.027 (3)	0.021 (3)	−0.010 (3)	−0.014 (3)	0.010 (3)
C19A	0.034 (3)	0.023 (3)	0.013 (2)	−0.003 (2)	0.002 (2)	0.006 (2)
C20A	0.021 (3)	0.052 (4)	0.013 (2)	0.005 (3)	−0.001 (2)	0.006 (2)
C1B	0.025 (3)	0.008 (3)	0.014 (3)	−0.005 (2)	−0.003 (3)	0.000 (2)
C2B	0.018 (3)	0.018 (4)	0.018 (3)	−0.001 (3)	−0.002 (3)	0.005 (3)
C3B	0.029 (4)	0.021 (3)	0.009 (3)	0.000 (3)	−0.002 (3)	0.004 (3)
C4B	0.018 (3)	0.020 (3)	0.014 (3)	0.001 (2)	−0.001 (3)	0.009 (3)
C5B	0.019 (4)	0.015 (4)	0.012 (4)	0.005 (2)	0.005 (4)	0.003 (2)
C6B	0.013 (3)	0.024 (3)	0.011 (3)	0.000 (2)	−0.003 (2)	−0.003 (3)
C7B	0.026 (3)	0.007 (3)	0.009 (3)	−0.004 (2)	−0.006 (2)	0.000 (2)
C8B	0.018 (4)	0.020 (4)	0.018 (4)	−0.001 (2)	0.003 (3)	−0.002 (2)
C9B	0.015 (2)	0.014 (3)	0.012 (2)	−0.0012 (17)	0.0026 (17)	−0.0013 (18)
C10B	0.017 (2)	0.017 (2)	0.015 (2)	−0.0012 (19)	0.0045 (18)	−0.0056 (19)
C11B	0.010 (2)	0.012 (2)	0.019 (2)	0.0002 (17)	0.0004 (17)	−0.0055 (19)
C12B	0.015 (2)	0.021 (3)	0.015 (2)	−0.002 (2)	−0.003 (2)	−0.001 (2)
C13B	0.011 (2)	0.020 (3)	0.017 (2)	0.001 (2)	−0.002 (2)	−0.002 (2)
C14B	0.016 (2)	0.018 (3)	0.018 (2)	−0.0035 (18)	0.0007 (19)	−0.003 (2)
C15B	0.015 (2)	0.017 (3)	0.014 (2)	0.000 (2)	0.005 (2)	−0.0024 (19)
C16B	0.011 (2)	0.015 (2)	0.011 (2)	0.003 (2)	0.0034 (18)	−0.0021 (18)
C17B	0.025 (3)	0.017 (2)	0.012 (2)	0.001 (2)	−0.0023 (19)	−0.0071 (19)
C18B	0.034 (4)	0.029 (4)	0.020 (4)	0.004 (2)	−0.007 (3)	−0.006 (2)
C19B	0.032 (3)	0.032 (3)	0.013 (2)	−0.001 (2)	0.001 (2)	−0.009 (2)
C20B	0.020 (3)	0.039 (3)	0.019 (3)	−0.005 (2)	−0.001 (2)	−0.009 (2)
O1A	0.026 (2)	0.022 (2)	0.028 (3)	−0.006 (2)	0.008 (2)	−0.011 (2)
O2A	0.017 (3)	0.012 (3)	0.016 (3)	0.0001 (14)	0.003 (2)	−0.0024 (14)
O3A	0.0153 (16)	0.0121 (18)	0.0187 (17)	0.0002 (12)	0.0058 (13)	0.0006 (14)
O4A	0.017 (3)	0.011 (3)	0.022 (3)	−0.0002 (14)	0.006 (2)	0.0029 (15)
O1B	0.025 (2)	0.020 (2)	0.022 (2)	−0.0031 (18)	0.0022 (19)	−0.008 (2)
O2B	0.013 (3)	0.018 (3)	0.025 (3)	−0.0051 (15)	0.004 (2)	−0.0064 (17)
O3B	0.0175 (16)	0.0105 (18)	0.0198 (17)	0.0008 (13)	0.0047 (13)	0.0000 (14)
O4B	0.016 (3)	0.008 (2)	0.016 (3)	0.0006 (14)	0.002 (2)	−0.0016 (15)

Br1A—C5A	1.889 (7)	C20A—H20C	0.9800
Br1B—C5B	1.897 (8)	C1B—O1B	1.199 (8)
C1A—O1A	1.217 (8)	C1B—O2B	1.334 (7)
C1A—O2A	1.354 (8)	C1B—C2B	1.485 (9)
C1A—C2A	1.489 (8)	C2B—C7B	1.385 (10)
C2A—C7A	1.380 (10)	C2B—C3B	1.396 (9)
C2A—C3A	1.391 (9)	C3B—C4B	1.393 (9)
C3A—C4A	1.371 (9)	C3B—H3B	0.9500
C3A—H3A	0.9500	C4B—C5B	1.370 (9)
C4A—C5A	1.408 (9)	C4B—H4B	0.9500
C4A—H4A	0.9500	C5B—C6B	1.381 (9)
C5A—C6A	1.376 (9)	C6B—C7B	1.390 (8)
C6A—C7A	1.395 (9)	C6B—H6B	0.9500
C6A—H6A	0.9500	C7B—H7B	0.9500
C7A—H7A	0.9500	C8B—O2B	1.443 (9)
C8A—O2A	1.450 (8)	C8B—C9B	1.509 (8)
C8A—C9A	1.508 (8)	C8B—H8B1	0.9900
C8A—H8A1	0.9900	C8B—H8B2	0.9900
C8A—H8A2	0.9900	C9B—O3B	1.427 (5)
C9A—O3A	1.424 (5)	C9B—C10B	1.528 (6)
C9A—C10A	1.536 (6)	C9B—H9B	1.0000
C9A—H9A	1.0000	C10B—O4B	1.421 (6)
C10A—O4A	1.423 (7)	C10B—H10C	0.9900
C10A—H10A	0.9900	C10B—H10D	0.9900
C10A—H10B	0.9900	C11B—O4B	1.420 (6)
C11A—O4A	1.422 (6)	C11B—O3B	1.426 (6)
C11A—O3A	1.429 (6)	C11B—C12B	1.517 (7)
C11A—C16A	1.524 (6)	C11B—C16B	1.530 (6)
C11A—C12A	1.533 (7)	C12B—C13B	1.559 (8)
C12A—C13A	1.531 (8)	C12B—H12C	0.9900
C12A—H12A	0.9900	C12B—H12D	0.9900
C12A—H12B	0.9900	C13B—C20B	1.527 (7)
C13A—C20A	1.537 (7)	C13B—C14B	1.536 (7)
C13A—C14A	1.538 (7)	C13B—H13B	1.0000
C13A—H13A	1.0000	C14B—C15B	1.517 (7)
C14A—C15A	1.513 (7)	C14B—H14C	0.9900
C14A—H14A	0.9900	C14B—H14D	0.9900
C14A—H14B	0.9900	C15B—C16B	1.529 (8)
C15A—C16A	1.535 (7)	C15B—H15C	0.9900
C15A—H15A	0.9900	C15B—H15D	0.9900
C15A—H15B	0.9900	C16B—C17B	1.535 (7)
C16A—C17A	1.542 (7)	C16B—H16B	1.0000
C16A—H16A	1.0000	C17B—C18B	1.522 (9)
C17A—C19A	1.520 (6)	C17B—C19B	1.527 (7)
C17A—C18A	1.543 (9)	C17B—H17B	1.0000
C17A—H17A	1.0000	C18B—H18D	0.9800
C18A—H18A	0.9800	C18B—H18E	0.9800
C18A—H18B	0.9800	C18B—H18F	0.9800
C18A—H18C	0.9800	C19B—H19D	0.9800
C19A—H19A	0.9800	C19B—H19E	0.9800
C19A—H19B	0.9800	C19B—H19F	0.9800
C19A—H19C	0.9800	C20B—H20D	0.9800
C20A—H20A	0.9800	C20B—H20E	0.9800
C20A—H20B	0.9800	C20B—H20F	0.9800
O1A—C1A—O2A	124.4 (6)	C7B—C2B—C3B	120.2 (6)
O1A—C1A—C2A	124.0 (6)	C7B—C2B—C1B	122.1 (6)
O2A—C1A—C2A	111.6 (6)	C3B—C2B—C1B	117.7 (6)
C7A—C2A—C3A	120.2 (6)	C4B—C3B—C2B	119.5 (7)
C7A—C2A—C1A	122.6 (6)	C4B—C3B—H3B	120.3
C3A—C2A—C1A	117.1 (6)	C2B—C3B—H3B	120.3
C4A—C3A—C2A	121.3 (6)	C5B—C4B—C3B	119.1 (7)
C4A—C3A—H3A	119.3	C5B—C4B—H4B	120.5
C2A—C3A—H3A	119.3	C3B—C4B—H4B	120.5
C3A—C4A—C5A	117.9 (6)	C4B—C5B—C6B	122.6 (7)
C3A—C4A—H4A	121.0	C4B—C5B—Br1B	118.3 (6)
C5A—C4A—H4A	121.0	C6B—C5B—Br1B	119.1 (5)
C6A—C5A—C4A	121.4 (7)	C5B—C6B—C7B	118.2 (6)
C6A—C5A—Br1A	119.1 (5)	C5B—C6B—H6B	120.9
C4A—C5A—Br1A	119.5 (5)	C7B—C6B—H6B	120.9
C5A—C6A—C7A	119.6 (6)	C2B—C7B—C6B	120.5 (6)
C5A—C6A—H6A	120.2	C2B—C7B—H7B	119.8
C7A—C6A—H6A	120.2	C6B—C7B—H7B	119.8
C2A—C7A—C6A	119.5 (6)	O2B—C8B—C9B	106.8 (6)
C2A—C7A—H7A	120.3	O2B—C8B—H8B1	110.4
C6A—C7A—H7A	120.3	C9B—C8B—H8B1	110.4
O2A—C8A—C9A	109.6 (6)	O2B—C8B—H8B2	110.4
O2A—C8A—H8A1	109.8	C9B—C8B—H8B2	110.4
C9A—C8A—H8A1	109.8	H8B1—C8B—H8B2	108.6
O2A—C8A—H8A2	109.8	O3B—C9B—C8B	108.8 (4)
C9A—C8A—H8A2	109.8	O3B—C9B—C10B	103.9 (4)
H8A1—C8A—H8A2	108.2	C8B—C9B—C10B	113.9 (4)
O3A—C9A—C8A	108.2 (4)	O3B—C9B—H9B	110.0
O3A—C9A—C10A	104.0 (4)	C8B—C9B—H9B	110.0
C8A—C9A—C10A	113.7 (4)	C10B—C9B—H9B	110.0
O3A—C9A—H9A	110.3	O4B—C10B—C9B	103.2 (4)
C8A—C9A—H9A	110.3	O4B—C10B—H10C	111.1
C10A—C9A—H9A	110.3	C9B—C10B—H10C	111.1
O4A—C10A—C9A	103.0 (4)	O4B—C10B—H10D	111.1
O4A—C10A—H10A	111.2	C9B—C10B—H10D	111.1
C9A—C10A—H10A	111.2	H10C—C10B—H10D	109.1
O4A—C10A—H10B	111.2	O4B—C11B—O3B	105.4 (4)
C9A—C10A—H10B	111.2	O4B—C11B—C12B	111.7 (4)
H10A—C10A—H10B	109.1	O3B—C11B—C12B	108.6 (4)
O4A—C11A—O3A	105.5 (3)	O4B—C11B—C16B	109.4 (4)
O4A—C11A—C16A	109.9 (4)	O3B—C11B—C16B	110.4 (4)
O3A—C11A—C16A	110.4 (4)	C12B—C11B—C16B	111.3 (4)
O4A—C11A—C12A	111.5 (4)	C11B—C12B—C13B	111.6 (4)
O3A—C11A—C12A	108.9 (4)	C11B—C12B—H12C	109.3
C16A—C11A—C12A	110.6 (4)	C13B—C12B—H12C	109.3
C13A—C12A—C11A	112.4 (4)	C11B—C12B—H12D	109.3
C13A—C12A—H12A	109.1	C13B—C12B—H12D	109.3
C11A—C12A—H12A	109.1	H12C—C12B—H12D	108.0
C13A—C12A—H12B	109.1	C20B—C13B—C14B	111.4 (4)
C11A—C12A—H12B	109.1	C20B—C13B—C12B	109.9 (4)
H12A—C12A—H12B	107.9	C14B—C13B—C12B	109.5 (4)
C12A—C13A—C20A	110.8 (5)	C20B—C13B—H13B	108.7
C12A—C13A—C14A	109.0 (4)	C14B—C13B—H13B	108.7
C20A—C13A—C14A	110.8 (4)	C12B—C13B—H13B	108.7
C12A—C13A—H13A	108.7	C15B—C14B—C13B	112.4 (4)
C20A—C13A—H13A	108.7	C15B—C14B—H14C	109.1
C14A—C13A—H13A	108.7	C13B—C14B—H14C	109.1
C15A—C14A—C13A	112.0 (4)	C15B—C14B—H14D	109.1
C15A—C14A—H14A	109.2	C13B—C14B—H14D	109.1
C13A—C14A—H14A	109.2	H14C—C14B—H14D	107.9
C15A—C14A—H14B	109.2	C14B—C15B—C16B	112.1 (4)
C13A—C14A—H14B	109.2	C14B—C15B—H15C	109.2
H14A—C14A—H14B	107.9	C16B—C15B—H15C	109.2
C14A—C15A—C16A	111.5 (4)	C14B—C15B—H15D	109.2
C14A—C15A—H15A	109.3	C16B—C15B—H15D	109.2
C16A—C15A—H15A	109.3	H15C—C15B—H15D	107.9
C14A—C15A—H15B	109.3	C15B—C16B—C11B	109.2 (4)
C16A—C15A—H15B	109.3	C15B—C16B—C17B	114.0 (4)
H15A—C15A—H15B	108.0	C11B—C16B—C17B	115.3 (4)
C11A—C16A—C15A	109.7 (4)	C15B—C16B—H16B	105.8
C11A—C16A—C17A	115.0 (4)	C11B—C16B—H16B	105.8
C15A—C16A—C17A	113.1 (4)	C17B—C16B—H16B	105.8
C11A—C16A—H16A	106.1	C18B—C17B—C19B	109.1 (5)
C15A—C16A—H16A	106.1	C18B—C17B—C16B	114.6 (5)
C17A—C16A—H16A	106.1	C19B—C17B—C16B	110.0 (4)
C19A—C17A—C16A	110.6 (4)	C18B—C17B—H17B	107.6
C19A—C17A—C18A	109.7 (5)	C19B—C17B—H17B	107.6
C16A—C17A—C18A	114.1 (5)	C16B—C17B—H17B	107.6
C19A—C17A—H17A	107.4	C17B—C18B—H18D	109.5
C16A—C17A—H17A	107.4	C17B—C18B—H18E	109.5
C18A—C17A—H17A	107.4	H18D—C18B—H18E	109.5
C17A—C18A—H18A	109.5	C17B—C18B—H18F	109.5
C17A—C18A—H18B	109.5	H18D—C18B—H18F	109.5
H18A—C18A—H18B	109.5	H18E—C18B—H18F	109.5
C17A—C18A—H18C	109.5	C17B—C19B—H19D	109.5
H18A—C18A—H18C	109.5	C17B—C19B—H19E	109.5
H18B—C18A—H18C	109.5	H19D—C19B—H19E	109.5
C17A—C19A—H19A	109.5	C17B—C19B—H19F	109.5
C17A—C19A—H19B	109.5	H19D—C19B—H19F	109.5
H19A—C19A—H19B	109.5	H19E—C19B—H19F	109.5
C17A—C19A—H19C	109.5	C13B—C20B—H20D	109.5
H19A—C19A—H19C	109.5	C13B—C20B—H20E	109.5
H19B—C19A—H19C	109.5	H20D—C20B—H20E	109.5
C13A—C20A—H20A	109.5	C13B—C20B—H20F	109.5
C13A—C20A—H20B	109.5	H20D—C20B—H20F	109.5
H20A—C20A—H20B	109.5	H20E—C20B—H20F	109.5
C13A—C20A—H20C	109.5	C1A—O2A—C8A	117.1 (5)
H20A—C20A—H20C	109.5	C9A—O3A—C11A	109.1 (3)
H20B—C20A—H20C	109.5	C11A—O4A—C10A	105.8 (4)
O1B—C1B—O2B	122.8 (6)	C1B—O2B—C8B	119.5 (5)
O1B—C1B—C2B	125.2 (6)	C11B—O3B—C9B	109.2 (3)
O2B—C1B—C2B	111.9 (6)	C11B—O4B—C10B	106.0 (4)
O1A—C1A—C2A—C7A	−176.4 (7)	C1B—C2B—C7B—C6B	−178.8 (6)
O2A—C1A—C2A—C7A	5.4 (9)	C5B—C6B—C7B—C2B	−0.7 (10)
O1A—C1A—C2A—C3A	1.6 (10)	O2B—C8B—C9B—O3B	179.1 (4)
O2A—C1A—C2A—C3A	−176.6 (6)	O2B—C8B—C9B—C10B	63.7 (6)
C7A—C2A—C3A—C4A	−1.5 (10)	O3B—C9B—C10B—O4B	−22.7 (5)
C1A—C2A—C3A—C4A	−179.6 (6)	C8B—C9B—C10B—O4B	95.5 (5)
C2A—C3A—C4A—C5A	1.7 (10)	O4B—C11B—C12B—C13B	64.6 (5)
C3A—C4A—C5A—C6A	−1.7 (10)	O3B—C11B—C12B—C13B	−179.6 (4)
C3A—C4A—C5A—Br1A	−179.5 (5)	C16B—C11B—C12B—C13B	−57.9 (5)
C4A—C5A—C6A—C7A	1.5 (10)	C11B—C12B—C13B—C20B	176.8 (4)
Br1A—C5A—C6A—C7A	179.3 (5)	C11B—C12B—C13B—C14B	54.1 (6)
C3A—C2A—C7A—C6A	1.3 (10)	C20B—C13B—C14B—C15B	−174.8 (4)
C1A—C2A—C7A—C6A	179.2 (6)	C12B—C13B—C14B—C15B	−53.0 (6)
C5A—C6A—C7A—C2A	−1.2 (10)	C13B—C14B—C15B—C16B	55.9 (6)
O2A—C8A—C9A—O3A	−170.9 (4)	C14B—C15B—C16B—C11B	−56.9 (5)
O2A—C8A—C9A—C10A	74.2 (6)	C14B—C15B—C16B—C17B	172.5 (4)
O3A—C9A—C10A—O4A	−23.3 (5)	O4B—C11B—C16B—C15B	−65.8 (5)
C8A—C9A—C10A—O4A	94.1 (5)	O3B—C11B—C16B—C15B	178.7 (4)
O4A—C11A—C12A—C13A	65.0 (5)	C12B—C11B—C16B—C15B	58.0 (5)
O3A—C11A—C12A—C13A	−179.0 (4)	O4B—C11B—C16B—C17B	64.0 (5)
C16A—C11A—C12A—C13A	−57.5 (6)	O3B—C11B—C16B—C17B	−51.5 (5)
C11A—C12A—C13A—C20A	177.6 (4)	C12B—C11B—C16B—C17B	−172.1 (4)
C11A—C12A—C13A—C14A	55.4 (6)	C15B—C16B—C17B—C18B	44.4 (7)
C12A—C13A—C14A—C15A	−55.0 (6)	C11B—C16B—C17B—C18B	−83.1 (6)
C20A—C13A—C14A—C15A	−177.2 (5)	C15B—C16B—C17B—C19B	−79.0 (5)
C13A—C14A—C15A—C16A	57.1 (6)	C11B—C16B—C17B—C19B	153.6 (4)
O4A—C11A—C16A—C15A	−66.9 (5)	O1A—C1A—O2A—C8A	5.8 (10)
O3A—C11A—C16A—C15A	177.2 (4)	C2A—C1A—O2A—C8A	−176.0 (5)
C12A—C11A—C16A—C15A	56.5 (5)	C9A—C8A—O2A—C1A	−106.5 (6)
O4A—C11A—C16A—C17A	61.9 (5)	C8A—C9A—O3A—C11A	−118.0 (4)
O3A—C11A—C16A—C17A	−54.1 (5)	C10A—C9A—O3A—C11A	3.2 (5)
C12A—C11A—C16A—C17A	−174.7 (4)	O4A—C11A—O3A—C9A	18.3 (5)
C14A—C15A—C16A—C11A	−57.0 (5)	C16A—C11A—O3A—C9A	137.0 (4)
C14A—C15A—C16A—C17A	173.2 (4)	C12A—C11A—O3A—C9A	−101.4 (4)
C11A—C16A—C17A—C19A	150.3 (4)	O3A—C11A—O4A—C10A	−34.0 (5)
C15A—C16A—C17A—C19A	−82.6 (5)	C16A—C11A—O4A—C10A	−153.0 (4)
C11A—C16A—C17A—C18A	−85.5 (6)	C12A—C11A—O4A—C10A	84.2 (5)
C15A—C16A—C17A—C18A	41.6 (6)	C9A—C10A—O4A—C11A	35.1 (5)
O1B—C1B—C2B—C7B	175.2 (7)	O1B—C1B—O2B—C8B	−4.0 (10)
O2B—C1B—C2B—C7B	−3.2 (9)	C2B—C1B—O2B—C8B	174.5 (6)
O1B—C1B—C2B—C3B	−2.9 (10)	C9B—C8B—O2B—C1B	146.1 (6)
O2B—C1B—C2B—C3B	178.7 (6)	O4B—C11B—O3B—C9B	18.4 (5)
C7B—C2B—C3B—C4B	1.0 (10)	C12B—C11B—O3B—C9B	−101.4 (4)
C1B—C2B—C3B—C4B	179.1 (6)	C16B—C11B—O3B—C9B	136.4 (4)
C2B—C3B—C4B—C5B	0.2 (10)	C8B—C9B—O3B—C11B	−119.0 (4)
C3B—C4B—C5B—C6B	−1.7 (10)	C10B—C9B—O3B—C11B	2.8 (5)
C3B—C4B—C5B—Br1B	178.4 (5)	O3B—C11B—O4B—C10B	−33.6 (5)
C4B—C5B—C6B—C7B	1.9 (10)	C12B—C11B—O4B—C10B	84.1 (5)
Br1B—C5B—C6B—C7B	−178.1 (5)	C16B—C11B—O4B—C10B	−152.3 (4)
C3B—C2B—C7B—C6B	−0.7 (10)	C9B—C10B—O4B—C11B	34.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C3A—H3A···O1Bi	0.95	2.61	3.295 (8)	129.
C13B—H13B···O3Bi	1.00	2.69	3.541 (6)	143.
C15B—H15C···O3Bi	0.99	2.62	3.484 (6)	145.
C8A—H8A1···O4Aii	0.99	2.68	3.452 (8)	135.
C15A—H15A···O3Ai	0.99	2.59	3.486 (6)	150.
C3B—H3B···O1Aii	0.95	2.51	3.195 (8)	129.
C8B—H8B1···O4Bii	0.99	2.56	3.394 (8)	143.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3A—H3A⋯O1Bi	0.95	2.61	3.295 (8)	129
C13B—H13B⋯O3Bi	1.00	2.69	3.541 (6)	143
C15B—H15C⋯O3Bi	0.99	2.62	3.484 (6)	145
C8A—H8A1⋯O4Aii	0.99	2.68	3.452 (8)	135
C15A—H15A⋯O3Ai	0.99	2.59	3.486 (6)	150
C3B—H3B⋯O1Aii	0.95	2.51	3.195 (8)	129
C8B—H8B1⋯O4Bii	0.99	2.56	3.394 (8)	143

Symmetry codes: (i) ; (ii) .