Crystal structure of 3-(thio­phen-2-yl)-5-p-tolyl-4,5-di­hydro-1H-pyrazole-1-carbo­thio­amide

Naveen, S.; Pavithra, G.; Abdoh, M.; Ajay Kumar, K.; Warad, I.; Lokanath, N.K.

doi:10.1107/S2056989015010774

research communications

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ISSN: 2056-9890

Volume 71| Part 7| July 2015| Pages 763-765

doi:10.1107/S2056989015010774

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Crystal structure of 3-(thiophen-2-yl)-5-p-tolyl-4,5-dihydro-1H-pyrazole-1-carbothioamide

S. Naveen,^a G. Pavithra,^b Muneer Abdoh,^c ^* K. Ajay Kumar,^b Ismail Warad ^d and N. K. Lokanath ^e

^aInstitution of Excellence, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysore 570 006, India, ^cDepartment of Physics, Science College, An-Najah National University, PO Box 7, Nablus, Palestinian Territories, ^dDepartment of Chemistry, Science College, An-Najah National University, PO Box 7, Nablus, Palestinian Territories, and ^eDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore 570 006, India
^*Correspondence e-mail: muneer@najah.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 28 May 2015; accepted 3 June 2015; online 10 June 2015)

In the title compound, C₁₅H₁₅N₃S₂, the central pyrazole ring adopts a twisted conformation on the –CH—CH₂– bond. Its mean plane makes dihedral angles of 7.19 (12) and 71.13 (11)° with those of the thiophene and toluene rings, respectively. The carbothiamide group [C(=S)—N] is inclined to the pyrazole ring mean plane by 16.8 (2)°. In the crystal, molecules are linked by N—H⋯S hydrogen bonds, forming chains propagating along [010]. Within the chains, there are N—H⋯π interactions present. Between the chains there are weak parallel slipped π–π interactions involving inversion-related thiophene and pyrazole rings [inter-centroid distance = 3.7516 (14) Å; inter-planar distance = 3.5987 (10) Å; slippage = 1.06 Å].

Keywords: crystal structure; pyrazole; thiophene; carbothioamide; C—H⋯S hydrogen bonds; N—H⋯π interactions; π–π interactions.

CCDC reference: 1404788

1. Chemical context

Five-membered heterocyclic pyrazole analogues have been used extensively as building blocks in organic synthesis. They have been transformed efficiently into molecules of potential medicinal and pharmaceutical important. Pyrazole derivatives have known to exhibit diverse biological applications such as antidiabetic,anaesthetic, antimicrobial and antioxidant. In addition, they have also shown potential anticancer and antiamoebic activity and to be potent and selective inhibitors of tissue-nonspecific alkaline phosphatase (Sidique et al. 2009 ). Earlier we synthesized α and β-unsaturated compounds which served as useful intermediates for the synthesis of pyrazolines (Manjula et al., 2013 ) and thiazepines (Manjunath et al., 2014 ). As part of our ongoing research on pyrazole analogues, the title compound was synthesized and we report herein on its crystal structure. Studies of the biological activity of the title compound are underway and will be reported elsewhere.

2. Structural commentary

The molecular structure of the title compound is illustrated in Fig. 1. The central pyrazole ring (N7/N8/C8–C10) adopts a twisted conformation with respect to the C9—C10 bond and its mean plane makes dihedral angles of 7.19 (12) and 71.13 (11)° with the thiophene (S1/C2–C5) and toluene (C14–C19) rings, respectively. The carbothiamide group [C11(=S13)N12] lies in the plane of the pyrazole ring, as indicated by the torsion angles N12—C11—N8—N7 = 0.6 (3) and S13—C11—N8—N7 = 179.96 (16)°, and adopts +syn-periplanar and +anti-periplanar conformations, respectively. The title compound possess a chiral center at atom C9 but crystallized as a racemate.

Figure 1
View of the molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, molecules are linked by N—H⋯S hydrogen bonds, forming chains propagating along [010]. Within the chains there are N—H⋯π interactions involving the toluene ring (Fig. 2 and Table 1). Between the chains there are weak parallel slipped π–π interactions involving inversion-related thiophene and pyrazole rings [Cg1⋯Cg2ⁱ = 3.7516 (14) Å; inter-planar distance = 3.5987 (10) Å; slippage = 1.06 Å; Cg1 and Cg2 are the centroids of rings S1/C2–C5 and N7/N8/C8–C10, respectively; symmetry code: (i) −x + 2, −y + 1, −z + 1].

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the benzene ring C14–C19.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N12—H12A⋯S13ⁱ	0.86	2.83	3.620 (2)	154
N12—H12B⋯Cg3ⁱ	0.86	2.81	3.443 (2)	132
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A view along the a axis of the crystal packing of the title compound. The hydrogen bonds and C—H⋯π interactions are shown as dashed lines (see Table 1

for details). C-bound H atoms have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (Version 5.36, May 2015; Groom & Allen, 2014 ) revealed seven structures containing the 3-(thiophen-2-yl)-pyrazole unit. Amongst these are two thioamides; the phenyl derivative of the title compound, 5-phenyl-3-(2-thienyl)-2-pyrazoline-1-thioamide (HEFXEW; Işık et al., 2006 ), and 1-(N-ethylthiocarbamoyl)-3,5-bis(2-thienyl)-2-pyrazoline (YINFUX; Köysal et al., 2007 ). In these two compounds, the pyrazole rings have envelope conformations with the methine C atom as the flap, and the mean planes of the two rings are inclined to one another by 11.98 and 10.13°, respectively. This is in contrast to the situation in the title compound where the pyrazole ring has a twisted conformation on the –CH–CH₂– bond and its mean plane is inclined to the thiophene ring by 7.19 (12)°. In the crystal of the phenyl derivative (HEFXEW), molecules are also linked by N—H⋯S hydrogen bonds, forming chains.

5. Synthesis and crystallization

A mixture of 3-(4-methylphenyl)-1-(thiophen-2-yl)prop-2-en-1-one (0.001 mol) and thiosemicarbazine hydrochloride (0.01 mol) and potassium hydroxide (0.02 mol) in ethyl alcohol (20 ml) was refluxed on a water bath for 6–8 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was poured into ice-cold water and stirred. The solid that separated was filtered, and washed with ice-cold water. The product was recrystallized from ethyl alcohol to give the title compound as rectangular yellow crystals. Analysis calculated for C₁₅H₁₅N₃S₂: C, 59.77; H, 5.02; N, 13.94%; found: C, 59.74; H, 5.06; N, 13.88%. ¹H NMR (CDCl₃): δ 2.297 (s, 3H, CH3), (dd, 1H, C4—Hb: J = 18.0, 8.5 Hz), (dd, 1H, C4—Hb: J 18.0, 8.5 Hz), 5.976–6.013 (dd, 1H, C—Ha: J = 18.0, 12.0 Hz), 6.163–7.169 (m, 7H, Ar—H and thiophene ring-H), 7.330 (s, 2H, –NH₂). ¹³C NMR (CDCl₃): δ 43.77, 1 C, C-4), 63.34 (1 C, C-5), 125.35 (2C, Ar—C), 127.88 (1C, 5 m ring-C), 129.57 (1C, Ar—C), 129.67 (1C, Ar—C), 129.72 (1C, 5 m ring-C), 130.01 (1C, 5 m ring-C), 134.12, (1C, 5 m ring-C), 137.31 (1C, Ar—C), 138.67 (1C, Ar—C), 151.38 (1C, C-3), 176.36 (1C, C=S). MS (m/z): 303 (M+2, 10) 302 (M+1, 18), 301 (M+, 100), 284 (40), 161 (15).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were fixed geometrically and allowed to ride on their parent atoms: C—H = 0.93–0.98 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₅N₃S₂
M_r	301.44
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.1035 (4), 12.0193 (5), 15.1312 (7)
β (°)	94.347 (2)
V (Å³)	1469.52 (12)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	3.22
Crystal size (mm)	0.27 × 0.25 × 0.24

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.477, 0.512
No. of measured, independent and observed [I > 2σ(I)] reflections	11926, 2397, 2262
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.583

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.127, 1.07
No. of reflections	2397
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.44
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1404788

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015010774/su5147sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015010774/su5147Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015010774/su5147Isup3.cml

checkCIF report

Chemical context top

Five-membered heterocyclic pyrazole analogues have been used extensively as building blocks in organic synthesis. They have been transformed efficiently into molecules of potential medicinal and pharmaceutical important. Pyrazole derivatives have known to exhibit diverse biological applications such as antidiabetic,anaesthetic, antimicrobial and antioxidant. In addition, they have also shown potential anticancer and antiamoebic activity and to be potent and selective inhibitors of tissue-nonspecific alkaline phosphatase (Sidique et al. 2009). Earlier we synthesized α and β-unsaturated compounds which served as useful intermediates for the synthesis of pyrazolines (Manjula et al., 2013) and thiazepines (Manjunath et al., 2014). As part of our ongoing research on pyrazole analogues, the title compound was synthesized and we report herein on its crystal structure. Studies of the biological activity of the title compound are underway and will be reported elsewhere.

Structural commentary top

The molecular structure of the title compound is illustrated in Fig. 1. The central pyrazole ring (N7/N8/C8–C10) adopts a twisted conformation with respect to the C9—C10 bond and its mean plane makes dihedral angles of 7.19 (12) and 71.13 (11)° with the thiophene (S1/C2–C5) and toluene (C14–C19) rings, respectively. The carbothiamide group [C11(═S13)N12] lies in the plane of the pyrazole ring, as indicated by the torsion angles N12—C11—N8—N7 = 0.6 (3) and S13—C11—N8—N7 = 179.96 (16)°, and adopts +synperiplanar and +antiperiplanar conformations, respectively. The title compound possess a chiral center at atom C9 but crystallized as a racemate.

Supramolecular features top

In the crystal, molecules are linked by N—H···S hydrogen bonds, forming chains propagating along [010]. Within the chains there are N—H···π interactions involving the toluene ring (Fig. 2 and Table 1). Between the chains there are weak parallel slipped π–π interactions involving inversion-related thiophene and pyrazole rings [Cg1···Cg2ⁱ = 3.7516 (14) Å; inter-planar distance = 3.5987 (10) Å; slippage = 1.06 Å; Cg1 and Cg2 are the centroids of rings S1/C2–C5 and N7/N8/C8–C10, respectively; symmetry code: (i) -x + 2, -y + 1, -z + 1].

Database survey top

A search of the Cambridge Structural Database (Version 5.36, May 2015; Groom & Allen, 2014) revealed seven structures containing the 3-(thiophen-2-yl)-pyrazole unit. Amongst these are two thioamides; the phenyl derivative of the title compound, 5-phenyl-3-(2-thienyl)-2-pyrazoline-1-thioamide (HEFXEW; Işık et al., 2006), and 1-(N-ethylthiocarbamoyl)-3,5-bis(2-thienyl)-2-pyrazoline (YINFUX; Köysal et al., 2007). In these two compounds, the pyrazole rings have envelope conformations with the methine C atom as the flap, and the mean planes of the two rings are inclined to one another by 11.98 and 10.13°, respectively. This is in contrast to the situation in the title compound where the pyrazole ring has a twisted conformation on the –CH–CH₂– bond and its mean plane is inclined to the thiophene ring by 7.19 (12)°. In the crystal of the phenyl derivative (HEFXEW), molecules are also linked by N—H···S hydrogen bonds, forming chains.

Synthesis and crystallization top

A mixture of 3-(4-methylphenyl)-1-(thiophen-2-yl)prop-2-en-1-one (0.001 mol) and thiosemicarbazine hydrochloride (0.01 mol) and potassium hydroxide (0.02 mol) in ethyl alcohol (20 ml) was refluxed on a water bath for 6–8 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was poured into ice-cold water and stirred. The solid that separated was filtered, and washed with ice-cold water. The product was recrystallized from ethyl alcohol to give the title compound as rectangular yellow crystals. Analysis calculated for C₁₅H₁₅N₃S₂: C, 59.77; H, 5.02; N, 13.94 %; found: C, 59.74; H, 5.06; N, 13.88 %. ¹H NMR (CDCl₃): δ 2.297 (s, 3H, CH3), (dd, 1H, C4—Hb: J = 18.0, 8.5 Hz), (dd, 1H, C4—Hb: J 18.0, 8.5 Hz), 5.976–6.013 (dd, 1H, C—Ha: J = 18.0, 12.0 Hz), 6.163–7.169 (m, 7H, Ar—H and thiophene ring-H), 7.330 (s, 2H, –NH₂). ¹³C NMR (CDCl₃): δ 43.77, 1 C, C-4), 63.34 (1 C, C-5), 125.35 (2C, Ar—C), 127.88 (1C, 5 m ring-C), 129.57 (1C, Ar—C), 129.67 (1C, Ar—C), 129.72 (1C, 5 m ring-C), 130.01 (1C, 5 m ring-C), 134.12, (1C, 5 m ring-C), 137.31 (1C, Ar—C), 138.67 (1C, Ar—C), 151.38 (1C, C-3), 176.36 (1C, C═S). MS (m/z): 303 (M+2, 10) 302 (M+1, 18), 301 (M+, 100), 284 (40), 161 (15).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were fixed geometrically and allowed to ride on their parent atoms: C—H = 0.93 – 0.98 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

Related literature top

For related literature, see: Groom & Allen (2014); Işık, Köysal, Özdemir & Bilgin (2006); Köysal et al. (2007); Manjula et al. (2013); Manjunath et al. (2014); Sidique et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view along the a axis of the crystal packing of the title compound. The hydrogen bonds and C—H···π interactions are shown as dashed lines (see Table 1 for details). C-bound H atoms have been omitted for clarity.

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

Crystal data top

C₁₅H₁₅N₃S₂	F(000) = 632
M_r = 301.44	D_x = 1.362 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 2262 reflections
a = 8.1035 (4) Å	θ = 5.5–64.1°
b = 12.0193 (5) Å	µ = 3.22 mm⁻¹
c = 15.1312 (7) Å	T = 296 K
β = 94.347 (2)°	Rectangle, yellow
V = 1469.52 (12) Å³	0.27 × 0.25 × 0.24 mm
Z = 4

Data collection top

Bruker X8 Proteum diffractometer	2397 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	2262 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 18.4 pixels mm^-1	θ_max = 64.1°, θ_min = 5.5°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −13→13
T_min = 0.477, T_max = 0.512	l = −16→17
11926 measured reflections

Refinement top

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.074P)² + 0.626P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2397 reflections	Δρ_max = 0.37 e Å⁻³
183 parameters	Δρ_min = −0.44 e Å⁻³
0 restraints	Extinction correction: SHELXL, FC^*=KFC[1+0.001XFC²Λ³/SIN(2Θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0160 (12)

Crystal data top

C₁₅H₁₅N₃S₂	V = 1469.52 (12) Å³
M_r = 301.44	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 8.1035 (4) Å	µ = 3.22 mm⁻¹
b = 12.0193 (5) Å	T = 296 K
c = 15.1312 (7) Å	0.27 × 0.25 × 0.24 mm
β = 94.347 (2)°

Data collection top

Bruker X8 Proteum diffractometer	2397 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	2262 reflections with I > 2σ(I)
T_min = 0.477, T_max = 0.512	R_int = 0.044
11926 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.07	Δρ_max = 0.37 e Å⁻³
2397 reflections	Δρ_min = −0.44 e Å⁻³
183 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
S1	0.83886 (8)	0.35843 (5)	0.55113 (4)	0.0527 (2)
S13	0.41488 (9)	0.76951 (5)	0.77019 (4)	0.0611 (3)
N7	0.6560 (2)	0.55350 (14)	0.63166 (11)	0.0396 (5)
N8	0.5837 (2)	0.65224 (14)	0.65865 (11)	0.0418 (6)
N12	0.5024 (3)	0.55813 (17)	0.77851 (13)	0.0572 (7)
C2	0.9012 (3)	0.3098 (2)	0.45389 (18)	0.0561 (8)
C3	0.8661 (3)	0.3801 (2)	0.38623 (17)	0.0613 (9)
C4	0.7858 (3)	0.4794 (2)	0.41081 (15)	0.0494 (8)
C5	0.7627 (3)	0.47817 (18)	0.50124 (13)	0.0400 (6)
C6	0.6841 (2)	0.56438 (17)	0.54966 (13)	0.0368 (6)
C9	0.5786 (3)	0.73914 (17)	0.58990 (13)	0.0381 (6)
C10	0.6257 (3)	0.67214 (18)	0.50885 (13)	0.0417 (6)
C11	0.5039 (3)	0.65429 (18)	0.73411 (14)	0.0438 (7)
C14	0.6974 (2)	0.83434 (15)	0.61077 (13)	0.0326 (5)
C15	0.8130 (3)	0.83437 (18)	0.68204 (14)	0.0421 (7)
C16	0.9258 (3)	0.92083 (19)	0.69439 (15)	0.0469 (7)
C17	0.9243 (3)	1.00979 (18)	0.63663 (14)	0.0437 (7)
C18	0.8065 (3)	1.00989 (18)	0.56564 (15)	0.0470 (7)
C19	0.6951 (3)	0.92360 (18)	0.55243 (14)	0.0419 (6)
C20	1.0453 (4)	1.1050 (2)	0.65103 (19)	0.0688 (10)
H2	0.95400	0.24170	0.44810	0.0670*
H3	0.89180	0.36530	0.32850	0.0740*
H4	0.75340	0.53690	0.37220	0.0590*
H9	0.46560	0.76780	0.57940	0.0460*
H10A	0.53080	0.66110	0.46670	0.0500*
H10B	0.71300	0.70870	0.47930	0.0500*
H12A	0.55020	0.50040	0.75860	0.0690*
H12B	0.45370	0.55400	0.82700	0.0690*
H15	0.81560	0.77590	0.72240	0.0500*
H16	1.00410	0.91880	0.74260	0.0560*
H18	0.80230	1.06920	0.52610	0.0560*
H19	0.61750	0.92520	0.50390	0.0500*
H20A	0.98990	1.16790	0.67420	0.1030*
H20B	1.08790	1.12470	0.59560	0.1030*
H20C	1.13490	1.08270	0.69240	0.1030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0578 (4)	0.0494 (4)	0.0530 (4)	−0.0001 (3)	0.0172 (3)	−0.0061 (2)
S13	0.0750 (5)	0.0495 (4)	0.0628 (4)	−0.0051 (3)	0.0306 (3)	−0.0180 (3)
N7	0.0483 (10)	0.0317 (9)	0.0408 (9)	−0.0044 (7)	0.0164 (7)	−0.0045 (7)
N8	0.0561 (11)	0.0321 (9)	0.0395 (9)	−0.0044 (8)	0.0188 (8)	−0.0026 (7)
N12	0.0786 (14)	0.0492 (12)	0.0478 (11)	−0.0064 (10)	0.0304 (10)	0.0030 (9)
C2	0.0557 (14)	0.0474 (14)	0.0681 (16)	−0.0092 (11)	0.0240 (12)	−0.0190 (12)
C3	0.0728 (17)	0.0637 (16)	0.0506 (14)	−0.0182 (13)	0.0258 (12)	−0.0257 (13)
C4	0.0583 (14)	0.0489 (13)	0.0429 (12)	−0.0148 (11)	0.0156 (10)	−0.0163 (10)
C5	0.0403 (11)	0.0424 (12)	0.0386 (10)	−0.0145 (9)	0.0112 (8)	−0.0087 (9)
C6	0.0377 (10)	0.0362 (11)	0.0372 (10)	−0.0118 (8)	0.0084 (8)	−0.0055 (8)
C9	0.0409 (11)	0.0348 (11)	0.0391 (11)	−0.0036 (8)	0.0070 (8)	−0.0004 (8)
C10	0.0509 (12)	0.0387 (11)	0.0357 (10)	−0.0121 (9)	0.0050 (9)	−0.0036 (9)
C11	0.0491 (12)	0.0444 (12)	0.0398 (11)	−0.0122 (10)	0.0157 (9)	−0.0080 (9)
C14	0.0362 (10)	0.0275 (9)	0.0349 (9)	0.0015 (8)	0.0087 (8)	−0.0029 (7)
C15	0.0504 (12)	0.0342 (11)	0.0410 (11)	0.0016 (9)	−0.0004 (9)	0.0053 (8)
C16	0.0491 (12)	0.0474 (13)	0.0430 (11)	−0.0019 (10)	−0.0040 (9)	−0.0065 (10)
C17	0.0495 (12)	0.0371 (12)	0.0459 (11)	−0.0077 (9)	0.0137 (9)	−0.0128 (9)
C18	0.0642 (14)	0.0324 (11)	0.0451 (11)	−0.0070 (10)	0.0090 (10)	0.0057 (9)
C19	0.0508 (12)	0.0375 (11)	0.0366 (10)	−0.0002 (9)	−0.0010 (9)	0.0022 (8)
C20	0.0790 (19)	0.0592 (17)	0.0697 (17)	−0.0309 (15)	0.0151 (14)	−0.0182 (14)

Geometric parameters (Å, º) top

S1—C2	1.695 (3)	C15—C16	1.387 (3)
S1—C5	1.718 (2)	C16—C17	1.381 (3)
S13—C11	1.672 (2)	C17—C18	1.382 (3)
N7—N8	1.398 (2)	C17—C20	1.512 (4)
N7—C6	1.285 (3)	C18—C19	1.380 (3)
N8—C9	1.473 (3)	C2—H2	0.9300
N8—C11	1.354 (3)	C3—H3	0.9300
N12—C11	1.337 (3)	C4—H4	0.9300
N12—H12B	0.8600	C9—H9	0.9800
N12—H12A	0.8600	C10—H10A	0.9700
C2—C3	1.341 (4)	C10—H10B	0.9700
C3—C4	1.422 (3)	C15—H15	0.9300
C4—C5	1.395 (3)	C16—H16	0.9300
C5—C6	1.445 (3)	C18—H18	0.9300
C6—C10	1.496 (3)	C19—H19	0.9300
C9—C14	1.513 (3)	C20—H20A	0.9600
C9—C10	1.539 (3)	C20—H20B	0.9600
C14—C19	1.389 (3)	C20—H20C	0.9600
C14—C15	1.374 (3)

C2—S1—C5	91.62 (11)	C18—C17—C20	120.9 (2)
N8—N7—C6	107.73 (16)	C17—C18—C19	121.2 (2)
N7—N8—C9	112.69 (15)	C14—C19—C18	120.8 (2)
N7—N8—C11	119.94 (17)	S1—C2—H2	124.00
C9—N8—C11	126.37 (17)	C3—C2—H2	124.00
H12A—N12—H12B	120.00	C2—C3—H3	123.00
C11—N12—H12A	120.00	C4—C3—H3	123.00
C11—N12—H12B	120.00	C3—C4—H4	125.00
S1—C2—C3	112.67 (19)	C5—C4—H4	125.00
C2—C3—C4	113.8 (2)	N8—C9—H9	110.00
C3—C4—C5	110.2 (2)	C10—C9—H9	110.00
S1—C5—C4	111.68 (17)	C14—C9—H9	110.00
S1—C5—C6	122.38 (15)	C6—C10—H10A	111.00
C4—C5—C6	125.9 (2)	C6—C10—H10B	111.00
N7—C6—C10	114.39 (17)	C9—C10—H10A	111.00
N7—C6—C5	122.27 (18)	C9—C10—H10B	111.00
C5—C6—C10	123.33 (17)	H10A—C10—H10B	109.00
N8—C9—C10	101.33 (16)	C14—C15—H15	120.00
N8—C9—C14	113.93 (17)	C16—C15—H15	120.00
C10—C9—C14	111.69 (18)	C15—C16—H16	119.00
C6—C10—C9	102.35 (16)	C17—C16—H16	119.00
N8—C11—N12	115.5 (2)	C17—C18—H18	119.00
S13—C11—N12	122.08 (18)	C19—C18—H18	119.00
S13—C11—N8	122.39 (16)	C14—C19—H19	120.00
C9—C14—C15	123.31 (18)	C18—C19—H19	120.00
C9—C14—C19	118.29 (18)	C17—C20—H20A	109.00
C15—C14—C19	118.32 (18)	C17—C20—H20B	109.00
C14—C15—C16	120.6 (2)	C17—C20—H20C	109.00
C15—C16—C17	121.4 (2)	H20A—C20—H20B	110.00
C16—C17—C20	121.4 (2)	H20A—C20—H20C	109.00
C16—C17—C18	117.7 (2)	H20B—C20—H20C	110.00

C5—S1—C2—C3	−0.2 (2)	C4—C5—C6—N7	174.6 (2)
C2—S1—C5—C4	0.1 (2)	C4—C5—C6—C10	−4.2 (3)
C2—S1—C5—C6	179.6 (2)	C5—C6—C10—C9	−171.56 (19)
C6—N7—N8—C9	−5.9 (2)	N7—C6—C10—C9	9.6 (2)
C6—N7—N8—C11	163.41 (18)	C10—C9—C14—C15	−107.0 (2)
N8—N7—C6—C5	178.34 (17)	C10—C9—C14—C19	69.6 (2)
N8—N7—C6—C10	−2.8 (2)	N8—C9—C14—C19	−176.34 (18)
C11—N8—C9—C14	82.7 (3)	N8—C9—C10—C6	−11.5 (2)
C9—N8—C11—N12	168.3 (2)	C14—C9—C10—C6	110.18 (18)
N7—N8—C11—S13	179.96 (16)	N8—C9—C14—C15	7.1 (3)
N7—N8—C9—C10	11.3 (2)	C9—C14—C15—C16	175.7 (2)
C11—N8—C9—C10	−157.2 (2)	C19—C14—C15—C16	−0.9 (3)
N7—N8—C11—N12	0.6 (3)	C9—C14—C19—C18	−176.6 (2)
N7—N8—C9—C14	−108.84 (18)	C15—C14—C19—C18	0.2 (3)
C9—N8—C11—S13	−12.4 (3)	C14—C15—C16—C17	0.9 (4)
S1—C2—C3—C4	0.3 (3)	C15—C16—C17—C18	−0.1 (4)
C2—C3—C4—C5	−0.3 (3)	C15—C16—C17—C20	178.9 (2)
C3—C4—C5—S1	0.1 (3)	C16—C17—C18—C19	−0.6 (3)
C3—C4—C5—C6	−179.4 (2)	C20—C17—C18—C19	−179.6 (2)
S1—C5—C6—N7	−4.9 (3)	C17—C18—C19—C14	0.6 (3)
S1—C5—C6—C10	176.33 (17)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the benzene ring C14–C19.

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12A···S13ⁱ	0.86	2.83	3.620 (2)	154
N12—H12B···Cg3ⁱ	0.86	2.81	3.443 (2)	132

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the benzene ring C14–C19.

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12A···S13ⁱ	0.86	2.83	3.620 (2)	154
N12—H12B···Cg3ⁱ	0.86	2.81	3.443 (2)	132

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅N₃S₂
M_r	301.44
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.1035 (4), 12.0193 (5), 15.1312 (7)
β (°)	94.347 (2)
V (Å³)	1469.52 (12)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.22
Crystal size (mm)	0.27 × 0.25 × 0.24

Data collection
Diffractometer	Bruker X8 Proteum diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2013)
T_min, T_max	0.477, 0.512
No. of measured, independent and observed [I > 2σ(I)] reflections	11926, 2397, 2262
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.583

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.127, 1.07
No. of reflections	2397
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.44

Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors are thankful to the IOE, Vijnana Bhavana, University of Mysore, Mysore, for providing the single-crystal X-ray diffraction facility. IW is grateful to An-Najah National University and Zamala (fellowship program for the development of university education) for financial support.

References

Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CrossRef CAS Google Scholar
Işık, S., Köysal, Y., Özdemir, Z. & Bilgin, A. A. (2006). Acta Cryst. E62, o491–o493. Web of Science CSD CrossRef IUCr Journals Google Scholar
Köysal, Y., Işık, S., Özdemir, Z. & Bilgin, A. A. (2007). Anal. Sci. 23, x193–x194. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Manjula, M., Jayaroopa, P., Manjunath, B. C., Ajay kumar, K. & Lokanath, N. K. (2013). Acta Cryst. E69, o602. CSD CrossRef IUCr Journals Google Scholar
Manjunath, B. C., Manjula, M., Raghavendra, K. R., Shashikanth, S., Ajay Kumar, K. & Lokanath, N. K. (2014). Acta Cryst. E70, o121. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sidique, S., Ardecky, R., Su, Y., Narisawa, S., Brown, B., Millán, J. L., Sergienko, E. & Cosford, N. D. P. (2009). Bioorg. Med. Chem. Lett. 19, 222–225. Web of Science CrossRef PubMed CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 71| Part 7| July 2015| Pages 763-765

doi:10.1107/S2056989015010774

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of 3-(thio­phen-2-yl)-5-p-tolyl-4,5-di­hydro-1H-pyrazole-1-carbo­thio­amide

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of 3-(thiophen-2-yl)-5-p-tolyl-4,5-dihydro-1H-pyrazole-1-carbothioamide

3. Supramolecular features