(Z)-3-(4-Bromo-phen-yl)-2-[(2-phenyl-cyclo-hex-2-en-1-yl)imino]-1,3-thia-zol-idin-4-one.

The title compound, C(21)H(19)BrN(2)OS, exists in a cis conformation with respect to the N=C bond [1.2602 (14) Å]. The cyclo-hexene ring adopts a distorted half-chair conformation and the C-N bond lies in an equatorial orientation. The thia-zolidine ring forms dihedral angles of 53.76 (7) and 57.22 (7)° with the benzene and bromo-substituted benzene rings, respectively. The dihedral angle between the benzene and bromo-substituted benzene rings is 76.06 (7)°. In the crystal, inversion dimers linked by pairs of C-H⋯O hydrogen bonds generate R(2) (2)(14) loops. The crystal is further consolidated by weak C-H⋯π inter-actions.

Related literature

For related structures and background to thia­zolidin-4-one derivatives, see: Fun et al. (2011 ▶); Ooi et al. (2012a ▶,b ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C21H19BrN2OS

M = 427.35

Monoclinic,

a = 9.4573 (1) Å

b = 16.6662 (3) Å

c = 13.8812 (2) Å

β = 122.665 (1)°

V = 1841.88 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.36 mm−1

T = 100 K

0.45 × 0.29 × 0.25 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.418, T max = 0.587

24632 measured reflections

6727 independent reflections

5751 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.069

S = 1.04

6727 reflections

235 parameters

H-atom parameters constrained

Δρmax = 0.55 e Å−3

Δρmin = −0.27 e Å−3

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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812024646/hb6826sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024646/hb6826Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812024646/hb6826Isup3.cml

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

C21H19BrN2OS	F(000) = 872
Mr = 427.35	Dx = 1.541 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9954 reflections
a = 9.4573 (1) Å	θ = 2.8–32.6°
b = 16.6662 (3) Å	µ = 2.36 mm−1
c = 13.8812 (2) Å	T = 100 K
β = 122.665 (1)°	Block, yellow
V = 1841.88 (5) Å3	0.45 × 0.29 × 0.25 mm
Z = 4

Bruker SMART APEXII CCD diffractometer	6727 independent reflections
Radiation source: fine-focus sealed tube	5751 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 32.7°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→12
Tmin = 0.418, Tmax = 0.587	k = −25→25
24632 measured reflections	l = −21→20

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0366P)2 + 0.4872P] where P = (Fo2 + 2Fc2)/3
6727 reflections	(Δ/σ)max = 0.002
235 parameters	Δρmax = 0.55 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100 (1) K.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Br1	0.262828 (17)	−0.045374 (7)	0.626813 (11)	0.02221 (4)
S1	0.23445 (4)	0.328421 (18)	1.04486 (3)	0.02081 (7)
O1	0.31396 (12)	0.10045 (6)	1.08962 (8)	0.02302 (18)
N1	0.19965 (12)	0.30829 (6)	0.83807 (8)	0.01380 (17)
N2	0.26458 (12)	0.19597 (6)	0.95606 (8)	0.01426 (17)
C1	−0.18227 (16)	0.31078 (8)	0.68851 (12)	0.0211 (2)
H1A	−0.1535	0.3282	0.7605	0.025*
C2	−0.30028 (16)	0.25012 (8)	0.63418 (13)	0.0260 (3)
H2A	−0.3507	0.2276	0.6697	0.031*
C3	−0.34355 (17)	0.22278 (8)	0.52691 (13)	0.0305 (3)
H3A	−0.4219	0.1818	0.4910	0.037*
C4	−0.26912 (18)	0.25702 (9)	0.47385 (12)	0.0295 (3)
H4A	−0.2979	0.2392	0.4020	0.035*
C5	−0.15163 (16)	0.31794 (8)	0.52797 (10)	0.0217 (2)
H5A	−0.1024	0.3405	0.4917	0.026*
C6	−0.10613 (14)	0.34592 (7)	0.63606 (10)	0.0164 (2)
C7	0.02578 (14)	0.40843 (7)	0.69463 (9)	0.01424 (19)
C8	0.02723 (15)	0.47371 (7)	0.63914 (10)	0.0167 (2)
H8A	−0.0613	0.4805	0.5636	0.020*
C9	0.16181 (16)	0.53696 (7)	0.69010 (10)	0.0173 (2)
H9A	0.1092	0.5895	0.6721	0.021*
H9B	0.2270	0.5332	0.6552	0.021*
C10	0.27966 (16)	0.52939 (7)	0.81938 (10)	0.0180 (2)
H10A	0.2274	0.5531	0.8565	0.022*
H10B	0.3828	0.5584	0.8443	0.022*
C11	0.32010 (15)	0.44150 (7)	0.85432 (10)	0.0173 (2)
H11A	0.3981	0.4380	0.9365	0.021*
H11B	0.3736	0.4180	0.8179	0.021*
C12	0.16053 (14)	0.39451 (7)	0.81969 (9)	0.01417 (19)
H12A	0.1183	0.4119	0.8671	0.017*
C13	0.23002 (14)	0.27822 (7)	0.93069 (9)	0.01370 (19)
C14	0.28566 (16)	0.23800 (8)	1.12881 (10)	0.0194 (2)
H14A	0.3938	0.2437	1.2000	0.023*
H14B	0.2014	0.2276	1.1468	0.023*
C15	0.29094 (15)	0.16970 (7)	1.05911 (10)	0.0163 (2)
C16	0.26532 (14)	0.14088 (7)	0.87679 (9)	0.01387 (19)
C17	0.40768 (15)	0.09488 (7)	0.91258 (10)	0.0172 (2)
H17A	0.5026	0.1016	0.9857	0.021*
C18	0.40766 (16)	0.03854 (7)	0.83822 (11)	0.0182 (2)
H18A	0.5018	0.0070	0.8610	0.022*
C19	0.26453 (15)	0.03056 (7)	0.72975 (10)	0.0161 (2)
C20	0.12226 (15)	0.07709 (7)	0.69269 (10)	0.0165 (2)
H20A	0.0279	0.0708	0.6192	0.020*
C21	0.12320 (14)	0.13315 (7)	0.76719 (10)	0.0154 (2)
H21A	0.0296	0.1652	0.7439	0.018*

	U11	U22	U33	U12	U13	U23
Br1	0.02917 (7)	0.01757 (6)	0.02310 (7)	0.00051 (4)	0.01621 (6)	−0.00474 (4)
S1	0.03491 (17)	0.01512 (13)	0.01733 (13)	0.00423 (11)	0.01734 (13)	0.00082 (10)
O1	0.0320 (5)	0.0179 (4)	0.0258 (4)	0.0073 (4)	0.0200 (4)	0.0086 (3)
N1	0.0161 (4)	0.0116 (4)	0.0139 (4)	0.0011 (3)	0.0082 (3)	0.0007 (3)
N2	0.0187 (4)	0.0120 (4)	0.0137 (4)	0.0016 (3)	0.0098 (4)	0.0018 (3)
C1	0.0189 (5)	0.0175 (5)	0.0273 (6)	0.0013 (4)	0.0127 (5)	0.0019 (4)
C2	0.0164 (5)	0.0196 (6)	0.0399 (8)	0.0008 (4)	0.0139 (5)	0.0046 (5)
C3	0.0171 (6)	0.0174 (6)	0.0401 (8)	−0.0024 (5)	0.0042 (6)	−0.0016 (5)
C4	0.0245 (6)	0.0219 (6)	0.0236 (6)	0.0002 (5)	0.0007 (5)	−0.0047 (5)
C5	0.0227 (6)	0.0183 (5)	0.0179 (5)	−0.0001 (4)	0.0068 (5)	0.0002 (4)
C6	0.0141 (5)	0.0129 (5)	0.0183 (5)	0.0021 (4)	0.0062 (4)	0.0015 (4)
C7	0.0148 (5)	0.0133 (5)	0.0146 (5)	0.0008 (4)	0.0079 (4)	−0.0002 (4)
C8	0.0182 (5)	0.0156 (5)	0.0141 (5)	0.0011 (4)	0.0074 (4)	0.0013 (4)
C9	0.0217 (5)	0.0131 (5)	0.0181 (5)	0.0002 (4)	0.0113 (4)	0.0018 (4)
C10	0.0205 (5)	0.0127 (5)	0.0180 (5)	−0.0023 (4)	0.0086 (4)	−0.0012 (4)
C11	0.0170 (5)	0.0137 (5)	0.0168 (5)	−0.0002 (4)	0.0062 (4)	0.0003 (4)
C12	0.0173 (5)	0.0112 (5)	0.0138 (4)	0.0011 (4)	0.0083 (4)	0.0009 (3)
C13	0.0150 (5)	0.0118 (5)	0.0143 (4)	0.0005 (4)	0.0079 (4)	−0.0005 (3)
C14	0.0268 (6)	0.0180 (5)	0.0164 (5)	0.0025 (4)	0.0137 (5)	0.0021 (4)
C15	0.0172 (5)	0.0183 (5)	0.0157 (5)	0.0028 (4)	0.0104 (4)	0.0034 (4)
C16	0.0172 (5)	0.0113 (5)	0.0149 (5)	0.0003 (4)	0.0099 (4)	0.0004 (3)
C17	0.0176 (5)	0.0153 (5)	0.0171 (5)	0.0022 (4)	0.0082 (4)	0.0014 (4)
C18	0.0201 (5)	0.0154 (5)	0.0204 (5)	0.0041 (4)	0.0118 (5)	0.0017 (4)
C19	0.0217 (5)	0.0115 (5)	0.0189 (5)	−0.0010 (4)	0.0134 (5)	−0.0014 (4)
C20	0.0183 (5)	0.0152 (5)	0.0167 (5)	−0.0013 (4)	0.0099 (4)	−0.0004 (4)
C21	0.0158 (5)	0.0144 (5)	0.0166 (5)	0.0006 (4)	0.0092 (4)	0.0007 (4)

Br1—C19	1.9023 (11)	C8—H8A	0.9300
S1—C13	1.7725 (11)	C9—C10	1.5230 (17)
S1—C14	1.8039 (12)	C9—H9A	0.9700
O1—C15	1.2080 (14)	C9—H9B	0.9700
N1—C13	1.2602 (14)	C10—C11	1.5254 (16)
N1—C12	1.4714 (14)	C10—H10A	0.9700
N2—C15	1.3839 (14)	C10—H10B	0.9700
N2—C13	1.4090 (14)	C11—C12	1.5293 (16)
N2—C16	1.4360 (14)	C11—H11A	0.9700
C1—C2	1.3884 (18)	C11—H11B	0.9700
C1—C6	1.3992 (17)	C12—H12A	0.9800
C1—H1A	0.9300	C14—C15	1.5122 (17)
C2—C3	1.391 (2)	C14—H14A	0.9700
C2—H2A	0.9300	C14—H14B	0.9700
C3—C4	1.387 (2)	C16—C17	1.3875 (16)
C3—H3A	0.9300	C16—C21	1.3894 (15)
C4—C5	1.3887 (19)	C17—C18	1.3953 (16)
C4—H4A	0.9300	C17—H17A	0.9300
C5—C6	1.3990 (17)	C18—C19	1.3846 (17)
C5—H5A	0.9300	C18—H18A	0.9300
C6—C7	1.4858 (16)	C19—C20	1.3889 (17)
C7—C8	1.3374 (16)	C20—C21	1.3902 (16)
C7—C12	1.5177 (15)	C20—H20A	0.9300
C8—C9	1.5032 (17)	C21—H21A	0.9300
C13—S1—C14	92.97 (5)	C10—C11—H11A	109.5
C13—N1—C12	117.57 (9)	C12—C11—H11A	109.5
C15—N2—C13	117.01 (9)	C10—C11—H11B	109.5
C15—N2—C16	121.13 (9)	C12—C11—H11B	109.5
C13—N2—C16	121.80 (9)	H11A—C11—H11B	108.1
C2—C1—C6	120.71 (13)	N1—C12—C7	108.97 (9)
C2—C1—H1A	119.6	N1—C12—C11	109.42 (9)
C6—C1—H1A	119.6	C7—C12—C11	110.99 (9)
C1—C2—C3	120.39 (13)	N1—C12—H12A	109.1
C1—C2—H2A	119.8	C7—C12—H12A	109.1
C3—C2—H2A	119.8	C11—C12—H12A	109.1
C4—C3—C2	119.56 (12)	N1—C13—N2	122.43 (10)
C4—C3—H3A	120.2	N1—C13—S1	127.37 (9)
C2—C3—H3A	120.2	N2—C13—S1	110.21 (8)
C3—C4—C5	120.05 (13)	C15—C14—S1	107.80 (8)
C3—C4—H4A	120.0	C15—C14—H14A	110.1
C5—C4—H4A	120.0	S1—C14—H14A	110.1
C4—C5—C6	121.14 (13)	C15—C14—H14B	110.1
C4—C5—H5A	119.4	S1—C14—H14B	110.1
C6—C5—H5A	119.4	H14A—C14—H14B	108.5
C5—C6—C1	118.15 (11)	O1—C15—N2	124.24 (11)
C5—C6—C7	120.14 (11)	O1—C15—C14	123.83 (10)
C1—C6—C7	121.65 (11)	N2—C15—C14	111.93 (10)
C8—C7—C6	121.45 (10)	C17—C16—C21	121.27 (10)
C8—C7—C12	121.33 (10)	C17—C16—N2	118.95 (10)
C6—C7—C12	117.22 (9)	C21—C16—N2	119.76 (10)
C7—C8—C9	124.66 (10)	C16—C17—C18	119.62 (11)
C7—C8—H8A	117.7	C16—C17—H17A	120.2
C9—C8—H8A	117.7	C18—C17—H17A	120.2
C8—C9—C10	113.05 (9)	C19—C18—C17	118.61 (11)
C8—C9—H9A	109.0	C19—C18—H18A	120.7
C10—C9—H9A	109.0	C17—C18—H18A	120.7
C8—C9—H9B	109.0	C18—C19—C20	122.15 (11)
C10—C9—H9B	109.0	C18—C19—Br1	119.19 (9)
H9A—C9—H9B	107.8	C20—C19—Br1	118.65 (9)
C9—C10—C11	110.65 (9)	C19—C20—C21	118.93 (11)
C9—C10—H10A	109.5	C19—C20—H20A	120.5
C11—C10—H10A	109.5	C21—C20—H20A	120.5
C9—C10—H10B	109.5	C16—C21—C20	119.40 (11)
C11—C10—H10B	109.5	C16—C21—H21A	120.3
H10A—C10—H10B	108.1	C20—C21—H21A	120.3
C10—C11—C12	110.87 (10)
C6—C1—C2—C3	0.61 (19)	C15—N2—C13—N1	−178.09 (11)
C1—C2—C3—C4	−0.6 (2)	C16—N2—C13—N1	−0.77 (17)
C2—C3—C4—C5	0.3 (2)	C15—N2—C13—S1	1.31 (12)
C3—C4—C5—C6	0.0 (2)	C16—N2—C13—S1	178.64 (8)
C4—C5—C6—C1	0.04 (18)	C14—S1—C13—N1	179.95 (11)
C4—C5—C6—C7	177.08 (12)	C14—S1—C13—N2	0.58 (9)
C2—C1—C6—C5	−0.33 (18)	C13—S1—C14—C15	−2.07 (9)
C2—C1—C6—C7	−177.32 (11)	C13—N2—C15—O1	176.41 (11)
C5—C6—C7—C8	45.66 (16)	C16—N2—C15—O1	−0.94 (18)
C1—C6—C7—C8	−137.41 (12)	C13—N2—C15—C14	−2.97 (14)
C5—C6—C7—C12	−133.41 (11)	C16—N2—C15—C14	179.69 (10)
C1—C6—C7—C12	43.52 (15)	S1—C14—C15—O1	−176.23 (10)
C6—C7—C8—C9	−176.02 (11)	S1—C14—C15—N2	3.15 (12)
C12—C7—C8—C9	3.01 (18)	C15—N2—C16—C17	−58.28 (15)
C7—C8—C9—C10	−11.99 (17)	C13—N2—C16—C17	124.50 (12)
C8—C9—C10—C11	40.11 (14)	C15—N2—C16—C21	120.22 (12)
C9—C10—C11—C12	−60.99 (13)	C13—N2—C16—C21	−57.00 (15)
C13—N1—C12—C7	−142.56 (10)	C21—C16—C17—C18	−1.30 (17)
C13—N1—C12—C11	95.92 (12)	N2—C16—C17—C18	177.17 (10)
C8—C7—C12—N1	−143.05 (11)	C16—C17—C18—C19	0.38 (17)
C6—C7—C12—N1	36.02 (13)	C17—C18—C19—C20	0.48 (18)
C8—C7—C12—C11	−22.49 (15)	C17—C18—C19—Br1	179.52 (9)
C6—C7—C12—C11	156.58 (10)	C18—C19—C20—C21	−0.43 (18)
C10—C11—C12—N1	171.22 (9)	Br1—C19—C20—C21	−179.48 (9)
C10—C11—C12—C7	50.93 (13)	C17—C16—C21—C20	1.35 (17)
C12—N1—C13—N2	178.28 (10)	N2—C16—C21—C20	−177.11 (10)
C12—N1—C13—S1	−1.01 (15)	C19—C20—C21—C16	−0.48 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18A···O1i	0.93	2.33	3.2333 (15)	164
C17—H17A···Cg1ii	0.93	2.88	3.5802 (15)	133

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18A⋯O1i	0.93	2.33	3.2333 (15)	164
C17—H17A⋯Cg1ii	0.93	2.88	3.5802 (15)	133

Symmetry codes: (i) ; (ii) .