A cocrystal of (2S,3aS,4R,5R,7aS)- and (2R,3aS,4R,5R,7aS)-7-bromo-2-(4-methoxy­phen­yl)-3a,4,5,7a-tetra­hydro-1,3-benzodioxole-4,5-diol (17:3)

The title compounds, both C₁₄H₁₅BrO₅, cocrystallize and their structures, including absolute stereochemistries, have been solved simultaneously. The structures differ in the configuration (R versus S) at the acetal C atom bearing the 4-methoxy­phenyl group.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.030
• wR factor = 0.076
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT301_ALERT_3_B Main Residue  Disorder .........................      31.00 Perc.

Alert level C
PLAT354_ALERT_3_C Short   O-H Bond (0.82A)   O8     -   H2     ...       0.67 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          8

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.45
           From the CIF: _reflns_number_total               3111
           Count of symmetry unique reflns         1681
           Completeness (_total/calc)            185.07%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1430
           Fraction of Friedel pairs measured     0.851
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C1     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10    = .          S
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         35

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

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

---

S1. Comment

During the course of establishing a total synthesis of the non-natural enantiomeric form of the montanine alkaloid brunsvigine (Banwell et al., 2007a) we had occasion to convert (1S,2S)-3-bromo-3,5-cyclohexadiene-1,2-diol (I) (Boyd et al., 1991) into the corresponding 4-methoxybenzylidene acetal (II). This was achieved under standard conditions and provided compound (II) as a ca 5:3 mixture of epimers arising from a variation in stereochemistry at the newly installed acetal carbon. Subjection of this mixture to cis-dihydroxylation under the so-called UpJohn conditions resulted in each epimer reacting exclusively at the non-halogenated double bond and in a diastereofacially selective manner to give the corresponding mixture of cis-diols (III) and (IV) as a solid after recrystallization from ethyl acetate. In order to establish the relative stereochemistries within these two compounds a single-crystal X-ray analysis was undertaken. The present structures represent only the third and fourth reported for a 4-methoxyphenylacetal derivative of a cis-cyclohexane-1,2-diol (Banwell et al., 2007b; Hulme et al., 2005).

The crystallographic asymmetric unit consists of one molecule of C₁₄H₁₅BrO₅, but with some atoms disordered. The disordered atoms appear to indicate that two isomers have co-crystallized, with the atoms that are not disordered being common to both. The major epimer includes sites O18 and C10 to C19 (crystallographic labelling), and the minor epimer includes O118 and C110 to C119. The structures vary in configuration (R versus S) at the acetal carbon bearing the 4-methoxyphenyl group. The minor isomer atom sites have been refined with isotropic displacement parameters set equal to U_eq of the closest site of the major epimer. Restraints were applied to distances and angles of the minor sites so they would tend to match the corresponding values in the major epimer and so O118 and C110 to C117 would tend to be coplanar. The relative occupancies of the two isomers were refined.

The compounds are enantiomerically pure and their absolute configurations have been determined by refinement of the Flack parameter. The outcomes of these determinations are in agreement with those predicted on the basis of the absolute configuration of the precursor (I) (Boyd et al., 1991).

The largest peaks in the final difference electron-density map are located near the Br atom and at the juncture between disordered and ordered parts of the structure(s).

Related literature

For related literature, see: Banwell et al. (2007a,b); Boyd et al. (1991); Hulme et al. (2005).

S2. Experimental

A magnetically stirred suspension of (1S,2S)-3-bromo-3,5-cyclohexadiene-1,2-diol (I) (20.0 g, 104.7 mmol) and 4-methoxybenzaldehyde dimethyl acetal (20.9 ml, 115.2 mmol) in anhydrous dichloromethane (200 ml) was cooled to 253 K then (1S)-(+)-camphor-10-sulfonic acid monohydrate (2.4 g, 10.4 mmol) was added. After 1 h the reaction mixture was quenched with sodium hydroxide (200 ml of a 1 M aqueous solution) and the separated aqueous phase extracted with dichloromethane (2 × 100 ml). The combined organic phases were washed with brine (1 × 100 ml) then dried (MgSO₄), filtered and concentrated under reduced pressure to give a white solid assumed to contain an epimeric mixture of the benzylidene acetals (II). A magnetically stirred solution of this material in acetone/water (300 ml of a 2:1 v/v mixture) was cooled to 273 K then treated with N-methylmorpholine N-oxide (27.1 g, 232 mmol) and osmium tetraoxide (7.0 ml of a 2.5% w/v solution in tert-butanol, 0.53 mmol). The ensuing mixture was stirred at 291 K for 20 h then treated with sodium metabisulfite (200 ml of a 20% w/v aqueous solution). After 4 h the reaction mixture was concentrated under reduced pressure to give a brown residue that was treated with diethyl ether (500 ml) then water (500 ml). The separated aqueous phase was extracted with diethyl ether (4 × 150 ml) and the combined organic fractions were then dried (MgSO₄), filtered and concentrated under reduced pressure to give a brown solid. Subjection of this material to flash chromatography (silica, 1:19 v/v methanol/dichloromethane elution) and concentration of the appropriate fractions (R_f = 0.3) afforded a ca. 4:1 mixture of the title compounds (III) and (IV) (23.3 g, 65%) as a white, crystalline solid, m.p. = 406–407 K [Found: (M – H^.)⁺, 384.0570. C, 48.67; H, 4.40; Br 23.42. C₁₄H₁₅⁷⁹BrO₅ requires (M – H^.)⁺, 384.0572. C, 49.00; H, 4.41; Br 23.28%]. ¹H NMR [300 MHz, (CD₃)₂CO] δ (major epimer) 7.42 (2H, d, J = 8.9 Hz), 6.95 (2H, d, J = 8.9 Hz), 6.29 (1H, m), 5.80 (1H, s), 4.90 (1H, d, J = 5.1 Hz), 4.55 (1H, m), 4.40 (3H, m), 4.25 (1H, m), 3.81 (3H, s); δ (minor epimer) 7.37 (2H, d, J = 8.7 Hz), 6.93 (2H, d, J = 8.7 Hz), 6.17 (1H, dd, J = 2.7 and 1.2 Hz), 5.87 (1H, s), 4.69 (1H, dd, J = 6.0 and 1.2 Hz), 4.51 (1H, t, J = 4.8 Hz), 4.42 (3H, m), 4.31 (1H, m), 3.80 (3H, s); ¹³C NMR [75 MHz, (CD₃)₂CO] δ (major epimer) 161.4, 135.6, 130.8, 129.0, 120.7, 114.3, 103.1, 77.9, 77.1, 69.6, 67.6, 55.5; δ (minor epimer) 161.5, 133.7, 130.3, 129.3, 122.2, 114.3, 104.7, 79.0, 77.9, 70.0, 68.0, 55.5; ν_max (NaCl)/cm^-1 3518, 3392, 2954, 2907, 2834, 1615, 1515, 1390, 1304, 1248, 1170, 1074, 1050, 1030, 924; MS (EI, 70 eV) 343 and 341 [(M – H^.)⁺, both 5%], 172 (10), 153 (13), 135 (100), 108 (39), 77 (22), 65 (18), 39 (18).

S3. Refinement

The alcohol hydrogen atoms were included at locations revealed in a difference electron density map and were then refined positionally. Other hydrogen atoms were added at calculated positions (C—H distance 1.0 Å, U_iso(H) = 1.2×U_eq(C)) and, during refinement, each was set to ride on the carbon atom to which it is attached.

Computing details

Data collection: COLLECT (Nonius, 1997); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEPII (Johnson, 1976) in TEXSAN (Molecular Structure Corporation, 1997); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures

	Fig. 1. Anisotropic displacement ellipsoid plot of the major isomer of C14H15BrO5 with labelling of selected atoms. Ellipsoids show 30% probability levels. Hydrogen atoms are drawn as circles with small radii.
	Fig. 2. Anisotropic displacement ellipsoid plot of the minor isomer of C14H15BrO5 with labelling of selected atoms. Ellipsoids show 30% probability levels. Hydrogen atoms are drawn as circles with small radii.
	Fig. 3. Unit cell packing diagram of C14H15BrO5 projected down the b axis. Hydrogen atoms of the alcohol groups are drawn as circles with small radii and the others have been deleted.
	Fig. 4. The structure of (I)–(IV).

Cocrystal of (2S,3aS,4R,5R,7aS)- and (2R,3aS,4R,5R,7aS)-7-bromo- 2-(4-methoxyphenyl)-3a,4,5,7a-tetrahydro-1,3-benzodioxole-4,5-diol (17:3)

Crystal data

C14H15BrO5	F(000) = 348
Mr = 343.17	Dx = 1.643 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 30770 reflections
a = 7.2245 (4) Å	θ = 2.6–27.5°
b = 9.7093 (5) Å	µ = 2.98 mm^−1
c = 9.9373 (5) Å	T = 200 K
β = 95.689 (3)°	Block, colourless
V = 693.62 (6) Å^3	0.40 × 0.29 × 0.26 mm
Z = 2

Data collection

Nonius KappaCCD area-detector diffractometer	2802 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
φ and ω scans with CCD	θmax = 27.5°, θmin = 3.5°
Absorption correction: integration via Gaussian method (Coppens, 1970) implemented in maXus (Mackay et al., 1999)	h = −9→9
Tmin = 0.372, Tmax = 0.586	k = −12→11
12613 measured reflections	l = −12→12
3108 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.030	Method = Modified Sheldrick w = 1/[σ^2(F^2) + (0.038P)^2 + 0.097P], where P = [max(Fo^2,0) + 2Fc^2]/3
wR(F^2) = 0.076	(Δ/σ)max = 0.043
S = 0.99	Δρmax = 0.45 e Å^−3
3108 reflections	Δρmin = −0.90 e Å^−3
216 parameters	Absolute structure: Flack (1983), with 1430 Friedel pairs
35 restraints	Absolute structure parameter: −0.019 (10)
Primary atom site location: structure-invariant direct methods

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br20	0.43964 (4)	0.3005 (3)	0.34759 (3)	0.0547
O7	1.0479 (3)	0.0958 (4)	0.5926 (3)	0.0594
O8	1.0545 (3)	0.3760 (4)	0.5778 (2)	0.0476
O9	0.7101 (3)	0.3574 (4)	0.8155 (2)	0.0468
O11	0.4712 (3)	0.4076 (4)	0.65992 (19)	0.0444
O18	0.0214 (4)	0.1796 (4)	1.1172 (3)	0.0562	0.853 (4)
O118	0.0317 (17)	0.3946 (16)	1.1645 (12)	0.0555*	0.147 (4)
C1	0.8881 (4)	0.1684 (4)	0.6274 (3)	0.0414
C2	0.9556 (3)	0.3090 (5)	0.6760 (2)	0.0382
C3	0.7968 (4)	0.4054 (4)	0.7008 (3)	0.0406
C4	0.6353 (4)	0.4100 (4)	0.5872 (3)	0.0367
C5	0.6293 (3)	0.2884 (5)	0.4953 (2)	0.0374
C6	0.7390 (4)	0.1786 (4)	0.5112 (3)	0.0397
C10	0.5344 (5)	0.4276 (5)	0.7997 (3)	0.0398	0.853 (4)
C12	0.4022 (5)	0.3619 (5)	0.8875 (4)	0.0373	0.853 (4)
C13	0.3774 (6)	0.2201 (5)	0.8878 (4)	0.0411	0.853 (4)
C14	0.2495 (6)	0.1620 (5)	0.9669 (5)	0.0473	0.853 (4)
C15	0.1463 (6)	0.2471 (6)	1.0447 (4)	0.0408	0.853 (4)
C16	0.1678 (6)	0.3889 (6)	1.0432 (4)	0.0428	0.853 (4)
C17	0.2976 (6)	0.4437 (6)	0.9649 (4)	0.0411	0.853 (4)
C19	−0.1055 (9)	0.2620 (8)	1.1849 (5)	0.0683	0.853 (4)
C110	0.5244 (13)	0.3003 (17)	0.7692 (10)	0.0396*	0.147 (4)
C112	0.3909 (16)	0.3102 (19)	0.8776 (12)	0.0380*	0.147 (4)
C113	0.294 (2)	0.1981 (19)	0.9244 (16)	0.0469*	0.147 (4)
C114	0.170 (2)	0.219 (2)	1.0228 (16)	0.0414*	0.147 (4)
C115	0.1473 (18)	0.3534 (17)	1.0695 (13)	0.0433*	0.147 (4)
C116	0.246 (2)	0.4612 (17)	1.0201 (15)	0.0403*	0.147 (4)
C117	0.3638 (19)	0.4373 (19)	0.9260 (15)	0.0403*	0.147 (4)
C119	−0.089 (6)	0.292 (4)	1.213 (4)	0.0688*	0.147 (4)
H1	1.006 (7)	0.035 (5)	0.542 (4)	0.0710*
H2	1.135 (6)	0.342 (4)	0.579 (4)	0.0570*
H11	0.8363	0.1192	0.7038	0.0491*
H21	1.0394	0.2984	0.7617	0.0455*
H31	0.8463	0.5005	0.7188	0.0484*
H41	0.6399	0.4972	0.5341	0.0439*
H61	0.7221	0.1014	0.4445	0.0471*
H101	0.5503	0.5278	0.8211	0.0473*	0.853
H131	0.4513	0.1600	0.8314	0.0489*	0.853
H141	0.2315	0.0599	0.9680	0.0562*	0.853
H161	0.0915	0.4498	1.0971	0.0512*	0.853
H171	0.3164	0.5458	0.9643	0.0492*	0.853
H191	−0.1880	0.2006	1.2334	0.0835*	0.853
H192	−0.0340	0.3240	1.2515	0.0835*	0.853
H193	−0.1832	0.3188	1.1169	0.0835*	0.853
H1101	0.5314	0.2051	0.7316	0.0475*	0.147
H1131	0.312	0.1036	0.8881	0.0563*	0.147
H1141	0.099	0.141	1.0585	0.0497*	0.147
H1161	0.229	0.5569	1.0541	0.0484*	0.147
H1171	0.4335	0.5165	0.8911	0.0484*	0.147
H1191	−0.165	0.335	1.281	0.0826*	0.147
H1192	−0.012	0.215	1.256	0.0826*	0.147
H1193	−0.173	0.255	1.135	0.0826*	0.147

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br20	0.04465 (15)	0.06961 (18)	0.04579 (15)	0.00756 (18)	−0.01518 (10)	−0.00620 (18)
O7	0.0408 (12)	0.0565 (13)	0.0777 (17)	0.0121 (10)	−0.0104 (11)	−0.0169 (12)
O8	0.0301 (10)	0.0530 (13)	0.0602 (14)	0.0004 (9)	0.0068 (10)	0.0097 (10)
O9	0.0317 (9)	0.0736 (13)	0.0343 (9)	0.0055 (8)	−0.0015 (8)	−0.0005 (8)
O11	0.0299 (9)	0.0683 (13)	0.0347 (10)	0.0063 (9)	0.0009 (7)	0.0002 (9)
O18	0.0533 (15)	0.0628 (17)	0.0538 (16)	−0.0029 (13)	0.0123 (13)	0.0109 (13)
C1	0.0332 (13)	0.0424 (14)	0.0471 (16)	0.0012 (11)	−0.0029 (12)	0.0044 (11)
C2	0.0278 (10)	0.0473 (13)	0.0386 (11)	−0.0018 (15)	−0.0018 (8)	0.0010 (16)
C3	0.0319 (13)	0.0486 (14)	0.0404 (14)	0.0008 (11)	−0.0013 (11)	−0.0020 (12)
C4	0.0302 (12)	0.0443 (13)	0.0354 (13)	0.0025 (10)	0.0014 (10)	0.0007 (11)
C5	0.0306 (10)	0.0466 (15)	0.0341 (10)	−0.0029 (13)	−0.0010 (8)	−0.0003 (14)
C6	0.0348 (13)	0.0428 (14)	0.0401 (14)	−0.0020 (11)	−0.0021 (11)	−0.0018 (11)
C10	0.0344 (16)	0.0482 (18)	0.0357 (16)	0.0023 (13)	−0.0025 (13)	−0.0012 (13)
C12	0.0325 (17)	0.045 (2)	0.0333 (17)	0.0037 (15)	−0.0030 (14)	0.0001 (16)
C13	0.036 (2)	0.044 (2)	0.042 (2)	0.0050 (16)	−0.0012 (17)	−0.0032 (16)
C14	0.043 (2)	0.049 (2)	0.048 (2)	0.0008 (17)	−0.0018 (17)	0.0051 (17)
C15	0.0352 (17)	0.053 (3)	0.0336 (18)	−0.0010 (15)	−0.0010 (14)	0.0048 (15)
C16	0.042 (2)	0.049 (2)	0.0373 (19)	−0.0002 (17)	0.0013 (15)	−0.0054 (15)
C17	0.039 (2)	0.045 (2)	0.038 (2)	0.0009 (14)	0.0008 (16)	−0.0036 (15)
C19	0.066 (3)	0.086 (4)	0.057 (3)	−0.011 (2)	0.027 (3)	−0.005 (2)

Geometric parameters (Å, º)

Br20—C5	1.910 (2)	C12—C13	1.388 (5)
O7—C1	1.424 (3)	C12—C17	1.382 (6)
O7—H1	0.82 (5)	C13—C14	1.391 (6)
O8—C2	1.422 (4)	C13—H131	1.000
O8—H2	0.67 (4)	C14—C15	1.397 (6)
O9—C3	1.432 (4)	C14—H141	1.000
O9—C10	1.436 (4)	C15—C16	1.385 (6)
O9—C110	1.482 (11)	C16—C17	1.384 (7)
O11—C4	1.449 (3)	C16—H161	1.000
O11—C10	1.432 (4)	C17—H171	1.000
O11—C110	1.527 (12)	C19—H191	1.000
O18—C15	1.376 (5)	C19—H192	1.000
O18—C19	1.433 (7)	C19—H193	1.000
O118—C115	1.380 (16)	C110—C112	1.518 (15)
O118—C119	1.434 (19)	C110—H1101	1.000
C1—C2	1.512 (5)	C112—C113	1.399 (17)
C1—C6	1.503 (4)	C112—C117	1.346 (17)
C1—H11	1.000	C113—C114	1.406 (17)
C2—C3	1.520 (4)	C113—H1131	1.000
C2—H21	1.000	C114—C115	1.397 (17)
C3—C4	1.542 (4)	C114—H1141	1.000
C3—H31	1.000	C115—C116	1.382 (16)
C4—C5	1.490 (4)	C116—C117	1.347 (16)
C4—H41	1.000	C116—H1161	1.000
C5—C6	1.328 (4)	C117—H1171	1.000
C6—H61	1.000	C119—H1191	1.000
C10—C12	1.498 (6)	C119—H1192	1.000
C10—H101	1.000	C119—H1193	1.000
C1—O7—H1	104 (4)	C14—C13—H131	120.1
C2—O8—H2	105 (3)	C13—C14—C15	119.6 (4)
C3—O9—C10	102.1 (2)	C13—C14—H141	120.2
C3—O9—C110	109.2 (4)	C15—C14—H141	120.2
C4—O11—C10	106.5 (2)	C14—C15—O18	115.0 (4)
C4—O11—C110	101.9 (5)	C14—C15—C16	121.0 (5)
C15—O18—C19	117.6 (3)	O18—C15—C16	124.0 (4)
C115—O118—C119	117.1 (16)	C15—C16—C17	118.1 (5)
O7—C1—C2	106.3 (2)	C15—C16—H161	120.9
O7—C1—C6	112.5 (2)	C17—C16—H161	120.9
C2—C1—C6	111.7 (2)	C16—C17—C12	122.0 (4)
O7—C1—H11	108.8	C16—C17—H171	119.0
C2—C1—H11	108.8	C12—C17—H171	119.0
C6—C1—H11	108.8	O18—C19—H191	109.5
C1—C2—O8	111.3 (2)	O18—C19—H192	109.5
C1—C2—C3	112.5 (2)	H191—C19—H192	109.5
O8—C2—C3	105.5 (3)	O18—C19—H193	109.5
C1—C2—H21	109.1	H191—C19—H193	109.5
O8—C2—H21	109.1	H192—C19—H193	109.5
C3—C2—H21	109.1	O11—C110—O9	97.0 (8)
C2—C3—O9	109.0 (2)	O11—C110—C112	109.2 (8)
C2—C3—C4	115.3 (2)	O9—C110—C112	112.0 (8)
O9—C3—C4	103.5 (2)	O11—C110—H1101	112.5
C2—C3—H31	109.6	O9—C110—H1101	112.6
O9—C3—H31	109.6	C112—C110—H1101	112.5
C4—C3—H31	109.6	C110—C112—C113	124.2 (12)
C3—C4—O11	103.4 (2)	C110—C112—C117	115.9 (12)
C3—C4—C5	113.5 (2)	C113—C112—C117	119.9 (11)
O11—C4—C5	108.5 (2)	C112—C113—C114	119.5 (12)
C3—C4—H41	110.4	C112—C113—H1131	120.2
O11—C4—H41	110.4	C114—C113—H1131	120.3
C5—C4—H41	110.4	C113—C114—C115	118.1 (13)
Br20—C5—C4	113.4 (2)	C113—C114—H1141	121.0
Br20—C5—C6	121.0 (2)	C115—C114—H1141	121.0
C4—C5—C6	125.6 (2)	C114—C115—O118	126.5 (12)
C1—C6—C5	121.2 (2)	C114—C115—C116	120.5 (11)
C1—C6—H61	119.4	O118—C115—C116	113.0 (11)
C5—C6—H61	119.4	C115—C116—C117	120.0 (12)
O9—C10—O11	103.6 (2)	C115—C116—H1161	120.0
O9—C10—C12	109.9 (3)	C117—C116—H1161	120.0
O11—C10—C12	110.3 (3)	C116—C117—C112	122.0 (12)
O9—C10—H101	110.9	C116—C117—H1171	119.0
O11—C10—H101	110.9	C112—C117—H1171	119.0
C12—C10—H101	110.9	O118—C119—H1191	109.4
C10—C12—C13	120.9 (4)	O118—C119—H1192	109.5
C10—C12—C17	119.6 (4)	O118—C119—H1193	109.5
C13—C12—C17	119.4 (5)	H1191—C119—H1192	109.5
C12—C13—C14	119.8 (5)	H1191—C119—H1193	109.5
C12—C13—H131	120.1	H1192—C119—H1193	109.5
C10—O9—C3—C2	−162.1 (3)	C2—C3—C4—C5	19.4 (4)
C10—O9—C3—C4	−38.9 (4)	O9—C3—C4—O11	17.8 (4)
C3—O9—C10—O11	46.4 (4)	O11—C4—C5—Br20	69.7 (3)
C3—O9—C10—C12	164.3 (3)	O11—C4—C5—C6	−109.0 (3)
C10—O11—C4—C3	10.3 (4)	C3—C4—C5—C6	5.3 (4)
C10—O11—C4—C5	131.2 (3)	C3—C4—C5—Br20	−175.9 (2)
C4—O11—C10—O9	−35.0 (4)	Br20—C5—C6—C1	−179.8 (2)
C4—O11—C10—C12	−152.7 (4)	C4—C5—C6—C1	−1.2 (5)
C19—O18—C15—C14	−172.0 (4)	O9—C10—C12—C13	−48.6 (5)
C19—O18—C15—C16	6.0 (6)	O9—C10—C12—C17	134.2 (4)
O7—C1—C2—C3	173.0 (2)	O11—C10—C12—C13	65.1 (5)
C6—C1—C2—O8	−68.3 (3)	O11—C10—C12—C17	−112.1 (4)
O7—C1—C2—O8	54.8 (3)	C10—C12—C13—C14	−177.9 (4)
C2—C1—C6—C5	−27.0 (4)	C17—C12—C13—C14	−0.7 (6)
C6—C1—C2—C3	49.9 (3)	C13—C12—C17—C16	−0.1 (6)
O7—C1—C6—C5	−146.4 (3)	C10—C12—C17—C16	177.2 (4)
C1—C2—C3—C4	−47.1 (4)	C12—C13—C14—C15	0.4 (6)
O8—C2—C3—O9	−169.8 (2)	C13—C14—C15—O18	178.9 (4)
O8—C2—C3—C4	74.3 (3)	C13—C14—C15—C16	0.7 (7)
C1—C2—C3—O9	68.7 (3)	C14—C15—C16—C17	−1.5 (6)
O9—C3—C4—C5	−99.6 (3)	O18—C15—C16—C17	−179.4 (4)
C2—C3—C4—O11	136.7 (3)	C15—C16—C17—C12	1.2 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1···O8^i	0.81 (4)	1.97 (5)	2.779 (5)	171 (5)
O8—H2···O7	0.67 (4)	2.48 (4)	2.725 (5)	105 (4)
O8—H2···O11^ii	0.67 (4)	2.56 (4)	3.055 (3)	133 (4)

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