(2E)-2-(2,4-Dichloro-phenyl-sulfon-yl)-3-(4-methyl-anilino)-3-(methyl-sulfan-yl)acrylonitrile.

The title compound, C(17)H(14)Cl(2)N(2)O(2)S(2), and the 3-methoxy-anilino analogue reported in the preceding paper have been used as starting materials to develop benzothia-zine derivatives with anti-malarial activity. The mol-ecule displays an E (trans) configuration about the central double bond. Due to conjugation in the C=C-C N group, the putative single bond shows a significant shortening [1.418 (3) Å]. The mol-ecule has a six-membered ring involving an intra-molecular N-H⋯O(sulfon-yl) bond, which is an example of resonance-assisted hydrogen bonding. In the crystal structure, bonds of the C-H⋯O(sulfon-yl) and C-H⋯N(cyano) types form double layers of mol-ecules parallel to (01). Within these layers there are π-π inter-actions between benzene rings of pairs of centrosymmetrically related mol-ecules, with distances of 3.7969 (12) Å between centroids. C-H⋯π interactions are also present.

Related literature

For related literature, see: Allen (2002 ▶); Allen et al. (1987 ▶); Baraza­rte et al. (2008 ▶); Capparelli et al. (2008 ▶); Charris et al. (2005 ▶, 2007 ▶); Gilli et al. (1989 ▶); Hirshfeld (1976 ▶); Kennard et al. (2003 ▶); Krivokolysko et al. (2002 ▶); Song et al. (2005 ▶); Tominaga et al. (1989 ▶, 2002 ▶).

Experimental

Crystal data

C17H14Cl2N2O2S2

M = 413.32

Monoclinic,

a = 11.3975 (6) Å

b = 14.8147 (8) Å

c = 11.7215 (6) Å

β = 109.444 (1)°

V = 1866.30 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.58 mm−1

T = 296 (2) K

0.55 × 0.36 × 0.27 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.765, T max = 0.851

12685 measured reflections

4562 independent reflections

3674 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.117

S = 1.03

4562 reflections

229 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.30 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808012531/bg2185sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012531/bg2185Isup2.hkl

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

C17H14Cl2N2O2S2	F000 = 848
Mr = 413.32	Dx = 1.471 Mg m−3
Monoclinic, P21/n	Melting point = 455–457 K
Hall symbol: -P 2yn	Mo Kα radiation λ = 0.71073 Å
a = 11.3975 (6) Å	Cell parameters from 5367 reflections
b = 14.8147 (8) Å	θ = 2.3–28.5º
c = 11.7215 (6) Å	µ = 0.59 mm−1
β = 109.444 (1)º	T = 296 (2) K
V = 1866.30 (17) Å3	Prism, colorless
Z = 4	0.55 × 0.36 × 0.27 mm

Bruker SMART APEX diffractometer	4562 independent reflections
Radiation source: fine-focus sealed tube	3674 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.015
Detector resolution: 8.13 pixels mm-1	θmax = 29.0º
T = 296(2) K	θmin = 2.2º
φ and ω scans	h = −14→12
Absorption correction: multi-scan(SADABS; Bruker, 2001)	k = −19→19
Tmin = 0.765, Tmax = 0.851	l = −15→14
12685 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.117	w = 1/[σ2(Fo2) + (0.0628P)2 + 0.5083P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
4562 reflections	Δρmax = 0.38 e Å−3
229 parameters	Δρmin = −0.30 e Å−3
2 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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
S1	0.36812 (4)	0.42470 (4)	0.06767 (4)	0.04761 (14)
S2	0.64407 (5)	0.37305 (4)	0.41840 (4)	0.05631 (15)
Cl1	0.30933 (5)	0.54484 (4)	0.27681 (5)	0.05801 (15)
Cl2	−0.14871 (5)	0.40783 (6)	0.14708 (6)	0.0824 (2)
O1	0.35547 (15)	0.36287 (12)	−0.02987 (13)	0.0681 (4)
O2	0.40074 (13)	0.51660 (10)	0.05390 (12)	0.0553 (3)
N1	0.4303 (2)	0.21530 (14)	0.23381 (18)	0.0737 (6)
N2	0.60865 (15)	0.51086 (11)	0.25871 (13)	0.0494 (4)
H2	0.5904	0.5266	0.1842	0.059*
C11	0.22335 (17)	0.42192 (12)	0.09442 (15)	0.0438 (4)
C12	0.19883 (17)	0.47436 (12)	0.18235 (16)	0.0445 (4)
C13	0.08383 (18)	0.47058 (14)	0.19803 (18)	0.0522 (4)
H13	0.0672	0.5062	0.2562	0.063*
C14	−0.00560 (18)	0.41325 (15)	0.12618 (18)	0.0542 (5)
C15	0.0156 (2)	0.36108 (15)	0.0379 (2)	0.0610 (5)
H15	−0.0462	0.3234	−0.0105	0.073*
C16	0.1306 (2)	0.36578 (14)	0.02256 (18)	0.0554 (5)
H16	0.1460	0.3308	−0.0368	0.066*
C21	0.67534 (18)	0.57496 (13)	0.34797 (16)	0.0466 (4)
C22	0.7764 (2)	0.61972 (15)	0.33448 (19)	0.0577 (5)
H22	0.7990	0.6098	0.2662	0.061 (6)*
C23	0.8437 (2)	0.67925 (16)	0.4231 (2)	0.0639 (6)
H23	0.9115	0.7092	0.4133	0.077*
C24	0.8129 (2)	0.69545 (14)	0.5260 (2)	0.0586 (5)
C25	0.7089 (2)	0.65227 (14)	0.53511 (19)	0.0583 (5)
H25	0.6848	0.6634	0.6022	0.070*
C26	0.6398 (2)	0.59308 (14)	0.44742 (19)	0.0534 (5)
H26	0.5695	0.5655	0.4553	0.064*
C1	0.45350 (19)	0.28900 (14)	0.22053 (17)	0.0524 (4)
C2	0.47563 (17)	0.38061 (13)	0.19901 (15)	0.0453 (4)
C3	0.57197 (17)	0.42866 (13)	0.28006 (15)	0.0438 (4)
C4	0.8069 (2)	0.3985 (2)	0.4575 (2)	0.0769 (7)
H4A	0.8543	0.3577	0.5193	0.115*
H4B	0.8219	0.4594	0.4869	0.115*
H4C	0.8316	0.3922	0.3872	0.115*
C5	0.8896 (3)	0.75847 (17)	0.6233 (3)	0.0873 (8)
H5A	0.9753	0.7403	0.6484	0.131*
H5B	0.8605	0.7563	0.6912	0.131*
H5C	0.8819	0.8189	0.5921	0.131*

	U11	U22	U33	U12	U13	U23
S1	0.0439 (2)	0.0669 (3)	0.0322 (2)	0.0030 (2)	0.01291 (17)	−0.00344 (19)
S2	0.0637 (3)	0.0598 (3)	0.0387 (2)	−0.0013 (2)	0.0081 (2)	0.0079 (2)
Cl1	0.0546 (3)	0.0655 (3)	0.0544 (3)	−0.0084 (2)	0.0188 (2)	−0.0189 (2)
Cl2	0.0437 (3)	0.1218 (6)	0.0828 (4)	−0.0037 (3)	0.0227 (3)	0.0103 (4)
O1	0.0607 (9)	0.1015 (12)	0.0413 (7)	0.0062 (8)	0.0161 (6)	−0.0211 (7)
O2	0.0475 (7)	0.0724 (9)	0.0458 (7)	−0.0004 (6)	0.0153 (6)	0.0141 (6)
N1	0.0953 (15)	0.0615 (12)	0.0611 (11)	−0.0123 (11)	0.0217 (11)	−0.0057 (9)
N2	0.0524 (9)	0.0587 (9)	0.0349 (7)	−0.0031 (7)	0.0116 (6)	0.0047 (6)
C11	0.0420 (9)	0.0517 (10)	0.0366 (8)	0.0000 (7)	0.0115 (7)	0.0002 (7)
C12	0.0428 (9)	0.0503 (10)	0.0379 (8)	−0.0005 (7)	0.0100 (7)	−0.0004 (7)
C13	0.0476 (10)	0.0653 (12)	0.0455 (10)	0.0058 (9)	0.0177 (8)	0.0005 (9)
C14	0.0409 (10)	0.0707 (13)	0.0496 (10)	0.0016 (9)	0.0132 (8)	0.0121 (9)
C15	0.0523 (12)	0.0683 (13)	0.0556 (12)	−0.0123 (10)	0.0088 (9)	−0.0044 (10)
C16	0.0544 (11)	0.0624 (12)	0.0465 (10)	−0.0041 (9)	0.0130 (9)	−0.0104 (9)
C21	0.0468 (10)	0.0504 (10)	0.0412 (9)	0.0003 (8)	0.0129 (7)	0.0037 (7)
C22	0.0588 (12)	0.0696 (13)	0.0495 (11)	−0.0061 (10)	0.0243 (9)	0.0057 (9)
C23	0.0618 (13)	0.0639 (13)	0.0672 (13)	−0.0165 (10)	0.0228 (11)	0.0040 (10)
C24	0.0699 (13)	0.0439 (10)	0.0570 (11)	−0.0023 (9)	0.0145 (10)	0.0035 (9)
C25	0.0749 (14)	0.0521 (11)	0.0532 (11)	0.0017 (10)	0.0282 (10)	−0.0035 (9)
C26	0.0534 (11)	0.0566 (11)	0.0554 (11)	−0.0028 (9)	0.0251 (9)	−0.0004 (9)
C1	0.0586 (12)	0.0573 (10)	0.0413 (9)	0.0000 (9)	0.0167 (8)	−0.0073 (8)
C2	0.0472 (10)	0.0520 (9)	0.0358 (8)	0.0051 (8)	0.0128 (7)	−0.0026 (7)
C3	0.0445 (9)	0.0543 (10)	0.0334 (8)	0.0070 (8)	0.0139 (7)	0.0004 (7)
C4	0.0582 (14)	0.1022 (19)	0.0608 (14)	0.0158 (13)	0.0070 (11)	0.0216 (13)
C5	0.112 (2)	0.0604 (14)	0.0782 (17)	−0.0191 (14)	0.0166 (16)	−0.0122 (12)

S1—O1	1.4343 (15)	C16—H16	0.9300
S1—O2	1.4345 (15)	C21—C26	1.382 (3)
S1—C2	1.7442 (18)	C21—C22	1.383 (3)
S1—C11	1.7796 (19)	C22—C23	1.384 (3)
S2—C3	1.7596 (18)	C22—H22	0.9300
S2—C4	1.798 (3)	C23—C24	1.385 (3)
Cl1—C12	1.7245 (18)	C23—H23	0.9300
Cl2—C14	1.730 (2)	C24—C25	1.382 (3)
N1—C1	1.146 (3)	C24—C5	1.508 (3)
N2—C3	1.338 (2)	C25—C26	1.381 (3)
N2—C21	1.430 (2)	C25—H25	0.9300
N2—H2	0.8600	C26—H26	0.9300
C11—C16	1.388 (3)	C1—C2	1.418 (3)
C11—C12	1.391 (3)	C2—C3	1.386 (3)
C12—C13	1.384 (3)	C4—H4A	0.9600
C13—C14	1.378 (3)	C4—H4B	0.9600
C13—H13	0.9300	C4—H4C	0.9600
C14—C15	1.375 (3)	C5—H5A	0.9600
C15—C16	1.383 (3)	C5—H5B	0.9600
C15—H15	0.9300	C5—H5C	0.9600
O1—S1—O2	118.52 (10)	C23—C22—H22	120.2
O1—S1—C2	108.61 (9)	C22—C23—C24	121.7 (2)
O2—S1—C2	108.81 (9)	C22—C23—H23	119.1
O1—S1—C11	105.82 (9)	C24—C23—H23	119.1
O2—S1—C11	109.39 (9)	C25—C24—C23	117.4 (2)
C2—S1—C11	104.83 (9)	C25—C24—C5	121.6 (2)
C3—S2—C4	105.22 (10)	C23—C24—C5	121.0 (2)
C3—N2—C21	126.20 (15)	C26—C25—C24	121.8 (2)
C3—N2—H2	116.9	C26—C25—H25	119.1
C21—N2—H2	116.9	C24—C25—H25	119.1
C16—C11—C12	118.95 (17)	C25—C26—C21	119.76 (19)
C16—C11—S1	118.07 (14)	C25—C26—H26	120.1
C12—C11—S1	122.97 (14)	C21—C26—H26	120.1
C13—C12—C11	120.56 (17)	N1—C1—C2	176.8 (2)
C13—C12—Cl1	117.44 (14)	C3—C2—C1	121.12 (17)
C11—C12—Cl1	122.00 (14)	C3—C2—S1	125.19 (14)
C14—C13—C12	118.97 (18)	C1—C2—S1	113.64 (14)
C14—C13—H13	120.5	N2—C3—C2	124.40 (16)
C12—C13—H13	120.5	N2—C3—S2	121.29 (14)
C15—C14—C13	121.78 (19)	C2—C3—S2	114.31 (14)
C15—C14—Cl2	119.36 (17)	S2—C4—H4A	109.5
C13—C14—Cl2	118.85 (16)	S2—C4—H4B	109.5
C14—C15—C16	118.76 (19)	H4A—C4—H4B	109.5
C14—C15—H15	120.6	S2—C4—H4C	109.5
C16—C15—H15	120.6	H4A—C4—H4C	109.5
C15—C16—C11	120.96 (19)	H4B—C4—H4C	109.5
C15—C16—H16	119.5	C24—C5—H5A	109.5
C11—C16—H16	119.5	C24—C5—H5B	109.5
C26—C21—C22	119.52 (19)	H5A—C5—H5B	109.5
C26—C21—N2	120.82 (17)	C24—C5—H5C	109.5
C22—C21—N2	119.66 (17)	H5A—C5—H5C	109.5
C21—C22—C23	119.66 (19)	H5B—C5—H5C	109.5
C21—C22—H22	120.2
O1—S1—C11—C16	−0.27 (19)	C21—C22—C23—C24	0.1 (4)
O2—S1—C11—C16	128.48 (16)	C22—C23—C24—C25	−2.3 (3)
C2—S1—C11—C16	−114.99 (16)	C22—C23—C24—C5	178.2 (2)
O1—S1—C11—C12	−179.20 (16)	C23—C24—C25—C26	1.9 (3)
O2—S1—C11—C12	−50.45 (17)	C5—C24—C25—C26	−178.7 (2)
C2—S1—C11—C12	66.08 (17)	C24—C25—C26—C21	0.8 (3)
C16—C11—C12—C13	0.1 (3)	C22—C21—C26—C25	−3.1 (3)
S1—C11—C12—C13	178.98 (15)	N2—C21—C26—C25	177.15 (18)
C16—C11—C12—Cl1	179.16 (15)	O1—S1—C2—C3	133.90 (16)
S1—C11—C12—Cl1	−1.9 (2)	O2—S1—C2—C3	3.58 (19)
C11—C12—C13—C14	0.8 (3)	C11—S1—C2—C3	−113.35 (17)
Cl1—C12—C13—C14	−178.37 (15)	O1—S1—C2—C1	−48.61 (17)
C12—C13—C14—C15	−1.3 (3)	O2—S1—C2—C1	−178.93 (14)
C12—C13—C14—Cl2	179.34 (15)	C11—S1—C2—C1	64.14 (15)
C13—C14—C15—C16	0.9 (3)	C21—N2—C3—C2	157.68 (18)
Cl2—C14—C15—C16	−179.72 (17)	C21—N2—C3—S2	−21.5 (3)
C14—C15—C16—C11	0.0 (3)	C1—C2—C3—N2	170.85 (18)
C12—C11—C16—C15	−0.4 (3)	S1—C2—C3—N2	−11.8 (3)
S1—C11—C16—C15	−179.42 (17)	C1—C2—C3—S2	−9.9 (2)
C3—N2—C21—C26	−46.0 (3)	S1—C2—C3—S2	167.40 (11)
C3—N2—C21—C22	134.3 (2)	C4—S2—C3—N2	−39.06 (19)
C26—C21—C22—C23	2.6 (3)	C4—S2—C3—C2	141.68 (16)
N2—C21—C22—C23	−177.62 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	2.20	2.756 (2)	123
C4—H4A···N1i	0.96	2.61	3.504 (3)	156
C5—H5C···O2ii	0.96	2.50	3.442 (3)	167
C16—H16···O1	0.93	2.41	2.828 (3)	107
C4—H4B···Cg2	0.96	2.76	3.582 (3)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.86	2.20	2.756 (2)	123
C4—H4A⋯N1i	0.96	2.61	3.504 (3)	156
C5—H5C⋯O2ii	0.96	2.50	3.442 (3)	167
C4—H4B⋯Cg2	0.96	2.76	3.582 (3)	144

Symmetry codes: (i) ; (ii) . Cg2 is the centroid of the C21–C26 ring.