1-(3-Chloro­phen­yl)-5-(4-chloro­phen­yl)-3-(5-chloro­thio­phen-2-yl)-4,5-di­hydro-1H-pyrazole

Prabhudeva, M.G.; Naveen, S.; Raghavendra, K.R.; Dileep Kumar, A.; Kumara, K.; Lokanath, N.K.; Ajay Kumar, K.

doi:10.1107/S2414314616020484

organic compounds

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ISSN: 2414-3146

Volume 2| Part 1| January 2017| x162048

https://doi.org/10.1107/S2414314616020484

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1-(3-Chlorophenyl)-5-(4-chlorophenyl)-3-(5-chlorothiophen-2-yl)-4,5-dihydro-1H-pyrazole

M. G. Prabhudeva,^a S. Naveen,^b ^* K. R. Raghavendra,^c A. Dileep Kumar,^a Karthik Kumara,^d N. K. Lokanath ^d and K. Ajay Kumar ^a ^*

^aDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysuru 570 005, India, ^bInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, ^cDepartment of Chemistry, SBRR Mahajana College, Mysuru 570 006, India, and ^dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India
^*Correspondence e-mail: naveen@ioe.uni-mysore.ac.in, ajaykumar@ycm.uni-mysore.ac.in

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 17 December 2016; accepted 24 December 2016; online 13 January 2017)

In the title compound, C₁₉H₁₃Cl₃N₂S, the central dihydropyrazole ring adopts an envelope conformation with the chiral C atom as the flap. In the crystal, molecules are linked by weak C—H⋯Cl hydrogen bonds into supramolecular chains propagating along the b-axis direction.

Keywords: crystal structure; pyrazoles; envelope conformation; hydrogen bonds.

CCDC reference: 1524745

Structure description

Five-membered nitrogen heterocycles such as pyrazoles have been studied extensively for their enormous number of synthetic utilities and pharmaceutical applications. These classes of compounds have known to exhibit varied biological activities such as antiamoebic (Abid & Azam, 2006 ). In view of their potential applications and in a continuation of our work on pyrazolines (Assem et al., 2016 ), we report herein on the synthesis and crystal structure of the title compound.

The structure of the molecule is shown in Fig. 1. The central pyrazole ring adopts an envelope conformation with the C3 flap atom having a maximum deviation of 0.138 (4) Å, and puckering parameters Q = 0.220 (3) Å and φ = 78.7 (8)°. The mean plane through the pyrazole ring forms dihedral angles of 5.41 (17), 5.54 (16) and 76.89 (17)° with the chlorothiophene, chlorophenyl (C8–C13) and chlorophenyl (C14–C19) rings, respectively, whereas the dihedral angle between the chlorophenyl rings is 81.19 (16)°.

Figure 1
The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

The title compound is chiral. In the arbitrarily chosen asymmetric molecule, the compound possess a chiral center at C3 with an R conformation. Since the compound crystallizes in a centrosymmetric space group, we can surmise that the compound is a racemic mixture. In the crystal, the molecules are connected by C3—H3⋯Cl2 interactions (Table 1) into the supramolecular chains propagating along the b axis.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl2ⁱ	0.98	2.82	3.700 (4)	150
Symmetry code: (i) x, y+1, z.

Synthesis and crystallization

To a solution of (E)-3-(4-chlorophenyl)-1-(5-chlorothiophen-2-yl)prop-2-en-1-one, (5 mmol) and (3-chlorophenyl)hydrazine hydrochloride (5 mmol) in methyl alcohol (25 ml), 4–5 drops of conc. hydrochloric acid were added. The mixture was refluxed on a water bath for 4 h. The progress of the reaction was monitored by TLC. After completion, 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 crystallized from methyl alcohol to get the title compound in 82% yield, m.p. 375–373 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₃Cl₃N₂S
M_r	407.73
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	7.6071 (2), 11.3292 (4), 11.7601 (4)
α, β, γ (°)	64.529 (1), 75.255 (2), 81.149 (2)
V (Å³)	883.73 (5)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	5.83
Crystal size (mm)	0.27 × 0.24 × 0.22

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.302, 0.360
No. of measured, independent and observed [I > 2σ(I)] reflections	9181, 2912, 2661
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.586

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.152, 1.06
No. of reflections	2912
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.37
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1524745

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616020484/xu4020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616020484/xu4020Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616020484/xu4020Isup3.cml

checkCIF report

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: Mercury (Macrae et al., 2008).

1-(3-Chlorophenyl)-5-(4-chlorophenyl)-3-(5-chlorothiophen-2-yl)-4,5-dihydro-1H-pyrazole top

Crystal data top

C₁₉H₁₃Cl₃N₂S	Z = 2
M_r = 407.73	F(000) = 416
Triclinic, P1	D_x = 1.532 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 7.6071 (2) Å	Cell parameters from 2661 reflections
b = 11.3292 (4) Å	θ = 6.0–64.6°
c = 11.7601 (4) Å	µ = 5.83 mm⁻¹
α = 64.529 (1)°	T = 296 K
β = 75.255 (2)°	Rectangle, yellow
γ = 81.149 (2)°	0.27 × 0.24 × 0.22 mm
V = 883.73 (5) Å³

Data collection top

Bruker X8 Proteum diffractometer	2912 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	2661 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.045
Detector resolution: 18.4 pixels mm^-1	θ_max = 64.6°, θ_min = 6.0°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −13→13
T_min = 0.302, T_max = 0.360	l = −13→13
9181 measured reflections

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) = 0.152	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.106P)² + 0.5652P] where P = (F_o² + 2F_c²)/3
2912 reflections	(Δ/σ)_max = 0.001
226 parameters	Δρ_max = 0.88 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

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 esds 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 > 2sigma(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
Cl1	−0.48103 (10)	0.67564 (8)	0.97162 (7)	0.0279 (3)
Cl2	0.38383 (13)	−0.08824 (8)	0.66214 (9)	0.0374 (3)
Cl3	0.10331 (10)	0.79457 (8)	0.07472 (7)	0.0318 (3)
S1	0.31946 (10)	0.19980 (7)	0.57645 (7)	0.0212 (2)
N1	0.2567 (3)	0.4921 (2)	0.5288 (2)	0.0193 (7)
N2	0.2453 (3)	0.6185 (2)	0.5214 (2)	0.0203 (8)
C1	0.3072 (4)	0.4138 (3)	0.6350 (3)	0.0185 (8)
C2	0.3445 (4)	0.4841 (3)	0.7088 (3)	0.0207 (9)
C3	0.2528 (4)	0.6197 (3)	0.6446 (3)	0.0181 (8)
C4	0.3357 (4)	0.2748 (3)	0.6743 (3)	0.0199 (9)
C5	0.3715 (4)	0.0492 (3)	0.6913 (3)	0.0241 (9)
C6	0.3988 (4)	0.0550 (3)	0.7975 (3)	0.0242 (9)
C7	0.3786 (4)	0.1844 (3)	0.7879 (3)	0.0215 (9)
C8	0.1945 (4)	0.7240 (3)	0.4180 (3)	0.0194 (8)
C9	0.1718 (4)	0.7085 (3)	0.3108 (3)	0.0203 (9)
C10	0.1291 (4)	0.8178 (3)	0.2075 (3)	0.0249 (9)
C11	0.1064 (4)	0.9423 (3)	0.2034 (3)	0.0282 (10)
C12	0.1267 (4)	0.9567 (3)	0.3110 (3)	0.0278 (10)
C13	0.1690 (4)	0.8507 (3)	0.4173 (3)	0.0228 (9)
C14	0.0662 (4)	0.6366 (3)	0.7233 (3)	0.0185 (8)
C15	−0.0936 (4)	0.6215 (3)	0.6946 (3)	0.0210 (9)
C16	−0.2608 (4)	0.6325 (3)	0.7706 (3)	0.0231 (9)
C17	−0.2694 (4)	0.6589 (3)	0.8767 (3)	0.0206 (8)
C18	−0.1130 (4)	0.6748 (3)	0.9073 (3)	0.0231 (9)
C19	0.0545 (4)	0.6625 (3)	0.8308 (3)	0.0229 (9)
H2A	0.47410	0.48940	0.69850	0.0250*
H2B	0.28980	0.44210	0.79980	0.0250*
H3	0.33100	0.68840	0.62950	0.0220*
H6	0.42730	−0.01750	0.86840	0.0290*
H7	0.39300	0.20660	0.85240	0.0260*
H9	0.18540	0.62610	0.30930	0.0240*
H11	0.07860	1.01400	0.13160	0.0340*
H12	0.11150	1.03970	0.31130	0.0330*
H13	0.18080	0.86250	0.48850	0.0270*
H15	−0.08740	0.60380	0.62340	0.0250*
H16	−0.36690	0.62240	0.75100	0.0280*
H18	−0.12020	0.69340	0.97810	0.0280*
H19	0.16040	0.67160	0.85140	0.0270*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0218 (4)	0.0380 (5)	0.0211 (4)	0.0026 (3)	−0.0010 (3)	−0.0129 (3)
Cl2	0.0569 (6)	0.0207 (4)	0.0377 (5)	−0.0023 (4)	−0.0138 (4)	−0.0127 (4)
Cl3	0.0274 (4)	0.0462 (5)	0.0197 (4)	0.0043 (3)	−0.0075 (3)	−0.0121 (4)
S1	0.0242 (4)	0.0200 (4)	0.0193 (4)	−0.0007 (3)	−0.0058 (3)	−0.0074 (3)
N1	0.0179 (12)	0.0210 (13)	0.0180 (13)	0.0001 (10)	−0.0027 (10)	−0.0080 (11)
N2	0.0262 (14)	0.0202 (13)	0.0127 (12)	0.0006 (10)	−0.0036 (10)	−0.0059 (10)
C1	0.0161 (14)	0.0212 (15)	0.0160 (15)	−0.0008 (11)	−0.0022 (11)	−0.0064 (12)
C2	0.0214 (15)	0.0215 (15)	0.0189 (16)	0.0025 (12)	−0.0060 (12)	−0.0083 (13)
C3	0.0199 (15)	0.0204 (14)	0.0148 (15)	−0.0017 (12)	−0.0055 (12)	−0.0067 (12)
C4	0.0165 (14)	0.0247 (16)	0.0185 (15)	−0.0003 (12)	−0.0017 (11)	−0.0102 (13)
C5	0.0221 (16)	0.0210 (15)	0.0261 (17)	0.0002 (12)	−0.0029 (13)	−0.0084 (13)
C6	0.0228 (16)	0.0230 (16)	0.0214 (16)	−0.0002 (13)	−0.0037 (12)	−0.0049 (13)
C7	0.0215 (15)	0.0245 (15)	0.0181 (15)	−0.0003 (12)	−0.0039 (12)	−0.0089 (13)
C8	0.0133 (14)	0.0238 (15)	0.0166 (15)	−0.0030 (11)	−0.0002 (11)	−0.0052 (12)
C9	0.0142 (14)	0.0251 (15)	0.0195 (16)	−0.0001 (12)	−0.0015 (12)	−0.0087 (13)
C10	0.0152 (15)	0.0386 (18)	0.0151 (15)	−0.0025 (13)	−0.0019 (12)	−0.0059 (13)
C11	0.0249 (17)	0.0293 (17)	0.0219 (17)	−0.0021 (13)	−0.0052 (13)	−0.0022 (14)
C12	0.0255 (17)	0.0224 (16)	0.0289 (18)	−0.0014 (13)	−0.0061 (14)	−0.0042 (14)
C13	0.0213 (15)	0.0253 (16)	0.0211 (16)	−0.0032 (12)	−0.0058 (12)	−0.0075 (13)
C14	0.0226 (15)	0.0162 (14)	0.0145 (14)	−0.0012 (11)	−0.0040 (12)	−0.0041 (12)
C15	0.0237 (16)	0.0259 (16)	0.0151 (15)	−0.0017 (12)	−0.0036 (12)	−0.0102 (13)
C16	0.0190 (15)	0.0311 (16)	0.0217 (16)	−0.0018 (13)	−0.0080 (12)	−0.0109 (13)
C17	0.0182 (15)	0.0202 (14)	0.0170 (15)	0.0013 (12)	−0.0007 (12)	−0.0041 (12)
C18	0.0278 (17)	0.0261 (16)	0.0166 (15)	−0.0005 (13)	−0.0027 (12)	−0.0113 (13)
C19	0.0227 (16)	0.0276 (16)	0.0196 (16)	−0.0025 (13)	−0.0070 (12)	−0.0090 (13)

Geometric parameters (Å, º) top

Cl1—C17	1.746 (3)	C12—C13	1.380 (5)
Cl2—C5	1.717 (4)	C14—C15	1.394 (5)
Cl3—C10	1.753 (3)	C14—C19	1.395 (5)
S1—C4	1.734 (4)	C15—C16	1.379 (5)
S1—C5	1.725 (3)	C16—C17	1.387 (5)
N1—N2	1.387 (3)	C17—C18	1.385 (5)
N1—C1	1.296 (4)	C18—C19	1.386 (5)
N2—C3	1.470 (4)	C2—H2A	0.9700
N2—C8	1.380 (4)	C2—H2B	0.9700
C1—C2	1.503 (5)	C3—H3	0.9800
C1—C4	1.435 (5)	C6—H6	0.9300
C2—C3	1.535 (5)	C7—H7	0.9300
C3—C14	1.519 (5)	C9—H9	0.9300
C4—C7	1.372 (5)	C11—H11	0.9300
C5—C6	1.347 (5)	C12—H12	0.9300
C6—C7	1.408 (5)	C13—H13	0.9300
C8—C9	1.400 (5)	C15—H15	0.9300
C8—C13	1.415 (5)	C16—H16	0.9300
C9—C10	1.378 (5)	C18—H18	0.9300
C10—C11	1.376 (5)	C19—H19	0.9300
C11—C12	1.392 (5)

C4—S1—C5	90.38 (16)	C15—C16—C17	119.4 (3)
N2—N1—C1	107.8 (2)	Cl1—C17—C16	119.6 (2)
N1—N2—C3	111.9 (2)	Cl1—C17—C18	119.3 (3)
N1—N2—C8	121.2 (2)	C16—C17—C18	121.1 (3)
C3—N2—C8	125.6 (3)	C17—C18—C19	119.0 (3)
N1—C1—C2	113.2 (3)	C14—C19—C18	120.8 (3)
N1—C1—C4	123.5 (3)	C1—C2—H2A	112.00
C2—C1—C4	123.2 (3)	C1—C2—H2B	112.00
C1—C2—C3	101.5 (3)	C3—C2—H2A	111.00
N2—C3—C2	100.6 (3)	C3—C2—H2B	111.00
N2—C3—C14	113.1 (3)	H2A—C2—H2B	109.00
C2—C3—C14	112.4 (3)	N2—C3—H3	110.00
S1—C4—C1	121.9 (2)	C2—C3—H3	110.00
S1—C4—C7	110.9 (3)	C14—C3—H3	110.00
C1—C4—C7	127.2 (3)	C5—C6—H6	124.00
Cl2—C5—S1	119.45 (19)	C7—C6—H6	124.00
Cl2—C5—C6	127.1 (3)	C4—C7—H7	123.00
S1—C5—C6	113.5 (3)	C6—C7—H7	123.00
C5—C6—C7	111.6 (3)	C8—C9—H9	121.00
C4—C7—C6	113.6 (3)	C10—C9—H9	121.00
N2—C8—C9	120.8 (3)	C10—C11—H11	121.00
N2—C8—C13	120.3 (3)	C12—C11—H11	121.00
C9—C8—C13	118.9 (3)	C11—C12—H12	119.00
C8—C9—C10	118.6 (3)	C13—C12—H12	119.00
Cl3—C10—C9	117.3 (3)	C8—C13—H13	120.00
Cl3—C10—C11	119.0 (2)	C12—C13—H13	120.00
C9—C10—C11	123.7 (3)	C14—C15—H15	120.00
C10—C11—C12	117.3 (3)	C16—C15—H15	120.00
C11—C12—C13	121.5 (3)	C15—C16—H16	120.00
C8—C13—C12	120.0 (3)	C17—C16—H16	120.00
C3—C14—C15	122.0 (3)	C17—C18—H18	121.00
C3—C14—C19	119.1 (3)	C19—C18—H18	121.00
C15—C14—C19	118.9 (3)	C14—C19—H19	120.00
C14—C15—C16	120.7 (3)	C18—C19—H19	120.00

C5—S1—C4—C1	179.6 (3)	C2—C3—C14—C19	78.1 (4)
C5—S1—C4—C7	−0.2 (3)	S1—C4—C7—C6	0.0 (4)
C4—S1—C5—Cl2	−179.7 (2)	C1—C4—C7—C6	−179.7 (3)
C4—S1—C5—C6	0.3 (3)	Cl2—C5—C6—C7	179.6 (3)
C1—N1—N2—C3	−12.7 (3)	S1—C5—C6—C7	−0.3 (4)
C1—N1—N2—C8	179.9 (3)	C5—C6—C7—C4	0.2 (4)
N2—N1—C1—C2	−2.8 (3)	N2—C8—C9—C10	−177.1 (3)
N2—N1—C1—C4	−179.2 (3)	C13—C8—C9—C10	1.3 (5)
N1—N2—C3—C2	21.5 (3)	N2—C8—C13—C12	176.9 (3)
N1—N2—C3—C14	−98.6 (3)	C9—C8—C13—C12	−1.5 (5)
C8—N2—C3—C2	−171.7 (3)	C8—C9—C10—Cl3	179.6 (2)
C8—N2—C3—C14	68.2 (4)	C8—C9—C10—C11	−0.3 (5)
N1—N2—C8—C9	−6.9 (4)	Cl3—C10—C11—C12	179.6 (2)
N1—N2—C8—C13	174.7 (3)	C9—C10—C11—C12	−0.6 (5)
C3—N2—C8—C9	−172.5 (3)	C10—C11—C12—C13	0.4 (5)
C3—N2—C8—C13	9.1 (5)	C11—C12—C13—C8	0.6 (5)
N1—C1—C2—C3	15.8 (3)	C3—C14—C15—C16	177.5 (3)
C4—C1—C2—C3	−167.9 (3)	C19—C14—C15—C16	0.3 (5)
N1—C1—C4—S1	4.5 (5)	C3—C14—C19—C18	−178.1 (3)
N1—C1—C4—C7	−175.9 (3)	C15—C14—C19—C18	−0.8 (5)
C2—C1—C4—S1	−171.5 (2)	C14—C15—C16—C17	0.0 (5)
C2—C1—C4—C7	8.1 (5)	C15—C16—C17—Cl1	178.9 (3)
C1—C2—C3—N2	−20.6 (3)	C15—C16—C17—C18	0.2 (5)
C1—C2—C3—C14	99.9 (3)	Cl1—C17—C18—C19	−179.4 (3)
N2—C3—C14—C15	14.0 (5)	C16—C17—C18—C19	−0.7 (5)
N2—C3—C14—C19	−168.8 (3)	C17—C18—C19—C14	1.0 (5)
C2—C3—C14—C15	−99.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl2ⁱ	0.98	2.82	3.700 (4)	150

Symmetry code: (i) x, y+1, z.

Acknowledgements

The authors are grateful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, India, for providing the single-crystal X-ray diffractometer facility.

References

Abid, M. & Azam, A. (2006). Bioorg. Med. Chem. Lett. 16, 2812–2816. Web of Science CrossRef CAS Google Scholar
Assem, B., Naveen, S., Nagamallu, R., Ajay Kumar, K., Abdoh, M., Warad, I. & Lokanath, N. K. (2016). Z. Kristallogr. 231, 267–269. Google Scholar
Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. 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 CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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