Polymorphism of (Z)-4-bromo-N-(pent-2-enyl)-N-(3-phenyl­prop-2-ynyl)benzene­sulfonamide

The title compound, C₂₀H₂₀BrNO₂S, has two polymorphic crystal structures with very similar lattice constants. A number of crystals are composites of the two polymorphs. Both crystal structures contain identical layers of mol­ecules. The packing of the layers, however, is different for the two polymorphs.

S1. Comment

The title compound, (I), was prepared as a starting material for an enantioselective rhodium(I)/BINAP-catalyzed enyne cyclization (Hashmi et al., 2004). The structure of (I) was confirmed by X-ray analysis. During the experiments, it was found that several crystals showed split reflections and these were initially expected to be twinned. Indexing of the reflections of both domains, however, revealed the crystals to be composites of two polymorphs, hereinafter called modifications (Ia) and (Ib). A total of four crystals of the title compound were measured. One crystal was a pure (Ia) polymorph, and three crystals were composites of mainly polymorph (Ib) with minor contributions of polymorph (Ia). The contributions of the minor polymorph were estimated as 0.30, 0.30 and 0.04, respectively. The second of these three crystals showed the lowest R_int and wR(F²) values after the contributions from (Ia) had been subtracted from the observed reflection intensities. Its structure is reported here as the (Ib) polymorph and compared with that of the pure (Ia) polymorph.

The lattice constants of polymorphs (Ia) and (Ib) are closely related. The a and b axes of polymorph (Ia) coincide with the b and a axes of polymorph (Ib) in the composite crystals. The following relationship is found: a_(Ib) =-b_(Ia), b_(Ib) =-a_(Ia) and c_(Ib) = −0.395a_(Ia) + 0.334b_(Ia)– c_(Ia). The similarity of the unit-cell dimensions suggests that the crystal structures of (Ia) and (Ib) also are closely related. If the structures were the same then the fractional coordinates of the atoms would be related by x_(Ib) = y_(Ia) + 0.334z_(Ia), y_(Ib) = x_(Ia) − 0.395z_(Ia) and z_(Ib) = z_(Ia). For the atoms in the asymmetric unit, these relations are indeed confirmed.

The geometries of molecules (Ia) and (Ib) are almost identical (Fig. 1). The phenyl groups are essentially planar. The angles between the planes of the two phenyl groups are 49.18 (6)° in (Ia) and 49.66 (16)° in (Ib). The N atom is nonplanar: the sums of the three valence angles about N are 349.9 (2)° in (Ia) and 350.0 (4)° in (Ib).

The molecules show a number of intramolecular C—H···O and C—H···π contacts. For (Ia), these are H6···O1 2.50, H7A···O1 2.48, H16B···O2 2.41, H7B···C17 2.71, H16A···C8 2.66, H11···C4 3.00, H11···C5 2.98, H19A···C8 3.04 and H20C···C8 2.93 Å. Very similar contact distances are found in (Ib).

The intermolecular contacts are reported in Tables 1 and 2. The molecules form centrosymmetric dimers connected by two symmetry-related intermolecular C—H···Br contacts, with H···Br distances of 2.89 Å (Ia) or 2.87 Å (Ib). These dimers are connected by two intermolecular C—H···O contacts and two intermolecular C(phenyl)—H···π(phenyl) interactions to form layers parallel to the 001 plane. The layers with −1/4 < z < 1/4 are identical in (Ia) and (Ib), as shown in Figs. 2 and 3. Neighbouring layers, however, are arranged differently in (Ia) and (Ib). In both structures, the segments of the unit cell between −1/4 < z < 1/4 and 1/4 < z < 3/4 are related by a c-glide plane. The direction of the symmetry axis, however, is different in the two structures and is a result of different intermolecular interactions between the layer structures in (Ia) and (Ib). A weak intermolecular C20—H20B···C18(1 − x, 1/2 + y, 1/2 − z) interaction is observed in (Ia), while a weak intermolecular interaction between the C17—H17 bond and the C17═C18 double bond at (1 − x, y − 1/2, 1/2 − z) is observed in (Ib). The only other interaction between the layers is an intermolecular C18—H18···O2, contact with a H···O distance of 2.78 Å in (Ia) and 2.73 Å in (Ib). This interaction also acts differently in (Ia) and (Ib). The long H···O distance shows this interaction to be very weak.

The similarity of the unit-cell parameters of (Ia) and (Ib) results from the occurrence of identical two-dimensional structural domains in both polymorphs. The arrangement of adjacent domains in the c direction, however, is different in (Ia) and (Ib). Variations in the packing of the domains result in composite crystals. The occurrence of composite crystals consisting of two polymorphs is very rare - of over one thousand crystal structures determined in our laboratory, this is only the second example. The other case is the crystal structure of (2E,4S,5S,15R)-4,5-dihydroxyhexadec-2-en-15-olide (Cambridge Structural Database refcode JOKSAD). Here, the reflection data resulted from a combination of an orthorhombic lattice with a = 10.797 (1), b = 5.440 (3) and c = 28.390 (4) Å and a monoclinic lattice with a = 10.796 (1), b = 5.440 (3), c = 14.48 (2) Å and β = 100.40 (10)°. Both cells have the a and b axes in common. As this crystal structure was determined long before area detectors came into general use, only the structure of the major orthorhombic polymorph was determined (Quinkert et al., 1991). Another example of a composite crystal of two polymorphs with very similar crystal structures was reported by Freer & Kraut (1965).

S2. Experimental

The synthesis of the title compound was reported by Hashmi et al. (2004). Colourless plates were obtained from a solution of (I) in dichloromethane by diffusion of n-hexane.

S3. Refinement

The measured intensities of (Ib) were corrected for contributions from composite reflections of (Ia). If the positions of both reflections in reciprocal space differ by less than 0.3 reciprocal lattice units, then I_Ib,corrected = I_Ib,obs– k I_Ia,obs. Different values for the scaling factor k were tried and the best result was obtained for k = 0.3. Thus, 7431 of the 12467 measured reflections were corrected. The R_int value was 0.152 before the correction and 0.120 afterwards. wR(F²) decreased from 0.277 to 0.171. The still rather large value of R_int results from incomplete background corrections, due to many partially overlapping refection profiles. The 0.96-(Ib)/0.04-(Ia) crystal was of poor quality, resulting in broad reflection profiles. Consquently, this crystal had larger wR(F²) values than the 0.70-(Ib)/0.30-(Ia) crystal. H atoms were positioned geometrically at fixed distances of C(sp²)—H = 0.95, C_secondary—H = 0.99 and C_methyl—H = 0.98 Å, and refined as riding, with U_iso(H) = 1.2U_eq(C), or U_iso(H) = 1.5U_eq(methyl C). The torsion angle about the C—C axis was refined for the methyl group.

Computing details

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1996); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The structure of (Ia) at 157 K, shown with 50% probability displacement ellipsoids. The structure of (Ib) is similar.
	Fig. 2. The crystal packing of (Ia) at 157 K, viewed down a. The intermolecular C—H···Br contacts are represented as dashed lines.
	Fig. 3. The crystal packing of (Ib) at 156 K, viewed down b. The intermolecular C—H···Br contacts are represented as dashed lines.

(Ia) (Z)-4-bromo-N-(pent-2-enyl)-N-(3-phenylprop-2-ynyl)benzenesulfonamide

Crystal data

C20H20BrNO2S	F(000) = 856
Mr = 418.34	Dx = 1.486 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 193 reflections
a = 6.3199 (6) Å	θ = 3–23°
b = 7.3333 (9) Å	µ = 2.32 mm^−1
c = 40.438 (7) Å	T = 157 K
β = 93.571 (12)°	Plate, colourless
V = 1870.5 (4) Å^3	0.48 × 0.30 × 0.07 mm
Z = 4

Data collection

Siemens SMART 1K CCD area-detector diffractometer	5721 independent reflections
Radiation source: normal-focus sealed tube	4562 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
ω scans	θmax = 31.5°, θmin = 2.0°
Absorption correction: numerical (SHELXTL; Sheldrick, 1996)	h = −9→9
Tmin = 0.441, Tmax = 0.848	k = −10→9
21361 measured reflections	l = −56→60

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.19	w = 1/[σ^2(Fo^2) + (0.02P)^2 + 2P] where P = (Fo^2 + 2Fc^2)/3
5721 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.84 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
Br	0.15612 (6)	0.28797 (5)	0.016860 (7)	0.05126 (11)
S	−0.22811 (9)	0.32167 (8)	0.159524 (14)	0.02626 (13)
O1	−0.4434 (3)	0.3816 (3)	0.15456 (5)	0.0396 (4)
O2	−0.1818 (3)	0.1490 (2)	0.17502 (4)	0.0334 (4)
N	−0.1009 (3)	0.4766 (3)	0.18210 (5)	0.0227 (4)
C1	−0.1218 (3)	0.3183 (3)	0.12006 (5)	0.0227 (4)
C2	0.0792 (4)	0.2448 (3)	0.11711 (6)	0.0244 (5)
H2	0.1582	0.1990	0.1361	0.029*
C3	0.1629 (4)	0.2390 (3)	0.08624 (6)	0.0261 (5)
H3	0.3008	0.1914	0.0838	0.031*
C4	0.0416 (4)	0.3038 (3)	0.05903 (6)	0.0290 (5)
C5	−0.1582 (4)	0.3790 (3)	0.06166 (6)	0.0307 (5)
H5	−0.2377	0.4234	0.0426	0.037*
C6	−0.2389 (4)	0.3877 (3)	0.09272 (6)	0.0275 (5)
H6	−0.3739	0.4410	0.0953	0.033*
C7	−0.1225 (4)	0.6660 (3)	0.16996 (6)	0.0274 (5)
H7A	−0.2688	0.6841	0.1603	0.033*
H7B	−0.1009	0.7501	0.1890	0.033*
C8	0.0275 (4)	0.7144 (3)	0.14492 (6)	0.0266 (5)
C9	0.1519 (4)	0.7494 (3)	0.12479 (6)	0.0259 (5)
C10	0.3010 (4)	0.7936 (3)	0.10051 (6)	0.0248 (4)
C11	0.2499 (4)	0.7616 (3)	0.06685 (6)	0.0332 (5)
H11	0.1176	0.7078	0.0600	0.040*
C12	0.3921 (5)	0.8085 (4)	0.04344 (7)	0.0415 (7)
H12	0.3560	0.7885	0.0206	0.050*
C13	0.5868 (4)	0.8844 (4)	0.05335 (7)	0.0388 (6)
H13	0.6839	0.9159	0.0373	0.047*
C14	0.6396 (4)	0.9141 (3)	0.08647 (7)	0.0335 (6)
H14	0.7741	0.9642	0.0932	0.040*
C15	0.4973 (4)	0.8714 (3)	0.11015 (6)	0.0277 (5)
H15	0.5334	0.8950	0.1329	0.033*
C16	0.1098 (3)	0.4313 (3)	0.19848 (6)	0.0250 (5)
H16A	0.2234	0.4665	0.1839	0.030*
H16B	0.1198	0.2983	0.2025	0.030*
C17	0.1370 (4)	0.5325 (3)	0.23081 (5)	0.0257 (5)
H17	0.0523	0.4931	0.2481	0.031*
C18	0.2668 (4)	0.6709 (3)	0.23770 (6)	0.0280 (5)
H18	0.2678	0.7172	0.2596	0.034*
C19	0.4123 (4)	0.7635 (3)	0.21515 (6)	0.0297 (5)
H19A	0.4111	0.6960	0.1939	0.036*
H19B	0.5587	0.7607	0.2254	0.036*
C20	0.3471 (4)	0.9611 (4)	0.20830 (7)	0.0354 (6)
H20A	0.4530	1.0204	0.1952	0.053*
H20B	0.3379	1.0260	0.2293	0.053*
H20C	0.2088	0.9638	0.1959	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br	0.0770 (2)	0.05261 (19)	0.02607 (14)	0.02482 (17)	0.01880 (13)	0.00633 (13)
S	0.0209 (3)	0.0330 (3)	0.0256 (3)	−0.0048 (2)	0.0071 (2)	−0.0016 (2)
O1	0.0190 (8)	0.0585 (12)	0.0418 (11)	−0.0042 (8)	0.0070 (7)	−0.0068 (9)
O2	0.0403 (10)	0.0305 (9)	0.0303 (9)	−0.0112 (8)	0.0103 (7)	0.0022 (7)
N	0.0204 (9)	0.0257 (9)	0.0222 (9)	0.0002 (7)	0.0026 (7)	0.0011 (7)
C1	0.0217 (10)	0.0244 (11)	0.0224 (10)	−0.0038 (8)	0.0038 (8)	−0.0031 (8)
C2	0.0244 (11)	0.0259 (11)	0.0226 (10)	−0.0011 (9)	0.0001 (8)	0.0009 (8)
C3	0.0282 (11)	0.0233 (11)	0.0273 (11)	0.0022 (9)	0.0065 (9)	0.0000 (9)
C4	0.0425 (13)	0.0231 (11)	0.0224 (10)	0.0024 (10)	0.0084 (9)	−0.0004 (9)
C5	0.0372 (13)	0.0304 (13)	0.0239 (12)	0.0042 (10)	−0.0034 (10)	−0.0001 (9)
C6	0.0242 (11)	0.0271 (12)	0.0309 (12)	0.0015 (9)	−0.0002 (9)	−0.0030 (9)
C7	0.0267 (11)	0.0274 (12)	0.0284 (12)	0.0054 (9)	0.0047 (9)	0.0041 (9)
C8	0.0303 (12)	0.0244 (11)	0.0249 (11)	0.0018 (9)	−0.0017 (9)	0.0030 (9)
C9	0.0305 (12)	0.0214 (11)	0.0254 (11)	0.0018 (9)	−0.0008 (9)	0.0033 (8)
C10	0.0294 (11)	0.0183 (10)	0.0271 (11)	0.0022 (9)	0.0039 (9)	0.0015 (9)
C11	0.0383 (14)	0.0317 (13)	0.0299 (12)	−0.0092 (11)	0.0028 (10)	−0.0040 (10)
C12	0.0560 (17)	0.0413 (16)	0.0282 (13)	−0.0097 (13)	0.0101 (12)	−0.0076 (11)
C13	0.0436 (15)	0.0329 (14)	0.0421 (15)	−0.0041 (12)	0.0203 (12)	−0.0041 (11)
C14	0.0259 (12)	0.0246 (12)	0.0505 (16)	0.0010 (9)	0.0061 (11)	−0.0024 (11)
C15	0.0289 (12)	0.0248 (11)	0.0288 (12)	0.0043 (9)	−0.0028 (9)	0.0001 (9)
C16	0.0227 (11)	0.0262 (11)	0.0264 (11)	0.0021 (9)	0.0029 (9)	0.0013 (9)
C17	0.0265 (11)	0.0318 (12)	0.0192 (10)	0.0019 (9)	0.0038 (8)	0.0052 (9)
C18	0.0280 (12)	0.0342 (13)	0.0217 (11)	0.0046 (10)	0.0016 (9)	−0.0011 (9)
C19	0.0233 (11)	0.0364 (13)	0.0295 (12)	−0.0034 (10)	0.0041 (9)	−0.0036 (10)
C20	0.0340 (13)	0.0339 (14)	0.0383 (14)	−0.0087 (11)	0.0033 (11)	−0.0010 (11)

Geometric parameters (Å, º)

Br—C4	1.897 (2)	C10—C11	1.399 (3)
S—O1	1.4323 (18)	C11—C12	1.389 (4)
S—O2	1.4351 (19)	C11—H11	0.9500
S—N	1.637 (2)	C12—C13	1.386 (4)
S—C1	1.770 (2)	C12—H12	0.9500
N—C7	1.477 (3)	C13—C14	1.378 (4)
N—C16	1.488 (3)	C13—H13	0.9500
C1—C6	1.388 (3)	C14—C15	1.389 (3)
C1—C2	1.392 (3)	C14—H14	0.9500
C2—C3	1.386 (3)	C15—H15	0.9500
C2—H2	0.9500	C16—C17	1.504 (3)
C3—C4	1.385 (3)	C16—H16A	0.9900
C3—H3	0.9500	C16—H16B	0.9900
C4—C5	1.388 (4)	C17—C18	1.324 (3)
C5—C6	1.386 (3)	C17—H17	0.9500
C5—H5	0.9500	C18—C19	1.497 (3)
C6—H6	0.9500	C18—H18	0.9500
C7—C8	1.473 (3)	C19—C20	1.527 (4)
C7—H7A	0.9900	C19—H19A	0.9900
C7—H7B	0.9900	C19—H19B	0.9900
C8—C9	1.194 (3)	C20—H20A	0.9800
C9—C10	1.440 (3)	C20—H20B	0.9800
C10—C15	1.399 (3)	C20—H20C	0.9800
O1—S—O2	119.87 (12)	C12—C11—H11	120.0
O1—S—N	107.14 (11)	C10—C11—H11	120.0
O2—S—N	106.82 (10)	C13—C12—C11	120.2 (3)
O1—S—C1	106.77 (11)	C13—C12—H12	119.9
O2—S—C1	107.64 (11)	C11—C12—H12	119.9
N—S—C1	108.15 (10)	C14—C13—C12	120.1 (2)
C7—N—C16	114.81 (18)	C14—C13—H13	120.0
C7—N—S	115.82 (15)	C12—C13—H13	120.0
C16—N—S	119.23 (15)	C13—C14—C15	120.4 (2)
C6—C1—C2	121.2 (2)	C13—C14—H14	119.8
C6—C1—S	119.98 (17)	C15—C14—H14	119.8
C2—C1—S	118.83 (17)	C14—C15—C10	120.0 (2)
C3—C2—C1	119.4 (2)	C14—C15—H15	120.0
C3—C2—H2	120.3	C10—C15—H15	120.0
C1—C2—H2	120.3	N—C16—C17	109.12 (18)
C4—C3—C2	118.8 (2)	N—C16—H16A	109.9
C4—C3—H3	120.6	C17—C16—H16A	109.9
C2—C3—H3	120.6	N—C16—H16B	109.9
C3—C4—C5	122.4 (2)	C17—C16—H16B	109.9
C3—C4—Br	118.02 (18)	H16A—C16—H16B	108.3
C5—C4—Br	119.54 (18)	C18—C17—C16	126.6 (2)
C6—C5—C4	118.4 (2)	C18—C17—H17	116.7
C6—C5—H5	120.8	C16—C17—H17	116.7
C4—C5—H5	120.8	C17—C18—C19	128.0 (2)
C5—C6—C1	119.8 (2)	C17—C18—H18	116.0
C5—C6—H6	120.1	C19—C18—H18	116.0
C1—C6—H6	120.1	C18—C19—C20	111.8 (2)
C8—C7—N	113.91 (19)	C18—C19—H19A	109.3
C8—C7—H7A	108.8	C20—C19—H19A	109.3
N—C7—H7A	108.8	C18—C19—H19B	109.3
C8—C7—H7B	108.8	C20—C19—H19B	109.3
N—C7—H7B	108.8	H19A—C19—H19B	107.9
H7A—C7—H7B	107.7	C19—C20—H20A	109.5
C9—C8—C7	178.3 (3)	C19—C20—H20B	109.5
C8—C9—C10	179.4 (3)	H20A—C20—H20B	109.5
C15—C10—C11	119.1 (2)	C19—C20—H20C	109.5
C15—C10—C9	120.6 (2)	H20A—C20—H20C	109.5
C11—C10—C9	120.3 (2)	H20B—C20—H20C	109.5
C12—C11—C10	120.1 (2)
O1—S—N—C7	−51.89 (18)	C4—C5—C6—C1	−1.4 (4)
O2—S—N—C7	178.48 (15)	C2—C1—C6—C5	2.0 (4)
C1—S—N—C7	62.87 (18)	S—C1—C6—C5	−177.73 (19)
O1—S—N—C16	164.49 (16)	C16—N—C7—C8	60.6 (3)
O2—S—N—C16	34.86 (18)	S—N—C7—C8	−84.6 (2)
C1—S—N—C16	−80.75 (18)	C15—C10—C11—C12	−0.6 (4)
O1—S—C1—C6	7.1 (2)	C9—C10—C11—C12	178.5 (2)
O2—S—C1—C6	137.01 (19)	C10—C11—C12—C13	1.1 (4)
N—S—C1—C6	−107.92 (19)	C11—C12—C13—C14	−0.2 (4)
O1—S—C1—C2	−172.67 (18)	C12—C13—C14—C15	−1.1 (4)
O2—S—C1—C2	−42.8 (2)	C13—C14—C15—C10	1.5 (4)
N—S—C1—C2	72.3 (2)	C11—C10—C15—C14	−0.7 (3)
C6—C1—C2—C3	−0.7 (3)	C9—C10—C15—C14	−179.7 (2)
S—C1—C2—C3	179.06 (17)	C7—N—C16—C17	68.9 (2)
C1—C2—C3—C4	−1.2 (3)	S—N—C16—C17	−147.17 (16)
C2—C3—C4—C5	1.8 (4)	N—C16—C17—C18	−109.5 (3)
C2—C3—C4—Br	−178.20 (17)	C16—C17—C18—C19	1.9 (4)
C3—C4—C5—C6	−0.5 (4)	C17—C18—C19—C20	114.6 (3)
Br—C4—C5—C6	179.52 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Br^i	0.95	2.89	3.588 (3)	132
C16—H16A···O1^ii	0.99	2.56	3.448 (3)	149
C18—H18···O2^iii	0.95	2.78	3.607 (3)	147
C20—H20A···O2^iv	0.98	2.67	3.616 (3)	163
C3—H3···C14^v	0.95	2.95	3.841 (4)	157
C3—H3···C15^v	0.95	2.83	3.524 (4)	130
C14—H14···C1^iv	0.95	2.88	3.557 (4)	130
C14—H14···C2^iv	0.95	2.94	3.835 (3)	157
C20—H20B···C18^vi	0.98	2.96	3.525 (4)	118

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

(Ib) (Z)-4-bromo-N-(2-pentenyl)-N-(3-phenyl-2-propynyl)benzenesulfonamide

Crystal data

C20H20BrNO2S	F(000) = 856
Mr = 418.34	Dx = 1.482 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 73 reflections
a = 7.3219 (18) Å	θ = 3–23°
b = 6.3291 (17) Å	µ = 2.32 mm^−1
c = 40.535 (17) Å	T = 156 K
β = 93.419 (12)°	Plate, colourless
V = 1875.1 (10) Å^3	0.40 × 0.30 × 0.04 mm
Z = 4

Data collection

Siemens SMART 1K CCD area-detector diffractometer	4140 independent reflections
Radiation source: normal-focus sealed tube	3013 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.120
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: numerical (SHELXTL; Sheldrick, 1996)	h = −7→9
Tmin = 0.450, Tmax = 0.912	k = −8→8
12467 measured reflections	l = −38→53

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)] = 0.087	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H-atom parameters constrained
S = 1.19	w = 1/[σ^2(Fo^2) + (0.03P)^2 + 9P] where P = (Fo^2 + 2Fc^2)/3
4140 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.66 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
Br	0.29264 (11)	0.14739 (14)	0.016816 (17)	0.0494 (3)
S	0.3750 (2)	−0.2928 (2)	0.15912 (4)	0.0252 (3)
O1	0.4365 (6)	−0.5055 (7)	0.15402 (11)	0.0377 (11)
O2	0.2062 (6)	−0.2545 (7)	0.17428 (10)	0.0337 (10)
N	0.5358 (6)	−0.1726 (7)	0.18160 (11)	0.0211 (10)
C1	0.3578 (7)	−0.1715 (9)	0.11969 (14)	0.0225 (12)
C2	0.2833 (8)	0.0290 (9)	0.11665 (14)	0.0239 (12)
H2	0.2443	0.1004	0.1356	0.029*
C3	0.2656 (7)	0.1253 (10)	0.08605 (14)	0.0258 (12)
H3	0.2156	0.2634	0.0837	0.031*
C4	0.3224 (8)	0.0162 (11)	0.05877 (14)	0.0281 (13)
C5	0.3984 (8)	−0.1816 (10)	0.06154 (15)	0.0306 (14)
H5	0.4366	−0.2526	0.0425	0.037*
C6	0.4191 (8)	−0.2778 (10)	0.09251 (14)	0.0257 (12)
H6	0.4741	−0.4133	0.0949	0.031*
C7	0.7221 (8)	−0.1884 (10)	0.16946 (14)	0.0264 (12)
H7A	0.8126	−0.1744	0.1885	0.032*
H7B	0.7375	−0.3303	0.1598	0.032*
C8	0.7613 (8)	−0.0285 (10)	0.14467 (14)	0.0256 (12)
C9	0.7902 (7)	0.1038 (10)	0.12476 (14)	0.0255 (12)
C10	0.8261 (7)	0.2611 (10)	0.10051 (14)	0.0238 (12)
C11	0.7822 (8)	0.2248 (11)	0.06656 (16)	0.0333 (14)
H11	0.7263	0.0956	0.0596	0.040*
C12	0.8204 (9)	0.3765 (13)	0.04356 (16)	0.0411 (17)
H12	0.7914	0.3499	0.0208	0.049*
C13	0.9000 (8)	0.5661 (11)	0.05298 (16)	0.0357 (15)
H13	0.9257	0.6693	0.0369	0.043*
C14	0.9420 (8)	0.6047 (10)	0.08636 (17)	0.0322 (14)
H14	0.9950	0.7359	0.0931	0.039*
C15	0.9072 (7)	0.4531 (9)	0.10973 (15)	0.0264 (13)
H15	0.9389	0.4802	0.1324	0.032*
C16	0.4958 (8)	0.0307 (9)	0.19794 (14)	0.0254 (12)
H16A	0.3635	0.0394	0.2016	0.030*
H16B	0.5273	0.1498	0.1835	0.030*
C17	0.6044 (8)	0.0468 (10)	0.23033 (14)	0.0274 (13)
H17	0.5706	−0.0447	0.2475	0.033*
C18	0.7438 (8)	0.1773 (10)	0.23723 (14)	0.0283 (13)
H18	0.7951	0.1729	0.2593	0.034*
C19	0.8299 (9)	0.3295 (10)	0.21484 (15)	0.0328 (14)
H19A	0.8280	0.4725	0.2247	0.039*
H19B	0.7572	0.3342	0.1935	0.039*
C20	1.0259 (9)	0.2705 (11)	0.20868 (17)	0.0382 (16)
H20A	1.0809	0.3820	0.1958	0.057*
H20B	1.0272	0.1370	0.1964	0.057*
H20C	1.0962	0.2543	0.2299	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br	0.0508 (4)	0.0735 (6)	0.0244 (3)	0.0249 (4)	0.0060 (3)	0.0171 (4)
S	0.0314 (8)	0.0195 (7)	0.0243 (7)	−0.0051 (6)	−0.0012 (6)	0.0054 (6)
O1	0.055 (3)	0.020 (2)	0.038 (3)	−0.003 (2)	−0.004 (2)	0.0023 (19)
O2	0.030 (2)	0.041 (3)	0.030 (2)	−0.0132 (19)	0.0040 (18)	0.009 (2)
N	0.021 (2)	0.021 (2)	0.021 (2)	0.0010 (19)	−0.0002 (18)	0.0018 (19)
C1	0.020 (3)	0.021 (3)	0.026 (3)	−0.002 (2)	−0.002 (2)	0.001 (2)
C2	0.025 (3)	0.026 (3)	0.021 (3)	−0.001 (2)	0.002 (2)	−0.003 (2)
C3	0.021 (3)	0.029 (3)	0.027 (3)	0.003 (2)	0.001 (2)	0.008 (3)
C4	0.022 (3)	0.046 (4)	0.016 (3)	0.000 (3)	0.001 (2)	0.006 (3)
C5	0.027 (3)	0.036 (4)	0.028 (3)	0.001 (3)	0.001 (2)	−0.006 (3)
C6	0.025 (3)	0.024 (3)	0.028 (3)	0.002 (2)	−0.001 (2)	−0.001 (2)
C7	0.025 (3)	0.029 (3)	0.025 (3)	0.004 (2)	0.005 (2)	0.002 (2)
C8	0.022 (3)	0.029 (3)	0.026 (3)	0.005 (2)	0.005 (2)	−0.004 (3)
C9	0.021 (3)	0.027 (3)	0.028 (3)	0.002 (2)	0.005 (2)	−0.002 (3)
C10	0.019 (3)	0.030 (3)	0.023 (3)	0.004 (2)	0.005 (2)	0.002 (2)
C11	0.030 (3)	0.035 (3)	0.034 (3)	−0.008 (3)	−0.001 (3)	0.001 (3)
C12	0.037 (4)	0.057 (5)	0.027 (3)	−0.003 (3)	−0.011 (3)	0.008 (3)
C13	0.029 (3)	0.042 (4)	0.036 (4)	0.002 (3)	0.000 (3)	0.020 (3)
C14	0.024 (3)	0.022 (3)	0.051 (4)	0.004 (2)	0.004 (3)	0.004 (3)
C15	0.021 (3)	0.026 (3)	0.032 (3)	0.008 (2)	0.000 (2)	−0.002 (2)
C16	0.023 (3)	0.024 (3)	0.030 (3)	−0.001 (2)	0.005 (2)	0.001 (2)
C17	0.026 (3)	0.036 (3)	0.021 (3)	0.003 (3)	0.007 (2)	0.005 (2)
C18	0.034 (3)	0.030 (3)	0.021 (3)	0.005 (3)	0.003 (2)	−0.003 (2)
C19	0.042 (4)	0.024 (3)	0.031 (3)	−0.006 (3)	−0.007 (3)	0.001 (3)
C20	0.036 (4)	0.040 (4)	0.039 (4)	−0.017 (3)	−0.004 (3)	0.007 (3)

Geometric parameters (Å, º)

Br—C4	1.893 (6)	C10—C11	1.413 (8)
S—O2	1.433 (5)	C11—C12	1.379 (9)
S—O1	1.439 (5)	C11—H11	0.9500
S—N	1.633 (5)	C12—C13	1.378 (10)
S—C1	1.770 (6)	C12—H12	0.9500
N—C7	1.481 (7)	C13—C14	1.391 (9)
N—C16	1.484 (7)	C13—H13	0.9500
C1—C2	1.384 (8)	C14—C15	1.383 (9)
C1—C6	1.388 (8)	C14—H14	0.9500
C2—C3	1.382 (8)	C15—H15	0.9500
C2—H2	0.9500	C16—C17	1.497 (8)
C3—C4	1.388 (9)	C16—H16A	0.9900
C3—H3	0.9500	C16—H16B	0.9900
C4—C5	1.372 (9)	C17—C18	1.330 (9)
C5—C6	1.395 (8)	C17—H17	0.9500
C5—H5	0.9500	C18—C19	1.489 (9)
C6—H6	0.9500	C18—H18	0.9500
C7—C8	1.466 (8)	C19—C20	1.518 (9)
C7—H7A	0.9900	C19—H19A	0.9900
C7—H7B	0.9900	C19—H19B	0.9900
C8—C9	1.190 (8)	C20—H20A	0.9800
C9—C10	1.434 (8)	C20—H20B	0.9800
C10—C15	1.393 (9)	C20—H20C	0.9800
O2—S—O1	120.3 (3)	C12—C11—H11	119.9
O2—S—N	107.1 (3)	C10—C11—H11	119.9
O1—S—N	107.1 (3)	C13—C12—C11	121.3 (6)
O2—S—C1	107.3 (3)	C13—C12—H12	119.4
O1—S—C1	106.4 (3)	C11—C12—H12	119.4
N—S—C1	108.2 (2)	C12—C13—C14	119.2 (6)
C7—N—C16	114.6 (4)	C12—C13—H13	120.4
C7—N—S	115.5 (4)	C14—C13—H13	120.4
C16—N—S	119.9 (4)	C15—C14—C13	120.4 (6)
C2—C1—C6	121.2 (5)	C15—C14—H14	119.8
C2—C1—S	119.0 (4)	C13—C14—H14	119.8
C6—C1—S	119.8 (4)	C14—C15—C10	121.0 (6)
C3—C2—C1	120.0 (5)	C14—C15—H15	119.5
C3—C2—H2	120.0	C10—C15—H15	119.5
C1—C2—H2	120.0	N—C16—C17	110.0 (5)
C2—C3—C4	118.6 (6)	N—C16—H16A	109.7
C2—C3—H3	120.7	C17—C16—H16A	109.7
C4—C3—H3	120.7	N—C16—H16B	109.7
C5—C4—C3	121.9 (5)	C17—C16—H16B	109.7
C5—C4—Br	119.9 (5)	H16A—C16—H16B	108.2
C3—C4—Br	118.3 (5)	C18—C17—C16	126.0 (5)
C4—C5—C6	119.6 (6)	C18—C17—H17	117.0
C4—C5—H5	120.2	C16—C17—H17	117.0
C6—C5—H5	120.2	C17—C18—C19	128.4 (5)
C1—C6—C5	118.7 (5)	C17—C18—H18	115.8
C1—C6—H6	120.7	C19—C18—H18	115.8
C5—C6—H6	120.7	C18—C19—C20	112.3 (5)
C8—C7—N	113.8 (5)	C18—C19—H19A	109.1
C8—C7—H7A	108.8	C20—C19—H19A	109.1
N—C7—H7A	108.8	C18—C19—H19B	109.1
C8—C7—H7B	108.8	C20—C19—H19B	109.1
N—C7—H7B	108.8	H19A—C19—H19B	107.9
H7A—C7—H7B	107.7	C19—C20—H20A	109.5
C9—C8—C7	178.6 (6)	C19—C20—H20B	109.5
C8—C9—C10	179.3 (6)	H20A—C20—H20B	109.5
C15—C10—C11	118.1 (6)	C19—C20—H20C	109.5
C15—C10—C9	120.9 (5)	H20A—C20—H20C	109.5
C11—C10—C9	120.9 (6)	H20B—C20—H20C	109.5
C12—C11—C10	120.1 (6)
O2—S—N—C7	−178.4 (4)	C2—C1—C6—C5	−2.3 (8)
O1—S—N—C7	51.2 (5)	S—C1—C6—C5	177.9 (4)
C1—S—N—C7	−63.1 (4)	C4—C5—C6—C1	1.5 (8)
O2—S—N—C16	−34.7 (5)	C16—N—C7—C8	−60.6 (6)
O1—S—N—C16	−165.0 (4)	S—N—C7—C8	85.1 (6)
C1—S—N—C16	80.7 (4)	C15—C10—C11—C12	0.3 (9)
O2—S—C1—C2	43.5 (5)	C9—C10—C11—C12	−179.0 (6)
O1—S—C1—C2	173.5 (4)	C10—C11—C12—C13	−0.6 (10)
N—S—C1—C2	−71.7 (5)	C11—C12—C13—C14	−0.1 (10)
O2—S—C1—C6	−136.7 (5)	C12—C13—C14—C15	1.0 (9)
O1—S—C1—C6	−6.6 (5)	C13—C14—C15—C10	−1.3 (8)
N—S—C1—C6	108.2 (5)	C11—C10—C15—C14	0.6 (8)
C6—C1—C2—C3	1.3 (8)	C9—C10—C15—C14	179.9 (5)
S—C1—C2—C3	−178.9 (4)	C7—N—C16—C17	−69.6 (6)
C1—C2—C3—C4	0.5 (8)	S—N—C16—C17	146.3 (4)
C2—C3—C4—C5	−1.3 (9)	N—C16—C17—C18	110.2 (7)
C2—C3—C4—Br	178.7 (4)	C16—C17—C18—C19	−2.8 (10)
C3—C4—C5—C6	0.3 (9)	C17—C18—C19—C20	−114.3 (7)
Br—C4—C5—C6	−179.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Br^i	0.95	2.87	3.579 (7)	132
C16—H16B···O1^ii	0.99	2.56	3.447 (7)	150
C18—H18···O2^iii	0.95	2.73	3.610 (7)	154
C20—H20A···O2^iv	0.98	2.64	3.598 (8)	165
C3—H3···C14^v	0.95	2.95	3.850 (9)	158
C3—H3···C15^v	0.95	2.82	3.523 (9)	132
C14—H14···C1^iv	0.95	2.87	3.551 (9)	130
C14—H14···C2^iv	0.95	2.93	3.821 (9)	157
C17—H17···C17^vi	0.95	3.05	3.901 (9)	150
C17—H17···C18^vi	0.95	3.00	3.761 (9)	138

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