Crystal structure and Hirshfeld surface analysis of 1-(2,4-di­chloro­benz­yl)-5-methyl-N-(thio­phene-2-sulfon­yl)-1H-pyrazole-3-carboxamide

Aydin, A.; Akkurt, M.; Gur, Z.T.; Banoğlu, E.

doi:10.1107/S2056989018006242

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 74| Part 5| May 2018| Pages 747-751

https://doi.org/10.1107/S2056989018006242

Open

access

Crystal structure and Hirshfeld surface analysis of 1-(2,4-dichlorobenzyl)-5-methyl-N-(thiophene-2-sulfonyl)-1H-pyrazole-3-carboxamide

Abdullah Aydin,^a ^* Mehmet Akkurt,^b Zehra Tugce Gur ^c and Erden Banoğlu ^c

^aDepartment of Mathematics and Science Education, Faculty of Education, Kastamonu University, 37200 Kastamonu, Turkey, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^cDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, Gazi University, 06330 Ankara, Turkey
^*Correspondence e-mail: aaydin@kastamonu.edu.tr

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 18 April 2018; accepted 24 April 2018; online 27 April 2018)

In the title compound, C₁₆H₁₃Cl₂N₃O₃S₂, the thiophene ring is disordered in a 0.762 (3):0.238 (3) ratio by an approximate 180° rotation of the ring around the S—C bond linking the ring to the sulfonyl unit. The dichlorobenzene group is also disordered over two sets of sites with the same occupancy ratio. The molecular conformation is stabilized by intramolecular C—H⋯Cl and C—H⋯N hydrogen bonds, forming rings with graph-set notation S(5). In the crystal, pairs of molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds, forming inversion dimers with graph-set notation R₂²(8) and R₁²(11), which are connected by C—H⋯O hydrogen-bonding interactions into ribbons parallel to (100). The ribbons are further connected into a three-dimensional network by C—H⋯π interactions and π–π stacking interactions between benzene and thiophene rings, with centroid-to-centroid distances of 3.865 (2), 3.867 (7) and 3.853 (2) Å. Hirshfeld surface analysis has been used to confirm and quantify the supramolecular interactions.

Keywords: crystal structure; dimer; 1H-pyrazole ring; thiophene ring; disorder; hydrogen-bonding patterns.

CCDC reference: 1839201

1. Chemical context

The pyrazole core structure has been widely used as a common heterocyclic scaffold in medicinal chemistry to produce novel drug candidates with a great variety of pharmacological activities including anti-inflammatory, antiplatelet, anticancer, antimycobacterial, antidepressant and anticonvulsant properties (Küçükgüzel & Şenkardeş, 2015 ; Çalışkan et al., 2013 ; Ding et al., 2009 ; Baraldi et al., 2004 ; Palaska et al., 2008 ). Among them, pyrazole-carboxamide derivatives have been shown to exhibit antimycobacterial, antifungal and antiviral activities (Sun & Zhou, 2015 ; Yan et al., 2018 ; Comber et al., 1992 ). In the course of our ongoing research into bioactive pyrazole derivatives (Banoğlu et al., 2005 ; Şüküroğlu et al., 2005 ; Ergün et al., 2010 ; Çalışkan et al., 2011 ; Levent et al., 2013 ; Cankara Pirol et al., 2014 ), we have relied on the aforementioned biological properties of pyrazole-carboxamides and designed novel pyrazole-3-carboxamide derivatives for their potential antimicrobial activity. In this work, we report the crystallographic characterization and Hirshfeld surface analysis of one of these compounds bearing the 2,4-dichlorobenzyl substituent at one of the pyrazole nitrogen atoms.

2. Structural commentary

In the molecule of the title compound (Fig. 1), the dihedral angles between the planes of the pyrazole ring A (N2/N3/C6–C8), the major and minor components B (S1/C1–C4) and B′ (S1A/C1/C2/C3A/C4) of the disordered thiophene ring, and the disordered benzene ring C (C11–C16) and C′ (C11A–C16A) are A/B = 67.62 (16)°, A/B′ = 68.1 (5)°, B/B′ = 3.3 (5)°, A/C = 70.09 (16)°, B/C = 83.06 (19)° and B′/C = 80.2 (5)°, A/C′ = 78.4 (4)°, B/C′ = 77.3 (4)° and B′/C′ = 74.2 (6)°. The molecular conformation is stabilized by intramolecular C—H⋯Cl and C—H⋯N hydrogen bonds (Table 1), forming rings with graph-set notation S(5).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the major component (S1/C1–C4) of the disordered thiophene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.84 (3)	2.27 (3)	3.029 (3)	150 (3)
C7—H7⋯O3ⁱⁱ	0.93	2.59	3.437 (3)	152
C10—H10B⋯O1ⁱⁱⁱ	0.97	2.52	3.141 (3)	122
C12—H12⋯N3	0.93	2.61	3.224 (3)	124
C12—H12⋯O2ⁱ	0.93	2.51	3.348 (3)	150
C15—H15⋯Cg1^iv	0.93	2.97	3.893 (3)	174
C15A—H15A⋯Cg1^iv	0.93	2.95	3.836 (8)	159
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, -y, -z+1; (iii) -x+1, -y, -z+1; (iv) x, y, z-1.

Figure 1
The molecular structure of the title compound with displacement ellipsoids for non-H atoms drawn at the 30% probability level. The minor components of the disordered thiophene and dichlorobenzene groups have been omitted.

3. Supramolecular features

In the crystal, pairs of molecules are linked by intermolecular N—H⋯O and C—H⋯O hydrogen bonds (Table 1; Figs. 2 and 3), forming inversion dimers with graph-set notation $[R_{2}^{2}]$ (8) and $[R_{1}^{2}]$ (11), which are connected by C—H⋯O hydrogen-bonding interactions into ribbons parallel to (100). The ribbons are further connected into a three-dimensional network by C—H⋯π interactions (Table 1) and π–π stacking interactions between the benzene and thiophene rings, with centroid-to-centroid distances of 3.865 (2) Å for Cg1⋯Cg1^v, 3.867 (7) Å for Cg2⋯Cg2^v and 3.853 (2) Å for Cg4⋯Cg4^vi where Cg1, Cg2 and Cg4 are the centroids of the thiophene ring B, the thiophene ring B′ and the benzene ring C [symmetry codes: (v) 2 − x, 1 − y, 1 − z; (vi) 1 − x, 1 − y, −z].

Figure 2
Crystal structure of the title compound viewed along the a axis. Dashed lines show hydrogen-bonding interactions. The minor components of the disordered groups have been omitted.

Figure 3
Crystal structure of the title compound viewed along the b axis. Dashed lines show hydrogen-bonding interactions. The minor components of the disordered groups have been omitted.

4. Hirshfeld surface analysis

A Hirshfeld surface analysis (Hirshfeld, 1977 ; Spackman & Jayatilaka, 2009 ) of the title compound was carried out to investigate the location of atoms with potential to form hydrogen bonds and the quantitative ratio of these interactions. CrystalExplorer17.5 (Turner et al., 2017 ) was used to generate the Hirshfeld surface and two-dimensional fingerprint plots (Parkin et al., 2007 ; Rohl et al., 2008 ), using the atomic coordinates of the major disorder component of the disordered atoms (Figs. 4 and 5). The electrostatic potentials were calculated using TONTO (Spackman et al., 2009) integrated into CrystalExplorer, wherein the respective experimental structure was used as the input to TONTO. Further, the electrostatic potentials were mapped on Hirshfeld surfaces using the STO-3G basis set at the Hartree–Fock level of theory.

Figure 4
The Hirshfeld surface of the title compound mapped over d_norm.

Figure 5
The two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) C⋯H, (d) Cl⋯H, (e) Cl⋯Cl and (f) C⋯C interactions. The outline of the full fingerprint plots is shown in grey. d_i is the closest internal distance from a given point on the Hirshfeld surface and d_e is the closest external contact.

The intermolecular distance information on the surface can be condensed into a two-dimensional histogram of d_e and d_i, which is a unique identifier for molecules in a crystal structure, and is known as a fingerprint plot. Instead of plotting d_e and d_i on the Hirshfeld surface, contact distances are normalized in CrystalExplorer using the van der Waals radius of the appropriate internal (r_i^vdw) and external (r_e^vdw) atom of the surface:

d_norm= (d_i − r_i^vdw)/r_i^vdw + (d_e − r_e^vdw)/r_e^vdw.

The molecular Hirshfeld surfaces were obtained using a standard (high) surface resolution with the three-dimentional d_norm surfaces mapped over a fixed colour scale of −1.9033 (red) to 1.1934 (blue). In the fingerprint plots (Rohl et al., 2008), shown in Fig. 5, the points indicated by b, c, d and e correspond to H⋯H, C⋯H, Cl⋯H, Cl⋯Cl and C⋯C interactions with relative contributions of 28.4, 7.0, 6.8, 6.5 and 5.7%, respectively. These types of interactions add up to 54.4% of the intermolecular contacts of the Hirshfeld surface area. The remaining contributions (8.3%) correspond to C⋯Cl (1.3%), N⋯C (1.3%) and other less important interactions (<1%). C⋯C contacts correspond to intermolecular π–π interactions. The occurrence of non-high interaction rates can be attributed to the fact that the small disordered portion of the molecule is not considered.

5. Database survey

All bond lengths and angles are within normal ranges and are similar to those reported for related molecules such as trans-rac-[1-oxo-2-phenethyl-3-(2-thienyl)-1,2,3,4-tetrahydroisoquinolin-4-yl]methyl 4-methylbenzenesulfonate (Akkurt et al., 2008 ), 2-benzenesulfonamidobenzoic acid (Asiri et al., 2009 ), propyl 2-(4-methylbenzenesulfonamido)benzoate (Mustafa, Khan et al., 2012 ), 2-{4-[acetyl(ethyl)amino]benzenesulfonamido}benzoic acid (Mustafa, Muhmood et al., 2012 ), 2-(5-bromopyridin-3-yl)-5-[3-(4,5,6,7-tetrahydrothieno[3,2-c]pyridine-5-ylsulfonyl)thiophen-2-yl]-1,3,4-oxadiazole (Fun et al., 2011a ) and 2-(biphenyl-4-yl)-5-[3-(4,5,6,7-tetrahydrothieno[3,2-c]pyridine-5-ylsulfonyl) thiophen-2-yl]-1,3,4-oxadiazole (Fun et al., 2011b ).

6. Synthesis and crystallization

To a solution of methyl 1-(2,4-dichlorobenzyl)-5-methyl-1H-pyrazole-3-carboxylate (200 mg, 0.70 mmol, 1 equiv.) in dichloromethane (DCM) were added 2-thiophenesulfonamide (126 mg, 0. 77 mmol, 1.1 equiv.), 1-ethyl-3-(3-dimethylamino-propyl)carbodiimide (EDC; 148 mg, 0.77 mmol, 1.1 equiv.) and 4-dimethyl-aminopyridine (DMAP; 17.8 mg, 0.14 mmol, 0.2 equiv.), and the resulting mixture was stirred overnight at room temperature. Upon completion of the reaction, the reaction mixture was partitioned between DCM and water. The collected organic layer was dried over anhydrous Na₂SO₄, filtered and evaporated to give the crude compound, which was purified with automated-flash chromatography (120.6 mg, 39.95%). The obtained product was recrystallized from hexane and ethyl acetate (4:1), m.p. 464.8–465.3 K. ¹H NMR (CDCl₃): δ 2.24 (3H, s), 5.33 (2H, s), 6.64 (2H, m), 7.12 (1H, m), 7.21 (1H, dd, J = 8.4, 2.1 Hz), 7.45 (1H, d, J = 2.1 Hz), 7.69 (1H, dd, J = 5.1, 1.2 Hz), 7.97 (1H, dd, J = 3.9, 1.2 Hz), 9.29 (1H, bs); ¹³C NMR (CDCl₃): 11.2, 50.5, 107.6, 127.3, 127.9, 129.1, 129.6, 131.7, 132.9, 133.8, 134.8, 135.1, 139.2, 142.0, 143.5, 158.4. HRMS m/z calculated for C₁₆H₁₃Cl₂N₃O₃S₂ [M + H]⁺ 429.9854; found: 429.9857.

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms bound to carbon atoms were positioned geometrically and treated as riding with C—H = 0.93-0.97 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H atoms. A rotating model was used for the methyl group. The nitrogen-bound H atom (H1N) was located in a difference-Fourier map and refined with the constraint N1—H1N = 0.84 (3) Å and U_iso(H) = 1.2U_eq(N). The thiophene ring is rotationally disordered by approximately 180° over two positions, the ratio of refined occupancies being 0.762 (3):0.238 (3). The dichlorobenzene group of the title compound is also disordered over two sets of sites with the same occupancy ratio. The disordered dicholorobenzene groups (C: C11–C16 and C′: C11A–C16A) were refined as rigid hexagons with bond lengths of 1.39 Å. The displacement ellipsoids for the corresponding carbon atoms in the disordered dicholorobenzene groups were constrained by using the EADP command. Six outliers (633, $[\overline{5}]$ 30, $[\overline{1}]$ 30, 515, 5 $[\overline{6}]$ 1, 520) were omitted in the final cycles of refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₃Cl₂N₃O₃S₂
M_r	430.31
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	8.2706 (4), 8.7726 (4), 13.6433 (7)
α, β, γ (°)	76.091 (2), 74.610 (2), 87.970 (2)
V (Å³)	925.98 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.60
Crystal size (mm)	0.99 × 0.68 × 0.52

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 )
T_min, T_max	0.60, 0.75
No. of measured, independent and observed [I > 2σ(I)] reflections	19595, 4598, 4134
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.155, 1.03
No. of reflections	4598
No. of parameters	216
No. of restraints	14
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.20, −0.82
Computer programs: APEX2 and SAINT (Bruker, 2007), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1839201

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989018006242/rz5232sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018006242/rz5232Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018006242/rz5232Isup4.cml

Checkcif Report. DOI: https://doi.org/10.1107/S2056989018006242/rz5232sup4.pdf

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXT-2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and WinGX (Farrugia, 2012).

1-(2,4-Dichlorobenzyl)-5-methyl-N-(thiophene-2-sulfonyl)-1H-pyrazole-3-carboxamide top

Crystal data top

C₁₆H₁₃Cl₂N₃O₃S₂	Z = 2
M_r = 430.31	F(000) = 440
Triclinic, P1	D_x = 1.543 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2706 (4) Å	Cell parameters from 9888 reflections
b = 8.7726 (4) Å	θ = 2.4–28.3°
c = 13.6433 (7) Å	µ = 0.60 mm⁻¹
α = 76.091 (2)°	T = 296 K
β = 74.610 (2)°	Prism, translucent light white
γ = 87.970 (2)°	0.99 × 0.68 × 0.52 mm
V = 925.98 (8) Å³

Data collection top

Bruker APEXII CCD diffractometer	4598 independent reflections
Radiation source: sealed tube	4134 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
φ and ω scans	θ_max = 28.4°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→11
T_min = 0.60, T_max = 0.75	k = −11→11
19595 measured reflections	l = −17→18

Refinement top

Refinement on F²	14 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.155	w = 1/[σ²(F_o²) + (0.082P)² + 0.8819P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4598 reflections	Δρ_max = 1.20 e Å⁻³
216 parameters	Δρ_min = −0.82 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	Occ. (<1)
C1	1.0018 (3)	0.5302 (5)	0.6433 (2)	0.0643 (8)
H1	1.109594	0.540142	0.650187	0.077*
C2	0.9085 (4)	0.6538 (4)	0.6217 (3)	0.0615 (8)
H2	0.943899	0.757761	0.609474	0.074*
C3	0.7555 (6)	0.6082 (6)	0.6199 (4)	0.0426 (11)	0.762 (3)
H3	0.670625	0.678061	0.610153	0.051*	0.762 (3)
S1	0.91332 (19)	0.35743 (15)	0.65722 (17)	0.0492 (3)	0.762 (3)
C3A	0.901 (2)	0.382 (2)	0.655 (2)	0.0426 (11)	0.238 (3)
H3A	0.933907	0.278893	0.670858	0.051*	0.238 (3)
S1A	0.7356 (7)	0.6272 (6)	0.6034 (4)	0.0492 (3)	0.238 (3)
C4	0.7359 (3)	0.4413 (3)	0.63434 (16)	0.0334 (4)
C5	0.7050 (3)	0.1354 (2)	0.52207 (17)	0.0330 (4)
C6	0.7152 (3)	0.0968 (2)	0.42142 (16)	0.0313 (4)
C7	0.8307 (3)	0.0022 (3)	0.37032 (19)	0.0375 (5)
H7	0.916655	−0.053427	0.393564	0.045*
C8	0.7892 (3)	0.0094 (3)	0.27811 (18)	0.0361 (4)
C9	0.8648 (4)	−0.0637 (4)	0.1890 (2)	0.0529 (6)
H9A	0.794588	−0.150751	0.192409	0.079*
H9B	0.974150	−0.100242	0.193074	0.079*
H9C	0.874250	0.012686	0.124042	0.079*
C10	0.5646 (3)	0.1512 (3)	0.19870 (18)	0.0397 (5)
H10A	0.448790	0.169220	0.231841	0.048*
H10B	0.565068	0.066145	0.164493	0.048*
C11	0.6400 (5)	0.2998 (3)	0.1159 (2)	0.0466 (3)	0.762 (3)
C12	0.6577 (4)	0.4311 (3)	0.15290 (16)	0.0466 (3)	0.762 (3)
H12	0.629582	0.423813	0.224578	0.056*	0.762 (3)
C13	0.7173 (4)	0.5732 (3)	0.08277 (18)	0.0466 (3)	0.762 (3)
H13	0.729125	0.660962	0.107532	0.056*	0.762 (3)
C14	0.7593 (4)	0.5840 (2)	−0.02436 (17)	0.0466 (3)	0.762 (3)
C15	0.7416 (5)	0.4528 (3)	−0.06137 (17)	0.0466 (3)	0.762 (3)
H15	0.769664	0.460061	−0.133046	0.056*	0.762 (3)
C16	0.6819 (6)	0.3107 (3)	0.0088 (3)	0.0466 (3)	0.762 (3)
Cl1	0.8269 (3)	0.7564 (2)	−0.11887 (17)	0.0835 (5)	0.762 (3)
Cl2	0.6424 (5)	0.1501 (4)	−0.0388 (2)	0.0805 (7)	0.762 (3)
C11A	0.6465 (15)	0.3022 (11)	0.1193 (7)	0.0466 (3)	0.238 (3)
C12A	0.7063 (12)	0.4320 (11)	0.1423 (5)	0.0466 (3)	0.238 (3)
H12A	0.696770	0.433593	0.211501	0.056*	0.238 (3)
C13A	0.7802 (12)	0.5595 (9)	0.0618 (6)	0.0466 (3)	0.238 (3)
H13A	0.820202	0.646324	0.077136	0.056*	0.238 (3)
C14A	0.7945 (12)	0.5571 (9)	−0.0417 (5)	0.0466 (3)	0.238 (3)
C15A	0.7347 (15)	0.4273 (11)	−0.0646 (6)	0.0466 (3)	0.238 (3)
H15A	0.744229	0.425767	−0.133838	0.056*	0.238 (3)
C16A	0.6608 (17)	0.2999 (11)	0.0159 (9)	0.0466 (3)	0.238 (3)
Cl1A	0.8896 (10)	0.7355 (9)	−0.1136 (7)	0.0835 (5)	0.238 (3)
Cl2A	0.6826 (18)	0.1514 (15)	−0.0300 (9)	0.0805 (7)	0.238 (3)
N1	0.6005 (2)	0.2605 (2)	0.53833 (15)	0.0363 (4)
H1N	0.571 (4)	0.317 (3)	0.4869 (18)	0.044*
N2	0.6550 (2)	0.1036 (2)	0.27928 (14)	0.0340 (4)
N3	0.6080 (2)	0.1593 (2)	0.36579 (14)	0.0334 (4)
O1	0.5273 (2)	0.2101 (2)	0.73271 (13)	0.0479 (4)
O2	0.4310 (2)	0.4460 (2)	0.62514 (13)	0.0412 (4)
O3	0.7814 (2)	0.0698 (2)	0.58384 (14)	0.0473 (4)
S2	0.55880 (6)	0.33499 (6)	0.64141 (4)	0.03159 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1094 (16)	0.0562 (7)	0.0754 (7)	−0.0290 (10)	−0.0317 (10)	0.0150 (5)
Cl1A	0.1094 (16)	0.0562 (7)	0.0754 (7)	−0.0290 (10)	−0.0317 (10)	0.0150 (5)
Cl2	0.144 (2)	0.0649 (5)	0.0438 (7)	−0.0339 (10)	−0.0276 (8)	−0.0255 (5)
Cl2A	0.144 (2)	0.0649 (5)	0.0438 (7)	−0.0339 (10)	−0.0276 (8)	−0.0255 (5)
S1	0.0461 (5)	0.0507 (7)	0.0605 (6)	0.0166 (4)	−0.0260 (4)	−0.0205 (6)
S1A	0.0461 (5)	0.0507 (7)	0.0605 (6)	0.0166 (4)	−0.0260 (4)	−0.0205 (6)
S2	0.0325 (3)	0.0336 (3)	0.0302 (3)	0.0020 (2)	−0.0086 (2)	−0.0102 (2)
O1	0.0609 (11)	0.0441 (9)	0.0348 (8)	−0.0091 (8)	−0.0098 (7)	−0.0038 (7)
O2	0.0342 (8)	0.0474 (9)	0.0468 (9)	0.0105 (7)	−0.0122 (7)	−0.0204 (7)
O3	0.0556 (10)	0.0487 (10)	0.0485 (10)	0.0187 (8)	−0.0304 (8)	−0.0160 (8)
N1	0.0458 (10)	0.0360 (9)	0.0336 (9)	0.0126 (8)	−0.0186 (8)	−0.0135 (7)
N2	0.0386 (9)	0.0332 (8)	0.0323 (9)	0.0031 (7)	−0.0116 (7)	−0.0099 (7)
N3	0.0366 (9)	0.0338 (8)	0.0330 (9)	0.0061 (7)	−0.0125 (7)	−0.0108 (7)
C1	0.0361 (12)	0.105 (3)	0.0567 (17)	−0.0026 (14)	−0.0139 (11)	−0.0267 (17)
C2	0.0577 (16)	0.0581 (17)	0.0667 (19)	−0.0200 (14)	−0.0091 (14)	−0.0164 (14)
C3	0.0345 (19)	0.0394 (19)	0.051 (2)	−0.0035 (14)	−0.0204 (15)	0.0060 (15)
C3A	0.0345 (19)	0.0394 (19)	0.051 (2)	−0.0035 (14)	−0.0204 (15)	0.0060 (15)
C4	0.0306 (9)	0.0381 (10)	0.0336 (10)	0.0034 (8)	−0.0096 (7)	−0.0122 (8)
C5	0.0344 (10)	0.0310 (9)	0.0369 (10)	0.0036 (7)	−0.0137 (8)	−0.0103 (8)
C6	0.0332 (9)	0.0285 (9)	0.0344 (10)	0.0027 (7)	−0.0119 (8)	−0.0088 (8)
C7	0.0361 (10)	0.0351 (10)	0.0468 (12)	0.0078 (8)	−0.0157 (9)	−0.0158 (9)
C8	0.0372 (10)	0.0317 (10)	0.0411 (11)	0.0031 (8)	−0.0091 (8)	−0.0139 (8)
C9	0.0538 (14)	0.0576 (15)	0.0525 (15)	0.0090 (12)	−0.0087 (12)	−0.0298 (13)
C10	0.0471 (12)	0.0413 (11)	0.0348 (11)	−0.0009 (9)	−0.0173 (9)	−0.0094 (9)
C11	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C11A	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C12	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C12A	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C13	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C13A	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C14	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C14A	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C15	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C15A	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C16	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)
C16A	0.0639 (8)	0.0396 (6)	0.0367 (6)	−0.0054 (6)	−0.0098 (5)	−0.0130 (5)

Geometric parameters (Å, º) top

Cl1—C14	1.733 (3)	C10—C11	1.530 (4)
Cl1A—C14A	1.723 (12)	C11—C12	1.391 (4)
Cl2—C16	1.760 (5)	C11—C16	1.390 (5)
Cl2A—C16A	1.561 (17)	C11A—C16A	1.389 (15)
S1—C4	1.688 (3)	C11A—C12A	1.391 (14)
S1—C1	1.654 (4)	C12—C13	1.390 (4)
S1A—C4	1.583 (6)	C12A—C13A	1.390 (11)
S1A—C2	1.550 (7)	C13—C14	1.390 (3)
S2—O2	1.4362 (18)	C13A—C14A	1.391 (10)
S2—N1	1.641 (2)	C14—C15	1.390 (3)
S2—C4	1.733 (3)	C14A—C15A	1.390 (13)
S2—O1	1.4184 (18)	C15—C16	1.390 (4)
O3—C5	1.210 (3)	C15A—C16A	1.390 (14)
N1—C5	1.396 (3)	C1—H1	0.9300
N2—N3	1.343 (3)	C2—H2	0.9300
N2—C8	1.359 (3)	C3—H3	0.9300
N2—C10	1.461 (3)	C3A—H3A	0.9300
N3—C6	1.336 (3)	C7—H7	0.9300
C1—C2	1.329 (5)	C9—H9A	0.9600
C1—C3A	1.522 (19)	C9—H9C	0.9600
N1—H1N	0.84 (3)	C9—H9B	0.9600
C2—C3	1.349 (6)	C10—H10A	0.9700
C3—C4	1.439 (6)	C10—H10B	0.9700
C3A—C4	1.516 (19)	C12—H12	0.9300
C5—C6	1.472 (3)	C12A—H12A	0.9300
C6—C7	1.399 (3)	C13—H13	0.9300
C7—C8	1.376 (3)	C13A—H13A	0.9300
C8—C9	1.491 (4)	C15—H15	0.9300
C10—C11A	1.540 (10)	C15A—H15A	0.9300

C1—S1—C4	91.91 (16)	Cl1—C14—C15	115.95 (18)
C2—S1A—C4	96.3 (4)	C13—C14—C15	120.0 (2)
O1—S2—N1	108.73 (10)	Cl1A—C14A—C13A	104.5 (7)
O1—S2—C4	108.83 (11)	Cl1A—C14A—C15A	135.5 (6)
O1—S2—O2	120.05 (10)	C13A—C14A—C15A	120.0 (7)
O2—S2—C4	107.17 (12)	C14—C15—C16	120.0 (2)
N1—S2—C4	107.33 (10)	C14A—C15A—C16A	120.0 (8)
O2—S2—N1	104.06 (10)	Cl2—C16—C11	120.2 (3)
S2—N1—C5	126.32 (16)	Cl2—C16—C15	119.6 (3)
N3—N2—C8	112.91 (18)	C11—C16—C15	120.0 (3)
N3—N2—C10	119.06 (18)	C11A—C16A—C15A	120.0 (10)
C8—N2—C10	128.01 (19)	Cl2A—C16A—C11A	126.3 (10)
N2—N3—C6	104.17 (16)	Cl2A—C16A—C15A	107.6 (9)
S1—C1—C2	115.5 (2)	S1—C1—H1	122.00
C2—C1—C3A	108.6 (7)	C2—C1—H1	122.00
S2—N1—H1N	113.9 (18)	C3A—C1—H1	129.00
C5—N1—H1N	118.5 (18)	S1A—C2—H2	116.00
C1—C2—C3	110.9 (4)	C1—C2—H2	125.00
S1A—C2—C1	118.7 (4)	C3—C2—H2	125.00
C2—C3—C4	113.7 (4)	C2—C3—H3	123.00
C1—C3A—C4	104.5 (12)	C4—C3—H3	123.00
S1—C4—C3	107.9 (3)	C4—C3A—H3A	128.00
S2—C4—C3A	129.1 (7)	C1—C3A—H3A	128.00
S1A—C4—S2	119.4 (3)	C8—C7—H7	128.00
S2—C4—C3	128.3 (3)	C6—C7—H7	128.00
S1—C4—S2	123.50 (17)	C8—C9—H9A	109.00
S1A—C4—C3A	111.6 (8)	H9A—C9—H9B	109.00
O3—C5—C6	124.5 (2)	C8—C9—H9B	110.00
O3—C5—N1	122.7 (2)	C8—C9—H9C	110.00
N1—C5—C6	112.78 (19)	H9B—C9—H9C	109.00
C5—C6—C7	128.2 (2)	H9A—C9—H9C	109.00
N3—C6—C7	111.90 (19)	N2—C10—H10B	109.00
N3—C6—C5	119.91 (19)	C11—C10—H10A	109.00
C6—C7—C8	104.9 (2)	C11A—C10—H10A	110.00
C7—C8—C9	131.6 (3)	C11A—C10—H10B	111.00
N2—C8—C9	122.3 (2)	C11—C10—H10B	109.00
N2—C8—C7	106.1 (2)	N2—C10—H10A	109.00
N2—C10—C11A	110.0 (5)	H10A—C10—H10B	108.00
N2—C10—C11	113.2 (2)	C13—C12—H12	120.00
C10—C11—C12	116.2 (2)	C11—C12—H12	120.00
C10—C11—C16	123.7 (3)	C13A—C12A—H12A	120.00
C12—C11—C16	120.0 (2)	C11A—C12A—H12A	120.00
C10—C11A—C12A	126.4 (7)	C14—C13—H13	120.00
C10—C11A—C16A	113.6 (8)	C12—C13—H13	120.00
C12A—C11A—C16A	120.0 (9)	C14A—C13A—H13A	120.00
C11—C12—C13	120.0 (2)	C12A—C13A—H13A	120.00
C11A—C12A—C13A	120.0 (7)	C16—C15—H15	120.00
C12—C13—C14	120.0 (2)	C14—C15—H15	120.00
C12A—C13A—C14A	120.0 (8)	C14A—C15A—H15A	120.00
Cl1—C14—C13	123.98 (18)	C16A—C15A—H15A	120.00

C1—S1—C4—S2	−176.25 (16)	C2—C3—C4—S1	3.8 (5)
C1—S1—C4—C3	−2.0 (3)	C2—C3—C4—S2	177.7 (3)
C4—S1—C1—C2	−0.1 (3)	O3—C5—C6—C7	−12.2 (4)
O1—S2—N1—C5	−44.1 (2)	N1—C5—C6—N3	−11.7 (3)
O2—S2—N1—C5	−173.15 (18)	N1—C5—C6—C7	166.0 (2)
C4—S2—N1—C5	73.5 (2)	O3—C5—C6—N3	170.1 (2)
O2—S2—C4—S1	175.63 (16)	N3—C6—C7—C8	0.1 (3)
N1—S2—C4—S1	−73.11 (18)	C5—C6—C7—C8	−177.8 (2)
O1—S2—C4—C3	−128.6 (3)	C6—C7—C8—C9	179.3 (3)
O2—S2—C4—C3	2.6 (3)	C6—C7—C8—N2	−0.5 (3)
N1—S2—C4—C3	113.9 (3)	N2—C10—C11—C12	−55.0 (4)
O1—S2—C4—S1	44.39 (19)	N2—C10—C11—C16	128.4 (4)
S2—N1—C5—C6	179.75 (16)	C10—C11—C12—C13	−176.8 (3)
S2—N1—C5—O3	−2.0 (3)	C16—C11—C12—C13	0.0 (6)
C8—N2—C10—C11	−88.0 (3)	C10—C11—C16—Cl2	2.2 (6)
C8—N2—N3—C6	−0.6 (2)	C10—C11—C16—C15	176.6 (4)
N3—N2—C8—C7	0.7 (3)	C12—C11—C16—Cl2	−174.4 (3)
N3—N2—C10—C11	90.2 (2)	C12—C11—C16—C15	0.0 (7)
C10—N2—C8—C7	178.9 (2)	C11—C12—C13—C14	0.0 (5)
C10—N2—N3—C6	−179.01 (19)	C12—C13—C14—Cl1	177.4 (3)
C10—N2—C8—C9	−0.8 (4)	C12—C13—C14—C15	0.0 (5)
N3—N2—C8—C9	−179.1 (2)	Cl1—C14—C15—C16	−177.6 (3)
N2—N3—C6—C5	178.40 (18)	C13—C14—C15—C16	0.0 (6)
N2—N3—C6—C7	0.3 (2)	C14—C15—C16—Cl2	174.4 (3)
S1—C1—C2—C3	2.4 (4)	C14—C15—C16—C11	0.0 (7)
C1—C2—C3—C4	−4.0 (5)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the major component (S1/C1–C4) of the disordered thiophene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N3	0.84 (3)	2.35 (3)	2.694 (3)	105 (2)
N1—H1N···O2ⁱ	0.84 (3)	2.27 (3)	3.029 (3)	150 (3)
C7—H7···O3ⁱⁱ	0.93	2.59	3.437 (3)	152
C10—H10B···Cl2	0.97	2.60	3.134 (4)	115
C10—H10B···Cl2A	0.97	2.50	3.012 (12)	112
C10—H10B···O1ⁱⁱⁱ	0.97	2.52	3.141 (3)	122
C12—H12···N3	0.93	2.61	3.224 (3)	124
C12—H12···O2ⁱ	0.93	2.51	3.348 (3)	150
C15—H15···Cg1^iv	0.93	2.97	3.893 (3)	174
C15A—H15A···Cg1^iv	0.93	2.95	3.836 (8)	159

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y, −z+1; (iii) −x+1, −y, −z+1; (iv) x, y, z−1.

Acknowledgements

The authors acknowledge the Aksaray University, Science and Technology Application and Research Center, Aksaray, Turkey, for the use of the Bruker SMART BREEZE CCD diffractometer (purchased under grant No. 2010 K120480 of the State of Planning Organization)

References

Akkurt, M., Öztürk Yıldırım, S., Bogdanov, M. G., Kandinska, M. I. & Büyükgüngör, O. (2008). Acta Cryst. E64, o1955–o1956. Web of Science CSD CrossRef IUCr Journals Google Scholar
Asiri, A. M., Akkurt, M., Khan, S. A., Arshad, M. N., Khan, I. U. & Sharif, H. M. A. (2009). Acta Cryst. E65, o1246–o1247. Web of Science CSD CrossRef IUCr Journals Google Scholar
Banoğlu, E., Akoğlu, Ç., Ünlü, S., Ergün, B., Küpeli, E., Yeşilada, E. & Şahin, M. (2005). Arzneimittelforschung, 55, 520–527. Google Scholar
Baraldi, P. G., Beria, I., Cozzi, P., Geroni, C., Espinosa, A., Gallo, M. A., Entrena, A., Bingham, J. P., Hartley, J. A. & Romagnoli, R. (2004). Bioorg. Med. Chem. 12, 3911–3921. CrossRef CAS Google Scholar
Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Çalışkan, B., Luderer, S., Özkan, Y., Werz, O. & Banoğlu, E. (2011). Eur. J. Med. Chem. 46, 5021–5033. Google Scholar
Çalışkan, B., Yılmaz, A., Evren, İ., Menevşe, S., Uludag, O. & Banoğlu, E. (2013). Med. Chem. Res. 22, 782–793. Google Scholar
Cankara Pirol, Ş., Çalışkan, B., Durmaz, İ., Atalay, R. & Banoğlu, E. (2014). Eur. J. Med. Chem. 87, 140–149. CrossRef CAS Google Scholar
Comber, R. N., Gray, R. J. & Secrist, J. A. (1992). Carbohydr. Res. 216, 441–452. CrossRef Google Scholar
Ding, X. L., Zhang, H. Y., Qi, L., Zhao, B. X., Lian, S., Lv, H. S. & Miao, J. Y. (2009). Bioorg. Med. Chem. Lett. 19, 5325–5328. CrossRef CAS Google Scholar
Ergün, B. C., Nuñez, M. T., Labeaga, L., Ledo, F., Darlington, J., Bain, G., Cakir, B. & Banoğlu, E. (2010). Arzneimittelforschung, 60, 497–505. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fun, H.-K., Hemamalini, M., Rai, S., Isloor, A. M. & Shetty, P. (2011a). Acta Cryst. E67, o2743–o2744. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Hemamalini, M., Rai, S., Isloor, A. M. & Shetty, P. (2011b). Acta Cryst. E67, o2781–o2782. CrossRef IUCr Journals Google Scholar
Hirshfeld, H. L. (1977). Theor. Chim. Acta, 44, 129–138. CrossRef CAS Web of Science Google Scholar
Küçükgüzel, Ş. G. & Şenkardeş, S. (2015). Eur. J. Med. Chem. 97, 786–815. Google Scholar
Levent, S., Çalışkan, B., Çiftçi, M., Özkan, Y., Yenicesu, İ., Ünver, H. & Banoğlu, E. (2013). Eur. J. Med. Chem. 64, 42–53. CrossRef CAS Google Scholar
Mustafa, G., Khan, I. U., Khan, F. M. & Akkurt, M. (2012). Acta Cryst. E68, o1305. CSD CrossRef IUCr Journals Google Scholar
Mustafa, G., Muhmood, T., Khan, I. U. & Akkurt, M. (2012). Acta Cryst. E68, o1388. CrossRef IUCr Journals Google Scholar
Palaska, E., Aydin, F., Uçar, G. & Erol, D. (2008). Arch. Pharm. Chem. Life Sci. 341, 209–215. CrossRef CAS Google Scholar
Parkin, A., Barr, G., Dong, W., Gilmore, C. J., Jayatilaka, D., McKinnon, J. J., Spackman, M. A. & Wilson, C. C. (2007). CrystEngComm, 9, 648–652. Web of Science CrossRef CAS Google Scholar
Rohl, A. L., Moret, M., Kaminsky, W., Claborn, K., McKinnon, J. J. & Kahr, B. (2008). Cryst. Growth Des. 8, 4517–4525. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Şüküroğlu, M., Ergün, B. Ç., Ünlü, S., Sahin, M. F., Küpeli, E., Yesilada, E. & Banoğlu, E. (2005). Arch. Pharm. Res. 28, 509–517. Google Scholar
Sun, J. & Zhou, Y. (2015). Molecules, 20, 4383–4394. CrossRef CAS Google Scholar
Turner, M. J., MacKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17.5. University of Western Australia. Google Scholar
Yan, Z., Liu, A., Huang, M., Liu, M., Pei, H., Huang, L., Yi, H., Liu, W. & Hu, A. (2018). Eur. J. Med. Chem. 149, 170–181. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 74| Part 5| May 2018| Pages 747-751

https://doi.org/10.1107/S2056989018006242

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

Crystal structure and Hirshfeld surface analysis of 1-(2,4-di­chloro­benz­yl)-5-methyl-N-(thio­phene-2-sulfon­yl)-1H-pyrazole-3-carboxamide

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis

5. Database survey

6. Synthesis and crystallization

7. Refinement details

Supporting information

Acknowledgements

References

research communications

Crystal structure and Hirshfeld surface analysis of 1-(2,4-dichlorobenzyl)-5-methyl-N-(thiophene-2-sulfonyl)-1H-pyrazole-3-carboxamide

3. Supramolecular features