3-(4-Chloro­phen­yl)-5-(thio­phen-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothio­amide

Fun, H.-K.; Suwunwong, T.; Chantrapromma, S.

doi:10.1107/S1600536811054754

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages o259-o260

doi:10.1107/S1600536811054754

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3-(4-Chlorophenyl)-5-(thiophen-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide

Hoong-Kun Fun,^a ^*‡ Thitipone Suwunwong ^b and Suchada Chantrapromma ^b §

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand
^*Correspondence e-mail: hkfun@usm.my

(Received 3 December 2011; accepted 20 December 2011; online 7 January 2012)

In the title pyrazoline derivative, C₁₄H₁₂ClN₃S₂, 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 intramolecular N(amide)—H⋯N(pyrazoline) hydrogen bond generates an S(5) ring motif. In the crystal, molecules are linked by weak C—H⋯S and N(amide)—H⋯S interactions into a tape along [10 $[\overline{1}]$ ]. C—H⋯π interactions 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_r = 321.86
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.049
wR(F²) = 0.138
S = 1.10
4206 reflections
211 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.59 e Å⁻³

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) -x+2, -y+2, -z+1; (ii) -x+1, -y+2, -z+2; (iii) x-1, y, z.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811054754/is5024sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811054754/is5024Isup3.cml

checkCIF report

Comment top

The synthesis of pyrazoline derivatives which contain 5-membered heterocyclic structure have attracted a lot of interests in many fields, for example as in medicinal chemistry owing to their biological properties such as antiamoebic (Husain et al., 2008), anti-inflammatory (Shoman et al., 2009), analgesic (Khode et al., 2009) and antioxidant (Taj et al., 2011) activities, as well as in fluorescence (Bai et al., 2007; Gong et al., 2011) studies. Our on-going research on biological activities and fluorescent property of pyrazoline derivatives has led us to synthesize the title compound (I) in order to compare its biological activity with the related compounds (Fun et al., 2011; Nonthason et al., 2011).

In the molecule of (I), C₁₄H₁₂ClN₃S₂, the thiophene ring is disordered over two positions with the refined site-occupancy ratio of 0.832 (4):0.168 (4). The dihedral angles between the benzene and the major and minor components of the thiophene rings are 88.6 (3) and 85.6 (15)° respectively. The pyrazoline ring is in an envelope conformation [pucker atom at C5 with deviation of -0.125 (3) Å] with puckering parameter Q = 0.206 (3) Å and ϕ = 137.6 (7)° (Cremer & Pople, 1975). The dihedral angle between the mean plane through pyrazoline ring and the benzene ring is 11.86 (13)°, whereas these values are 80.1 (3) and 83.0 (15)° between the pyrazoline and the major and minor components of the thiophene ring. The carbothioamide unit lies almost on the same plane with pyrazoline ring as can be indicated by the torsion angles N2–N1–C14–N3 = -3.3 (4)° and C5–N1–C14–S2 = 0.4 (3)°. Intramolecular N3—H1N3···N2 hydrogen bond generate an S(5) ring motif (Bernstein et al., 1995). Bond distances of (I) are in normal range (Allen et al., 1987)

In the crystal packing, (Fig. 2), the molecules are linked by weak C5—H5A···S1A intermolecular interactions (Table 1) into cyclic centrosymmetric R²₂(8) dimers (Bernstein et al., 1995). These dimers are further linked by N3—H2N3···S2 hydrogen bonds (Table 1) into a tape along the [101] direction (Fig. 2). The crystal is stabilized by N—H···S hydrogen bonds together with weak C—H···S and C—H···π interactions (Table 1).

Related literature top

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 top

The title compound was synthesized by dissolving (E)-1-(4-chlorophenyl)-3-(2-thienyl)prop-2-en-1-one (0.25 g, 1.0 mmol) in a solution of KOH (0.06 g, 1.0 mmol) in ethanol (20 ml). An excess thiosemicarbazide (0.14 g, 1.5 mmol) in ethanol (20 ml) was then added, and the reaction mixture was vigorously stirred and refluxed for 4 h. The pale-yellow solid of the title compound obtained after cooling of the reaction was filtered off under vacuum. Pale yellow needle-shaped single crystals of the title compound suitable for X-ray structure determination were recrystalized from CH₃OH/CH₂Cl₂ (1:1 v/v) by slow evaporation of the solvent at room temperature after several days.

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound, showing 45% probability displacement ellipsoids and the atom-numbering scheme. Open bond show the minor B component. Intramolecular N—H···N hydrogen bond was shown as dash line.
	Fig. 2. The crystal packing of the title compound viewed along the a axis. Only the major component was shown. For clarify, only H atoms involved in hydrogen bonds were shown. Hydrogen bonds were shown as dashed lines.

3-(4-Chlorophenyl)-5-(thiophen-2-yl)-4,5-dihydro-1H- pyrazole-1-carbothioamide top

Crystal data top

C₁₄H₁₂ClN₃S₂	F(000) = 664
M_r = 321.86	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0644P)² + 1.9543P] where P = (F_o² + 2F_c²)/3
4206 reflections	(Δ/σ)_max = 0.002
211 parameters	Δρ_max = 0.33 e Å⁻³
10 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₁₄H₁₂ClN₃S₂	V = 1446.15 (11) Å³
M_r = 321.86	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7784 (3) Å	µ = 0.55 mm⁻¹
b = 25.2104 (11) Å	T = 100 K
c = 8.4628 (4) Å	0.56 × 0.09 × 0.08 mm
β = 90.339 (2)°

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	4206 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3801 reflections with I > 2σ(I)
T_min = 0.749, T_max = 0.958	R_int = 0.047
32828 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	10 restraints
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.33 e Å⁻³
4206 reflections	Δρ_min = −0.59 e Å⁻³
211 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z+2; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂ClN₃S₂
M_r	321.86
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	6.7784 (3), 25.2104 (11), 8.4628 (4)
β (°)	90.339 (2)
V (Å³)	1446.15 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.56 × 0.09 × 0.08

Data collection
Diffractometer	Bruker APEX DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.749, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	32828, 4206, 3801
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.138, 1.10
No. of reflections	4206
No. of parameters	211
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.59

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z+2; (iii) x−1, y, z.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Additional correspondence author, e-mail: suchada.c@psu.ac.th. Thomson Reuters ResearcherID: A-5085-2009.

Acknowledgements

The authors thank the Prince of Songkla University for financial support. The authors also thank the Thailand Research Fund (TRF) for a research grant (RSA5280033) and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

References

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Volume 68| Part 2| February 2012| Pages o259-o260

doi:10.1107/S1600536811054754

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3-(4-Chloro­phen­yl)-5-(thio­phen-2-yl)-4,5-di­hydro-1H-pyrazole-1-carbo­thio­amide

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

3-(4-Chlorophenyl)-5-(thiophen-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide