3-(4-Chloro-phen-yl)-5-(thio-phen-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothio-amide.

In the title pyrazoline derivative, C(14)H(12)ClN(3)S(2), the thiophene ring is disordered over two orientations with a refined site-occupancy ratio of 0.832 (4):0.168 (4). The pyrazoline ring adopts an envelope conformation with the C atom linking the thiophene ring at the flap. The dihedral angles between the benzene ring and the major and minor components of the thiophene ring are 88.6 (3) and 85.6 (15)°, respectively while the dihedral angle between the disorder components of the ring is 3.1 (16)°. The mean plane of the pyrazoline ring makes dihedral angles of 11.86 (13), 80.1 (3) and 83.0 (15)°, respectively, with the benzene ring, and the major and minor components of the thiophene ring. An intra-molecular N(amide)-H⋯N(pyrazoline) hydrogen bond generates an S(5) ring motif. In the crystal, mol-ecules are linked by weak C-H⋯S and N(amide)-H⋯S inter-actions into a tape along [10[Formula: see text]]. C-H⋯π inter-actions are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For related structures, see: Fun et al. (2011 ▶); Nonthason et al. (2011 ▶). For background to and applications of pyrazoline derivatives, see: Bai et al. (2007 ▶); Gong et al. (2011 ▶); Husain et al. (2008 ▶); Khode et al. (2009 ▶); Shoman et al. (2009 ▶); Taj et al. (2011 ▶). For the stability of the temperature controller, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C14H12ClN3S2

M = 321.86

Monoclinic,

a = 6.7784 (3) Å

b = 25.2104 (11) Å

c = 8.4628 (4) Å

β = 90.339 (2)°

V = 1446.15 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.55 mm−1

T = 100 K

0.56 × 0.09 × 0.08 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.749, T max = 0.958

32828 measured reflections

4206 independent reflections

3801 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.138

S = 1.10

4206 reflections

211 parameters

10 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.59 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/S1600536811054754/is5024sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811054754/is5024Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811054754/is5024Isup3.cml

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

C14H12ClN3S2	F(000) = 664
Mr = 321.86	Dx = 1.478 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4206 reflections
a = 6.7784 (3) Å	θ = 0.8–30.0°
b = 25.2104 (11) Å	µ = 0.55 mm−1
c = 8.4628 (4) Å	T = 100 K
β = 90.339 (2)°	Needle, pale-yellow
V = 1446.15 (11) Å3	0.56 × 0.09 × 0.08 mm
Z = 4

Bruker APEX DUO CCD area-detector diffractometer	4206 independent reflections
Radiation source: sealed tube	3801 reflections with I > 2σ(I)
graphite	Rint = 0.047
φ and ω scans	θmax = 30.0°, θmin = 0.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
Tmin = 0.749, Tmax = 0.958	k = −35→35
32828 measured reflections	l = −11→11

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.0644P)2 + 1.9543P] where P = (Fo2 + 2Fc2)/3
4206 reflections	(Δ/σ)max = 0.002
211 parameters	Δρmax = 0.33 e Å−3
10 restraints	Δρmin = −0.59 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 esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Cl1	−0.33129 (11)	0.74126 (3)	0.43185 (9)	0.02922 (17)
S2	0.81787 (10)	1.01564 (3)	0.70895 (8)	0.02383 (16)
N1	0.5530 (3)	0.93930 (8)	0.6751 (3)	0.0187 (4)
N2	0.4447 (3)	0.90237 (8)	0.5877 (2)	0.0182 (4)
C9	−0.0433 (4)	0.85079 (10)	0.6843 (3)	0.0200 (5)
H9A	−0.0680	0.8721	0.7747	0.024*
N3	0.7384 (4)	0.95592 (10)	0.4561 (3)	0.0264 (5)
C4	0.5995 (4)	0.91382 (10)	0.9528 (3)	0.0190 (4)
S1A	0.81128 (18)	0.93898 (4)	1.03729 (11)	0.0196 (2)	0.832 (4)
C1A	0.8584 (10)	0.8815 (2)	1.1384 (9)	0.0242 (10)	0.832 (4)
H1AA	0.9681	0.8764	1.2071	0.029*	0.832 (4)
C2A	0.7184 (16)	0.8437 (3)	1.1078 (12)	0.0289 (15)	0.832 (4)
H2AA	0.7203	0.8090	1.1519	0.035*	0.832 (4)
C3A	0.5701 (18)	0.8623 (3)	1.0024 (14)	0.0263 (16)	0.832 (4)
H3AA	0.4610	0.8413	0.9692	0.032*	0.832 (4)
S1B	0.544 (2)	0.8499 (4)	0.9965 (18)	0.0243 (19)	0.168 (4)
C1B	0.751 (7)	0.8414 (15)	1.110 (8)	0.038 (14)*	0.168 (4)
H1BA	0.7880	0.8089	1.1588	0.046*	0.168 (4)
C2B	0.856 (7)	0.8873 (15)	1.122 (7)	0.041 (9)*	0.168 (4)
H2BA	0.9726	0.8912	1.1832	0.049*	0.168 (4)
C3B	0.770 (4)	0.9289 (10)	1.031 (4)	0.041 (9)*	0.168 (4)
H3BA	0.8240	0.9636	1.0250	0.049*	0.168 (4)
C5	0.4780 (4)	0.94575 (10)	0.8380 (3)	0.0186 (4)
H5A	0.4751	0.9840	0.8691	0.022*
C6	0.2675 (4)	0.92375 (11)	0.8167 (3)	0.0210 (5)
H6A	0.2293	0.9009	0.9067	0.025*
H6B	0.1698	0.9527	0.8047	0.025*
C7	0.2870 (3)	0.89198 (9)	0.6660 (3)	0.0170 (4)
C8	0.1379 (4)	0.85466 (9)	0.6075 (3)	0.0174 (4)
C10	−0.1881 (4)	0.81612 (10)	0.6300 (3)	0.0207 (5)
H10A	−0.3117	0.8140	0.6819	0.025*
C11	−0.1501 (4)	0.78485 (10)	0.4997 (3)	0.0213 (5)
C12	0.0296 (4)	0.78746 (11)	0.4212 (3)	0.0238 (5)
H12A	0.0537	0.7655	0.3321	0.029*
C13	0.1730 (4)	0.82256 (10)	0.4750 (3)	0.0219 (5)
H13A	0.2957	0.8249	0.4217	0.026*
C14	0.6989 (4)	0.96747 (10)	0.6069 (3)	0.0205 (5)
H1N3	0.673 (6)	0.9294 (15)	0.408 (5)	0.030 (9)*
H2N3	0.851 (6)	0.9675 (15)	0.416 (4)	0.032 (9)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0269 (3)	0.0216 (3)	0.0391 (4)	−0.0052 (2)	−0.0061 (3)	−0.0048 (3)
S2	0.0228 (3)	0.0227 (3)	0.0259 (3)	−0.0056 (2)	−0.0034 (2)	0.0011 (2)
N1	0.0178 (9)	0.0199 (10)	0.0183 (9)	−0.0026 (7)	−0.0012 (7)	−0.0010 (8)
N2	0.0172 (9)	0.0188 (9)	0.0186 (9)	−0.0006 (7)	−0.0026 (7)	0.0008 (7)
C9	0.0199 (11)	0.0196 (11)	0.0204 (11)	0.0018 (9)	−0.0006 (8)	−0.0018 (9)
N3	0.0265 (11)	0.0329 (13)	0.0198 (10)	−0.0107 (10)	0.0001 (9)	0.0018 (9)
C4	0.0185 (10)	0.0215 (11)	0.0171 (10)	−0.0012 (8)	0.0002 (8)	−0.0041 (9)
S1A	0.0192 (4)	0.0206 (4)	0.0188 (4)	0.0009 (4)	−0.0021 (3)	−0.0030 (3)
C1A	0.029 (2)	0.024 (2)	0.019 (2)	0.0046 (15)	−0.0052 (13)	−0.0011 (15)
C2A	0.037 (3)	0.023 (2)	0.027 (3)	−0.003 (2)	−0.006 (2)	0.0051 (14)
C3A	0.028 (3)	0.027 (4)	0.024 (2)	−0.009 (3)	−0.005 (2)	0.000 (3)
S1B	0.026 (4)	0.022 (4)	0.025 (3)	−0.007 (3)	−0.007 (2)	0.000 (3)
C5	0.0171 (10)	0.0196 (11)	0.0191 (10)	−0.0004 (8)	0.0004 (8)	−0.0037 (8)
C6	0.0185 (11)	0.0222 (11)	0.0224 (11)	−0.0010 (9)	0.0003 (9)	−0.0052 (9)
C7	0.0172 (10)	0.0163 (10)	0.0174 (10)	0.0007 (8)	−0.0031 (8)	0.0001 (8)
C8	0.0196 (11)	0.0150 (10)	0.0175 (10)	0.0009 (8)	−0.0020 (8)	0.0010 (8)
C10	0.0182 (10)	0.0182 (11)	0.0257 (12)	−0.0002 (9)	−0.0008 (9)	0.0008 (9)
C11	0.0218 (11)	0.0158 (10)	0.0263 (12)	−0.0019 (9)	−0.0047 (9)	−0.0003 (9)
C12	0.0270 (12)	0.0211 (12)	0.0231 (12)	−0.0001 (10)	−0.0027 (10)	−0.0062 (9)
C13	0.0219 (11)	0.0216 (11)	0.0222 (11)	0.0004 (10)	0.0011 (9)	−0.0028 (9)
C14	0.0200 (11)	0.0213 (11)	0.0201 (11)	−0.0015 (9)	−0.0029 (9)	0.0045 (9)

Cl1—C11	1.743 (3)	C2A—H2AA	0.9500
S2—C14	1.692 (3)	C3A—H3AA	0.9500
N1—C14	1.350 (3)	S1B—C1B	1.71 (2)
N1—N2	1.395 (3)	C1B—C2B	1.363 (18)
N1—C5	1.481 (3)	C1B—H1BA	0.9500
N2—C7	1.288 (3)	C2B—C3B	1.42 (2)
C9—C10	1.390 (3)	C2B—H2BA	0.9500
C9—C8	1.397 (3)	C3B—H3BA	0.9500
C9—H9A	0.9500	C5—C6	1.541 (3)
N3—C14	1.338 (3)	C5—H5A	1.0000
N3—H1N3	0.90 (4)	C6—C7	1.512 (3)
N3—H2N3	0.89 (4)	C6—H6A	0.9900
C4—C3A	1.379 (8)	C6—H6B	0.9900
C4—C3B	1.381 (18)	C7—C8	1.465 (3)
C4—C5	1.503 (3)	C8—C13	1.405 (3)
C4—S1B	1.696 (10)	C10—C11	1.381 (4)
C4—S1A	1.721 (3)	C10—H10A	0.9500
S1A—C1A	1.713 (6)	C11—C12	1.392 (4)
C1A—C2A	1.368 (6)	C12—C13	1.389 (4)
C1A—H1AA	0.9500	C12—H12A	0.9500
C2A—C3A	1.421 (12)	C13—H13A	0.9500
C14—N1—N2	120.6 (2)	C4—C3B—H3BA	123.4
C14—N1—C5	126.6 (2)	C2B—C3B—H3BA	123.4
N2—N1—C5	112.60 (19)	N1—C5—C4	110.7 (2)
C7—N2—N1	107.4 (2)	N1—C5—C6	100.05 (19)
C10—C9—C8	120.7 (2)	C4—C5—C6	112.7 (2)
C10—C9—H9A	119.6	N1—C5—H5A	111.0
C8—C9—H9A	119.6	C4—C5—H5A	111.0
C14—N3—H1N3	120 (3)	C6—C5—H5A	111.0
C14—N3—H2N3	118 (3)	C7—C6—C5	101.7 (2)
H1N3—N3—H2N3	119 (4)	C7—C6—H6A	111.4
C3A—C4—C3B	103.6 (13)	C5—C6—H6A	111.4
C3A—C4—C5	128.4 (5)	C7—C6—H6B	111.4
C3B—C4—C5	128.0 (11)	C5—C6—H6B	111.4
C3B—C4—S1B	110.0 (11)	H6A—C6—H6B	109.3
C5—C4—S1B	121.9 (5)	N2—C7—C8	122.0 (2)
C3A—C4—S1A	110.0 (5)	N2—C7—C6	113.8 (2)
C5—C4—S1A	121.56 (18)	C8—C7—C6	124.2 (2)
S1B—C4—S1A	116.4 (5)	C9—C8—C13	119.0 (2)
C1A—S1A—C4	92.7 (2)	C9—C8—C7	119.6 (2)
C2A—C1A—S1A	111.6 (4)	C13—C8—C7	121.4 (2)
C2A—C1A—H1AA	124.2	C11—C10—C9	119.2 (2)
S1A—C1A—H1AA	124.2	C11—C10—H10A	120.4
C1A—C2A—C3A	112.1 (5)	C9—C10—H10A	120.4
C1A—C2A—H2AA	124.0	C10—C11—C12	121.4 (2)
C3A—C2A—H2AA	124.0	C10—C11—Cl1	119.3 (2)
C4—C3A—C2A	113.5 (6)	C12—C11—Cl1	119.3 (2)
C4—C3A—H3AA	123.2	C13—C12—C11	119.1 (2)
C2A—C3A—H3AA	123.2	C13—C12—H12A	120.4
C4—S1B—C1B	93.5 (11)	C11—C12—H12A	120.4
C2B—C1B—S1B	111.0 (19)	C12—C13—C8	120.5 (2)
C2B—C1B—H1BA	124.5	C12—C13—H13A	119.8
S1B—C1B—H1BA	124.5	C8—C13—H13A	119.8
C1B—C2B—C3B	112 (2)	N3—C14—N1	116.4 (2)
C1B—C2B—H2BA	124.0	N3—C14—S2	123.1 (2)
C3B—C2B—H2BA	124.0	N1—C14—S2	120.50 (19)
C4—C3B—C2B	113.3 (17)
C14—N1—N2—C7	−163.4 (2)	S1B—C4—C5—N1	−89.2 (7)
C5—N1—N2—C7	12.0 (3)	S1A—C4—C5—N1	86.6 (2)
C3A—C4—S1A—C1A	−0.4 (7)	C3A—C4—C5—C6	20.2 (8)
C3B—C4—S1A—C1A	9(13)	C3B—C4—C5—C6	−161.3 (19)
C5—C4—S1A—C1A	−178.3 (4)	S1B—C4—C5—C6	21.9 (7)
S1B—C4—S1A—C1A	−2.2 (7)	S1A—C4—C5—C6	−162.34 (18)
C4—S1A—C1A—C2A	0.7 (8)	N1—C5—C6—C7	19.1 (2)
S1A—C1A—C2A—C3A	−0.8 (14)	C4—C5—C6—C7	−98.4 (2)
C3B—C4—C3A—C2A	−1.1 (19)	N1—N2—C7—C8	179.6 (2)
C5—C4—C3A—C2A	177.7 (7)	N1—N2—C7—C6	2.6 (3)
S1B—C4—C3A—C2A	165 (11)	C5—C6—C7—N2	−14.8 (3)
S1A—C4—C3A—C2A	0.0 (12)	C5—C6—C7—C8	168.2 (2)
C1A—C2A—C3A—C4	0.5 (16)	C10—C9—C8—C13	−0.6 (4)
C3A—C4—S1B—C1B	−17 (10)	C10—C9—C8—C7	179.3 (2)
C3B—C4—S1B—C1B	−3(3)	N2—C7—C8—C9	−170.3 (2)
C5—C4—S1B—C1B	174 (3)	C6—C7—C8—C9	6.4 (4)
S1A—C4—S1B—C1B	−2(3)	N2—C7—C8—C13	9.6 (4)
C4—S1B—C1B—C2B	3(6)	C6—C7—C8—C13	−173.7 (2)
S1B—C1B—C2B—C3B	−3(8)	C8—C9—C10—C11	0.8 (4)
C3A—C4—C3B—C2B	4(4)	C9—C10—C11—C12	−0.3 (4)
C5—C4—C3B—C2B	−175 (3)	C9—C10—C11—Cl1	179.84 (19)
S1B—C4—C3B—C2B	2(4)	C10—C11—C12—C13	−0.4 (4)
S1A—C4—C3B—C2B	−168 (16)	Cl1—C11—C12—C13	179.5 (2)
C1B—C2B—C3B—C4	0(7)	C11—C12—C13—C8	0.5 (4)
C14—N1—C5—C4	−86.0 (3)	C9—C8—C13—C12	−0.1 (4)
N2—N1—C5—C4	98.9 (2)	C7—C8—C13—C12	−179.9 (2)
C14—N1—C5—C6	154.9 (2)	N2—N1—C14—N3	−3.3 (4)
N2—N1—C5—C6	−20.1 (3)	C5—N1—C14—N3	−178.0 (2)
C3A—C4—C5—N1	−90.9 (8)	N2—N1—C14—S2	175.10 (17)
C3B—C4—C5—N1	87.6 (19)	C5—N1—C14—S2	0.4 (3)

Cg1 and Cg2 are the centroids of the S1A/C1A–C3A/C4 and S1B/C1B–C3B/C4 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···N2	0.90 (4)	2.28 (4)	2.656 (3)	105 (3)
N3—H2N3···S2i	0.89 (4)	2.52 (4)	3.400 (3)	170 (3)
C5—H5A···S1Aii	1.00	2.86	3.664 (3)	138
C9—H9A···Cg1iii	0.95	2.79	3.628 (4)	148
C9—H9A···Cg2iii	0.95	2.77	3.595 (18)	145

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the S1A/C1A–C3A/C4 and S1B/C1B–C3B/C4 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯N2	0.90 (4)	2.28 (4)	2.656 (3)	105 (3)
N3—H2N3⋯S2i	0.89 (4)	2.52 (4)	3.400 (3)	170 (3)
C5—H5A⋯S1Aii	1.00	2.86	3.664 (3)	138
C9—H9A⋯Cg1iii	0.95	2.79	3.628 (4)	148
C9—H9A⋯Cg2iii	0.95	2.77	3.595 (18)	145

Symmetry codes: (i) ; (ii) ; (iii) .