1-(4-Bromo­phen­yl)-3-(3-methyl-2-thien­yl)prop-2-en-1-one

The title compound, C₁₄H₁₁BrOS, crystallizes with four independent mol­ecules (A, B, C and D) in the asymmetric unit which differ in the orientations of the thio­phene and benzene rings with respect to the enone unit. The dihedral angles between the benzene and thio­phene rings are 6.03 (14), 21.79 (14), 15.04 (14) and 4.92 (14)°, respectively, in mol­ecules A, B, C and D. Intra­molecular C—H...O and C—H...S inter­actions generate S(5) ring motifs. In the crystal structure, weak C—H...O inter­molecular hydrogen bonds link the mol­ecules into layers parallel to the [011] plane. In addition, short inter­molecular Br...O contacts [2.997 (2)–3.110 (2) Å] are observed.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.038
• wR factor = 0.108
• Data-to-parameter ratio = 23.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT431_ALERT_2_B Short Inter HL..A Contact  Br1B   ..  O1A     ..       3.00 Ang.
PLAT431_ALERT_2_B Short Inter HL..A Contact  Br1D   ..  O1C     ..       3.00 Ang.

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000)         200 Deg.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety       C14C
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1A   ..  O1B     ..       3.11 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1C   ..  O1D     ..       3.08 Ang.

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

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

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S1. Comment

Chalcone derivatives play an important role in non-linear optics (Patil, Dharmaprakash et al., 2006; Patil, Chantrapromma et al., 2007; Patil, Teh et al., 2006, 2007). We have synthesized a series of chalcone derivatives to study their non-linear optical properties (Patil, Teh et al., 2006; 2007; Patil, Dharmaprakash et al., 2006; Shettigar et al., 2006; Patil, Ng et al., 2007; Patil, Rosli et al., 2007; Patil, Chantrapromma et al., 2007). Now we report here the crystal and molecular structure of the title compound, (I). Compound (I) crystallizes in a centrosymmetric space group and hence this precludes the presence of second-order non-linear optical properties.

Compound (I) crystallizes with four independent molecules (A, B,, C and D) per asymmetric unit (Fig. 1). The dimensions of all four molecules are very similar, except for slightly different orientations of the thiophene and benzene rings with respect to the enone unit [C5–C7/O1]. The dihedral angles between the benzene and thiophene rings in molecules A, B, C and D are 6.03 (14)°, 21.79 (14)°, 15.04 (14)° and 4.92 (14)°, respectively. The enone unit in each molecule is slighly distorted from planarity, as indicated by the C5–C6–C7–O1 torsion angles of 2.8 (5)°, -3.9 (4)°, -4.7 (4) and 2.3 (4)°, respectively, in molecules A, B, C and D. The bond lengths and angles in (I) are within normal ranges (Allen et al., 1987) and comparable to those in related structures (Patil, Teh et al., 2006; Patil, Dharmaprakash et al., 2006; Shettigar et al., 2006; Patil, Ng et al., 2007; Patil, Chantrapromma et al., 2007).

In the molecular structure (Fig. 1), intramolecular C—H···O [H···O 2.41–2.46 Å, C···O 2.737 (4)–2.794 (4)Å and C—H···O 100–102°] and C—H···S [H···S 2.81–2.87 Å, C···S 3.171 (3)–3.190 (3) Å and C—H···S 103–104°] interactions generate S(5) ring motifs (Bernstein et al., 1995). In the crystal structure, the molecules are linked into layers parallel to the [0 1 1] plane by intermolecular C—H···O hydrogen bonds (Fig. 2 and Table 1). In addition, short intermolecular Br···O contacts [2.997 (2) Å-3.110 (2) Å] are observed.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data see: Allen et al. (1987). For related structures, see: Patil, Dharmaprakash et al. (2006); Patil, Ng et al. (2007); Patil, Rosli et al. (2007); Patil, Teh et al. (2006); Patil, Teh et al. (2007); Shettigar et al. (2006); Patil, Chantrapromma et al. (2007).

S2. Experimental

An aqueous solution of NaOH (10%, 10 ml) was slowly added with stirring (4 h) to a solution 3-methylthiophene-2-carbaldehyde (0.01 mol) and 4-bromoacetophenone (0.01 mol) in methanol (60 ml). The reaction mixture was diluted with water (250 ml), and kept aside for 12 h. The resulting solid was collected by filtration, dried and recrystallized from acetone. Yellow block-shaped single crystals of (I) suitable for X-ray analysis were grown by slow evaporation of an acetone solution at room temperature.

S3. Refinement

H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H distances in the range 0.93–0.96 Å. The U_iso values were constrained to be 1.5U_eq of the carrier atom for methyl H atoms and 1.2U_eq for the remaining H atoms. A rotating group model was used for the methyl groups. The highest residual density peak is located 0.87 Å from atom Br1B and the deepest hole is located 0.89 Å from atom Br1C.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures

	Fig. 1. The asymmetric unit of (I), showing 50% probability displacement ellipsoids and the atomic numbering. Dashed lines indicate hydrogen bonds.
	Fig. 2. The crystal packing of (I), viewed along the a axis. Hydrogen bonds are shown as dashed lines.

1-(4-Bromophenyl)-3-(3-methyl-2-thienyl)prop-2-en-1-one

Crystal data

C14H11BrOS	Z = 8
Mr = 307.20	F(000) = 1232
Triclinic, P1	Dx = 1.647 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4329 (3) Å	Cell parameters from 14381 reflections
b = 17.3541 (7) Å	θ = 1.1–30.0°
c = 19.2551 (8) Å	µ = 3.47 mm^−1
α = 90.736 (2)°	T = 100 K
β = 90.731 (2)°	Block, yellow
γ = 93.942 (2)°	0.56 × 0.54 × 0.34 mm
V = 2477.43 (17) Å^3

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer	14381 independent reflections
Radiation source: fine-focus sealed tube	10457 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 8.33 pixels mm^-1	θmax = 30.0°, θmin = 1.1°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −24→16
Tmin = 0.165, Tmax = 0.307	l = −27→27
42459 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0562P)^2 + 0.0358P] where P = (Fo^2 + 2Fc^2)/3
14381 reflections	(Δ/σ)max = 0.002
617 parameters	Δρmax = 1.18 e Å^−3
0 restraints	Δρmin = −0.91 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
Br1A	−0.10165 (4)	0.310304 (17)	−0.001640 (14)	0.02312 (7)
S1A	0.22066 (10)	0.02292 (4)	0.39343 (4)	0.02289 (15)
O1A	−0.0078 (3)	0.30625 (13)	0.34894 (11)	0.0365 (6)
C1A	0.2766 (4)	−0.02241 (17)	0.46806 (15)	0.0244 (6)
H1A	0.3248	−0.0704	0.4693	0.029*
C2A	0.2418 (4)	0.02041 (17)	0.52540 (15)	0.0239 (6)
H2A	0.2634	0.0043	0.5705	0.029*
C3A	0.1699 (4)	0.09143 (16)	0.51014 (14)	0.0210 (6)
C4A	0.1498 (4)	0.10185 (16)	0.43957 (15)	0.0222 (6)
C5A	0.0874 (4)	0.16816 (17)	0.40504 (15)	0.0238 (6)
H5A	0.0532	0.2082	0.4335	0.029*
C6A	0.0729 (4)	0.17880 (17)	0.33661 (16)	0.0249 (6)
H6A	0.0975	0.1392	0.3059	0.030*
C7A	0.0184 (4)	0.25267 (17)	0.30956 (16)	0.0256 (6)
C8A	−0.0036 (4)	0.26287 (17)	0.23283 (14)	0.0229 (6)
C9A	−0.0603 (4)	0.33339 (17)	0.21070 (16)	0.0259 (6)
H9A	−0.0794	0.3719	0.2433	0.031*
C10A	−0.0886 (4)	0.34700 (17)	0.14144 (16)	0.0254 (6)
H10A	−0.1261	0.3944	0.1272	0.031*
C11A	−0.0609 (4)	0.28962 (16)	0.09290 (14)	0.0204 (6)
C12A	−0.0034 (4)	0.21897 (17)	0.11279 (15)	0.0242 (6)
H12A	0.0159	0.1809	0.0798	0.029*
C13A	0.0250 (4)	0.20604 (18)	0.18297 (15)	0.0256 (6)
H13A	0.0636	0.1588	0.1970	0.031*
C14A	0.1198 (4)	0.14848 (17)	0.56469 (15)	0.0269 (6)
H14A	0.1440	0.2000	0.5480	0.040*
H14B	0.1896	0.1417	0.6062	0.040*
H14C	−0.0062	0.1401	0.5747	0.040*
Br1B	0.06425 (4)	0.641083 (17)	0.504583 (14)	0.02379 (7)
S1B	0.40741 (10)	0.35868 (4)	0.11048 (4)	0.02231 (15)
O1B	0.1524 (3)	0.63852 (12)	0.15444 (11)	0.0319 (5)
C1B	0.4340 (4)	0.30589 (17)	0.03649 (15)	0.0241 (6)
H1B	0.4787	0.2571	0.0358	0.029*
C2B	0.3829 (4)	0.34293 (17)	−0.02093 (15)	0.0235 (6)
H2B	0.3894	0.3222	−0.0655	0.028*
C3B	0.3184 (4)	0.41623 (16)	−0.00688 (15)	0.0216 (6)
C4B	0.3227 (4)	0.43335 (16)	0.06360 (14)	0.0190 (5)
C5B	0.2649 (4)	0.50129 (16)	0.09745 (15)	0.0223 (6)
H5B	0.2291	0.5403	0.0688	0.027*
C6B	0.2571 (4)	0.51440 (16)	0.16581 (15)	0.0219 (6)
H6B	0.2932	0.4773	0.1965	0.026*
C7B	0.1921 (4)	0.58672 (16)	0.19313 (15)	0.0220 (6)
C8B	0.1702 (4)	0.59630 (16)	0.26971 (14)	0.0195 (5)
C9B	0.1477 (4)	0.67065 (16)	0.29517 (14)	0.0216 (6)
H9B	0.1522	0.7119	0.2648	0.026*
C10B	0.1189 (4)	0.68366 (17)	0.36492 (15)	0.0239 (6)
H10B	0.1051	0.7334	0.3815	0.029*
C11B	0.1107 (4)	0.62180 (17)	0.40995 (14)	0.0213 (6)
C12B	0.1358 (4)	0.54770 (17)	0.38653 (15)	0.0237 (6)
H12B	0.1320	0.5067	0.4173	0.028*
C13B	0.1668 (4)	0.53542 (16)	0.31644 (15)	0.0224 (6)
H13B	0.1857	0.4859	0.3004	0.027*
C14B	0.2471 (4)	0.46610 (18)	−0.06228 (15)	0.0276 (6)
H14D	0.2317	0.5166	−0.0434	0.041*
H14E	0.1330	0.4436	−0.0792	0.041*
H14F	0.3308	0.4700	−0.0998	0.041*
Br1C	0.53300 (4)	0.176342 (17)	0.183227 (14)	0.02309 (7)
S1C	0.34254 (10)	0.49116 (4)	0.58077 (4)	0.02323 (15)
O1C	0.5620 (3)	0.20584 (12)	0.53536 (10)	0.0259 (4)
C1C	0.2863 (4)	0.53832 (17)	0.65503 (15)	0.0254 (6)
H1C	0.2566	0.5895	0.6566	0.031*
C2C	0.2900 (4)	0.49220 (17)	0.71170 (15)	0.0246 (6)
H2C	0.2642	0.5088	0.7564	0.029*
C3C	0.3371 (4)	0.41634 (17)	0.69565 (15)	0.0232 (6)
C4C	0.3716 (4)	0.40718 (16)	0.62578 (15)	0.0198 (5)
C5C	0.4270 (4)	0.33909 (16)	0.59083 (14)	0.0204 (6)
H5C	0.4495	0.2976	0.6190	0.024*
C6C	0.4501 (4)	0.32831 (16)	0.52246 (14)	0.0199 (5)
H6C	0.4243	0.3670	0.4917	0.024*
C7C	0.5159 (4)	0.25586 (16)	0.49582 (14)	0.0203 (6)
C8C	0.5224 (4)	0.24214 (16)	0.41909 (14)	0.0194 (5)
C9C	0.5869 (4)	0.17268 (17)	0.39661 (15)	0.0264 (6)
H9C	0.6282	0.1386	0.4291	0.032*
C10C	0.5906 (4)	0.15367 (17)	0.32688 (15)	0.0256 (6)
H10C	0.6329	0.1069	0.3125	0.031*
C11C	0.5307 (4)	0.20483 (16)	0.27847 (14)	0.0208 (6)
C12C	0.4694 (4)	0.27475 (16)	0.29928 (15)	0.0242 (6)
H12C	0.4318	0.3093	0.2665	0.029*
C13C	0.4644 (4)	0.29274 (16)	0.36920 (14)	0.0216 (6)
H13C	0.4216	0.3395	0.3833	0.026*
C14C	0.3428 (4)	0.35462 (18)	0.74890 (15)	0.0278 (7)
H14G	0.3778	0.3079	0.7274	0.042*
H14H	0.2256	0.3456	0.7688	0.042*
H14I	0.4287	0.3708	0.7848	0.042*
Br1D	0.43088 (4)	0.857276 (17)	0.320365 (14)	0.02597 (8)
S1D	0.12610 (10)	1.14678 (4)	−0.07243 (4)	0.02260 (15)
O1D	0.3873 (3)	0.86904 (12)	−0.03190 (10)	0.0272 (5)
C1D	0.0671 (4)	1.19363 (17)	−0.14590 (15)	0.0253 (6)
H1D	0.0313	1.2439	−0.1464	0.030*
C2D	0.0791 (4)	1.14818 (17)	−0.20368 (15)	0.0233 (6)
H2D	0.0525	1.1644	−0.2483	0.028*
C3D	0.1359 (4)	1.07380 (16)	−0.18900 (14)	0.0210 (6)
C4D	0.1677 (4)	1.06394 (16)	−0.11917 (14)	0.0190 (5)
C5D	0.2316 (4)	0.99729 (16)	−0.08575 (14)	0.0185 (5)
H5D	0.2602	0.9567	−0.1146	0.022*
C6D	0.2543 (4)	0.98747 (16)	−0.01763 (14)	0.0194 (5)
H6D	0.2193	1.0247	0.0136	0.023*
C7D	0.3352 (4)	0.91752 (16)	0.00857 (14)	0.0197 (5)
C8D	0.3539 (3)	0.90640 (16)	0.08476 (14)	0.0182 (5)
C9D	0.3961 (4)	0.83388 (16)	0.10723 (15)	0.0211 (6)
H9D	0.4086	0.7945	0.0748	0.025*
C10D	0.4196 (4)	0.81935 (17)	0.17707 (15)	0.0228 (6)
H10D	0.4465	0.7706	0.1917	0.027*
C11D	0.4025 (4)	0.87879 (17)	0.22492 (14)	0.0214 (6)
C12D	0.3609 (4)	0.95176 (17)	0.20408 (15)	0.0236 (6)
H12D	0.3494	0.9910	0.2367	0.028*
C13D	0.3366 (4)	0.96525 (16)	0.13381 (14)	0.0206 (6)
H13D	0.3086	1.0139	0.1193	0.025*
C14D	0.1559 (4)	1.01363 (17)	−0.24453 (14)	0.0263 (6)
H14L	0.1864	0.9663	−0.2235	0.039*
H14J	0.2498	1.0311	−0.2755	0.039*
H14K	0.0444	1.0050	−0.2700	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1A	0.02638 (14)	0.02635 (15)	0.01676 (14)	0.00262 (11)	−0.00219 (11)	0.00349 (11)
S1A	0.0299 (4)	0.0222 (3)	0.0168 (3)	0.0037 (3)	−0.0015 (3)	0.0019 (3)
O1A	0.0639 (16)	0.0296 (12)	0.0177 (11)	0.0158 (11)	−0.0010 (11)	0.0001 (9)
C1A	0.0302 (15)	0.0221 (14)	0.0215 (15)	0.0062 (12)	−0.0017 (12)	0.0047 (11)
C2A	0.0289 (15)	0.0262 (15)	0.0165 (14)	0.0014 (12)	−0.0041 (11)	0.0047 (11)
C3A	0.0217 (13)	0.0226 (14)	0.0188 (14)	0.0031 (11)	−0.0030 (11)	0.0014 (11)
C4A	0.0242 (14)	0.0218 (14)	0.0204 (14)	0.0007 (11)	0.0006 (11)	0.0025 (11)
C5A	0.0277 (15)	0.0224 (14)	0.0216 (15)	0.0042 (11)	−0.0044 (12)	0.0010 (11)
C6A	0.0300 (15)	0.0212 (14)	0.0235 (15)	0.0021 (12)	−0.0017 (12)	0.0043 (11)
C7A	0.0300 (15)	0.0257 (15)	0.0214 (15)	0.0041 (12)	−0.0008 (12)	0.0044 (12)
C8A	0.0246 (14)	0.0284 (15)	0.0153 (13)	0.0002 (12)	−0.0018 (11)	0.0013 (11)
C9A	0.0322 (16)	0.0226 (14)	0.0233 (15)	0.0048 (12)	0.0019 (12)	−0.0010 (12)
C10A	0.0300 (15)	0.0228 (15)	0.0244 (15)	0.0080 (12)	−0.0014 (12)	0.0047 (12)
C11A	0.0206 (13)	0.0229 (14)	0.0175 (13)	0.0012 (11)	−0.0004 (10)	0.0015 (11)
C12A	0.0292 (15)	0.0238 (15)	0.0196 (14)	0.0024 (12)	0.0008 (12)	0.0004 (11)
C13A	0.0310 (16)	0.0267 (15)	0.0194 (14)	0.0049 (12)	−0.0009 (12)	0.0031 (12)
C14A	0.0356 (16)	0.0253 (15)	0.0203 (15)	0.0064 (13)	−0.0007 (12)	0.0024 (12)
Br1B	0.02915 (15)	0.02746 (15)	0.01495 (13)	0.00330 (11)	−0.00046 (11)	0.00104 (11)
S1B	0.0277 (4)	0.0219 (3)	0.0177 (3)	0.0055 (3)	−0.0017 (3)	0.0024 (3)
O1B	0.0522 (14)	0.0242 (11)	0.0206 (11)	0.0120 (10)	−0.0044 (10)	0.0010 (9)
C1B	0.0242 (14)	0.0248 (15)	0.0239 (15)	0.0066 (11)	0.0011 (12)	0.0019 (12)
C2B	0.0272 (14)	0.0269 (15)	0.0172 (14)	0.0080 (12)	−0.0019 (11)	−0.0021 (11)
C3B	0.0235 (14)	0.0228 (14)	0.0186 (14)	0.0030 (11)	−0.0022 (11)	0.0000 (11)
C4B	0.0208 (13)	0.0193 (13)	0.0172 (13)	0.0030 (10)	−0.0038 (10)	0.0031 (10)
C5B	0.0223 (14)	0.0192 (14)	0.0257 (15)	0.0035 (11)	−0.0035 (11)	0.0021 (11)
C6B	0.0286 (15)	0.0196 (14)	0.0181 (14)	0.0056 (11)	−0.0024 (11)	0.0013 (11)
C7B	0.0262 (14)	0.0199 (14)	0.0198 (14)	0.0020 (11)	−0.0027 (11)	−0.0001 (11)
C8B	0.0200 (13)	0.0214 (14)	0.0175 (13)	0.0048 (10)	−0.0044 (10)	0.0020 (11)
C9B	0.0244 (14)	0.0220 (14)	0.0185 (14)	0.0029 (11)	−0.0029 (11)	0.0028 (11)
C10B	0.0292 (15)	0.0216 (14)	0.0211 (15)	0.0031 (11)	−0.0002 (12)	−0.0008 (11)
C11B	0.0242 (14)	0.0266 (15)	0.0126 (13)	−0.0015 (11)	−0.0009 (10)	−0.0003 (11)
C12B	0.0289 (15)	0.0233 (14)	0.0189 (14)	0.0019 (12)	−0.0040 (12)	0.0028 (11)
C13B	0.0293 (15)	0.0184 (13)	0.0199 (14)	0.0039 (11)	−0.0046 (11)	0.0015 (11)
C14B	0.0342 (16)	0.0283 (16)	0.0209 (15)	0.0079 (13)	−0.0043 (12)	0.0026 (12)
Br1C	0.03045 (15)	0.02499 (15)	0.01402 (13)	0.00372 (11)	−0.00169 (11)	−0.00025 (10)
S1C	0.0313 (4)	0.0205 (3)	0.0183 (3)	0.0029 (3)	0.0027 (3)	0.0027 (3)
O1C	0.0387 (12)	0.0236 (11)	0.0163 (10)	0.0097 (9)	−0.0019 (9)	0.0033 (8)
C1C	0.0303 (15)	0.0224 (15)	0.0239 (15)	0.0038 (12)	0.0034 (12)	−0.0017 (12)
C2C	0.0277 (15)	0.0260 (15)	0.0202 (14)	0.0039 (12)	−0.0002 (12)	−0.0021 (11)
C3C	0.0237 (14)	0.0253 (15)	0.0205 (14)	−0.0003 (11)	−0.0020 (11)	0.0025 (11)
C4C	0.0196 (13)	0.0198 (13)	0.0197 (14)	0.0009 (10)	−0.0033 (10)	0.0022 (11)
C5C	0.0223 (13)	0.0213 (14)	0.0175 (13)	0.0017 (11)	−0.0044 (11)	0.0012 (11)
C6C	0.0256 (14)	0.0182 (13)	0.0163 (13)	0.0034 (11)	−0.0027 (11)	0.0024 (10)
C7C	0.0252 (14)	0.0199 (13)	0.0160 (13)	0.0028 (11)	−0.0011 (11)	−0.0007 (10)
C8C	0.0236 (13)	0.0209 (14)	0.0135 (13)	0.0007 (11)	−0.0016 (10)	−0.0004 (10)
C9C	0.0377 (17)	0.0262 (15)	0.0165 (14)	0.0117 (13)	−0.0034 (12)	0.0040 (11)
C10C	0.0365 (16)	0.0226 (15)	0.0194 (14)	0.0140 (12)	0.0002 (12)	−0.0021 (11)
C11C	0.0261 (14)	0.0217 (14)	0.0142 (13)	−0.0011 (11)	−0.0008 (11)	−0.0013 (10)
C12C	0.0337 (16)	0.0205 (14)	0.0184 (14)	0.0012 (12)	−0.0039 (12)	0.0029 (11)
C13C	0.0279 (14)	0.0194 (14)	0.0179 (14)	0.0054 (11)	−0.0035 (11)	0.0001 (11)
C14C	0.0345 (16)	0.0287 (16)	0.0211 (15)	0.0068 (13)	−0.0004 (13)	0.0043 (12)
Br1D	0.03986 (17)	0.02542 (15)	0.01309 (13)	0.00557 (12)	−0.00239 (12)	0.00274 (11)
S1D	0.0296 (4)	0.0216 (3)	0.0173 (3)	0.0064 (3)	0.0000 (3)	0.0010 (3)
O1D	0.0411 (12)	0.0249 (11)	0.0166 (10)	0.0105 (9)	−0.0026 (9)	−0.0012 (8)
C1D	0.0305 (15)	0.0238 (15)	0.0225 (15)	0.0061 (12)	0.0034 (12)	0.0037 (12)
C2D	0.0262 (14)	0.0261 (15)	0.0183 (14)	0.0053 (12)	−0.0030 (11)	0.0063 (11)
C3D	0.0216 (13)	0.0242 (14)	0.0172 (13)	0.0033 (11)	−0.0028 (11)	0.0002 (11)
C4D	0.0193 (13)	0.0213 (13)	0.0165 (13)	0.0027 (10)	−0.0015 (10)	0.0003 (10)
C5D	0.0207 (13)	0.0200 (13)	0.0151 (13)	0.0041 (10)	−0.0024 (10)	−0.0004 (10)
C6D	0.0220 (13)	0.0199 (13)	0.0169 (13)	0.0057 (10)	−0.0027 (10)	0.0003 (10)
C7D	0.0221 (13)	0.0188 (13)	0.0186 (14)	0.0033 (10)	−0.0007 (11)	0.0014 (10)
C8D	0.0172 (12)	0.0232 (14)	0.0144 (13)	0.0024 (10)	−0.0027 (10)	0.0022 (10)
C9D	0.0253 (14)	0.0202 (14)	0.0181 (14)	0.0045 (11)	−0.0022 (11)	−0.0011 (11)
C10D	0.0292 (15)	0.0194 (14)	0.0202 (14)	0.0040 (11)	−0.0011 (12)	0.0027 (11)
C11D	0.0241 (14)	0.0255 (14)	0.0147 (13)	0.0028 (11)	−0.0016 (11)	0.0037 (11)
C12D	0.0302 (15)	0.0224 (14)	0.0184 (14)	0.0039 (12)	0.0000 (12)	−0.0002 (11)
C13D	0.0273 (14)	0.0192 (13)	0.0153 (13)	0.0032 (11)	−0.0018 (11)	−0.0006 (10)
C14D	0.0386 (17)	0.0251 (15)	0.0151 (14)	0.0032 (13)	−0.0083 (12)	−0.0003 (11)

Geometric parameters (Å, º)

Br1A—C11A	1.885 (3)	Br1C—C11C	1.894 (3)
S1A—C1A	1.707 (3)	S1C—C1C	1.709 (3)
S1A—C4A	1.739 (3)	S1C—C4C	1.730 (3)
O1A—C7A	1.220 (4)	O1C—C7C	1.225 (3)
C1A—C2A	1.360 (4)	C1C—C2C	1.363 (4)
C1A—H1A	0.93	C1C—H1C	0.93
C2A—C3A	1.410 (4)	C2C—C3C	1.417 (4)
C2A—H2A	0.93	C2C—H2C	0.93
C3A—C4A	1.381 (4)	C3C—C4C	1.382 (4)
C3A—C14A	1.502 (4)	C3C—C14C	1.495 (4)
C4A—C5A	1.438 (4)	C4C—C5C	1.440 (4)
C5A—C6A	1.337 (4)	C5C—C6C	1.342 (4)
C5A—H5A	0.93	C5C—H5C	0.93
C6A—C7A	1.470 (4)	C6C—C7C	1.469 (4)
C6A—H6A	0.93	C6C—H6C	0.93
C7A—C8A	1.499 (4)	C7C—C8C	1.495 (4)
C8A—C9A	1.392 (4)	C8C—C9C	1.394 (4)
C8A—C13A	1.396 (4)	C8C—C13C	1.394 (4)
C9A—C10A	1.374 (4)	C9C—C10C	1.380 (4)
C9A—H9A	0.93	C9C—H9C	0.93
C10A—C11A	1.384 (4)	C10C—C11C	1.386 (4)
C10A—H10A	0.93	C10C—H10C	0.93
C11A—C12A	1.383 (4)	C11C—C12C	1.382 (4)
C12A—C13A	1.388 (4)	C12C—C13C	1.380 (4)
C12A—H12A	0.93	C12C—H12C	0.93
C13A—H13A	0.93	C13C—H13C	0.93
C14A—H14A	0.96	C14C—H14G	0.96
C14A—H14B	0.96	C14C—H14H	0.96
C14A—H14C	0.96	C14C—H14I	0.96
Br1B—C11B	1.889 (3)	Br1D—C11D	1.892 (3)
S1B—C1B	1.705 (3)	S1D—C1D	1.708 (3)
S1B—C4B	1.737 (3)	S1D—C4D	1.734 (3)
O1B—C7B	1.224 (3)	O1D—C7D	1.225 (3)
C1B—C2B	1.349 (4)	C1D—C2D	1.363 (4)
C1B—H1B	0.93	C1D—H1D	0.93
C2B—C3B	1.414 (4)	C2D—C3D	1.416 (4)
C2B—H2B	0.93	C2D—H2D	0.93
C3B—C4B	1.385 (4)	C3D—C4D	1.377 (4)
C3B—C14B	1.497 (4)	C3D—C14D	1.501 (4)
C4B—C5B	1.434 (4)	C4D—C5D	1.437 (4)
C5B—C6B	1.336 (4)	C5D—C6D	1.335 (4)
C5B—H5B	0.93	C5D—H5D	0.93
C6B—C7B	1.469 (4)	C6D—C7D	1.482 (4)
C6B—H6B	0.93	C6D—H6D	0.93
C7B—C8B	1.494 (4)	C7D—C8D	1.488 (4)
C8B—C13B	1.396 (4)	C8D—C9D	1.391 (4)
C8B—C9B	1.396 (4)	C8D—C13D	1.396 (4)
C9B—C10B	1.381 (4)	C9D—C10D	1.383 (4)
C9B—H9B	0.93	C9D—H9D	0.93
C10B—C11B	1.387 (4)	C10D—C11D	1.388 (4)
C10B—H10B	0.93	C10D—H10D	0.93
C11B—C12B	1.383 (4)	C11D—C12D	1.387 (4)
C12B—C13B	1.388 (4)	C12D—C13D	1.388 (4)
C12B—H12B	0.93	C12D—H12D	0.93
C13B—H13B	0.93	C13D—H13D	0.93
C14B—H14D	0.96	C14D—H14L	0.96
C14B—H14E	0.96	C14D—H14J	0.96
C14B—H14F	0.96	C14D—H14K	0.96
C1A—S1A—C4A	91.91 (14)	C1C—S1C—C4C	91.55 (14)
C2A—C1A—S1A	111.6 (2)	C2C—C1C—S1C	112.1 (2)
C2A—C1A—H1A	124.2	C2C—C1C—H1C	123.9
S1A—C1A—H1A	124.2	S1C—C1C—H1C	123.9
C1A—C2A—C3A	113.7 (3)	C1C—C2C—C3C	113.1 (3)
C1A—C2A—H2A	123.2	C1C—C2C—H2C	123.4
C3A—C2A—H2A	123.2	C3C—C2C—H2C	123.4
C4A—C3A—C2A	112.2 (3)	C4C—C3C—C2C	111.8 (3)
C4A—C3A—C14A	124.3 (3)	C4C—C3C—C14C	125.5 (3)
C2A—C3A—C14A	123.6 (3)	C2C—C3C—C14C	122.8 (3)
C3A—C4A—C5A	127.6 (3)	C3C—C4C—C5C	127.5 (3)
C3A—C4A—S1A	110.6 (2)	C3C—C4C—S1C	111.4 (2)
C5A—C4A—S1A	121.7 (2)	C5C—C4C—S1C	121.0 (2)
C6A—C5A—C4A	127.3 (3)	C6C—C5C—C4C	127.8 (3)
C6A—C5A—H5A	116.3	C6C—C5C—H5C	116.1
C4A—C5A—H5A	116.3	C4C—C5C—H5C	116.1
C5A—C6A—C7A	120.5 (3)	C5C—C6C—C7C	120.6 (2)
C5A—C6A—H6A	119.8	C5C—C6C—H6C	119.7
C7A—C6A—H6A	119.8	C7C—C6C—H6C	119.7
O1A—C7A—C6A	120.7 (3)	O1C—C7C—C6C	121.2 (2)
O1A—C7A—C8A	119.4 (3)	O1C—C7C—C8C	119.5 (2)
C6A—C7A—C8A	119.9 (3)	C6C—C7C—C8C	119.4 (2)
C9A—C8A—C13A	118.5 (3)	C9C—C8C—C13C	118.3 (3)
C9A—C8A—C7A	117.1 (3)	C9C—C8C—C7C	117.0 (2)
C13A—C8A—C7A	124.4 (3)	C13C—C8C—C7C	124.7 (3)
C10A—C9A—C8A	121.0 (3)	C10C—C9C—C8C	121.0 (3)
C10A—C9A—H9A	119.5	C10C—C9C—H9C	119.5
C8A—C9A—H9A	119.5	C8C—C9C—H9C	119.5
C9A—C10A—C11A	119.5 (3)	C9C—C10C—C11C	119.4 (3)
C9A—C10A—H10A	120.2	C9C—C10C—H10C	120.3
C11A—C10A—H10A	120.2	C11C—C10C—H10C	120.3
C12A—C11A—C10A	121.2 (3)	C12C—C11C—C10C	120.7 (3)
C12A—C11A—Br1A	120.5 (2)	C12C—C11C—Br1C	120.8 (2)
C10A—C11A—Br1A	118.3 (2)	C10C—C11C—Br1C	118.5 (2)
C11A—C12A—C13A	118.7 (3)	C13C—C12C—C11C	119.3 (3)
C11A—C12A—H12A	120.7	C13C—C12C—H12C	120.3
C13A—C12A—H12A	120.7	C11C—C12C—H12C	120.3
C12A—C13A—C8A	121.1 (3)	C12C—C13C—C8C	121.2 (3)
C12A—C13A—H13A	119.5	C12C—C13C—H13C	119.4
C8A—C13A—H13A	119.5	C8C—C13C—H13C	119.4
C3A—C14A—H14A	109.5	C3C—C14C—H14G	109.5
C3A—C14A—H14B	109.5	C3C—C14C—H14H	109.5
H14A—C14A—H14B	109.5	H14G—C14C—H14H	109.5
C3A—C14A—H14C	109.5	C3C—C14C—H14I	109.5
H14A—C14A—H14C	109.5	H14G—C14C—H14I	109.5
H14B—C14A—H14C	109.5	H14H—C14C—H14I	109.5
C1B—S1B—C4B	91.52 (14)	C1D—S1D—C4D	92.09 (14)
C2B—C1B—S1B	112.3 (2)	C2D—C1D—S1D	111.6 (2)
C2B—C1B—H1B	123.8	C2D—C1D—H1D	124.2
S1B—C1B—H1B	123.8	S1D—C1D—H1D	124.2
C1B—C2B—C3B	113.6 (3)	C1D—C2D—C3D	113.3 (3)
C1B—C2B—H2B	123.2	C1D—C2D—H2D	123.4
C3B—C2B—H2B	123.2	C3D—C2D—H2D	123.4
C4B—C3B—C2B	111.6 (2)	C4D—C3D—C2D	112.3 (3)
C4B—C3B—C14B	125.4 (3)	C4D—C3D—C14D	125.1 (3)
C2B—C3B—C14B	122.9 (3)	C2D—C3D—C14D	122.5 (3)
C3B—C4B—C5B	127.6 (3)	C3D—C4D—C5D	127.7 (3)
C3B—C4B—S1B	110.9 (2)	C3D—C4D—S1D	110.7 (2)
C5B—C4B—S1B	121.5 (2)	C5D—C4D—S1D	121.5 (2)
C6B—C5B—C4B	126.8 (3)	C6D—C5D—C4D	126.9 (3)
C6B—C5B—H5B	116.6	C6D—C5D—H5D	116.5
C4B—C5B—H5B	116.6	C4D—C5D—H5D	116.5
C5B—C6B—C7B	120.8 (3)	C5D—C6D—C7D	120.4 (3)
C5B—C6B—H6B	119.6	C5D—C6D—H6D	119.8
C7B—C6B—H6B	119.6	C7D—C6D—H6D	119.8
O1B—C7B—C6B	121.4 (3)	O1D—C7D—C6D	120.6 (3)
O1B—C7B—C8B	119.5 (3)	O1D—C7D—C8D	119.8 (2)
C6B—C7B—C8B	119.1 (2)	C6D—C7D—C8D	119.6 (2)
C13B—C8B—C9B	118.7 (3)	C9D—C8D—C13D	119.1 (3)
C13B—C8B—C7B	123.9 (3)	C9D—C8D—C7D	117.5 (3)
C9B—C8B—C7B	117.4 (2)	C13D—C8D—C7D	123.4 (2)
C10B—C9B—C8B	120.8 (3)	C10D—C9D—C8D	121.0 (3)
C10B—C9B—H9B	119.6	C10D—C9D—H9D	119.5
C8B—C9B—H9B	119.6	C8D—C9D—H9D	119.5
C9B—C10B—C11B	119.4 (3)	C9D—C10D—C11D	118.9 (3)
C9B—C10B—H10B	120.3	C9D—C10D—H10D	120.5
C11B—C10B—H10B	120.3	C11D—C10D—H10D	120.5
C12B—C11B—C10B	121.1 (3)	C12D—C11D—C10D	121.4 (3)
C12B—C11B—Br1B	120.5 (2)	C12D—C11D—Br1D	120.3 (2)
C10B—C11B—Br1B	118.4 (2)	C10D—C11D—Br1D	118.3 (2)
C11B—C12B—C13B	119.0 (3)	C11D—C12D—C13D	119.0 (3)
C11B—C12B—H12B	120.5	C11D—C12D—H12D	120.5
C13B—C12B—H12B	120.5	C13D—C12D—H12D	120.5
C12B—C13B—C8B	121.0 (3)	C12D—C13D—C8D	120.6 (3)
C12B—C13B—H13B	119.5	C12D—C13D—H13D	119.7
C8B—C13B—H13B	119.5	C8D—C13D—H13D	119.7
C3B—C14B—H14D	109.5	C3D—C14D—H14L	109.5
C3B—C14B—H14E	109.5	C3D—C14D—H14J	109.5
H14D—C14B—H14E	109.5	H14L—C14D—H14J	109.5
C3B—C14B—H14F	109.5	C3D—C14D—H14K	109.5
H14D—C14B—H14F	109.5	H14L—C14D—H14K	109.5
H14E—C14B—H14F	109.5	H14J—C14D—H14K	109.5
C4A—S1A—C1A—C2A	0.4 (2)	C4C—S1C—C1C—C2C	0.2 (2)
S1A—C1A—C2A—C3A	−0.4 (3)	S1C—C1C—C2C—C3C	−0.7 (3)
C1A—C2A—C3A—C4A	0.2 (4)	C1C—C2C—C3C—C4C	1.0 (4)
C1A—C2A—C3A—C14A	179.7 (3)	C1C—C2C—C3C—C14C	−177.5 (3)
C2A—C3A—C4A—C5A	−177.5 (3)	C2C—C3C—C4C—C5C	178.4 (3)
C14A—C3A—C4A—C5A	3.1 (5)	C14C—C3C—C4C—C5C	−3.0 (5)
C2A—C3A—C4A—S1A	0.0 (3)	C2C—C3C—C4C—S1C	−0.9 (3)
C14A—C3A—C4A—S1A	−179.4 (2)	C14C—C3C—C4C—S1C	177.7 (2)
C1A—S1A—C4A—C3A	−0.2 (2)	C1C—S1C—C4C—C3C	0.4 (2)
C1A—S1A—C4A—C5A	177.4 (2)	C1C—S1C—C4C—C5C	−179.0 (2)
C3A—C4A—C5A—C6A	178.0 (3)	C3C—C4C—C5C—C6C	175.6 (3)
S1A—C4A—C5A—C6A	0.7 (4)	S1C—C4C—C5C—C6C	−5.2 (4)
C4A—C5A—C6A—C7A	−175.7 (3)	C4C—C5C—C6C—C7C	177.1 (3)
C5A—C6A—C7A—O1A	2.8 (5)	C5C—C6C—C7C—O1C	−4.7 (4)
C5A—C6A—C7A—C8A	−177.9 (3)	C5C—C6C—C7C—C8C	173.7 (3)
O1A—C7A—C8A—C9A	−2.4 (4)	O1C—C7C—C8C—C9C	−1.9 (4)
C6A—C7A—C8A—C9A	178.2 (3)	C6C—C7C—C8C—C9C	179.6 (3)
O1A—C7A—C8A—C13A	179.2 (3)	O1C—C7C—C8C—C13C	176.4 (3)
C6A—C7A—C8A—C13A	−0.2 (4)	C6C—C7C—C8C—C13C	−2.1 (4)
C13A—C8A—C9A—C10A	0.3 (4)	C13C—C8C—C9C—C10C	−1.2 (4)
C7A—C8A—C9A—C10A	−178.3 (3)	C7C—C8C—C9C—C10C	177.2 (3)
C8A—C9A—C10A—C11A	0.2 (5)	C8C—C9C—C10C—C11C	0.6 (5)
C9A—C10A—C11A—C12A	−0.7 (4)	C9C—C10C—C11C—C12C	0.7 (5)
C9A—C10A—C11A—Br1A	179.9 (2)	C9C—C10C—C11C—Br1C	−178.8 (2)
C10A—C11A—C12A—C13A	0.6 (4)	C10C—C11C—C12C—C13C	−1.4 (4)
Br1A—C11A—C12A—C13A	−180.0 (2)	Br1C—C11C—C12C—C13C	178.1 (2)
C11A—C12A—C13A—C8A	0.0 (4)	C11C—C12C—C13C—C8C	0.9 (4)
C9A—C8A—C13A—C12A	−0.4 (4)	C9C—C8C—C13C—C12C	0.4 (4)
C7A—C8A—C13A—C12A	178.0 (3)	C7C—C8C—C13C—C12C	−177.9 (3)
C4B—S1B—C1B—C2B	0.5 (2)	C4D—S1D—C1D—C2D	−0.2 (2)
S1B—C1B—C2B—C3B	−0.4 (3)	S1D—C1D—C2D—C3D	0.3 (3)
C1B—C2B—C3B—C4B	0.0 (4)	C1D—C2D—C3D—C4D	−0.3 (4)
C1B—C2B—C3B—C14B	−177.3 (3)	C1D—C2D—C3D—C14D	179.1 (3)
C2B—C3B—C4B—C5B	−178.6 (3)	C2D—C3D—C4D—C5D	−178.0 (3)
C14B—C3B—C4B—C5B	−1.3 (5)	C14D—C3D—C4D—C5D	2.6 (5)
C2B—C3B—C4B—S1B	0.3 (3)	C2D—C3D—C4D—S1D	0.2 (3)
C14B—C3B—C4B—S1B	177.6 (2)	C14D—C3D—C4D—S1D	−179.2 (2)
C1B—S1B—C4B—C3B	−0.4 (2)	C1D—S1D—C4D—C3D	0.0 (2)
C1B—S1B—C4B—C5B	178.6 (2)	C1D—S1D—C4D—C5D	178.3 (2)
C3B—C4B—C5B—C6B	174.5 (3)	C3D—C4D—C5D—C6D	−176.9 (3)
S1B—C4B—C5B—C6B	−4.4 (4)	S1D—C4D—C5D—C6D	5.1 (4)
C4B—C5B—C6B—C7B	−179.1 (3)	C4D—C5D—C6D—C7D	−175.2 (3)
C5B—C6B—C7B—O1B	−3.9 (4)	C5D—C6D—C7D—O1D	2.3 (4)
C5B—C6B—C7B—C8B	174.7 (3)	C5D—C6D—C7D—C8D	−178.0 (3)
O1B—C7B—C8B—C13B	163.1 (3)	O1D—C7D—C8D—C9D	−12.9 (4)
C6B—C7B—C8B—C13B	−15.5 (4)	C6D—C7D—C8D—C9D	167.4 (2)
O1B—C7B—C8B—C9B	−15.3 (4)	O1D—C7D—C8D—C13D	165.2 (3)
C6B—C7B—C8B—C9B	166.0 (3)	C6D—C7D—C8D—C13D	−14.5 (4)
C13B—C8B—C9B—C10B	−1.4 (4)	C13D—C8D—C9D—C10D	0.4 (4)
C7B—C8B—C9B—C10B	177.2 (3)	C7D—C8D—C9D—C10D	178.6 (3)
C8B—C9B—C10B—C11B	−0.6 (4)	C8D—C9D—C10D—C11D	−0.7 (4)
C9B—C10B—C11B—C12B	1.8 (4)	C9D—C10D—C11D—C12D	0.6 (4)
C9B—C10B—C11B—Br1B	−178.2 (2)	C9D—C10D—C11D—Br1D	178.9 (2)
C10B—C11B—C12B—C13B	−1.1 (4)	C10D—C11D—C12D—C13D	−0.2 (4)
Br1B—C11B—C12B—C13B	179.0 (2)	Br1D—C11D—C12D—C13D	−178.5 (2)
C11B—C12B—C13B—C8B	−0.9 (4)	C11D—C12D—C13D—C8D	−0.1 (4)
C9B—C8B—C13B—C12B	2.1 (4)	C9D—C8D—C13D—C12D	−0.1 (4)
C7B—C8B—C13B—C12B	−176.3 (3)	C7D—C8D—C13D—C12D	−178.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1A—H1A···O1C^i	0.93	2.55	3.478 (4)	175
C5A—H5A···O1A	0.93	2.43	2.773 (4)	102
C6A—H6A···S1A	0.93	2.84	3.190 (3)	104
C9A—H9A···O1A	0.93	2.41	2.737 (4)	100
C1B—H1B···O1D^ii	0.93	2.47	3.397 (4)	177
C5B—H5B···O1B	0.93	2.46	2.794 (4)	101
C6B—H6B···S1B	0.93	2.81	3.171 (3)	104
C5C—H5C···O1C	0.93	2.44	2.789 (3)	102
C6C—H6C···S1C	0.93	2.84	3.184 (3)	103
C9C—H9C···O1C	0.93	2.42	2.737 (3)	100
C1D—H1D···O1B^iii	0.93	2.54	3.440 (4)	164
C5D—H5D···O1D	0.93	2.44	2.784 (4)	102
C6D—H6D···S1D	0.93	2.82	3.174 (3)	104

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