2-Anilino-4-(1,3-benzothia-zol-2-yl)-5-(4-chloro-benzo-yl)thio-phene-3-carbonitrile.

In the title compound, C(25)H(14)ClN(3)OS(2), the central thio-phene ring [maximum deviation = 0.011 (1) Å] makes dihedral angles of 55.72 (5), 13.36 (5) and 46.77 (4)° with the adjacent chloro-substituted benzene ring, the benzene ring and the 1,3-benzothia-zole ring system [maximum deviation = 0.012 (1) Å], respectively. An intra-molecular C-H⋯S(thienyl) hydrogen bond generates an S(6) ring motif in the mol-ecule. In the crystal, mol-ecules are linked by pairs of N-H⋯N hydrogen bonds into inversion dimers and the dimers are further connected by C-H⋯O hydrogen bonds into tapes running along [100]. Aromatic π-π stacking inter-actions are also observed [centroid-to-centroid distances = 3.6116 (6) and 3.7081 (6) Å].

Related literature

For background to the chemistry and biological activity of thio­phenes, see: Fun et al. (2012 ▶); Abdel-Aziz et al. (2012 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C25H14ClN3OS2

M = 471.96

Triclinic,

a = 6.9469 (2) Å

b = 7.6722 (3) Å

c = 20.9874 (7) Å

α = 91.519 (1)°

β = 97.577 (1)°

γ = 107.791 (1)°

V = 1053.15 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.40 mm−1

T = 100 K

0.31 × 0.27 × 0.19 mm

Data collection

Bruker APEX DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.884, T max = 0.929

27413 measured reflections

7637 independent reflections

6820 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.083

S = 1.04

7637 reflections

293 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.20 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/S1600536812032588/hb6899sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032588/hb6899Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812032588/hb6899Isup3.cml

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

C25H14ClN3OS2	Z = 2
Mr = 471.96	F(000) = 484
Triclinic, P1	Dx = 1.488 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9469 (2) Å	Cell parameters from 9847 reflections
b = 7.6722 (3) Å	θ = 2.9–32.6°
c = 20.9874 (7) Å	µ = 0.40 mm−1
α = 91.519 (1)°	T = 100 K
β = 97.577 (1)°	Block, colourless
γ = 107.791 (1)°	0.31 × 0.27 × 0.19 mm
V = 1053.15 (6) Å3

Bruker APEX DUO CCD diffractometer	7637 independent reflections
Radiation source: fine-focus sealed tube	6820 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
φ and ω scans	θmax = 32.6°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.884, Tmax = 0.929	k = −11→10
27413 measured reflections	l = −30→31

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0429P)2 + 0.3666P] where P = (Fo2 + 2Fc2)/3
7637 reflections	(Δ/σ)max = 0.001
293 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.20 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 100.0 (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
Cl1	0.67827 (5)	0.27031 (5)	0.480308 (13)	0.03159 (7)
S1	0.70001 (3)	0.52966 (3)	0.221308 (11)	0.01676 (5)
S2	−0.06551 (3)	0.19907 (3)	0.123999 (10)	0.01383 (5)
O1	−0.14999 (11)	0.16428 (11)	0.25836 (4)	0.02145 (15)
N1	0.43041 (12)	0.61590 (11)	0.27982 (4)	0.01415 (13)
N2	0.56707 (13)	0.64723 (13)	0.05915 (4)	0.01993 (16)
N3	0.07913 (11)	0.30630 (11)	0.01040 (4)	0.01366 (13)
C1	0.61873 (14)	0.69007 (13)	0.31835 (4)	0.01479 (15)
C2	0.64997 (16)	0.78959 (14)	0.37781 (5)	0.01997 (18)
H2A	0.5390	0.8118	0.3949	0.024*
C3	0.84704 (17)	0.85469 (15)	0.41095 (5)	0.0243 (2)
H3A	0.8711	0.9229	0.4512	0.029*
C4	1.01158 (16)	0.82196 (16)	0.38628 (5)	0.0242 (2)
H4A	1.1449	0.8690	0.4101	0.029*
C5	0.98442 (15)	0.72275 (15)	0.32796 (5)	0.02089 (18)
H5A	1.0961	0.7000	0.3115	0.025*
C6	0.78522 (14)	0.65718 (13)	0.29421 (4)	0.01608 (16)
C7	0.45180 (13)	0.52813 (12)	0.22864 (4)	0.01309 (14)
C8	0.28097 (13)	0.41925 (12)	0.18064 (4)	0.01252 (14)
C9	0.28442 (13)	0.42981 (12)	0.11329 (4)	0.01245 (14)
C10	0.10676 (13)	0.31548 (12)	0.07552 (4)	0.01227 (14)
C11	0.10148 (13)	0.29707 (13)	0.19427 (4)	0.01379 (15)
C12	0.03336 (14)	0.23023 (13)	0.25535 (4)	0.01508 (15)
C13	0.19182 (14)	0.23782 (13)	0.31168 (4)	0.01467 (15)
C14	0.16736 (15)	0.29368 (14)	0.37321 (4)	0.01761 (16)
H14A	0.0484	0.3248	0.3793	0.021*
C15	0.31665 (16)	0.30384 (15)	0.42550 (5)	0.02027 (18)
H15A	0.3021	0.3438	0.4673	0.024*
C16	0.48753 (15)	0.25455 (15)	0.41560 (5)	0.01946 (17)
C17	0.51304 (15)	0.19385 (14)	0.35523 (5)	0.01772 (16)
H17A	0.6296	0.1583	0.3496	0.021*
C18	0.36368 (14)	0.18651 (13)	0.30334 (4)	0.01565 (16)
H18A	0.3786	0.1461	0.2616	0.019*
C19	−0.08240 (13)	0.19674 (12)	−0.03545 (4)	0.01251 (14)
C20	−0.07628 (14)	0.24323 (13)	−0.09960 (4)	0.01489 (15)
H20A	0.0331	0.3427	−0.1098	0.018*
C21	−0.22951 (14)	0.14427 (14)	−0.14810 (4)	0.01668 (16)
H21A	−0.2250	0.1767	−0.1914	0.020*
C22	−0.39039 (14)	−0.00277 (14)	−0.13365 (4)	0.01648 (16)
H22A	−0.4972	−0.0688	−0.1666	0.020*
C23	−0.39207 (13)	−0.05112 (13)	−0.07028 (4)	0.01541 (15)
H23A	−0.4994	−0.1529	−0.0604	0.018*
C24	−0.23932 (13)	0.04676 (13)	−0.02097 (4)	0.01373 (15)
H24A	−0.2421	0.0117	0.0221	0.016*
C25	0.44274 (13)	0.55158 (13)	0.08486 (4)	0.01426 (15)
H1N3	0.190 (2)	0.358 (2)	−0.0051 (7)	0.026 (4)*

	U11	U22	U33	U12	U13	U23
Cl1	0.03233 (14)	0.04596 (18)	0.01750 (11)	0.01807 (12)	−0.00611 (9)	−0.00167 (10)
S1	0.01263 (9)	0.02322 (12)	0.01481 (10)	0.00628 (8)	0.00207 (7)	−0.00076 (8)
S2	0.01115 (9)	0.01691 (10)	0.01187 (9)	0.00199 (7)	0.00189 (7)	0.00100 (7)
O1	0.0153 (3)	0.0294 (4)	0.0191 (3)	0.0047 (3)	0.0057 (2)	0.0047 (3)
N1	0.0140 (3)	0.0143 (3)	0.0133 (3)	0.0035 (3)	0.0015 (2)	0.0005 (3)
N2	0.0184 (4)	0.0218 (4)	0.0171 (4)	0.0019 (3)	0.0045 (3)	0.0006 (3)
N3	0.0124 (3)	0.0159 (3)	0.0111 (3)	0.0022 (3)	0.0018 (2)	0.0010 (2)
C1	0.0157 (4)	0.0142 (4)	0.0129 (3)	0.0029 (3)	0.0007 (3)	0.0008 (3)
C2	0.0236 (4)	0.0189 (4)	0.0148 (4)	0.0040 (3)	0.0007 (3)	−0.0020 (3)
C3	0.0286 (5)	0.0213 (5)	0.0166 (4)	0.0014 (4)	−0.0036 (4)	−0.0019 (3)
C4	0.0203 (4)	0.0236 (5)	0.0212 (4)	−0.0007 (4)	−0.0063 (3)	0.0037 (4)
C5	0.0142 (4)	0.0236 (5)	0.0216 (4)	0.0023 (3)	−0.0012 (3)	0.0052 (4)
C6	0.0145 (4)	0.0175 (4)	0.0145 (4)	0.0032 (3)	0.0003 (3)	0.0023 (3)
C7	0.0115 (3)	0.0148 (4)	0.0127 (3)	0.0037 (3)	0.0018 (3)	0.0011 (3)
C8	0.0119 (3)	0.0135 (4)	0.0121 (3)	0.0040 (3)	0.0018 (3)	0.0001 (3)
C9	0.0121 (3)	0.0132 (4)	0.0118 (3)	0.0034 (3)	0.0021 (3)	0.0003 (3)
C10	0.0119 (3)	0.0132 (4)	0.0121 (3)	0.0043 (3)	0.0022 (3)	0.0013 (3)
C11	0.0126 (3)	0.0165 (4)	0.0116 (3)	0.0037 (3)	0.0019 (3)	0.0010 (3)
C12	0.0161 (4)	0.0168 (4)	0.0128 (3)	0.0051 (3)	0.0038 (3)	0.0014 (3)
C13	0.0167 (4)	0.0157 (4)	0.0117 (3)	0.0044 (3)	0.0035 (3)	0.0021 (3)
C14	0.0201 (4)	0.0205 (4)	0.0139 (4)	0.0075 (3)	0.0056 (3)	0.0017 (3)
C15	0.0257 (4)	0.0237 (5)	0.0122 (4)	0.0085 (4)	0.0036 (3)	0.0001 (3)
C16	0.0219 (4)	0.0226 (5)	0.0132 (4)	0.0072 (4)	−0.0004 (3)	0.0018 (3)
C17	0.0189 (4)	0.0199 (4)	0.0156 (4)	0.0074 (3)	0.0029 (3)	0.0028 (3)
C18	0.0180 (4)	0.0171 (4)	0.0126 (3)	0.0059 (3)	0.0037 (3)	0.0019 (3)
C19	0.0119 (3)	0.0140 (4)	0.0120 (3)	0.0051 (3)	0.0009 (3)	0.0000 (3)
C20	0.0162 (4)	0.0162 (4)	0.0127 (3)	0.0057 (3)	0.0020 (3)	0.0016 (3)
C21	0.0185 (4)	0.0200 (4)	0.0123 (3)	0.0078 (3)	0.0006 (3)	0.0002 (3)
C22	0.0144 (4)	0.0200 (4)	0.0148 (4)	0.0066 (3)	−0.0005 (3)	−0.0037 (3)
C23	0.0126 (3)	0.0167 (4)	0.0167 (4)	0.0048 (3)	0.0018 (3)	−0.0021 (3)
C24	0.0128 (3)	0.0153 (4)	0.0135 (3)	0.0048 (3)	0.0025 (3)	0.0004 (3)
C25	0.0144 (3)	0.0155 (4)	0.0122 (3)	0.0042 (3)	0.0012 (3)	−0.0013 (3)

Cl1—C16	1.7418 (10)	C9—C10	1.4017 (12)
S1—C6	1.7252 (10)	C9—C25	1.4188 (12)
S1—C7	1.7477 (9)	C11—C12	1.4754 (12)
S2—C10	1.7266 (9)	C12—C13	1.4923 (12)
S2—C11	1.7444 (9)	C13—C18	1.3963 (13)
O1—C12	1.2294 (11)	C13—C14	1.3975 (12)
N1—C7	1.3016 (11)	C14—C15	1.3900 (14)
N1—C1	1.3896 (11)	C14—H14A	0.9500
N2—C25	1.1543 (12)	C15—C16	1.3895 (14)
N3—C10	1.3517 (11)	C15—H15A	0.9500
N3—C19	1.4098 (11)	C16—C17	1.3899 (13)
N3—H1N3	0.864 (16)	C17—C18	1.3889 (13)
C1—C2	1.4016 (13)	C17—H17A	0.9500
C1—C6	1.4086 (13)	C18—H18A	0.9500
C2—C3	1.3856 (14)	C19—C24	1.3943 (12)
C2—H2A	0.9500	C19—C20	1.4046 (12)
C3—C4	1.4008 (17)	C20—C21	1.3876 (12)
C3—H3A	0.9500	C20—H20A	0.9500
C4—C5	1.3839 (16)	C21—C22	1.3967 (14)
C4—H4A	0.9500	C21—H21A	0.9500
C5—C6	1.4025 (13)	C22—C23	1.3908 (13)
C5—H5A	0.9500	C22—H22A	0.9500
C7—C8	1.4681 (12)	C23—C24	1.3940 (12)
C8—C11	1.3817 (12)	C23—H23A	0.9500
C8—C9	1.4209 (12)	C24—H24A	0.9500
C6—S1—C7	88.99 (4)	O1—C12—C13	121.52 (8)
C10—S2—C11	92.36 (4)	C11—C12—C13	118.41 (8)
C7—N1—C1	109.85 (8)	C18—C13—C14	119.68 (8)
C10—N3—C19	131.28 (8)	C18—C13—C12	120.18 (8)
C10—N3—H1N3	112.8 (10)	C14—C13—C12	120.13 (8)
C19—N3—H1N3	114.3 (10)	C15—C14—C13	120.15 (9)
N1—C1—C2	124.79 (9)	C15—C14—H14A	119.9
N1—C1—C6	115.30 (8)	C13—C14—H14A	119.9
C2—C1—C6	119.91 (9)	C16—C15—C14	118.89 (9)
C3—C2—C1	118.21 (10)	C16—C15—H15A	120.6
C3—C2—H2A	120.9	C14—C15—H15A	120.6
C1—C2—H2A	120.9	C15—C16—C17	122.13 (9)
C2—C3—C4	121.36 (10)	C15—C16—Cl1	119.51 (7)
C2—C3—H3A	119.3	C17—C16—Cl1	118.35 (8)
C4—C3—H3A	119.3	C18—C17—C16	118.27 (9)
C5—C4—C3	121.52 (9)	C18—C17—H17A	120.9
C5—C4—H4A	119.2	C16—C17—H17A	120.9
C3—C4—H4A	119.2	C17—C18—C13	120.84 (8)
C4—C5—C6	117.25 (10)	C17—C18—H18A	119.6
C4—C5—H5A	121.4	C13—C18—H18A	119.6
C6—C5—H5A	121.4	C24—C19—C20	119.73 (8)
C5—C6—C1	121.74 (9)	C24—C19—N3	124.30 (8)
C5—C6—S1	128.84 (8)	C20—C19—N3	115.94 (8)
C1—C6—S1	109.42 (7)	C21—C20—C19	120.18 (8)
N1—C7—C8	124.12 (8)	C21—C20—H20A	119.9
N1—C7—S1	116.43 (7)	C19—C20—H20A	119.9
C8—C7—S1	119.28 (6)	C20—C21—C22	120.36 (8)
C11—C8—C9	112.19 (8)	C20—C21—H21A	119.8
C11—C8—C7	125.47 (8)	C22—C21—H21A	119.8
C9—C8—C7	122.34 (8)	C23—C22—C21	119.06 (8)
C10—C9—C25	121.30 (8)	C23—C22—H22A	120.5
C10—C9—C8	113.63 (8)	C21—C22—H22A	120.5
C25—C9—C8	124.94 (8)	C22—C23—C24	121.31 (9)
N3—C10—C9	122.87 (8)	C22—C23—H23A	119.3
N3—C10—S2	126.75 (7)	C24—C23—H23A	119.3
C9—C10—S2	110.35 (6)	C23—C24—C19	119.31 (8)
C8—C11—C12	132.25 (8)	C23—C24—H24A	120.3
C8—C11—S2	111.44 (6)	C19—C24—H24A	120.3
C12—C11—S2	116.21 (6)	N2—C25—C9	177.03 (10)
O1—C12—C11	120.03 (8)
C7—N1—C1—C2	−178.49 (9)	C9—C8—C11—C12	175.01 (9)
C7—N1—C1—C6	0.68 (11)	C7—C8—C11—C12	−5.01 (16)
N1—C1—C2—C3	179.78 (9)	C9—C8—C11—S2	−1.36 (10)
C6—C1—C2—C3	0.65 (15)	C7—C8—C11—S2	178.62 (7)
C1—C2—C3—C4	−0.30 (16)	C10—S2—C11—C8	1.75 (7)
C2—C3—C4—C5	−0.25 (17)	C10—S2—C11—C12	−175.25 (7)
C3—C4—C5—C6	0.44 (16)	C8—C11—C12—O1	158.84 (10)
C4—C5—C6—C1	−0.08 (15)	S2—C11—C12—O1	−24.93 (12)
C4—C5—C6—S1	−179.66 (8)	C8—C11—C12—C13	−23.68 (15)
N1—C1—C6—C5	−179.68 (9)	S2—C11—C12—C13	152.55 (7)
C2—C1—C6—C5	−0.46 (14)	O1—C12—C13—C18	134.78 (10)
N1—C1—C6—S1	−0.03 (10)	C11—C12—C13—C18	−42.66 (13)
C2—C1—C6—S1	179.18 (8)	O1—C12—C13—C14	−44.25 (14)
C7—S1—C6—C5	179.18 (10)	C11—C12—C13—C14	138.31 (9)
C7—S1—C6—C1	−0.44 (7)	C18—C13—C14—C15	2.09 (15)
C1—N1—C7—C8	174.18 (8)	C12—C13—C14—C15	−178.87 (9)
C1—N1—C7—S1	−1.05 (10)	C13—C14—C15—C16	−1.14 (15)
C6—S1—C7—N1	0.90 (8)	C14—C15—C16—C17	−0.60 (16)
C6—S1—C7—C8	−174.57 (7)	C14—C15—C16—Cl1	178.87 (8)
N1—C7—C8—C11	−44.54 (14)	C15—C16—C17—C18	1.34 (16)
S1—C7—C8—C11	130.56 (8)	Cl1—C16—C17—C18	−178.14 (8)
N1—C7—C8—C9	135.44 (10)	C16—C17—C18—C13	−0.35 (14)
S1—C7—C8—C9	−49.46 (11)	C14—C13—C18—C17	−1.34 (14)
C11—C8—C9—C10	0.11 (11)	C12—C13—C18—C17	179.63 (9)
C7—C8—C9—C10	−179.88 (8)	C10—N3—C19—C24	−11.48 (15)
C11—C8—C9—C25	175.87 (9)	C10—N3—C19—C20	170.28 (9)
C7—C8—C9—C25	−4.11 (14)	C24—C19—C20—C21	2.20 (13)
C19—N3—C10—C9	177.25 (9)	N3—C19—C20—C21	−179.48 (8)
C19—N3—C10—S2	−4.70 (14)	C19—C20—C21—C22	−0.31 (14)
C25—C9—C10—N3	3.59 (14)	C20—C21—C22—C23	−1.52 (14)
C8—C9—C10—N3	179.53 (8)	C21—C22—C23—C24	1.51 (14)
C25—C9—C10—S2	−174.74 (7)	C22—C23—C24—C19	0.36 (13)
C8—C9—C10—S2	1.20 (10)	C20—C19—C24—C23	−2.20 (13)
C11—S2—C10—N3	−179.90 (8)	N3—C19—C24—C23	179.61 (8)
C11—S2—C10—C9	−1.66 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···N2i	0.862 (15)	2.163 (15)	2.9558 (12)	152.7 (13)
C17—H17A···O1ii	0.95	2.60	3.3496 (14)	136
C24—H24A···S2	0.95	2.49	3.1719 (9)	128

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯N2i	0.862 (15)	2.163 (15)	2.9558 (12)	152.7 (13)
C17—H17A⋯O1ii	0.95	2.60	3.3496 (14)	136
C24—H24A⋯S2	0.95	2.49	3.1719 (9)	128

Symmetry codes: (i) ; (ii) .