Crystal structure and Hirshfeld surface analysis of two (E)-N′-(para-substituted benzyl­idene) 4-chloro­benzene­sulfono­hydrazides

Salian, A.R.; Foro, S.; Gowda, B.T.

doi:10.1107/S205698901801592X

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 74| Part 12| December 2018| Pages 1808-1814

https://doi.org/10.1107/S205698901801592X

Open

access

Crystal structure and Hirshfeld surface analysis of two (E)-N′-(para-substituted benzylidene) 4-chlorobenzenesulfonohydrazides

Akshatha R. Salian,^a Sabine Foro ^b and B. Thimme Gowda ^a,^c ^*

^aDepartment of Chemistry, Mangalore University, Mangalagangotri-574 199, India, ^bInstitute of Materials Science, Darmstadt University of Technology, Alarich-Weiss-Str. 2, D-64287, Darmstadt, Germany, and ^cKarnataka State Rural Development and Panchayat Raj University, Gadag-582101, India
^*Correspondence e-mail: gowdabt@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 22 October 2018; accepted 9 November 2018; online 16 November 2018)

Two (E)-N′-(p-substituted benzylidene)-4-chlorobenzenesulfonohydrazides, namely, (E)-4-chloro-N′-(4-chlorobenzylidene)benzenesulfonohydrazide, C₁₃H₁₀Cl₂N₂O₂S, (I), and (E)-4-chloro-N′-(4-nitrobenzylidene)benzenesulfonohydrazide, C₁₃H₁₀ClN₃O₄S, (II), have been synthesized, characterized and their crystal structures studied to explore the effect of the nature of substituents on the structural parameters. Compound (II) crystallized with two independent molecules [(IIA) and IIB)] in the asymmetric unit. In both compounds, the configuration around the C=N bond is E. The molecules are twisted at the S atom with C—S—N—N torsion angles of −62.4 (2)° in (I), and −46.8 (2)° and 56.8 (2)° in the molecules A and B of (II). The 4-chlorophenylsulfonyl and 4-substituted benzylidene rings form dihedral angles of 81.0 (1)° in (I), 75.9 (1)° in (IIA) and 73.4 (1)° in (IIB). In the crystal of (I), molecules are linked via pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R₂²(8) ring motif. The dimers are linked by C—Cl⋯π interactions, forming a three-dimensional structure. In the crystal of (II), molecules are linked by C—H⋯π interactions and N—H⋯O hydrogen bonds, forming –A–B–A–B– chains along the c-axis direction. The chains are linked via C—H⋯O and C—H⋯π interactions, forming layers parallel to the bc plane. Two-dimensional fingerprint plots show that the most significant contacts contributing to the Hirshfeld surface for (I) are H⋯H contacts (26.6%), followed by Cl⋯H/H⋯Cl (21.3%), O⋯H/H⋯O (15.5%) and Cl⋯C/C⋯Cl (10.7%), while for (II) the O⋯H/H⋯O contacts are dominant, with a contribution of 34.8%, followed by H⋯H (15.2%), C⋯H/H⋯C (14.0%) and Cl⋯H/H⋯Cl (10.0%) contacts.

Keywords: crystal structure; hydrazones; N′-(arylidene)arylsulfonohydrazides; hydrogen bonding; graph-set motif; Hirshfeld surface analysis; fingerprint plots.

CCDC references: 1578709; 1578704

1. Chemical context

In the field of synthetic chemistry, hydrazones are frequently used as nucleophiles and electrophiles (Ogawa et al., 2004 ). They also play an important role in organic synthesis as one of the reaction intermediates due to their ring-closure reactions (Rollas & Küçükgüzel, 2007 ). Hydrazones have drawn considerable attention in the field of coordination chemistry (Weber et al., 2007 ). They also find various industrial applications (Reis et al., 2013 ) and exhibit a wide spectrum of biological activities (da Silva et al., 2011 ). Arylsulfonyl-hydrazones have shown antitumour activity in addition to their role as a versatile source of diazo compounds in many metal-catalysed and metal-free reactions (Hashemi, 2012 ). In a continuation of our efforts to explore the effect of site and nature of substituents on the crystal structures of 4-chloro-arylsulfonohydrazide derivatives (Salian et al., 2018 ), we report herein the synthesis, characterization, crystal structures and Hirshfeld surface analysis of the title compounds, (I) and (II), and compare them with those of the recently reported structures of (E)-4-chloro-N′-(benzylidene) benzenesulfonohydrazide (III), (E)-4-chloro-N′-(2-methylbenzylidene)benzenesulfonohydrazide (IV) and (E)-4-chloro-N′-(4-methylbenzylidene)benzenesulfonohydrazide (V) (Salian et al., 2018).

2. Structural commentary

Compound (I), crystallizes in the triclinic crystal system, space group P $[\overline{1}]$ , with one molecule in the asymmetric unit (Fig. 1), while compound (II) crystallizes in the monoclinic crystal system, space group P2₁/c, with two independent molecules [(IIA) and (IIB)] in the asymmetric unit (Fig. 2). For both the compounds, the configuration about the C=N bond is E and the conformations of the N—H and C—H bonds in the hydrazone segments are syn to each other.

Figure 1
Molecular structure of (I)

, with the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Figure 2
Molecular structure of (II)

, with the atom labelling and displacement ellipsoids drawn at the 50% probability level.

The C=N bond lengths of 1.269 (3), 1.269 (3) and 1.269 (3) Å in (I), (IIA) and (IIB), and the N—N bond lengths of 1.388 (2) 1.397 (3) and 1.390 (2) Å in (I), (IIA) and (IIB), respectively, indicate the delocalization of the π-electron density over the hydrazone part of the molecules. The other bond lengths are in close agreement with those of the parent compound (III), and the ortho-methyl (IV) and para-methyl (V) derivatives (Salian et al., 2018). Selected geometrical parameters of compounds (I)–(V) are compared in Table 1 (Salian et al., 2018).

Table 1
Comparison of selected geometrical parameters (Å, °) of compounds (I)–(V)

The dihedral angle is that between the aromatic rings. The equivalent bond lengths and torsion angles are given for (IIB).

Bond length	(I)	(II) Molecule A	(II) Molecule B	(III)	(IV)	(V)
C1—S1	1.763 (2)	1.754 (2)	1.760 (2)	1.752 (4)	1.751 (5)	1.761 (2)
S1—N1	1.631 (2)	1.645 (2)	1.641 (2)	1.644 (4)	1.645 (4)	1.625 (2)
N1—N2	1.388 (2)	1.397 (3)	1.390 (2)	1.394 (5)	1.407 (5)	1.393 (2)
N2—C7	1.269 (3)	1.269 (3)	1.269 (3)	1.258 (5)	1.272 (5)	1.273 (3)
C7—C8	1.463 (3)	1.465 (3)	1.462 (3)	1.473 (6)	1.461 (6)	1.458 (3)
Torsion angle
C1—S1—N1—N2	−62.4 (2)	−46.8 (2)	56.8 (2)	−66.0 (3)	−66.0 (3)	−58.4 (2)
S1—N1—N2—C7	158.9 (2)	171.4 (2)	−165.3 (2)	166.5 (3)	165.4 (3)	157.9 (2)
N1—N2—C7—C8	175.0 (2)	−175.9 (2)	178.2 (2)	177.8 (4)	175.8 (4)	175.8 (2)
Dihedral angle	81.0 (1)	75.9 (1)	73.4 (1)	78.4 (2)	74.8 (2)	76.9 (1)

In the title compounds the molecules are twisted at the S atom with C—S—N—N torsion angles of −62.4 (2)° in (I), and −46.8 (2) and 56.8 (2)° in (IIA) and (IIB), respectively. The respective S—N—N=C torsion angles of 158.9 (2)° in (I), and 171.4 (2) and −165.3 (2)° in (IIA) and (IIB), denote the non-planarity of the sulfonohydrazide parts of the molecules. However, the N—N—C—C torsion angles of 175.0 (2)° in (I), and −175.9 (2) and 178.2 (2)° in (IIA) and (IIB), indicate near coplanarity of the hydrazide units with the benzylidene rings. The dihedral angles between the 4-chloro-substituted phenylsulfonyl ring and 4-substituted benzylidene ring are 81.0 (1)° in (I), and 75.9 (1) and 73.4 (1°) in molecules A and B of compound (II). In comparison, the corresponding values in compounds (III), (IV) and (V) are 78.4 (2), 74.8 (2) and 76.9 (1)°, respectively (see Table 1). In (II) the A and B molecules are linked by a C—H⋯Cl interaction (Table 3).

Table 3
Hydrogen-bond geometry (Å, °) for (II)

Cg3 is the centroid of the C14–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O5ⁱ	0.85 (2)	2.06 (2)	2.887 (3)	163 (2)
N4—H4N⋯O1ⁱⁱ	0.84 (2)	2.13 (2)	2.918 (2)	157 (2)
C10—H10⋯O7ⁱⁱⁱ	0.93	2.58	3.465 (3)	159
C16—H16⋯O4^iv	0.93	2.58	3.259 (3)	131
C25—H25⋯O5ⁱⁱ	0.93	2.45	3.340 (3)	161
C12—H12⋯Cg3	0.93	2.96	3.843 (2)	160
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[-x, y+{\script{3\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

3. Supramolecular features

The pattern of the hydrogen-bonding interactions in the crystal structures of (I) and (II) are different. In the crystal of (I), molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers enclosing R₂²(8) loops (Fig. 3, Table 2). The dimers are linked by C—Cl⋯π interactions, forming a three-dimensional arrangement (Fig. 3). This is very similar to the situation observed in the crystal of compound (V) [(E)- 4-chloro-N′-(4-methylbenzylidene)benzenesulfonohydrazide; Salian et al., 2018].

Table 2
Hydrogen-bond geometry (Å, °) for (I)

Cg1 and Cg2 are the centroids of rings C1–C6 and C8–C13, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.83 (2)	2.07 (2)	2.903 (2)	178 (2)
C4—Cl1⋯Cg2ⁱⁱ	1.73 (1)	3.41 (1)	5.112 (2)	166 (1)
C11—Cl2⋯Cg1ⁱⁱⁱ	1.74 (1)	3.65 (1)	5.372 (3)	171 (1)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y-1, z; (iii) -x, -y+1, -z+1.

Figure 3
Crystal packing of (I)

, viewed along the a axis, with hydrogen bonds (Table 2

) shown as dashed lines and C—Cl⋯π interactions as blue arrows. C-bound H atoms have been omitted.

Replacement of the 4-chloro group in (I) by the 4-nitro group to produce compound (II) introduces C—H⋯O interactions, which stabilize the crystal packing (Table 3 and Figs. 4 and 5). The N—H⋯O hydrogen bond involving the sulfonyl O atom and the amino H atom of the hydrazide segment between the A and B molecules results in the formation of –A–B–A–B– chains propagating along the c-axis direction (Fig. 4). The chains are linked by C—H⋯O interactions involving O atoms O4 in (IIA) and O5 in (IIB) and O7 of the nitro group and the aromatic hydrogen atoms ortho to the Cl or NO₂ group. The sulfonyl O atom of (IIB), i.e. O5, shows bifurcated hydrogen bonding, one with the amino H atom of the hydrazide segment and the other with one of the aromatic H atoms (H25), adjacent to the nitro group. These interactions link the chains, forming layers lying parallel to the bc plane (Table 3 and Fig. 5).

Figure 4
A partial view along the a axis of the crystal packing of (II)

, with hydrogen bonds (Table 3

) shown as dashed lines. H atoms not involved in these interactions have been omitted. Colour code: black A molecules; red B molecules.

Figure 5
Crystal packing of (II)

, viewed along the b axis, with hydrogen bonds shown as dashed lines. H atoms not involved in these interactions have been omitted.

4. Hirshfeld surface analysis

Hirshfeld surfaces and two-dimensional fingerprint plots were generated for the two substituted compounds (I) and (II) using CrystalExplorer (Turner et al., 2017 ) to visualize the intermolecular interactions, to investigate the impact of each kind of intermolecular contact on the crystal packing and to study the relative strengths of the different interactions in the two compounds. The molecular Hirshfeld surfaces were generated using a standard (high) surface resolution. d_i and d_e are the contact distances from the Hirshfeld surface to the nearest atom inside and outside, respectively [Fig. 6(a) for (I) and Fig. 6(b) for (II)]. The strong hydrogen bonds appear as dark-red spots and weak interactions as light-red spots on the d_norm surface (McKinnon et al., 2004 ; Spackman & Jayatilaka, 2009 ).

Figure 6
(a) View of the Hirshfeld surface mapped over d_norm for (I)

; (b) two views of the Hirshfeld surface mapped over d_norm for (II)

Comparison of fingerprint plots for various atom–atom interactions show that the percentage contributions of these interactions to the Hirshfeld surfaces vary significantly from (I) to (II). The major contribution to the Hirshfeld surface in (I) is from H⋯H contacts (26.6%), followed by Cl⋯H/H⋯Cl (21.3%), O⋯H/H⋯O (15.5%), Cl⋯C/C⋯Cl (10.7%) and C⋯H/ H⋯C (9.1%) [Fig. 7(a)], while in (II), as a result of C—H⋯O interactions, O⋯H/H⋯O contacts are dominant and serve as the major contributors (34.8%) in the crystal packing, followed by H⋯H contacts (15.2%), C⋯H/ H⋯C (14.0%) and Cl⋯H/H⋯Cl (10.0%) [Fig. 7(b)]. The Cl⋯C/C⋯Cl contribution to the d_norm surface is almost negligible (0.5%) in (II). However, C⋯C, H⋯N/N⋯H and C⋯O/O⋯C contacts make very similar contributions in the two compounds, their respective contributions being 4.7, 2.8, 3.0%, in (I) and 5.3, 3.6 and 4.1% in (II). Two pairs of symmetrical, long narrow spikes are present at d_i + d_e ∼2.2 Å for the O⋯H/H⋯O contacts in the fingerprint plots of (I) and (II) and these values are very close to the H⋯A distances for the N—H⋯O hydrogen bonds observed in the crystal structures (Tables 2 and 3). The contributions of the other weak intermolecular contacts to the Hirshfeld surfaces are: Cl⋯N/N⋯Cl (1.0 and 1.5%), C⋯N/N⋯C (0.0 and 2.8%), O⋯O (0, 2.3%), N⋯N (0, 0.4%) in (I) and (II), respectively. The result of the quantitative analysis of all types of intermolecular contacts present in (I) and (II) is summarized in Fig. 8.

Figure 7
Two-dimensional fingerprint plots for (a) (I)

and (b) (II)

. d_i is the closest internal distance from a given point on the Hirshfeld surface and d_e is the closest external contact.

Figure 8
Quantitative results of different intermolecular interactions contributing to the Hirshfield surfaces of (I)

and (II)

5. Database survey

The structures reported in the literature similar to the title compounds include (E)-N′-(4-chlorobenzylidene)-p-toluenesulfonohydrazide 0.15-hydrate (Kia et al., 2009a ), (E)-N′-(4-chlorobenzylidene)-p-toluenesulfonohydrazide (Balaji et al., 2014 ), (E)-N′-(4-bromobenzylidene)-p-toluenesulfonohydrazide (Kia et al., 2009b ], (E)-N′-(4-nitrobenzylidene)benzenesulfonohydrazide (Hussain et al., 2017a ) and (E)-4-methyl-N′-(4-nitrobenzylidene)benzenesulfonohydrazide (Hussain et al., 2017b ). In all of these structures, intermolecular N—H⋯O hydrogen bonds link neighbouring molecules to form chains, which are linked by C—H⋯O hydrogen bonds. There are also intermolecular π–π interactions present, which further stabilize the crystal structures.

6. Synthesis and crystallization

Synthesis of 4-chlorobenzenesulfonohydrazide

4-Chlorobenzenesulfonohydrazide was synthesized by a recently reported procedure (Salian et al., 2018).

Synthesis of compounds (I) and (II)

A mixture of 4-chlorobenzenesulfonohydrazide (0.01 mol) and 4-chlorobenzaldehyde (0.01 mol) for (I), and 4-nitrobenzaldehyde (0.01 mol) for (II), in ethanol (30 ml) and two drops of glacial acetic acid were stirred for 4 h. The reaction mixtures were cooled to room temperature and concentrated by evaporating off the excess of solvent. The solid products obtained were washed with cold water, dried and recrystallized to constant melting points from ethanol to obtain the pure compounds. The purity of the compounds was checked by TLC.

Crystals of compounds (I) and (II), suitable for X-ray diffraction analysis, were obtained by slow evaporation of their DMF solutions at room temperature.

Both compounds were characterized by measuring their IR, ¹H and ¹³C NMR spectra.

(E)-4-Chloro-N′-(4-chlorobenzylidene)benzenesulfonohydrazide (I)

Colourless rod-shaped crystals; m.p. 432–433 K; IR (cm⁻¹): 3180.6 (N—H asym. stretch), 1573.9 (C=N), 1327.0 (S=O asym. stretch) and 1166.9 (S=O sym. stretch).

¹H NMR (400 MHz, DMSO-d₆): δ 7.32 (d, 1H, J = 8.4Hz, Ar-H), 7.51–7.56 (m, 4H, Ar-H), 7.87–7.89 (m, 2H, Ar-H), 7.92 (s, 1H), 11.50 (s, 1H). ¹³C NMR (100 MHz, DMSO-d₆): δ 128.38, 129.42, 130.73, 132.06, 134.96, 137.47, 138.39, 139.32, 145.66.

(E)-4-Chloro-N′-(4-nitrobenzylidene)benzenesulfonohydrazide (II)

Yellow rod-shaped crystals; m.p. 414–415 K; IR (cm⁻¹): 3093.8 (N—H asym. stretch), 1653.0 (C=N), 1392.6 (S=O asym. stretch) and 1153.4 (S=O sym. stretch).

¹H NMR (400 MHz, DMSO-d₆): δ 7.0 (d, 1H, J = 8.80, Ar-H), 7.38 (d, 1H, J = 8.52, Ar-H), 7.63 (d, 1H, J = 8.36, Ar-H), 7.64 (s, 1H), 7.79 (d, 1H, J = 8.56, Ar-H), 7.80 (d, 2H, J = 8.28, Ar-H), 7.90 (s, 1H), 11.60 (s, 1H). ¹³C NMR (100 MHz, DMSO-d₆): δ 115.49, 124.47, 128.45, 129.63, 136.85, 137.87, 138.28, 147.97, 159.43.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. C-bound H atoms were positioned with idealized geometry and refined using a riding model: C—H = 0.93 Å with U_iso(H) = 1.2U_eq(C). The amino H atoms were located in difference-Fourier maps and refined with an N—H distance restraint of 0.86 (2) Å and U_iso(H) = 1.2U_eq(N). In (I), reflection 011 was masked by the beam stop and omitted from the refinement. In (II), atom O3 is disordered and was refined using a split model. The corresponding site-occupation factors were fixed at 0.55:0.45 and the corresponding N—O bond lengths in the disordered group were restrained to be equal. The U^ij components of O3 and O3′ were restrained to be approximately isotropic.

Table 4
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₃H₁₀Cl₂N₂O₂S	C₁₃H₁₀ClN₃O₄S
M_r	329.19	339.75
Crystal system, space group	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/c
Temperature (K)	293	293
a, b, c (Å)	5.9306 (6), 9.477 (1), 13.040 (2)	19.903 (1), 10.2517 (7), 15.064 (1)
α, β, γ (°)	98.822 (9), 96.046 (9), 92.416 (9)	90, 103.929 (7), 90
V (Å³)	718.94 (15)	2983.3 (3)
Z	2	8
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.60	0.42
Crystal size (mm)	0.48 × 0.40 × 0.36	0.48 × 0.40 × 0.36

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	Oxford Diffraction Xcalibur diffractometer with Sapphire CCD
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, England.]$ )	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, England.]$ )
T_min, T_max	0.762, 0.814	0.825, 0.864
No. of measured, independent and observed [I > 2σ(I)] reflections	4153, 2626, 2321	19194, 5455, 4247
R_int	0.016	0.025
(sin θ/λ)_max (Å⁻¹)	0.602	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.102, 1.08	0.038, 0.101, 1.02
No. of reflections	2626	5455
No. of parameters	185	414
No. of restraints	1	15
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.35	0.43, −0.38
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, England.]$ ), SHELXS2013 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC references: 1578709; 1578704

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S205698901801592X/su5458sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901801592X/su5458Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S205698901801592X/su5458IIsup3.hkl

checkCIF report

Computing details top

For both structures, data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(E)-4-Chloro-N'-(4-chlorobenzylidene)benzenesulfonohydrazide (I) top

Crystal data top

C₁₃H₁₀Cl₂N₂O₂S	Z = 2
M_r = 329.19	F(000) = 336
Triclinic, P1	D_x = 1.521 Mg m⁻³
a = 5.9306 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.477 (1) Å	Cell parameters from 2722 reflections
c = 13.040 (2) Å	θ = 2.9–27.8°
α = 98.822 (9)°	µ = 0.60 mm⁻¹
β = 96.046 (9)°	T = 293 K
γ = 92.416 (9)°	Rod, colourless
V = 718.94 (15) Å³	0.48 × 0.40 × 0.36 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	2321 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.016
Rotation method data acquisition using ω scans.	θ_max = 25.4°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −4→7
T_min = 0.762, T_max = 0.814	k = −11→11
4153 measured reflections	l = −15→11
2626 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0523P)² + 0.3082P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.102	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 0.37 e Å⁻³
2626 reflections	Δρ_min = −0.35 e Å⁻³
185 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.025 (3)

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.3867 (3)	0.1943 (2)	0.08046 (14)	0.0366 (4)
C2	0.6099 (3)	0.2317 (2)	0.12163 (17)	0.0481 (5)
H2	0.6853	0.3119	0.1052	0.058*
C3	0.7193 (4)	0.1486 (3)	0.18737 (19)	0.0556 (6)
H3	0.8683	0.1731	0.2166	0.067*
C4	0.6054 (4)	0.0289 (2)	0.20921 (17)	0.0526 (6)
C5	0.3850 (4)	−0.0103 (2)	0.16683 (18)	0.0549 (6)
H5	0.3118	−0.0925	0.1813	0.066*
C6	0.2746 (4)	0.0736 (2)	0.10286 (16)	0.0450 (5)
H6	0.1248	0.0493	0.0747	0.054*
C7	0.1757 (3)	0.5784 (2)	0.22864 (16)	0.0423 (4)
H7	0.2965	0.6386	0.2185	0.051*
C8	0.0609 (3)	0.6140 (2)	0.32242 (16)	0.0427 (5)
C9	−0.1405 (4)	0.5433 (3)	0.33612 (18)	0.0542 (5)
H9	−0.2037	0.4681	0.2855	0.065*
C10	−0.2480 (4)	0.5832 (3)	0.4236 (2)	0.0618 (6)
H10	−0.3837	0.5356	0.4319	0.074*
C11	−0.1539 (4)	0.6935 (3)	0.49867 (18)	0.0575 (6)
C12	0.0449 (4)	0.7658 (3)	0.48740 (19)	0.0630 (6)
H12	0.1068	0.8410	0.5383	0.076*
C13	0.1518 (4)	0.7252 (3)	0.39922 (18)	0.0548 (6)
H13	0.2872	0.7734	0.3913	0.066*
N1	0.2346 (3)	0.45985 (18)	0.07324 (14)	0.0426 (4)
H1N	0.345 (3)	0.517 (2)	0.0743 (19)	0.051*
N2	0.1173 (3)	0.46871 (18)	0.16049 (13)	0.0414 (4)
O1	0.3856 (3)	0.33553 (16)	−0.07638 (11)	0.0487 (4)
O2	0.0199 (2)	0.24297 (16)	−0.03067 (12)	0.0492 (4)
Cl1	0.74291 (16)	−0.07477 (8)	0.29214 (6)	0.0886 (3)
Cl2	−0.29271 (14)	0.74500 (11)	0.60842 (6)	0.0909 (3)
S1	0.24404 (8)	0.30435 (5)	0.00069 (4)	0.03746 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0347 (9)	0.0351 (9)	0.0370 (9)	−0.0002 (7)	0.0035 (7)	−0.0024 (8)
C2	0.0372 (10)	0.0498 (12)	0.0547 (12)	−0.0056 (9)	0.0048 (9)	0.0032 (10)
C3	0.0394 (11)	0.0632 (15)	0.0580 (13)	0.0069 (10)	−0.0054 (10)	−0.0029 (11)
C4	0.0661 (14)	0.0415 (11)	0.0443 (11)	0.0170 (10)	−0.0079 (10)	−0.0060 (9)
C5	0.0682 (15)	0.0346 (11)	0.0581 (13)	−0.0040 (10)	−0.0038 (11)	0.0044 (9)
C6	0.0433 (11)	0.0377 (10)	0.0499 (11)	−0.0066 (8)	−0.0053 (9)	0.0033 (9)
C7	0.0429 (11)	0.0383 (10)	0.0459 (11)	0.0015 (8)	0.0056 (9)	0.0078 (9)
C8	0.0460 (11)	0.0406 (10)	0.0420 (11)	0.0083 (8)	0.0036 (9)	0.0068 (8)
C9	0.0571 (13)	0.0519 (13)	0.0501 (12)	−0.0022 (10)	0.0100 (10)	−0.0040 (10)
C10	0.0570 (14)	0.0708 (16)	0.0574 (14)	0.0003 (12)	0.0175 (11)	0.0030 (12)
C11	0.0581 (14)	0.0723 (16)	0.0416 (11)	0.0186 (12)	0.0071 (10)	0.0023 (11)
C12	0.0666 (16)	0.0666 (16)	0.0473 (13)	0.0053 (12)	−0.0027 (11)	−0.0117 (11)
C13	0.0522 (13)	0.0573 (13)	0.0512 (12)	0.0001 (10)	0.0031 (10)	−0.0004 (10)
N1	0.0459 (9)	0.0357 (9)	0.0461 (9)	−0.0045 (7)	0.0133 (8)	0.0032 (7)
N2	0.0426 (9)	0.0396 (9)	0.0438 (9)	0.0039 (7)	0.0110 (7)	0.0074 (7)
O1	0.0569 (9)	0.0475 (8)	0.0396 (7)	−0.0107 (7)	0.0117 (6)	0.0005 (6)
O2	0.0413 (8)	0.0474 (8)	0.0559 (9)	−0.0080 (6)	−0.0055 (6)	0.0093 (7)
Cl1	0.1200 (7)	0.0595 (4)	0.0754 (5)	0.0290 (4)	−0.0372 (4)	0.0025 (3)
Cl2	0.0868 (5)	0.1270 (7)	0.0546 (4)	0.0193 (5)	0.0230 (4)	−0.0133 (4)
S1	0.0382 (3)	0.0352 (3)	0.0372 (3)	−0.00503 (18)	0.00356 (19)	0.00245 (19)

Geometric parameters (Å, º) top

C1—C6	1.384 (3)	C8—C9	1.386 (3)
C1—C2	1.385 (3)	C9—C10	1.376 (3)
C1—S1	1.763 (2)	C9—H9	0.9300
C2—C3	1.382 (3)	C10—C11	1.373 (4)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.377 (4)	C11—C12	1.371 (4)
C3—H3	0.9300	C11—Cl2	1.741 (2)
C4—C5	1.377 (3)	C12—C13	1.382 (3)
C4—Cl1	1.734 (2)	C12—H12	0.9300
C5—C6	1.374 (3)	C13—H13	0.9300
C5—H5	0.9300	N1—N2	1.388 (2)
C6—H6	0.9300	N1—S1	1.6311 (17)
C7—N2	1.269 (3)	N1—H1N	0.830 (16)
C7—C8	1.463 (3)	O1—S1	1.4316 (14)
C7—H7	0.9300	O2—S1	1.4212 (15)
C8—C13	1.385 (3)

C6—C1—C2	120.77 (19)	C10—C9—H9	119.6
C6—C1—S1	120.05 (15)	C8—C9—H9	119.6
C2—C1—S1	119.18 (15)	C11—C10—C9	119.6 (2)
C3—C2—C1	119.3 (2)	C11—C10—H10	120.2
C3—C2—H2	120.4	C9—C10—H10	120.2
C1—C2—H2	120.4	C12—C11—C10	121.0 (2)
C4—C3—C2	119.3 (2)	C12—C11—Cl2	119.5 (2)
C4—C3—H3	120.3	C10—C11—Cl2	119.4 (2)
C2—C3—H3	120.3	C11—C12—C13	119.0 (2)
C5—C4—C3	121.6 (2)	C11—C12—H12	120.5
C5—C4—Cl1	119.19 (19)	C13—C12—H12	120.5
C3—C4—Cl1	119.22 (18)	C12—C13—C8	121.2 (2)
C6—C5—C4	119.2 (2)	C12—C13—H13	119.4
C6—C5—H5	120.4	C8—C13—H13	119.4
C4—C5—H5	120.4	N2—N1—S1	118.76 (13)
C5—C6—C1	119.84 (19)	N2—N1—H1N	118.8 (17)
C5—C6—H6	120.1	S1—N1—H1N	115.6 (17)
C1—C6—H6	120.1	C7—N2—N1	114.02 (16)
N2—C7—C8	122.74 (19)	O2—S1—O1	119.93 (9)
N2—C7—H7	118.6	O2—S1—N1	109.69 (9)
C8—C7—H7	118.6	O1—S1—N1	102.85 (9)
C13—C8—C9	118.4 (2)	O2—S1—C1	107.94 (9)
C13—C8—C7	119.19 (19)	O1—S1—C1	109.14 (9)
C9—C8—C7	122.40 (19)	N1—S1—C1	106.52 (9)
C10—C9—C8	120.8 (2)

C6—C1—C2—C3	−1.2 (3)	C10—C11—C12—C13	−0.6 (4)
S1—C1—C2—C3	177.57 (16)	Cl2—C11—C12—C13	−179.08 (19)
C1—C2—C3—C4	1.1 (3)	C11—C12—C13—C8	0.4 (4)
C2—C3—C4—C5	0.2 (3)	C9—C8—C13—C12	−0.3 (4)
C2—C3—C4—Cl1	−179.75 (17)	C7—C8—C13—C12	177.7 (2)
C3—C4—C5—C6	−1.3 (4)	C8—C7—N2—N1	175.01 (17)
Cl1—C4—C5—C6	178.64 (17)	S1—N1—N2—C7	158.96 (15)
C4—C5—C6—C1	1.1 (3)	N2—N1—S1—O2	54.13 (17)
C2—C1—C6—C5	0.1 (3)	N2—N1—S1—O1	−177.17 (15)
S1—C1—C6—C5	−178.67 (17)	N2—N1—S1—C1	−62.44 (17)
N2—C7—C8—C13	172.1 (2)	C6—C1—S1—O2	−0.97 (19)
N2—C7—C8—C9	−10.0 (3)	C2—C1—S1—O2	−179.78 (15)
C13—C8—C9—C10	0.3 (4)	C6—C1—S1—O1	−132.84 (16)
C7—C8—C9—C10	−177.6 (2)	C2—C1—S1—O1	48.35 (18)
C8—C9—C10—C11	−0.5 (4)	C6—C1—S1—N1	116.77 (17)
C9—C10—C11—C12	0.7 (4)	C2—C1—S1—N1	−62.04 (18)
C9—C10—C11—Cl2	179.13 (19)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of rings C1–C6 and C8–C13, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.83 (2)	2.07 (2)	2.903 (2)	178 (2)
C4—Cl1···Cg2ⁱⁱ	1.73 (1)	3.41 (1)	5.112 (2)	166 (1)
C11—Cl2···Cg1ⁱⁱⁱ	1.74 (1)	3.65 (1)	5.372 (3)	171 (1)

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

(E)-4-chloro-N'-(4-Nitrobenzylidene)benzenesulfonohydrazide (II) top

Crystal data top

C₁₃H₁₀ClN₃O₄S	F(000) = 1392
M_r = 339.75	D_x = 1.513 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.903 (1) Å	Cell parameters from 7054 reflections
b = 10.2517 (7) Å	θ = 2.8–27.8°
c = 15.064 (1) Å	µ = 0.42 mm⁻¹
β = 103.929 (7)°	T = 293 K
V = 2983.3 (3) Å³	Rod, yellow
Z = 8	0.48 × 0.40 × 0.36 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	4247 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.025
Rotation method data acquisition using ω scans.	θ_max = 25.4°, θ_min = 2.8°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −23→23
T_min = 0.825, T_max = 0.864	k = −12→12
19194 measured reflections	l = −18→18
5455 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0435P)² + 1.8451P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.101	(Δ/σ)_max = 0.001
S = 1.02	Δρ_max = 0.43 e Å⁻³
5455 reflections	Δρ_min = −0.38 e Å⁻³
414 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
15 restraints	Extinction coefficient: 0.0034 (3)

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.44715 (4)	0.44299 (7)	0.63321 (5)	0.0692 (2)
S1	0.41281 (3)	1.03308 (5)	0.53686 (4)	0.03843 (15)
O1	0.42255 (8)	1.04883 (15)	0.44626 (10)	0.0447 (4)
O2	0.44990 (8)	1.11288 (16)	0.60973 (11)	0.0529 (4)
O3	0.0285 (6)	0.5036 (8)	0.3381 (6)	0.081 (3)	0.55
O3'	0.0324 (8)	0.5149 (10)	0.3044 (7)	0.075 (3)	0.45
O4	−0.04648 (9)	0.6576 (2)	0.30599 (13)	0.0681 (5)
N1	0.33087 (10)	1.06413 (19)	0.53180 (14)	0.0449 (5)
H1N	0.3271 (13)	1.086 (2)	0.5849 (12)	0.054*
N2	0.28443 (9)	0.97344 (18)	0.48183 (12)	0.0426 (4)
N3	0.01310 (11)	0.6206 (2)	0.32944 (15)	0.0562 (5)
C1	0.42530 (10)	0.8671 (2)	0.56436 (14)	0.0367 (5)
C2	0.44115 (12)	0.8290 (2)	0.65534 (15)	0.0465 (6)
H2	0.4461	0.8912	0.7014	0.056*
C3	0.44953 (12)	0.6982 (3)	0.67705 (16)	0.0519 (6)
H3	0.4610	0.6714	0.7378	0.062*
C4	0.44062 (11)	0.6085 (2)	0.60760 (17)	0.0457 (6)
C5	0.42596 (13)	0.6447 (2)	0.51720 (17)	0.0534 (6)
H5	0.4209	0.5821	0.4714	0.064*
C6	0.41891 (13)	0.7760 (2)	0.49545 (15)	0.0484 (6)
H6	0.4099	0.8027	0.4347	0.058*
C7	0.22211 (11)	0.9867 (2)	0.48701 (16)	0.0438 (5)
H7	0.2100	1.0569	0.5192	0.053*
C8	0.16896 (11)	0.8929 (2)	0.44293 (15)	0.0406 (5)
C9	0.09969 (12)	0.9292 (2)	0.42131 (17)	0.0499 (6)
H9	0.0877	1.0142	0.4327	0.060*
C10	0.04837 (12)	0.8412 (2)	0.38318 (17)	0.0497 (6)
H10	0.0021	0.8661	0.3679	0.060*
C11	0.06736 (11)	0.7159 (2)	0.36837 (16)	0.0443 (5)
C12	0.13570 (12)	0.6763 (2)	0.38937 (18)	0.0508 (6)
H12	0.1472	0.5907	0.3787	0.061*
C13	0.18635 (12)	0.7649 (2)	0.42624 (17)	0.0476 (6)
H13	0.2326	0.7395	0.4402	0.057*
Cl2	0.11071 (4)	0.30845 (9)	0.53034 (6)	0.0814 (3)
S2	0.32436 (3)	0.34333 (5)	0.28991 (4)	0.04203 (16)
O5	0.28924 (9)	0.38026 (17)	0.19868 (11)	0.0542 (4)
O6	0.38459 (9)	0.41231 (17)	0.33703 (13)	0.0610 (5)
O7	0.10708 (11)	−0.49600 (19)	0.13632 (16)	0.0778 (6)
O8	0.03109 (10)	−0.3435 (2)	0.12357 (18)	0.0896 (7)
N4	0.34961 (10)	0.19182 (18)	0.28409 (13)	0.0413 (4)
H4N	0.3793 (11)	0.167 (2)	0.3306 (13)	0.050*
N5	0.29454 (9)	0.10878 (17)	0.24828 (12)	0.0386 (4)
N6	0.09076 (11)	−0.3814 (2)	0.14089 (16)	0.0582 (6)
C14	0.26262 (11)	0.3420 (2)	0.35620 (15)	0.0388 (5)
C15	0.19424 (12)	0.3099 (2)	0.31583 (15)	0.0432 (5)
H15	0.1803	0.2948	0.2532	0.052*
C16	0.14730 (12)	0.3006 (2)	0.36964 (17)	0.0479 (6)
H16	0.1014	0.2790	0.3437	0.058*
C17	0.16929 (13)	0.3237 (2)	0.46229 (17)	0.0483 (6)
C18	0.23655 (13)	0.3573 (3)	0.50252 (16)	0.0534 (6)
H18	0.2500	0.3742	0.5650	0.064*
C19	0.28388 (12)	0.3655 (2)	0.44925 (16)	0.0489 (6)
H19	0.3298	0.3868	0.4757	0.059*
C20	0.30626 (12)	−0.0126 (2)	0.25909 (15)	0.0413 (5)
H20	0.3503	−0.0419	0.2881	0.050*
C21	0.25043 (11)	−0.1061 (2)	0.22580 (15)	0.0395 (5)
C22	0.18148 (12)	−0.0665 (2)	0.20002 (18)	0.0496 (6)
H22	0.1707	0.0215	0.2026	0.060*
C23	0.12929 (12)	−0.1552 (2)	0.17098 (18)	0.0511 (6)
H23	0.0834	−0.1283	0.1534	0.061*
C24	0.14638 (12)	−0.2851 (2)	0.16848 (16)	0.0436 (5)
C25	0.21363 (12)	−0.3280 (2)	0.19346 (17)	0.0498 (6)
H25	0.2238	−0.4163	0.1907	0.060*
C26	0.26565 (12)	−0.2384 (2)	0.22262 (17)	0.0482 (6)
H26	0.3114	−0.2663	0.2404	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0651 (4)	0.0455 (4)	0.0853 (5)	−0.0022 (3)	−0.0048 (4)	0.0214 (3)
S1	0.0359 (3)	0.0367 (3)	0.0404 (3)	−0.0048 (2)	0.0046 (2)	−0.0003 (2)
O1	0.0414 (8)	0.0469 (9)	0.0454 (9)	−0.0022 (7)	0.0096 (7)	0.0086 (7)
O2	0.0544 (10)	0.0450 (10)	0.0524 (10)	−0.0110 (8)	−0.0006 (8)	−0.0087 (8)
O3	0.058 (3)	0.050 (3)	0.129 (7)	−0.007 (2)	0.010 (5)	−0.002 (4)
O3'	0.069 (4)	0.062 (4)	0.087 (5)	−0.005 (4)	0.005 (4)	−0.018 (4)
O4	0.0382 (10)	0.0845 (15)	0.0791 (13)	−0.0053 (9)	0.0093 (9)	−0.0026 (11)
N1	0.0406 (10)	0.0446 (11)	0.0488 (11)	−0.0001 (9)	0.0094 (9)	−0.0083 (9)
N2	0.0380 (10)	0.0443 (11)	0.0438 (10)	−0.0011 (9)	0.0065 (8)	−0.0028 (9)
N3	0.0421 (12)	0.0600 (15)	0.0649 (14)	−0.0050 (11)	0.0102 (10)	−0.0023 (12)
C1	0.0310 (10)	0.0404 (12)	0.0371 (11)	−0.0048 (9)	0.0051 (8)	0.0017 (9)
C2	0.0483 (13)	0.0506 (14)	0.0360 (12)	−0.0052 (11)	0.0014 (10)	−0.0009 (10)
C3	0.0507 (14)	0.0594 (16)	0.0393 (13)	−0.0033 (12)	−0.0015 (11)	0.0136 (12)
C4	0.0367 (12)	0.0401 (13)	0.0557 (14)	−0.0023 (10)	0.0021 (10)	0.0126 (11)
C5	0.0664 (16)	0.0405 (13)	0.0511 (14)	−0.0042 (12)	0.0097 (12)	−0.0031 (11)
C6	0.0650 (15)	0.0447 (14)	0.0337 (12)	−0.0035 (12)	0.0085 (11)	0.0028 (10)
C7	0.0400 (12)	0.0392 (12)	0.0527 (14)	0.0061 (10)	0.0119 (10)	0.0010 (10)
C8	0.0355 (11)	0.0437 (13)	0.0434 (12)	0.0033 (10)	0.0113 (9)	0.0039 (10)
C9	0.0397 (12)	0.0435 (13)	0.0667 (16)	0.0103 (11)	0.0131 (11)	−0.0002 (12)
C10	0.0324 (11)	0.0535 (15)	0.0614 (15)	0.0076 (11)	0.0081 (11)	0.0050 (12)
C11	0.0383 (12)	0.0475 (14)	0.0472 (13)	−0.0010 (10)	0.0105 (10)	0.0034 (11)
C12	0.0419 (13)	0.0418 (13)	0.0677 (16)	0.0059 (11)	0.0113 (11)	−0.0033 (12)
C13	0.0327 (11)	0.0481 (14)	0.0616 (15)	0.0079 (10)	0.0106 (10)	0.0033 (12)
Cl2	0.0824 (5)	0.0998 (6)	0.0759 (5)	−0.0171 (5)	0.0459 (4)	−0.0163 (4)
S2	0.0445 (3)	0.0341 (3)	0.0487 (3)	−0.0011 (2)	0.0137 (2)	0.0007 (2)
O5	0.0642 (11)	0.0510 (10)	0.0514 (10)	0.0132 (9)	0.0218 (8)	0.0169 (8)
O6	0.0524 (10)	0.0512 (10)	0.0824 (13)	−0.0141 (8)	0.0219 (9)	−0.0147 (9)
O7	0.0715 (13)	0.0450 (11)	0.1165 (18)	−0.0122 (10)	0.0217 (12)	−0.0072 (11)
O8	0.0452 (11)	0.0735 (15)	0.143 (2)	−0.0107 (10)	0.0096 (12)	−0.0044 (14)
N4	0.0401 (10)	0.0353 (10)	0.0446 (11)	0.0022 (8)	0.0027 (8)	−0.0006 (8)
N5	0.0395 (10)	0.0349 (10)	0.0397 (10)	−0.0002 (8)	0.0064 (8)	0.0001 (8)
N6	0.0521 (13)	0.0532 (14)	0.0700 (15)	−0.0095 (11)	0.0160 (11)	−0.0011 (11)
C14	0.0439 (12)	0.0315 (11)	0.0407 (12)	0.0031 (9)	0.0094 (9)	−0.0009 (9)
C15	0.0451 (13)	0.0432 (13)	0.0388 (12)	0.0024 (10)	0.0050 (10)	−0.0056 (10)
C16	0.0425 (13)	0.0468 (14)	0.0533 (14)	−0.0016 (11)	0.0093 (11)	−0.0062 (11)
C17	0.0542 (14)	0.0443 (13)	0.0511 (14)	−0.0032 (11)	0.0216 (11)	−0.0061 (11)
C18	0.0642 (16)	0.0565 (16)	0.0388 (13)	−0.0021 (13)	0.0110 (11)	−0.0084 (11)
C19	0.0462 (13)	0.0501 (14)	0.0474 (14)	−0.0060 (11)	0.0051 (11)	−0.0078 (11)
C20	0.0411 (12)	0.0405 (13)	0.0419 (12)	0.0052 (10)	0.0092 (10)	0.0001 (10)
C21	0.0423 (12)	0.0346 (12)	0.0413 (12)	0.0043 (10)	0.0094 (10)	0.0013 (10)
C22	0.0452 (13)	0.0356 (12)	0.0669 (16)	0.0070 (10)	0.0112 (12)	0.0032 (11)
C23	0.0389 (12)	0.0443 (14)	0.0683 (16)	0.0054 (11)	0.0089 (11)	0.0055 (12)
C24	0.0441 (13)	0.0399 (13)	0.0486 (13)	−0.0041 (10)	0.0149 (10)	−0.0008 (10)
C25	0.0517 (14)	0.0334 (12)	0.0660 (16)	0.0041 (11)	0.0173 (12)	−0.0051 (11)
C26	0.0404 (12)	0.0403 (13)	0.0631 (15)	0.0058 (10)	0.0107 (11)	−0.0031 (11)

Geometric parameters (Å, º) top

Cl1—C4	1.738 (2)	Cl2—C17	1.735 (2)
S1—O2	1.4245 (16)	S2—O6	1.4252 (17)
S1—O1	1.4331 (16)	S2—O5	1.4346 (17)
S1—N1	1.6452 (19)	S2—N4	1.6414 (19)
S1—C1	1.754 (2)	S2—C14	1.760 (2)
O3—N3	1.237 (8)	O7—N6	1.226 (3)
O3'—N3	1.239 (10)	O8—N6	1.217 (3)
O4—N3	1.213 (3)	N4—N5	1.390 (2)
N1—N2	1.397 (3)	N4—H4N	0.839 (16)
N1—H1N	0.849 (16)	N5—C20	1.269 (3)
N2—C7	1.269 (3)	N6—C24	1.467 (3)
N3—C11	1.469 (3)	C14—C19	1.384 (3)
C1—C6	1.379 (3)	C14—C15	1.390 (3)
C1—C2	1.386 (3)	C15—C16	1.380 (3)
C2—C3	1.381 (3)	C15—H15	0.9300
C2—H2	0.9300	C16—C17	1.379 (3)
C3—C4	1.372 (4)	C16—H16	0.9300
C3—H3	0.9300	C17—C18	1.374 (3)
C4—C5	1.373 (3)	C18—C19	1.379 (3)
C5—C6	1.385 (3)	C18—H18	0.9300
C5—H5	0.9300	C19—H19	0.9300
C6—H6	0.9300	C20—C21	1.462 (3)
C7—C8	1.465 (3)	C20—H20	0.9300
C7—H7	0.9300	C21—C26	1.393 (3)
C8—C9	1.389 (3)	C21—C22	1.394 (3)
C8—C13	1.396 (3)	C22—C23	1.370 (3)
C9—C10	1.380 (3)	C22—H22	0.9300
C9—H9	0.9300	C23—C24	1.377 (3)
C10—C11	1.372 (3)	C23—H23	0.9300
C10—H10	0.9300	C24—C25	1.373 (3)
C11—C12	1.381 (3)	C25—C26	1.375 (3)
C12—C13	1.371 (3)	C25—H25	0.9300
C12—H12	0.9300	C26—H26	0.9300
C13—H13	0.9300

O2—S1—O1	120.35 (10)	C8—C13—H13	119.8
O2—S1—N1	104.40 (10)	O6—S2—O5	120.24 (11)
O1—S1—N1	107.10 (10)	O6—S2—N4	105.33 (10)
O2—S1—C1	110.93 (10)	O5—S2—N4	106.46 (10)
O1—S1—C1	106.87 (10)	O6—S2—C14	109.87 (10)
N1—S1—C1	106.33 (10)	O5—S2—C14	107.46 (10)
N2—N1—S1	114.59 (15)	N4—S2—C14	106.70 (10)
N2—N1—H1N	118.9 (18)	N5—N4—S2	112.16 (14)
S1—N1—H1N	108.5 (17)	N5—N4—H4N	118.0 (17)
C7—N2—N1	115.17 (19)	S2—N4—H4N	113.8 (17)
O4—N3—O3	122.2 (6)	C20—N5—N4	116.56 (18)
O4—N3—O3'	122.5 (8)	O8—N6—O7	123.5 (2)
O4—N3—C11	118.8 (2)	O8—N6—C24	118.5 (2)
O3—N3—C11	117.5 (6)	O7—N6—C24	118.0 (2)
O3'—N3—C11	116.8 (8)	C19—C14—C15	120.8 (2)
C6—C1—C2	120.7 (2)	C19—C14—S2	119.21 (17)
C6—C1—S1	119.78 (17)	C15—C14—S2	119.83 (17)
C2—C1—S1	119.49 (17)	C16—C15—C14	119.3 (2)
C3—C2—C1	119.6 (2)	C16—C15—H15	120.3
C3—C2—H2	120.2	C14—C15—H15	120.3
C1—C2—H2	120.2	C17—C16—C15	119.2 (2)
C4—C3—C2	119.0 (2)	C17—C16—H16	120.4
C4—C3—H3	120.5	C15—C16—H16	120.4
C2—C3—H3	120.5	C18—C17—C16	121.9 (2)
C3—C4—C5	122.2 (2)	C18—C17—Cl2	118.95 (19)
C3—C4—Cl1	119.75 (19)	C16—C17—Cl2	119.19 (19)
C5—C4—Cl1	118.1 (2)	C17—C18—C19	119.2 (2)
C4—C5—C6	118.8 (2)	C17—C18—H18	120.4
C4—C5—H5	120.6	C19—C18—H18	120.4
C6—C5—H5	120.6	C18—C19—C14	119.6 (2)
C1—C6—C5	119.6 (2)	C18—C19—H19	120.2
C1—C6—H6	120.2	C14—C19—H19	120.2
C5—C6—H6	120.2	N5—C20—C21	119.9 (2)
N2—C7—C8	120.8 (2)	N5—C20—H20	120.1
N2—C7—H7	119.6	C21—C20—H20	120.1
C8—C7—H7	119.6	C26—C21—C22	118.8 (2)
C9—C8—C13	119.0 (2)	C26—C21—C20	119.8 (2)
C9—C8—C7	119.9 (2)	C22—C21—C20	121.3 (2)
C13—C8—C7	121.0 (2)	C23—C22—C21	121.0 (2)
C10—C9—C8	121.0 (2)	C23—C22—H22	119.5
C10—C9—H9	119.5	C21—C22—H22	119.5
C8—C9—H9	119.5	C22—C23—C24	118.5 (2)
C11—C10—C9	118.3 (2)	C22—C23—H23	120.8
C11—C10—H10	120.8	C24—C23—H23	120.8
C9—C10—H10	120.8	C25—C24—C23	122.3 (2)
C10—C11—C12	122.2 (2)	C25—C24—N6	118.8 (2)
C10—C11—N3	118.8 (2)	C23—C24—N6	118.9 (2)
C12—C11—N3	119.0 (2)	C24—C25—C26	118.9 (2)
C13—C12—C11	119.0 (2)	C24—C25—H25	120.6
C13—C12—H12	120.5	C26—C25—H25	120.6
C11—C12—H12	120.5	C25—C26—C21	120.6 (2)
C12—C13—C8	120.4 (2)	C25—C26—H26	119.7
C12—C13—H13	119.8	C21—C26—H26	119.7

O2—S1—N1—N2	−164.14 (15)	C7—C8—C13—C12	176.5 (2)
O1—S1—N1—N2	67.20 (18)	O6—S2—N4—N5	173.52 (15)
C1—S1—N1—N2	−46.79 (18)	O5—S2—N4—N5	−57.76 (17)
S1—N1—N2—C7	171.43 (17)	C14—S2—N4—N5	56.77 (17)
O2—S1—C1—C6	−153.93 (18)	S2—N4—N5—C20	−165.33 (16)
O1—S1—C1—C6	−21.0 (2)	O6—S2—C14—C19	−19.8 (2)
N1—S1—C1—C6	93.2 (2)	O5—S2—C14—C19	−152.28 (18)
O2—S1—C1—C2	26.4 (2)	N4—S2—C14—C19	93.9 (2)
O1—S1—C1—C2	159.36 (17)	O6—S2—C14—C15	163.92 (18)
N1—S1—C1—C2	−86.50 (19)	O5—S2—C14—C15	31.5 (2)
C6—C1—C2—C3	−1.0 (3)	N4—S2—C14—C15	−82.38 (19)
S1—C1—C2—C3	178.61 (18)	C19—C14—C15—C16	−0.5 (3)
C1—C2—C3—C4	−1.2 (4)	S2—C14—C15—C16	175.69 (17)
C2—C3—C4—C5	2.3 (4)	C14—C15—C16—C17	0.2 (3)
C2—C3—C4—Cl1	−177.17 (18)	C15—C16—C17—C18	0.8 (4)
C3—C4—C5—C6	−1.0 (4)	C15—C16—C17—Cl2	−178.57 (18)
Cl1—C4—C5—C6	178.45 (19)	C16—C17—C18—C19	−1.3 (4)
C2—C1—C6—C5	2.3 (4)	Cl2—C17—C18—C19	178.0 (2)
S1—C1—C6—C5	−177.32 (19)	C17—C18—C19—C14	1.0 (4)
C4—C5—C6—C1	−1.3 (4)	C15—C14—C19—C18	−0.1 (4)
N1—N2—C7—C8	−175.87 (19)	S2—C14—C19—C18	−176.29 (19)
N2—C7—C8—C9	−157.7 (2)	N4—N5—C20—C21	178.17 (18)
N2—C7—C8—C13	25.5 (3)	N5—C20—C21—C26	168.5 (2)
C13—C8—C9—C10	−0.5 (4)	N5—C20—C21—C22	−13.9 (3)
C7—C8—C9—C10	−177.3 (2)	C26—C21—C22—C23	−0.7 (4)
C8—C9—C10—C11	1.0 (4)	C20—C21—C22—C23	−178.4 (2)
C9—C10—C11—C12	−0.7 (4)	C21—C22—C23—C24	0.5 (4)
C9—C10—C11—N3	178.8 (2)	C22—C23—C24—C25	−0.4 (4)
O4—N3—C11—C10	4.8 (3)	C22—C23—C24—N6	177.7 (2)
O3—N3—C11—C10	−161.9 (5)	O8—N6—C24—C25	176.1 (2)
O3'—N3—C11—C10	169.5 (6)	O7—N6—C24—C25	−4.1 (4)
O4—N3—C11—C12	−175.6 (2)	O8—N6—C24—C23	−2.1 (4)
O3—N3—C11—C12	17.7 (6)	O7—N6—C24—C23	177.8 (2)
O3'—N3—C11—C12	−10.9 (6)	C23—C24—C25—C26	0.5 (4)
C10—C11—C12—C13	0.0 (4)	N6—C24—C25—C26	−177.6 (2)
N3—C11—C12—C13	−179.6 (2)	C24—C25—C26—C21	−0.7 (4)
C11—C12—C13—C8	0.5 (4)	C22—C21—C26—C25	0.8 (4)
C9—C8—C13—C12	−0.2 (4)	C20—C21—C26—C25	178.5 (2)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C14–C19 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O5ⁱ	0.85 (2)	2.06 (2)	2.887 (3)	163 (2)
N4—H4N···O1ⁱⁱ	0.84 (2)	2.13 (2)	2.918 (2)	157 (2)
C10—H10···O7ⁱⁱⁱ	0.93	2.58	3.465 (3)	159
C16—H16···O4^iv	0.93	2.58	3.259 (3)	131
C25—H25···O5ⁱⁱ	0.93	2.45	3.340 (3)	161
C12—H12···Cg3	0.93	2.96	3.843 (2)	160

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, y−1, z; (iii) −x, y+3/2, −z+1/2; (iv) −x, y−1/2, −z+1/2.

Comparison of selected geometrical parameters (Å, °) of compounds (I)–(V) top

The dihedral angle is that between the aromatic rings.

Bond length	(I)	(II) Molecule A	(II) Molecule B	(III)	(IV)	(V)
C1—S1	1.763 (2)	1.754 (2)	1.760 (2)	1.752 (4)	1.751 (5)	1.761 (2)
S1—N1	1.631 (2)	1.645 (2)	1.641 (2)	1.644 (4)	1.645 (4)	1.625 (2)
N1—N2	1.388 (2)	1.397 (3)	1.390 (2)	1.394 (5)	1.407 (5)	1.393 (2)
N2—C7	1.269 (3)	1.269 (3)	1.269 (3)	1.258 (5)	1.272 (5)	1.273 (3)
C7—C8	1.463 (3)	1.465 (3)	1.462 (3)	1.473 (6)	1.461 (6)	1.458 (3)
Torsion angle
C1—S1—N1—N2	-62.4 (2)	-46.8 (2)	56.8 (2)	-66.0 (3)	-66.0 (3)	-58.4 (2)
S1—N1—N2—C7	158.9 (2)	171.4 (2)	-165.3 (2)	166.5 (3)	165.4 (3)	157.9 (2)
N1—N2—C7—C8	175.0 (2)	-175.9 (2)	178.2 (2)	177.8 (4)	175.8 (4)	175.8 (2)
Dihedral angle	81.0 (1)	75.9 (1)	73.4 (1)	78.4 (2)	74.8 (2)	76.9 (1)

Acknowledgements

The authors thank SAIF Panjab University for extending the services of their NMR facility and Mangalore University for providing all the facilities required.

Funding information

ARS thanks the Department of Science and Technology, Government of India, New Delhi, for a research fellowship under its DST-PURSE Program and BTG thanks the University Grants Commission, Government of India, New Delhi, for a special grant under a UGC–BSR one-time grant to faculty.

References

Balaji, J., John Francis Xavier, J., Prabu, S. & Srinivasan, P. (2014). Acta Cryst. E70, o1250–o1251. CrossRef IUCr Journals Google Scholar
Hashemi, S. A. (2012). Tetrahedron Lett. 53, 5141–5143. CrossRef Google Scholar
Hussain, M. M., Rahman, M. M., Arshad, M. N. & Asiri, A. M. (2017a). ACS Omega, 2, 420–431. CrossRef Google Scholar
Hussain, M. M., Rahman, M. M., Arshad, M. N. & Asiri, A. M. (2017b). Sci. Rep. 7, 5832. CrossRef PubMed Google Scholar
Kia, R., Etemadi, B., Fun, H.-K. & Kargar, H. (2009b). Acta Cryst. E65, o821–o822. CrossRef IUCr Journals Google Scholar
Kia, R., Fun, H.-K. & Kargar, H. (2009a). Acta Cryst. E65, o1119–o1120. CrossRef IUCr Journals Google Scholar
McKinnon, J. J., Spackman, M. A. & Mitchell, A. S. (2004). Acta Cryst. B60, 627–668. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ogawa, C., Konishi, H., Sugiura, M. & Kobayashi, S. (2004). Org. Biomol. Chem. 2, 446–448. CrossRef PubMed CAS Google Scholar
Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, England. Google Scholar
Reis, D. C., Despaigne, A. A. R., Da Silva, J. G., Silva, N. F., Vilela, C. F., Mendes, I. C., Takahashi, J. A. & Beraldo, H. (2013). Molecules, 18, 12645–12662. CrossRef Google Scholar
Rollas, S. & Küçükgüzel, S. G. (2007). Molecules, 12, 1910–1939. Web of Science CrossRef PubMed CAS Google Scholar
Salian, A. R., Foro, S. & Gowda, B. T. (2018). Acta Cryst. E74, 1613–1618. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Silva, C. M. da, da Silva, D. L., Modolo, L. V., Alves, R. B., de Resende, M. A., Martins, C. V. B. & de Fátima, A. (2011). J. Adv. Res. 2, 1–8. 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
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). Crystal Explorer. The University of Western Australia. Google Scholar
Weber, B., Tandon, R. & Himsl, D. (2007). Z. Anorg. Allg. Chem. 633, 1159–1162. Web of Science 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 12| December 2018| Pages 1808-1814

https://doi.org/10.1107/S205698901801592X

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 two (E)-N′-(para-substituted benzyl­­idene) 4-chloro­benzene­sulfono­hydrazides

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis

5. Database survey

6. Synthesis and crystallization

7. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Crystal structure and Hirshfeld surface analysis of two (E)-N′-(para-substituted benzylidene) 4-chlorobenzenesulfonohydrazides

3. Supramolecular features