Crystal engineering in the gem-alkynol family: interplay between strong and weak interactions in structures of 2,3,5,6-tetrahalo[F,Cl,Br]-trans-1,4-diethynylcyclohexa-2,5-diene-1,4-diols

Structures of the title compounds are all mediated by strong cooperative arrangements of O—H...O hydrogen bonds, supported by a variety of weaker interactions which affect the type of O—H...O synthon that is formed. The tetrafluoro compound contains hexameric O—H...O synthons in a supramolecular chair conformation, together with C≡C—H...F interactions. However, the tetrachloro and tetrabromo compounds both form tetrameric O—H...O synthons. This dominant pattern is supported by halogen...halogen interactions having one C—Cl[Br]...Cl[Br] angle close to 180° and the other close to 90°, and by C≡C—H...Cl[Br] interactions.

Computing details

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

(7) 2,3,5,6-tetrafluoro-trans-1,4-diethynyl-cyclohexa-2,5-diene-1,4-diol

Crystal data

C10H4F4O2	F(000) = 348
Mr = 232.13	Dx = 1.633 Mg m^−3
Triclinic, P1	Melting point = 132–133 K
a = 8.9002 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2388 (18) Å	Cell parameters from 999 reflections
c = 9.6721 (19) Å	θ = 0.2–30.6°
α = 93.73 (3)°	µ = 0.17 mm^−1
β = 98.73 (3)°	T = 150 K
γ = 114.46 (3)°	Block, colourless
V = 708.3 (2) Å^3	0.7 × 0.3 × 0.2 mm
Z = 3

Data collection

Bruker SMART CCD diffractometer	3722 independent reflections
Radiation source: fine-focus sealed tube	3376 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: not relevant pixels mm^-1	θmax = 29.9°, θmin = 2.2°
ω scans	h = −12→12
Absorption correction: empirical (using intensity measurements) (XPREP in SHELX97; Sheldrick, 1997)	k = −12→12
Tmin = 0.289, Tmax = 0.382	l = −13→13
8674 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	All H-atom parameters refined
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.0484P)^2 + 0.2454P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3722 reflections	Δρmax = 0.46 e Å^−3
242 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.080 (5)

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
F1	0.13140 (9)	0.32812 (9)	0.85824 (8)	0.02992 (17)
F2	0.10278 (9)	0.82232 (8)	0.99013 (8)	0.02855 (17)
F21	−0.45397 (9)	−0.00542 (9)	0.78559 (7)	0.02882 (17)
F11	0.54677 (9)	0.58373 (9)	1.23827 (7)	0.03106 (18)
O21	−0.70633 (11)	−0.25896 (9)	0.57778 (9)	0.02384 (17)
F22	−0.18494 (8)	0.15228 (9)	0.66778 (7)	0.02902 (17)
O11	0.24851 (10)	0.53620 (9)	1.34412 (8)	0.02313 (17)
F12	0.18252 (8)	0.32907 (9)	1.54950 (8)	0.03013 (17)
O1	0.09274 (10)	0.60128 (10)	0.76376 (8)	0.02489 (18)
C24	−0.47257 (14)	−0.00009 (12)	0.64633 (10)	0.0204 (2)
C3	0.13028 (13)	0.58530 (12)	0.91000 (10)	0.0196 (2)
C5	0.05022 (13)	0.66421 (12)	0.99688 (11)	0.0204 (2)
C13	0.34702 (13)	0.44886 (12)	1.37978 (11)	0.0197 (2)
C23	−0.65179 (13)	−0.09123 (12)	0.56684 (11)	0.0197 (2)
C12	0.27270 (14)	0.29858 (13)	1.27786 (12)	0.0235 (2)
C25	−0.34131 (13)	0.07603 (12)	0.58808 (11)	0.0205 (2)
C14	0.52767 (13)	0.54587 (13)	1.36766 (11)	0.0212 (2)
C15	0.34023 (13)	0.40981 (12)	1.52821 (11)	0.0207 (2)
C4	0.06470 (13)	0.40977 (13)	0.92853 (11)	0.0205 (2)
C22	−0.76156 (14)	−0.02754 (13)	0.62251 (12)	0.0246 (2)
C1	0.46278 (16)	0.73049 (19)	0.99717 (14)	0.0373 (3)
C2	0.31531 (14)	0.66562 (14)	0.95594 (11)	0.0248 (2)
C21	−0.85068 (17)	0.02473 (16)	0.66346 (15)	0.0344 (3)
C11	0.21624 (16)	0.17711 (15)	1.19891 (14)	0.0305 (2)
H11A	0.264 (2)	0.601 (2)	1.417 (2)	0.041 (5)*
H11	0.175 (2)	0.081 (2)	1.137 (2)	0.046 (5)*
H21A	−0.758 (3)	−0.281 (2)	0.642 (2)	0.050 (5)*
H21	−0.924 (3)	0.069 (2)	0.692 (2)	0.053 (5)*
H1A	−0.018 (3)	0.560 (2)	0.735 (2)	0.051 (5)*
H1	0.582 (3)	0.786 (3)	1.037 (2)	0.067 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0307 (4)	0.0319 (4)	0.0319 (4)	0.0169 (3)	0.0119 (3)	−0.0009 (3)
F2	0.0314 (4)	0.0187 (3)	0.0331 (4)	0.0082 (3)	0.0060 (3)	0.0056 (3)
F21	0.0346 (4)	0.0356 (4)	0.0164 (3)	0.0145 (3)	0.0058 (3)	0.0063 (3)
F11	0.0311 (4)	0.0410 (4)	0.0206 (3)	0.0133 (3)	0.0069 (3)	0.0122 (3)
O21	0.0300 (4)	0.0176 (3)	0.0255 (4)	0.0088 (3)	0.0130 (3)	0.0059 (3)
F22	0.0207 (3)	0.0316 (4)	0.0273 (3)	0.0064 (3)	−0.0014 (3)	0.0024 (3)
O11	0.0241 (4)	0.0240 (4)	0.0232 (4)	0.0143 (3)	−0.0007 (3)	0.0011 (3)
F12	0.0187 (3)	0.0355 (4)	0.0327 (4)	0.0066 (3)	0.0080 (3)	0.0098 (3)
O1	0.0205 (4)	0.0346 (4)	0.0173 (3)	0.0086 (3)	0.0050 (3)	0.0079 (3)
C24	0.0248 (5)	0.0208 (5)	0.0164 (4)	0.0104 (4)	0.0038 (4)	0.0036 (3)
C3	0.0186 (4)	0.0234 (5)	0.0167 (4)	0.0079 (4)	0.0049 (3)	0.0049 (3)
C5	0.0210 (5)	0.0184 (4)	0.0205 (4)	0.0075 (4)	0.0028 (4)	0.0029 (3)
C13	0.0194 (4)	0.0201 (4)	0.0200 (4)	0.0098 (4)	0.0015 (3)	0.0028 (3)
C23	0.0212 (5)	0.0178 (4)	0.0206 (5)	0.0080 (4)	0.0066 (4)	0.0045 (3)
C12	0.0223 (5)	0.0248 (5)	0.0245 (5)	0.0118 (4)	0.0031 (4)	0.0032 (4)
C25	0.0200 (5)	0.0198 (4)	0.0198 (4)	0.0074 (4)	0.0015 (4)	0.0024 (3)
C14	0.0233 (5)	0.0225 (5)	0.0194 (5)	0.0104 (4)	0.0057 (4)	0.0060 (4)
C15	0.0184 (5)	0.0211 (5)	0.0232 (5)	0.0080 (4)	0.0059 (4)	0.0053 (4)
C4	0.0211 (5)	0.0224 (5)	0.0190 (4)	0.0106 (4)	0.0046 (4)	0.0010 (4)
C22	0.0244 (5)	0.0222 (5)	0.0276 (5)	0.0090 (4)	0.0086 (4)	0.0048 (4)
C1	0.0224 (6)	0.0503 (8)	0.0322 (6)	0.0081 (5)	0.0046 (5)	0.0132 (5)
C2	0.0221 (5)	0.0298 (5)	0.0214 (5)	0.0089 (4)	0.0061 (4)	0.0076 (4)
C21	0.0345 (6)	0.0317 (6)	0.0445 (7)	0.0177 (5)	0.0180 (5)	0.0079 (5)
C11	0.0312 (6)	0.0276 (6)	0.0313 (6)	0.0130 (5)	0.0029 (5)	−0.0010 (4)

Geometric parameters (Å, º)

F1—C4	1.3455 (12)	C3—C2	1.4775 (16)
F1—F22	2.8649 (17)	C3—C5	1.5091 (15)
F2—C5	1.3464 (12)	C3—C4	1.5128 (15)
F2—F1^i	2.6873 (14)	C5—C4^i	1.3203 (16)
F21—C24	1.3386 (12)	C13—C12	1.4833 (16)
F11—C14	1.3378 (12)	C13—C15	1.5069 (14)
F11—F1^ii	2.9527 (13)	C13—C14	1.5099 (15)
O21—C23	1.4361 (13)	C23—C22	1.4782 (15)
O21—H21A	0.81 (2)	C23—C25^v	1.5084 (14)
F22—C25	1.3487 (13)	C12—C11	1.1832 (18)
O11—C13	1.4384 (12)	C25—C23^v	1.5084 (14)
O11—H11A	0.851 (19)	C14—C15^iii	1.3238 (16)
F12—C15	1.3453 (13)	C15—C14^iii	1.3238 (16)
F12—F11^iii	2.7098 (15)	C4—C5^i	1.3203 (15)
F12—F1^iv	16.294 (3)	C22—C21	1.1862 (18)
O1—C3	1.4348 (12)	C1—C2	1.1829 (18)
O1—H1A	0.88 (2)	C1—H1	0.97 (2)
C24—C25	1.3221 (15)	C21—H21	0.96 (2)
C24—C23	1.5085 (16)	C11—H11	0.936 (19)
C4—F1—F22	90.58 (6)	C12—C13—C14	109.47 (9)
C5—F2—F1^i	59.41 (6)	C15—C13—C14	109.63 (9)
C14—F11—F1^ii	122.52 (7)	O21—C23—C22	111.66 (9)
C23—O21—H21A	109.3 (14)	O21—C23—C24	108.92 (9)
C25—F22—F1	173.72 (7)	C22—C23—C24	110.27 (9)
C13—O11—H11A	107.3 (12)	O21—C23—C25^v	106.61 (9)
C15—F12—F11^iii	58.65 (6)	C22—C23—C25^v	109.85 (9)
C15—F12—F1^iv	71.00 (7)	C24—C23—C25^v	109.46 (9)
F11^iii—F12—F1^iv	128.58 (3)	C11—C12—C13	178.10 (12)
C3—O1—H1A	109.4 (13)	C24—C25—F22	120.83 (10)
C25—C24—F21	121.05 (10)	C24—C25—C23^v	125.41 (10)
C25—C24—C23	125.09 (9)	F22—C25—C23^v	113.74 (9)
F21—C24—C23	113.84 (9)	C15^iii—C14—F11	120.87 (10)
O1—C3—C2	107.20 (9)	C15^iii—C14—C13	125.11 (10)
O1—C3—C5	110.26 (9)	F11—C14—C13	114.01 (9)
C2—C3—C5	109.96 (9)	C14^iii—C15—F12	121.33 (10)
O1—C3—C4	110.33 (9)	C14^iii—C15—C13	125.25 (10)
C2—C3—C4	110.07 (9)	F12—C15—C13	113.36 (9)
C5—C3—C4	109.02 (8)	C5^i—C4—F1	120.41 (10)
C4^i—C5—F2	120.64 (10)	C5^i—C4—C3	125.46 (10)
C4^i—C5—C3	125.45 (10)	F1—C4—C3	114.12 (9)
F2—C5—C3	113.89 (9)	C21—C22—C23	178.11 (13)
O11—C13—C12	107.14 (9)	C2—C1—H1	176.3 (13)
O11—C13—C15	109.96 (9)	C1—C2—C3	177.83 (12)
C12—C13—C15	110.04 (9)	C22—C21—H21	177.2 (12)
O11—C13—C14	110.57 (9)	C12—C11—H11	178.4 (11)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y+1, −z+3; (iv) x, y, z−1; (v) −x−1, −y, −z+1.

(8) 2,3,5,6-tetrachloro-trans-1,4-diethynyl-cyclohexa-2,5-diene-1,4-diol

Crystal data

C10H4Cl4O2	Dx = 1.590 Mg m^−3
Mr = 297.93	Melting point = 205–206 K
Tetragonal, I41/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 4ad	Cell parameters from 505 reflections
a = 16.758 (2) Å	θ = 5.3–25.3°
c = 8.865 (2) Å	µ = 0.93 mm^−1
V = 2489.6 (7) Å^3	T = 150 K
Z = 8	Block, colourless
F(000) = 1184	0.3 × 0.3 × 0.2 mm

Data collection

Bruker SMART CCD diffractometer	1421 independent reflections
Radiation source: fine-focus sealed tube	1202 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: not relevant pixels mm^-1	θmax = 27.4°, θmin = 2.4°
ω scans	h = −21→20
Absorption correction: multi-scan SADABS (Sheldrick 1996)	k = −21→19
Tmin = 0.665, Tmax = 0.830	l = −9→11
8404 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	All H-atom parameters refined
wR(F^2) = 0.125	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 5.8833P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
1421 reflections	Δρmax = 0.59 e Å^−3
82 parameters	Δρmin = −0.44 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0178 (11)

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
Cl1	0.77134 (5)	0.61807 (5)	−0.00252 (9)	0.0642 (3)
Cl2	0.61323 (6)	0.71900 (6)	−0.01517 (12)	0.0813 (4)
O1	0.89228 (11)	0.72875 (11)	−0.1540 (3)	0.0533 (6)
C4	0.75598 (14)	0.69120 (14)	−0.1362 (3)	0.0379 (6)
C5	0.68998 (14)	0.73415 (15)	−0.1411 (3)	0.0402 (6)
C2	0.84570 (16)	0.62493 (16)	−0.3155 (3)	0.0462 (6)
C3	0.82653 (13)	0.70177 (13)	−0.2419 (3)	0.0363 (6)
C1	0.8625 (2)	0.5634 (2)	−0.3678 (5)	0.0714 (10)
HA	0.922 (2)	0.696 (2)	−0.136 (4)	0.060 (10)*
H1	0.876 (3)	0.517 (3)	−0.407 (6)	0.112 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0768 (6)	0.0581 (5)	0.0576 (5)	0.0093 (4)	−0.0049 (4)	0.0228 (4)
Cl2	0.0696 (6)	0.0783 (6)	0.0961 (8)	0.0109 (4)	0.0469 (5)	0.0194 (5)
O1	0.0353 (10)	0.0313 (9)	0.0934 (16)	0.0033 (7)	−0.0256 (10)	−0.0102 (10)
C4	0.0398 (13)	0.0349 (12)	0.0388 (13)	0.0001 (9)	−0.0047 (10)	0.0033 (10)
C5	0.0342 (12)	0.0391 (13)	0.0473 (14)	−0.0003 (9)	0.0061 (10)	0.0012 (10)
C2	0.0417 (14)	0.0389 (14)	0.0579 (16)	0.0025 (11)	−0.0049 (12)	−0.0067 (12)
C3	0.0272 (11)	0.0311 (11)	0.0505 (14)	0.0012 (9)	−0.0062 (10)	−0.0037 (10)
C1	0.090 (3)	0.0497 (19)	0.074 (2)	0.0115 (18)	−0.004 (2)	−0.0184 (17)

Geometric parameters (Å, º)

Cl1—C4	1.724 (2)	C5—C3^i	1.518 (3)
Cl2—C5	1.722 (3)	C2—C1	1.165 (4)
O1—C3	1.423 (3)	C2—C3	1.479 (3)
O1—HA	0.76 (4)	C3—C5^i	1.518 (3)
C4—C5	1.320 (3)	C1—H1	0.88 (5)
C4—C3	1.519 (3)
C3—O1—HA	113 (3)	O1—C3—C2	110.49 (19)
C5—C4—C3	124.6 (2)	O1—C3—C5^i	106.88 (19)
C5—C4—Cl1	122.4 (2)	C2—C3—C5^i	110.7 (2)
C3—C4—Cl1	113.00 (17)	O1—C3—C4	107.6 (2)
C4—C5—C3^i	124.1 (2)	C2—C3—C4	109.9 (2)
C4—C5—Cl2	121.6 (2)	C5^i—C3—C4	111.22 (18)
C3^i—C5—Cl2	114.27 (17)	C2—C1—H1	179 (3)
C1—C2—C3	177.0 (3)

Symmetry code: (i) −x+3/2, −y+3/2, −z−1/2.

(9) 2,3,5,6-tetrabromo-trans-1,4-diethynyl-cyclohexa-2,5-diene-1,4-diol

Crystal data

C10H4Br4O2	F(000) = 880
Mr = 475.77	Dx = 2.477 Mg m^−3
Triclinic, P1	Melting point = 205–206 K
a = 8.9147 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.6402 (5) Å	Cell parameters from 510 reflections
c = 12.6547 (5) Å	θ = 5.1–23.7°
α = 85.738 (1)°	µ = 12.60 mm^−1
β = 69.625 (1)°	T = 150 K
γ = 72.72 (1)°	Block, colourless
V = 1275.76 (8) Å^3	0.3 × 0.2 × 0.2 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	5818 independent reflections
Radiation source: fine-focus sealed tube	4966 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: not relevant pixels mm^-1	θmax = 27.5°, θmin = 1.7°
ω scans	h = −11→11
Absorption correction: multi-scan SADABS (Sheldrick 1996)	k = −16→16
Tmin = 0.018, Tmax = 0.074	l = −16→16
14367 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)] = 0.034	Hydrogen site location: difference Fourier map
wR(F^2) = 0.078	All H-atom parameters refined
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0218P)^2 + 4.0324P] where P = (Fo^2 + 2Fc^2)/3
5818 reflections	(Δ/σ)max = 0.005
321 parameters	Δρmax = 0.80 e Å^−3
0 restraints	Δρmin = −1.05 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
Br32	0.23387 (6)	0.17095 (4)	0.93445 (4)	0.02955 (11)
Br21	0.26974 (6)	0.38542 (4)	1.13043 (4)	0.02820 (11)
Br22	0.40392 (6)	0.42595 (5)	0.85341 (4)	0.03255 (12)
Br11	0.78564 (6)	0.43745 (4)	0.62350 (4)	0.03124 (12)
Br31	0.40744 (6)	−0.09732 (4)	0.86395 (4)	0.02761 (11)
Br1	0.79084 (7)	−0.18445 (4)	0.59429 (4)	0.03404 (12)
Br2	0.84216 (7)	−0.08758 (5)	0.33470 (4)	0.03575 (13)
Br12	0.48669 (6)	0.68322 (4)	0.67843 (4)	0.02516 (10)
O3	−0.0988 (4)	0.3802 (3)	1.1712 (3)	0.0233 (7)
O1	1.0803 (5)	−0.1357 (3)	0.6498 (3)	0.0273 (7)
C34	0.1752 (5)	−0.0377 (3)	0.9406 (3)	0.0187 (8)
C25	0.1746 (5)	0.4672 (3)	0.9417 (4)	0.0183 (8)
C4	0.9092 (5)	−0.0793 (4)	0.5363 (4)	0.0218 (9)
C13	0.6262 (5)	0.3856 (3)	0.4816 (3)	0.0186 (8)
C3	0.9714 (5)	−0.0412 (3)	0.6199 (3)	0.0185 (8)
C5	0.9306 (6)	−0.0423 (4)	0.4334 (4)	0.0215 (9)
C35	0.1068 (5)	0.0694 (3)	0.9688 (3)	0.0187 (8)
C14	0.6176 (5)	0.4770 (4)	0.5572 (3)	0.0178 (8)
C15	0.5043 (5)	0.5748 (4)	0.5760 (3)	0.0183 (8)
C23	−0.0620 (5)	0.4806 (3)	1.1266 (3)	0.0182 (8)
C33	0.0778 (5)	−0.1231 (3)	0.9671 (3)	0.0163 (8)
C24	0.1214 (5)	0.4505 (3)	1.0519 (3)	0.0187 (8)
O4	0.0960 (4)	−0.1677 (3)	0.8614 (2)	0.0207 (6)
O2	0.7898 (4)	0.3546 (3)	0.3984 (3)	0.0202 (6)
C22	−0.0946 (5)	0.5578 (3)	1.2199 (4)	0.0201 (8)
C2	0.8281 (6)	0.0123 (4)	0.7218 (4)	0.0240 (9)
C32	0.1482 (6)	−0.2131 (4)	1.0344 (4)	0.0222 (9)
C21	−0.1280 (6)	0.6166 (4)	1.2985 (4)	0.0268 (10)
C12	0.5913 (6)	0.2906 (4)	0.5515 (4)	0.0233 (9)
C1	0.7190 (7)	0.0528 (5)	0.8056 (4)	0.0330 (11)
C11	0.5609 (7)	0.2152 (5)	0.6053 (5)	0.0385 (13)
C31	0.2033 (8)	−0.2869 (5)	1.0836 (5)	0.0367 (13)
H1A	1.056 (8)	−0.133 (5)	0.708 (6)	0.038 (19)*
H1	0.632 (8)	0.085 (5)	0.867 (6)	0.047 (18)*
H4A	0.094 (7)	−0.229 (5)	0.869 (5)	0.030 (15)*
H11	0.561 (8)	0.153 (5)	0.633 (5)	0.045 (18)*
H21	−0.158 (8)	0.673 (5)	1.357 (5)	0.045 (17)*
H4	0.240 (8)	−0.334 (5)	1.109 (5)	0.040 (19)*
H3A	−0.141 (8)	0.378 (5)	1.225 (5)	0.029 (17)*
H2A	0.786 (13)	0.306 (8)	0.390 (8)	0.10 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br32	0.0236 (2)	0.0204 (2)	0.0428 (3)	−0.00980 (17)	−0.0054 (2)	−0.00317 (19)
Br21	0.0283 (2)	0.0327 (2)	0.0253 (2)	−0.00188 (19)	−0.01715 (19)	0.00119 (18)
Br22	0.0175 (2)	0.0510 (3)	0.0243 (2)	−0.0069 (2)	−0.00360 (18)	0.0001 (2)
Br11	0.0227 (2)	0.0446 (3)	0.0255 (2)	0.0005 (2)	−0.01414 (19)	−0.0070 (2)
Br31	0.0182 (2)	0.0242 (2)	0.0356 (3)	−0.00451 (17)	−0.00288 (18)	−0.00867 (18)
Br1	0.0450 (3)	0.0365 (3)	0.0266 (2)	−0.0273 (2)	−0.0071 (2)	0.0038 (2)
Br2	0.0476 (3)	0.0472 (3)	0.0276 (2)	−0.0274 (3)	−0.0204 (2)	0.0041 (2)
Br12	0.0257 (2)	0.0266 (2)	0.0248 (2)	−0.00922 (18)	−0.00736 (18)	−0.00823 (17)
O3	0.0328 (18)	0.0211 (16)	0.0135 (15)	−0.0121 (14)	−0.0015 (14)	0.0018 (12)
O1	0.038 (2)	0.0239 (17)	0.0175 (17)	−0.0022 (14)	−0.0113 (15)	−0.0002 (13)
C34	0.017 (2)	0.022 (2)	0.0153 (19)	−0.0047 (16)	−0.0045 (16)	−0.0016 (15)
C25	0.0150 (19)	0.019 (2)	0.020 (2)	−0.0041 (16)	−0.0050 (16)	−0.0008 (16)
C4	0.020 (2)	0.022 (2)	0.022 (2)	−0.0086 (17)	−0.0025 (17)	−0.0024 (17)
C13	0.021 (2)	0.020 (2)	0.0146 (19)	−0.0061 (17)	−0.0056 (16)	0.0009 (15)
C3	0.020 (2)	0.018 (2)	0.018 (2)	−0.0048 (16)	−0.0077 (16)	0.0010 (15)
C5	0.024 (2)	0.024 (2)	0.019 (2)	−0.0083 (17)	−0.0087 (17)	−0.0006 (16)
C35	0.022 (2)	0.020 (2)	0.0161 (19)	−0.0084 (17)	−0.0070 (16)	−0.0005 (15)
C14	0.0172 (19)	0.024 (2)	0.0134 (18)	−0.0065 (16)	−0.0059 (16)	0.0009 (15)
C15	0.019 (2)	0.022 (2)	0.0155 (19)	−0.0088 (16)	−0.0046 (16)	−0.0016 (15)
C23	0.022 (2)	0.0175 (19)	0.0157 (19)	−0.0060 (16)	−0.0082 (17)	0.0024 (15)
C33	0.019 (2)	0.0131 (18)	0.0165 (19)	−0.0029 (15)	−0.0072 (16)	−0.0026 (15)
C24	0.019 (2)	0.019 (2)	0.019 (2)	−0.0057 (16)	−0.0076 (17)	−0.0011 (16)
O4	0.0311 (17)	0.0153 (15)	0.0172 (14)	−0.0073 (13)	−0.0097 (13)	−0.0001 (11)
O2	0.0181 (15)	0.0212 (16)	0.0173 (15)	−0.0041 (12)	−0.0022 (12)	−0.0014 (12)
C22	0.021 (2)	0.018 (2)	0.022 (2)	−0.0057 (16)	−0.0088 (17)	0.0032 (16)
C2	0.024 (2)	0.029 (2)	0.021 (2)	−0.0078 (18)	−0.0100 (19)	−0.0002 (18)
C32	0.022 (2)	0.022 (2)	0.023 (2)	−0.0065 (18)	−0.0080 (18)	0.0002 (17)
C21	0.029 (2)	0.027 (2)	0.025 (2)	−0.0069 (19)	−0.011 (2)	−0.0051 (19)
C12	0.022 (2)	0.023 (2)	0.021 (2)	−0.0043 (17)	−0.0055 (18)	0.0027 (17)
C1	0.026 (3)	0.045 (3)	0.024 (2)	−0.007 (2)	−0.005 (2)	−0.006 (2)
C11	0.035 (3)	0.033 (3)	0.037 (3)	−0.008 (2)	−0.004 (2)	0.010 (2)
C31	0.040 (3)	0.033 (3)	0.043 (3)	−0.009 (2)	−0.025 (3)	0.015 (2)

Geometric parameters (Å, º)

Br32—C35	1.886 (4)	C3—C2	1.491 (6)
Br21—C24	1.887 (4)	C3—C5^iii	1.537 (6)
Br22—C25	1.888 (4)	C5—C3^iii	1.537 (6)
Br11—C14	1.889 (4)	C35—C33^iv	1.522 (6)
Br31—C34	1.892 (4)	C14—C15	1.319 (6)
Br1—C4	1.889 (4)	C15—C13^ii	1.525 (6)
Br2—C5	1.889 (4)	C23—C22	1.481 (6)
Br12—C15	1.891 (4)	C23—C25^i	1.522 (6)
O3—C23	1.431 (5)	C23—C24	1.523 (6)
O3—H3A	0.66 (6)	C33—O4	1.428 (5)
O1—C3	1.419 (5)	C33—C32	1.488 (6)
O1—H1A	0.69 (6)	C33—C35^iv	1.522 (6)
C34—C35	1.329 (6)	O4—H4A	0.78 (6)
C34—C33	1.526 (6)	O2—H2A	0.64 (9)
C25—C24	1.330 (6)	C22—C21	1.185 (6)
C25—C23^i	1.522 (6)	C2—C1	1.183 (7)
C4—C5	1.318 (6)	C32—C31	1.164 (7)
C4—C3	1.517 (6)	C21—H21	0.98 (6)
C13—O2	1.429 (5)	C12—C11	1.172 (7)
C13—C12	1.481 (6)	C1—H1	0.90 (7)
C13—C14	1.522 (6)	C11—H11	0.83 (7)
C13—C15^ii	1.525 (6)	C31—H4	0.70 (7)
C23—O3—H3A	120 (5)	C15—C14—Br11	122.4 (3)
C3—O1—H1A	106 (5)	C13—C14—Br11	113.5 (3)
C35—C34—C33	124.3 (4)	C14—C15—C13^ii	124.6 (4)
C35—C34—Br31	121.5 (3)	C14—C15—Br12	123.3 (3)
C33—C34—Br31	114.2 (3)	C13^ii—C15—Br12	112.1 (3)
C24—C25—C23^i	125.0 (4)	O3—C23—C22	110.0 (3)
C24—C25—Br22	122.0 (3)	O3—C23—C25^i	107.9 (3)
C23^i—C25—Br22	112.9 (3)	C22—C23—C25^i	109.8 (3)
C5—C4—C3	124.5 (4)	O3—C23—C24	107.7 (3)
C5—C4—Br1	122.0 (3)	C22—C23—C24	110.6 (4)
C3—C4—Br1	113.5 (3)	C25^i—C23—C24	110.8 (3)
O2—C13—C12	111.3 (4)	O4—C33—C32	109.9 (3)
O2—C13—C14	107.8 (3)	O4—C33—C35^iv	109.2 (3)
C12—C13—C14	109.0 (3)	C32—C33—C35^iv	109.8 (3)
O2—C13—C15^ii	109.7 (3)	O4—C33—C34	106.7 (3)
C12—C13—C15^ii	108.0 (4)	C32—C33—C34	110.1 (3)
C14—C13—C15^ii	111.1 (3)	C35^iv—C33—C34	111.1 (3)
O1—C3—C2	110.5 (4)	C25—C24—C23	124.1 (4)
O1—C3—C4	107.8 (3)	C25—C24—Br21	122.3 (3)
C2—C3—C4	110.4 (4)	C23—C24—Br21	113.5 (3)
O1—C3—C5^iii	108.6 (4)	C33—O4—H4A	108 (4)
C2—C3—C5^iii	108.8 (3)	C13—O2—H2A	93 (9)
C4—C3—C5^iii	110.8 (3)	C21—C22—C23	176.0 (5)
C4—C5—C3^iii	124.7 (4)	C1—C2—C3	176.9 (5)
C4—C5—Br2	122.9 (3)	C31—C32—C33	176.9 (5)
C3^iii—C5—Br2	112.5 (3)	C22—C21—H21	173 (4)
C34—C35—C33^iv	124.7 (4)	C11—C12—C13	178.2 (6)
C34—C35—Br32	122.3 (3)	C2—C1—H1	177 (4)
C33^iv—C35—Br32	113.0 (3)	C12—C11—H11	167 (5)
C15—C14—C13	124.1 (4)	C32—C31—H4	175 (6)

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