Crystal structure of N′-[(E)-(4-chloro­phen­yl)(phen­yl)methyl­idene]-4-methyl­benzene­sulfono­hydrazide

J Balaji; S Prabu; J J F Xavier; P Srinivasan

doi:10.1107/S2056989014026723

. 2015 Jan 1;71(Pt 1):o45–o46. doi: 10.1107/S2056989014026723

Crystal structure of N′-[(E)-(4-chlorophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide

J Balaji ^a, S Prabu ^a, J J F Xavier ^b, P Srinivasan ^a,^*

PMCID: PMC4331850 PMID: 25705499

Abstract

The title compound, C₂₀H₁₇ClN₂O₂S, was obtained by a condensation reaction between 4-chlorobenzophenone and tosyl hydrazide. The plane of the methyl-substituted benzene ring forms dihedral angles of 20.12 (12) and 78.43 (13)° with those of the chlorine-substituted benzene ring and the benzene ring, respectively, with the last two rings forming a dihedral angle of 67.81 (13)°. The chlorine substituent was also found to be 0.868 (2):0.132 (2) disordered over these two rings. In the crystal, molecules are linked through pairs of N—H⋯O hydrogen bonds, giving centrosymmetric cyclic dimers [graph set R ₂ ²(8)], which are linked by weak C—H⋯O and C—H⋯Cl interactions into a chain structure which extends along the a-axis direction.

Keywords: crystal structure, benzenesulfonohydrazide, hydrogen bonding, condensation reaction, centrosymmetric dimers

Related literature

Benzophenone and its derivatives have been investigated extensively for their biological activities such as anti-fungal and anti-inflammatory, see: Khanum et al. (2004 ▸). For similar structures, see: Ajani et al. (2010 ▸); Gerdemann et al. (2002 ▸); Kutzke et al. (2000 ▸); Shen et al. (2012 ▸); Zhang (2011 ▸). graphic file with name e-71-00o45-scheme1.jpg

Experimental

Crystal data

C₂₀H₁₇ClN₂O₂S
M _r = 384.87
Monoclinic,
a = 12.6808 (6) Å
b = 9.3857 (5) Å
c = 16.3974 (7) Å
β = 106.187 (2)°
V = 1874.22 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T _min = 0.891, T _max = 0.930
21401 measured reflections
3300 independent reflections
2416 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.105
S = 1.06
3300 reflections
253 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: APEX2 and SAINT (Bruker, 2004 ▸); data reduction: SAINT and XPREP (Bruker, 2004 ▸); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989014026723/zs2319sup1.cif

e-71-00o45-sup1.cif^{(26.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014026723/zs2319Isup2.hkl

e-71-00o45-Isup2.hkl^{(161.9KB, hkl)}

Click here for additional data file.^{(6.8KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014026723/zs2319Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989014026723/zs2319fig1.tif

The molecular structure of the title compound showing the atom labelling scheme. The displacement ellipsoids are drawn at the 30% probability level

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989014026723/zs2319fig2.tif

A view of the crystal packing of the title compound. The various hydrogen bonds are indicated by dashed lines (see Table 1 for details).

CCDC reference: 1037752

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1AO2ⁱ	0.88(2)	2.19(2)	3.024(3)	160(2)
C10H10Cl1ⁱⁱ	0.93	2.76	3.476(7)	134
C16H16O1ⁱⁱⁱ	0.93	2.54	3.339(3)	145

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

Acknowledgments

JB thanks the CTDT, Anna University, for funding the project (AU/ROT/BIT/R&D/YFP/PAN/PHY/2013–14/001). The authors thank the SAIF, IITM, Madras, for helping with the XRD studies.

supplementary crystallographic information

S1. Chemical context

Currently the hydrazones have attracted considerable attention due to their biological activities and a number of crystal structures of these compounds have been reported (Ajani et al., 2010); Gerdemann et al., 2002; Kutzke et al., 2000); Zhang, 2011; Shen et al., 2012). Benzophenone and its derivatives have also been extensively investigated for their biological activities such as anti-fungal and anti-inflammatory (Khanum et al., 2004). In view of the importance of these analogs, the title compound, C₂₀H₁₇ClN₂O₂S, was synthesized in a Schiff base condensation reaction between 4-chlorobenzophenone and tosyl hydrazide and its structure is reported herein.

In this compound (Fig. 1) the benzene ring (C1–C6) forms dihedral angles of 20.12 (12) and 78.43 (13)° with the chlorine-substituted benzene ring (C8–C13) and the benzene ring (C14–C19), respectively. The molecule is twisted, with the dihedral angle between the two benzene rings (C8–C13 and C14–C19) of the parent moiety being 67.81 (13)°. In the crystal, molecules are linked through intermolecular N1—H···O2ⁱ hydrogen-bond pairs (Table 1) giving centrosymmetric cyclic dimers [graph set R²₂(8)] which are linked by weak C—H···O and C—H···Cl interactions into a chain structure which extends along a (Fig. 2).

S2. Synthesis and crystallization

4-Chlorobenzophenone (0.15g, 1 mmol) and tosyl hydrazide (0.186g, 1 mmol) were dissolved in ethanol (50 ml). The reaction mixture was heated under reflux for 3 hr and cooled gradually to room temperature. Crystals suitable for X-ray diffraction analysis were obtained by slow room temperature evaporation of the solution containing the compound.

S3. Refinement

All H atoms were positioned geometrically and treated as riding on their parent atoms with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and N1—H = 0.89±2 Å with U_iso(H) = 1.2 U_eq(N, C_aromatic) or 1.5 U_eq(C_methyl). The chlorine substituent was also found to be disordered over the C8–C13 (Cl1) and C14–C19 (Cl1') rings of the original benzophenone moiety [occupancy factors 0.868 (2):0.132 (2), respectively].