Crystal structures of three N-acyl­hydrazone isomers

Purandara, H.; Foro, S.; Thimme Gowda, B.

doi:10.1107/S2056989021006885

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ISSN: 2056-9890

Volume 77| Part 8| August 2021| Pages 780-784

https://doi.org/10.1107/S2056989021006885

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Crystal structures of three N-acylhydrazone isomers

H. Purandara,^a,^b Sabine Foro ^c and B. Thimme Gowda ^a,^d ^*

^aDepartment of Chemistry, Mangalore University, Mangalagangotri-574 199, Mangalore, India, ^bDepartment of Chemistry, Sri Dharmasthala Manjunatheshwara College (Autonomous), Ujire 574 240, India, ^cInstitute of Materials Science, Darmstadt University of Technology, Alarich-Weiss-Str. 2, D-64287, Darmstadt, Germany, and ^dKarnataka State Higher Education Council, Y. Ramachandra Road, Gandhingar, Bengaluru-560009, India
^*Correspondence e-mail: gowdabt@yahoo.com

Edited by J. T. Mague, Tulane University, USA (Received 10 May 2021; accepted 5 July 2021; online 9 July 2021)

The crystal structures of three isomers of (E)-4-chloro-N-{2-[2-(chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide, namely, (E)-4-chloro-N-{2-[2-(2-chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide (I), (E)-4-chloro-N-{2-[2-(3-chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide (II) and (E)-4-chloro-N-{2-[2-(4-chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide (III), with the general formula C₁₅H₁₃Cl₂N₃O₃S are described, with the chloro group in ortho, meta and para positions in the benzylidene benzene ring. All the three isomeric compounds crystallize in the centrosymmetric triclinic P $[\overline{1}]$ space group with one molecule each in the asymmetric unit and two molecules in the unit cell. The dihedral angles between the two phenyl rings are 11.09 (14), 53.79 (18) and 72.37 (11)° in (I), (II) and (III), respectively. The central part of the molecule (–C—N—N=C–) is almost linear with C—N—N—C torsion angles of 179.1 (2), −169.5 (3) and 178.5 (2)° for (I), (II) and (III), respectively. In all the three crystals, the molecules form inversion dimers with R₂²(8) ring motifs, which are further augmented by C—H⋯O interactions.

Keywords: crystal structure; N-acylhydrazone; dihedral angle; inversion dimers; C—H⋯O interaction.

CCDC references: 1433593; 1433594; 1433606

1. Chemical context

The properties of molecules in solution and the solid state are strongly influenced by weak non-covalent interactions. Weak molecular interactions are investigated routinely in the areas of molecular recognition (Brouwer et al., 1999 ), self-assembly (Seth et al., 2011 ), supramolecular chemistry and general host–guest interactions (Kim et al., 2000 ; Sharma et al., 2009 ). Analysis of intermolecular interactions and estimation of their energies provide greater insights into molecular conformations (Cao et al., 2020 ; Jablonski, 2020 ). The nature and site of substituents influence the extent of polarization of electron distribution in covalent compounds. In our previous work (Purandara et al., 2017a ,b ), the presence of the electron-withdrawing nitro group on the benzene ring was found to decrease the electronic density, rendering aromatic C—H protons acidic, whereas a methyl substituent did not activate aromatic protons for participation in intermolecular C—H⋯O interactions. In a continuation of these efforts to study the effect of substituents on weak molecular interactions, we report herein the synthesis, characterization and crystal structures of three isomeric molecules.

2. Structural commentary

All three isomers (I)–(III) (Figs. 1–3 ) crystallize in the centrosymmetric triclinic system with space group P $[\overline{1}]$ and with one molecule in the asymmetric unit and two molecules in the unit cell. The conformation of both the sulfonamide and hydrazine N—H bonds are syn with respect to the C=O bonds in all the three compounds. Similarly, the imine C—H bond in the amide part is also syn with respect to the amide N—H bond. All four such bonds in the central part are syn to each other. The C8—O3 and C9—N3 bond lengths of 1.224 (3)–1.236 (3) Å and 1.271 (3)–1.275 (4) Å, respectively, are in the ranges of normal C=O and C=N bond lengths, indicating double-bond character and thus confirming the keto tautomeric form and are comparable with those in related N-acylhydrazone structures (Purandara et al., 2017). The delocalization of π-electron density over the C9/N3/N2/C8/O3 fragment is indicated by the shortening of the C8—N2 [1.337 (3)–1.342 (4) Å] distances compared to the normal C—N single bond length of 1.40 Å (Allen et al., 1987 ). The sulfonamide bonds are synclinal, anticlinal and antiperiplanar with the S1—N1—C7—C8 torsion angle being 83.6 (3), −107.2 (3) and 171.09 (18)°, in compounds (I), (II) and (III), respectively. The major twist in the molecule occurs about the S1—N1 bond [C1—S1—N1—C7 = 97.6 (2) (I), 65.6 (2) (II) and −80.1 (2)° (III)], giving the molecule an approximate overall L-shape. All the molecules adopt an E configuration around the C9=N3 bond as indicated by the N2—N3—C9—C10 torsion angles of 179.6 (2), 179.1 (3) and 180.0 (2)° for (I), (II) and (III), respectively. The central fragment of the molecule, (C9/N3/N2/C8/O3) is nearly coplanar with the phenyl ring (C10–C15), as indicated by the dihedral angles between their best planes of 4.2 (2) in (I), 11.9 (3) in (II) and 7.0 (3)° in (III). The dihedral angles between the two phenyl rings, C1–C6 and C10–·C15 are 11.1 (1), 53.8 (1) and 72.4 (1)° for (I), (II) and (III), respectively, indicating non-planarity of the three molecules. An intramolecular hydrogen bond, N1—H1N⋯O3, is observed in (II) and (III), generating an S(5) ring motif.

Figure 1
Molecular structure of (I)

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

Figure 2
The molecular structure of (II)

, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level. The intramolecular hydrogen bond is depicted by a dashed line.

Figure 3
The molecular structure of (III)

, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level. The intramolecular hydrogen bond is depicted by a dashed line.

3. Supramolecular features

In the crystal of (I), the carbonyl oxygen (O3) shows bifurcated hydrogen bonding. In one part, the molecules are linked by a pair of N2—H2N⋯O3 hydrogen bonds involving the amide NH atom, forming inversion dimers with an $[R_{2}^{2}]$ (8) ring motif. In the other part, the molecules are linked by a pair of N1—H1N⋯O3 hydrogen bonds with the sulfonamide NH atom of another molecule, forming rings with an $[R_{2}^{2}]$ (10) graph-set motif, leading to a layered structure with the mean planes of the layers inclined to the ab plane by 16.1 (5)° (Table 1, Fig. 4). In the crystal of (II), the molecules are linked by two pairs of N—H⋯O hydrogen bonds (N1—H1N⋯O2 and N2—H2N⋯O3), involving both the sulfonyl and carbonyl O atoms with both sulfonamide and amide N—H bonds (N1—H1N and N2—H2N), forming inversion dimers with $[R_{2}^{2}]$ (8) ring motifs. These interactions are further strengthened by C—H⋯O hydrogen bonds. Thus, three-center N1—H1N/C6—H6⋯O1 hydrogen bonds result in molecular chains containing the R₂¹(7) ring motif (Fig. 5). These rings are extended along the principal diagonal of the ac plane via C7—H7⋯O2 hydrogen bonds, forming $[R_{2}^{2}]$ (10) ring motifs, and by C15—H15⋯O2 interactions. In addition, the crystal structure is reinforced by C—H⋯π(ring) interactions (Fig. 5), details of which are summarized in Table 2. In the crystal of (III), the molecules are also linked by two pairs of N—H⋯O hydrogen bonds (N1—H1N⋯O2 and N2—H2N⋯O3), forming inversion dimers with $[R_{2}^{2}]$ (8) ring motifs. These dimers are connected by intermolecular C15—H15⋯O1 interactions, forming ribbons two molecules wide and extending along the principal diagonal of the ab plane (Table 3, Fig. 6). The presence of the chlorine atom on the phenyl ring (C10–C15) of (I)–(III) makes the aromatic protons acidic, resulting in the formation of C—H⋯O hydrogen bonds with the sulfonyl O atom.

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3ⁱ	0.84 (2)	2.01 (2)	2.823 (3)	162 (3)
N2—H2N⋯O3ⁱⁱ	0.85 (2)	2.06 (2)	2.897 (2)	167 (2)
C12—H12⋯O2ⁱⁱⁱ	0.93	2.53	3.439 (3)	166
Symmetry codes: (i) ; (ii) ; (iii) x+1, y+1, z.

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

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.84 (2)	2.23 (2)	3.041 (3)	161 (3)
N2—H2N⋯O3ⁱⁱ	0.86 (2)	1.97 (2)	2.828 (3)	171 (3)
C6—H6⋯O1ⁱ	0.93	2.53	3.422 (4)	161
C7—H7B⋯O2ⁱⁱⁱ	0.97	2.47	3.434 (4)	172
C15—H15⋯O2^iv	0.93	2.58	3.474 (4)	162
C14—H14⋯Cg^v	0.93	2.84	3.675 (5)	150
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.82 (2)	2.25 (2)	3.032 (3)	162 (3)
N1—H1N⋯O3	0.82 (2)	2.23 (3)	2.609 (3)	109 (2)
N2—H2N⋯O3ⁱⁱ	0.86 (2)	1.98 (2)	2.829 (3)	170 (3)
C15—H15⋯O1ⁱⁱⁱ	0.93	2.45	3.330 (3)	157
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 4
A view of a portion of one chain of inversion dimers in (I)

connected by N—H⋯O hydrogen bonds (dashed lines) and extending along the a-axis direction.

Figure 5
A partial packing diagram for (II)

with N—H⋯O and C—H⋯O hydrogen bonds depicted, respectively, by light-blue and black dashed lines. The C—H⋯π(ring) interactions are depicted by violet dashed lines.

Figure 6
A portion of one chain in (III)

viewed along the a-axis direction with hydrogen bonds depicted as in Fig. 5

4. Database survey

Comparison of structures (I)–(III) with those of related N-acylhydrazone derivatives (Purandara et al., 2017, 2018 ) shows that the site of substitution of an electron-withdrawing group on the aromatic ring plays a major role in stabilizing the crystal packing by linking the molecules through various weak interactions.

5. Synthesis and crystallization

General procedure for the synthesis of N-(4-chlorobenzenesulfonyl) glycine hydrazone derivatives (I)–(III)

A mixture of N-(4-chlorobenzenesulfonyl) glycinyl hydrazide (0.01 mol) and the appropriate chlorobenzaldehyde (0.01 mol) in anhydrous methanol (30 mL) and two drops of glacial acetic acid was refluxed for 8 h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol. The purity of the compound was checked by TLC and characterized by its IR and NMR spectra. Single crystals suitable for the X-ray diffraction study were grown from DMF solution by slow evaporation of the solvent.

Compound (I): Prism-like yellow single crystals; m.p. 506–507 K; IR (KBr, γ, cm⁻¹): 3190.3 (N—H), 1672.3 (C=O), 1608.6 (C=N), 1334.7 (S=O, asym) and 1159.2 cm⁻¹ (S=O, sym); ¹H NMR (400 MHz, DMSO-d₆, δ ppm): 3.64, 4.14 (d, 2H), 7.36–7.45 (m, 2H, Ar-H), 7.47–7.50 (m, 1H, Ar-H), 7.61–7.67 (m, 2H, Ar-H), 7.83–7.95 (m, 3H, Ar-H), 8.12 (s, 1H), 8.13 (s, 1H), 11.64 (s, 1H). ¹³C NMR (400 MHz, DMSO-d₆, δ ppm): 43.27, 44.49, 126.82, 127.53, 128.54, 129.11, 129.82, 131.25, 133.02, 137.24, 139.19, 139.81, 143.18, 164.23, 169.08.

Compound (II): Prism-like colourless single crystals; m.p. 469–470 K; IR (KBr, γ, cm⁻¹): 3265.5 (N—-H), 1687.7 (C=O), 1589.3 (C=N), 1340.5 (S=O, asym) and 1168.9 cm⁻¹ (S=O, sym); ¹H NMR (400 MHz, DMSO-d₆, δ ppm): 3.64, 4.11 (2d, 2H), 7.39–7.44 (m, 2H, Ar-H), 7.54–7.65 (m, 4H, Ar-H), 7.84–7.87 (m, 2H, Ar-H), 7.91, 8.15 (2s, 1H), 8.01, 8.21 (2t, 1H), 11.51, 11.54 (2s, 1H). ¹³C NMR (400 MHz, DMSO-d₆, δ ppm): 43.24, 44.42, 125.52, 126.14, 128.44, 128.91, 129.47, 130.31, 133.70, 136.05, 137.34, 139.36, 142.18, 145.60, 164.17, 168.96.

Compound (III): Rod-like colourless single crystals; m.p. 473–475 K; IR (KBr, γ, cm⁻¹): 3246.2 (N—H), 1685.8 (C=O), 1591.3 (C=N), 1344.4 (S=O, asym) and 1168.9 cm⁻¹ (S=O, sym); ¹H NMR (400 MHz, DMSO-d₆, δ ppm): 3.62, 4.11 (2d, 2H), 7.48–7.51 (m, 2H, Ar-H), 7.63–7.71 (m, 4H, Ar-H), 7.81–7.85 (m, 2H, Ar-H), 7.92, 8.14 (2s, 1H), 8.01 (t, 1H), 11.49, 11.53 (2s, 1H). ¹³C NMR (400 MHz, DMSO-d₆, δ ppm): 43.21, 128.50, 128.70, 128.86, 129.14, 132.87, 134.34, 137.20, 139.50, 142.53, 145.80, 164.07, 168.96.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 4. H atoms bonded to C were positioned with idealized geometry using a riding model with C—H = 0.93 Å (aromatic) and 0.97 Å (methylene). The amino H atoms were refined with the N—H distances restrained to 0.86 (2) Å. All H atoms were assigned isotropic displacement parameters 1.2 × U_eq of the parent atom. In compound (III), the $[\overline{1}]$ $[\overline{1}]$ 3 reflection had a poor agreement with its calculated value and was omitted from the final refinement.

Table 4
Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₁₅H₁₃Cl₂N₃O₃S	C₁₅H₁₃Cl₂N₃O₃S	C₁₅H₁₃Cl₂N₃O₃S
M_r	386.24	386.24	386.24
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	293	293	293
a, b, c (Å)	7.7426 (7), 10.429 (1), 10.934 (1)	9.491 (1), 9.976 (1), 10.446 (1)	6.7234 (9), 10.281 (1), 13.611 (2)
α, β, γ (°)	85.51 (1), 76.92 (1), 81.04 (1)	67.22 (1), 66.80 (1), 86.32 (1)	74.98 (1), 87.11 (1), 75.34 (1)
V (Å³)	848.64 (14)	833.59 (17)	879.0 (2)
Z	2	2	2
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.52	0.53	0.51
Crystal size (mm)	0.48 × 0.36 × 0.10	0.36 × 0.14 × 0.08	0.46 × 0.42 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur with Sapphire CCD	Oxford Diffraction Xcalibur with Sapphire CCD	Oxford Diffraction Xcalibur 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 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ )	Multi-scan (CrysAlis RED, Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ )
T_min, T_max	0.787, 0.949	0.831, 0.959	0.801, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections	5699, 3417, 2359	5759, 3354, 2688	5737, 3598, 2600
R_int	0.018	0.018	0.019
(sin θ/λ)_max (Å⁻¹)	0.625	0.625	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.102, 1.04	0.054, 0.108, 1.22	0.048, 0.120, 1.04
No. of reflections	3417	3354	3598
No. of parameters	223	223	223
No. of restraints	2	2	2
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	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.29	0.27, −0.39	0.33, −0.30
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXS2013/1 (Sheldrick, 2008 ), SHELXL2014/6 (Sheldrick, 2015 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC references: 1433593; 1433594; 1433606

Crystal structure: contains datablocks I, II, III, global. DOI: https://doi.org/10.1107/S2056989021006885/mw2177sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006885/mw2177Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989021006885/mw2177IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989021006885/mw2177IIIsup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021006885/mw2177Isup5.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989021006885/mw2177IIsup6.cml

checkCIF report

Computing details top

For all 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: SHELXS2013/1 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: SHELXL2014/6 (Sheldrick, 2015).

(E)-4-Chloro-N-{2-[2-(2-chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide (I) top

Crystal data top

C₁₅H₁₃Cl₂N₃O₃S	Z = 2
M_r = 386.24	F(000) = 396
Triclinic, P1	D_x = 1.512 Mg m⁻³
a = 7.7426 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.429 (1) Å	Cell parameters from 2012 reflections
c = 10.934 (1) Å	θ = 2.8–27.8°
α = 85.51 (1)°	µ = 0.52 mm⁻¹
β = 76.92 (1)°	T = 293 K
γ = 81.04 (1)°	Prism, yellow
V = 848.64 (14) Å³	0.48 × 0.36 × 0.10 mm

Data collection top

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	2359 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.018
Rotation method data acquisition using ω scans.	θ_max = 26.4°, θ_min = 2.8°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −9→9
T_min = 0.787, T_max = 0.949	k = −10→13
5699 measured reflections	l = −13→13
3417 independent reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0321P)² + 0.3938P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3417 reflections	Δρ_max = 0.24 e Å⁻³
223 parameters	Δρ_min = −0.29 e Å⁻³

Special details top

Experimental. CrysAlis RED (Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.1746 (3)	0.6076 (2)	0.8440 (2)	0.0487 (6)
C2	0.1897 (4)	0.7192 (3)	0.8985 (3)	0.0687 (8)
H2	0.3023	0.7399	0.8985	0.082*
C3	0.0378 (5)	0.7997 (3)	0.9529 (3)	0.0852 (11)
H3	0.0473	0.8756	0.9888	0.102*
C4	−0.1270 (5)	0.7675 (4)	0.9540 (3)	0.0801 (11)
C5	−0.1448 (4)	0.6551 (4)	0.9042 (3)	0.0763 (10)
H5	−0.2579	0.6330	0.9083	0.092*
C6	0.0079 (4)	0.5742 (3)	0.8473 (3)	0.0595 (7)
H6	−0.0022	0.4982	0.8118	0.071*
C7	0.5597 (3)	0.6727 (2)	0.6046 (3)	0.0521 (7)
H7A	0.5504	0.7198	0.6794	0.063*
H7B	0.5376	0.7357	0.5378	0.063*
C8	0.7483 (3)	0.6002 (2)	0.5670 (2)	0.0386 (5)
C9	0.9738 (3)	0.8484 (2)	0.6184 (2)	0.0405 (6)
H9	1.0910	0.8074	0.5943	0.049*
C10	0.9368 (3)	0.9816 (2)	0.6622 (2)	0.0381 (5)
C11	1.0705 (3)	1.0515 (2)	0.6753 (2)	0.0430 (6)
C12	1.0322 (4)	1.1777 (2)	0.7149 (3)	0.0545 (7)
H12	1.1239	1.2217	0.7240	0.065*
C13	0.8572 (4)	1.2374 (3)	0.7408 (3)	0.0616 (8)
H13	0.8306	1.3224	0.7669	0.074*
C14	0.7213 (4)	1.1717 (3)	0.7281 (3)	0.0614 (8)
H14	0.6032	1.2124	0.7452	0.074*
C15	0.7610 (3)	1.0457 (2)	0.6902 (3)	0.0516 (7)
H15	0.6681	1.0019	0.6831	0.062*
N1	0.4241 (3)	0.5872 (2)	0.6292 (2)	0.0526 (6)
H1N	0.383 (3)	0.569 (3)	0.569 (2)	0.063*
N2	0.8820 (3)	0.66560 (18)	0.5716 (2)	0.0420 (5)
H2N	0.990 (2)	0.631 (2)	0.544 (2)	0.050*
N3	0.8430 (2)	0.79018 (18)	0.61392 (19)	0.0411 (5)
O1	0.5090 (3)	0.5131 (2)	0.8282 (2)	0.0751 (6)
O2	0.3180 (3)	0.39150 (17)	0.7388 (2)	0.0732 (6)
O3	0.7778 (2)	0.48784 (15)	0.53116 (17)	0.0483 (4)
Cl1	−0.31736 (16)	0.87209 (13)	1.01893 (11)	0.1407 (6)
Cl2	1.29502 (9)	0.98193 (7)	0.63926 (8)	0.0690 (3)
S1	0.36939 (9)	0.51159 (7)	0.76264 (7)	0.0529 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0476 (15)	0.0454 (15)	0.0497 (16)	−0.0040 (12)	−0.0062 (12)	0.0005 (12)
C2	0.0685 (19)	0.062 (2)	0.071 (2)	−0.0128 (16)	−0.0002 (16)	−0.0158 (17)
C3	0.105 (3)	0.062 (2)	0.071 (2)	0.004 (2)	0.011 (2)	−0.0138 (18)
C4	0.079 (2)	0.077 (2)	0.056 (2)	0.026 (2)	0.0122 (17)	0.0121 (18)
C5	0.0474 (17)	0.105 (3)	0.064 (2)	0.0034 (18)	−0.0040 (15)	0.019 (2)
C6	0.0504 (16)	0.0663 (19)	0.0597 (18)	−0.0082 (14)	−0.0104 (14)	0.0043 (15)
C7	0.0380 (13)	0.0404 (15)	0.0759 (19)	−0.0050 (11)	−0.0040 (13)	−0.0151 (13)
C8	0.0374 (12)	0.0324 (13)	0.0450 (14)	−0.0041 (10)	−0.0076 (11)	−0.0029 (11)
C9	0.0360 (12)	0.0333 (13)	0.0513 (15)	−0.0035 (10)	−0.0079 (11)	−0.0032 (11)
C10	0.0392 (12)	0.0289 (12)	0.0452 (14)	−0.0035 (10)	−0.0077 (11)	−0.0018 (11)
C11	0.0402 (13)	0.0371 (13)	0.0525 (16)	−0.0063 (10)	−0.0113 (11)	−0.0021 (12)
C12	0.0604 (17)	0.0397 (15)	0.0690 (19)	−0.0164 (13)	−0.0179 (14)	−0.0070 (14)
C13	0.075 (2)	0.0322 (14)	0.077 (2)	−0.0029 (14)	−0.0153 (16)	−0.0124 (14)
C14	0.0508 (16)	0.0414 (16)	0.086 (2)	0.0051 (13)	−0.0068 (15)	−0.0124 (15)
C15	0.0414 (14)	0.0391 (14)	0.0737 (19)	−0.0058 (11)	−0.0096 (13)	−0.0072 (13)
N1	0.0412 (12)	0.0617 (15)	0.0576 (15)	−0.0181 (11)	−0.0039 (10)	−0.0171 (12)
N2	0.0340 (10)	0.0305 (11)	0.0600 (14)	−0.0033 (9)	−0.0053 (10)	−0.0093 (10)
N3	0.0405 (11)	0.0298 (10)	0.0529 (13)	−0.0052 (9)	−0.0086 (9)	−0.0057 (9)
O1	0.0577 (12)	0.0822 (15)	0.0895 (16)	0.0029 (11)	−0.0313 (11)	−0.0095 (13)
O2	0.0696 (13)	0.0384 (11)	0.1099 (18)	−0.0079 (10)	−0.0132 (12)	−0.0116 (11)
O3	0.0393 (9)	0.0342 (9)	0.0725 (12)	−0.0030 (7)	−0.0115 (8)	−0.0153 (9)
Cl1	0.1177 (9)	0.1400 (10)	0.1047 (8)	0.0695 (8)	0.0332 (7)	0.0151 (7)
Cl2	0.0391 (4)	0.0617 (5)	0.1092 (7)	−0.0066 (3)	−0.0181 (4)	−0.0182 (4)
S1	0.0428 (4)	0.0433 (4)	0.0722 (5)	−0.0029 (3)	−0.0113 (3)	−0.0093 (3)

Geometric parameters (Å, º) top

C1—C2	1.380 (4)	C9—C10	1.469 (3)
C1—C6	1.381 (4)	C9—H9	0.9300
C1—S1	1.769 (3)	C10—C11	1.394 (3)
C2—C3	1.377 (4)	C10—C15	1.398 (3)
C2—H2	0.9300	C11—C12	1.385 (3)
C3—C4	1.367 (5)	C11—Cl2	1.745 (2)
C3—H3	0.9300	C12—C13	1.376 (4)
C4—C5	1.369 (5)	C12—H12	0.9300
C4—Cl1	1.736 (3)	C13—C14	1.379 (4)
C5—C6	1.391 (4)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.377 (3)
C6—H6	0.9300	C14—H14	0.9300
C7—N1	1.447 (3)	C15—H15	0.9300
C7—C8	1.518 (3)	N1—S1	1.604 (2)
C7—H7A	0.9700	N1—H1N	0.841 (16)
C7—H7B	0.9700	N2—N3	1.379 (3)
C8—O3	1.236 (3)	N2—H2N	0.852 (16)
C8—N2	1.337 (3)	O1—S1	1.4283 (19)
C9—N3	1.271 (3)	O2—S1	1.4312 (19)

C2—C1—C6	120.3 (3)	C11—C10—C9	123.2 (2)
C2—C1—S1	119.8 (2)	C15—C10—C9	120.2 (2)
C6—C1—S1	119.8 (2)	C12—C11—C10	122.1 (2)
C3—C2—C1	119.9 (3)	C12—C11—Cl2	117.61 (19)
C3—C2—H2	120.1	C10—C11—Cl2	120.32 (18)
C1—C2—H2	120.1	C13—C12—C11	119.4 (2)
C4—C3—C2	119.6 (3)	C13—C12—H12	120.3
C4—C3—H3	120.2	C11—C12—H12	120.3
C2—C3—H3	120.2	C12—C13—C14	120.2 (2)
C3—C4—C5	121.4 (3)	C12—C13—H13	119.9
C3—C4—Cl1	119.1 (3)	C14—C13—H13	119.9
C5—C4—Cl1	119.5 (3)	C15—C14—C13	119.7 (3)
C4—C5—C6	119.4 (3)	C15—C14—H14	120.1
C4—C5—H5	120.3	C13—C14—H14	120.1
C6—C5—H5	120.3	C14—C15—C10	121.9 (2)
C1—C6—C5	119.4 (3)	C14—C15—H15	119.0
C1—C6—H6	120.3	C10—C15—H15	119.0
C5—C6—H6	120.3	C7—N1—S1	122.21 (19)
N1—C7—C8	112.8 (2)	C7—N1—H1N	119 (2)
N1—C7—H7A	109.0	S1—N1—H1N	119 (2)
C8—C7—H7A	109.0	C8—N2—N3	119.52 (19)
N1—C7—H7B	109.0	C8—N2—H2N	119.0 (17)
C8—C7—H7B	109.0	N3—N2—H2N	121.4 (17)
H7A—C7—H7B	107.8	C9—N3—N2	117.61 (19)
O3—C8—N2	121.5 (2)	O1—S1—O2	120.84 (13)
O3—C8—C7	122.1 (2)	O1—S1—N1	107.43 (13)
N2—C8—C7	116.5 (2)	O2—S1—N1	107.08 (12)
N3—C9—C10	119.0 (2)	O1—S1—C1	107.99 (13)
N3—C9—H9	120.5	O2—S1—C1	107.31 (12)
C10—C9—H9	120.5	N1—S1—C1	105.16 (12)
C11—C10—C15	116.6 (2)

C6—C1—C2—C3	−2.1 (4)	C11—C12—C13—C14	0.5 (4)
S1—C1—C2—C3	174.7 (2)	C12—C13—C14—C15	0.4 (5)
C1—C2—C3—C4	0.9 (5)	C13—C14—C15—C10	−0.8 (4)
C2—C3—C4—C5	1.3 (5)	C11—C10—C15—C14	0.4 (4)
C2—C3—C4—Cl1	−178.2 (2)	C9—C10—C15—C14	−178.1 (3)
C3—C4—C5—C6	−2.3 (5)	C8—C7—N1—S1	83.6 (3)
Cl1—C4—C5—C6	177.2 (2)	O3—C8—N2—N3	−179.0 (2)
C2—C1—C6—C5	1.1 (4)	C7—C8—N2—N3	2.6 (3)
S1—C1—C6—C5	−175.7 (2)	C10—C9—N3—N2	179.6 (2)
C4—C5—C6—C1	1.1 (4)	C8—N2—N3—C9	179.1 (2)
N1—C7—C8—O3	17.0 (4)	C7—N1—S1—O1	−17.3 (2)
N1—C7—C8—N2	−164.6 (2)	C7—N1—S1—O2	−148.5 (2)
N3—C9—C10—C11	177.3 (2)	C7—N1—S1—C1	97.6 (2)
N3—C9—C10—C15	−4.3 (4)	C2—C1—S1—O1	36.9 (3)
C15—C10—C11—C12	0.5 (4)	C6—C1—S1—O1	−146.3 (2)
C9—C10—C11—C12	179.0 (2)	C2—C1—S1—O2	168.7 (2)
C15—C10—C11—Cl2	−178.54 (19)	C6—C1—S1—O2	−14.6 (3)
C9—C10—C11—Cl2	0.0 (3)	C2—C1—S1—N1	−77.6 (2)
C10—C11—C12—C13	−0.9 (4)	C6—C1—S1—N1	99.2 (2)
Cl2—C11—C12—C13	178.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3ⁱ	0.84 (2)	2.01 (2)	2.823 (3)	162 (3)
N2—H2N···O3ⁱⁱ	0.85 (2)	2.06 (2)	2.897 (2)	167 (2)
C12—H12···O2ⁱⁱⁱ	0.93	2.53	3.439 (3)	166

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

(E)-4-Chloro-N-{2-[2-(3-chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide (II) top

Crystal data top

C₁₅H₁₃Cl₂N₃O₃S	Z = 2
M_r = 386.24	F(000) = 396
Triclinic, P1	D_x = 1.539 Mg m⁻³
a = 9.491 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.976 (1) Å	Cell parameters from 2850 reflections
c = 10.446 (1) Å	θ = 2.6–27.9°
α = 67.22 (1)°	µ = 0.53 mm⁻¹
β = 66.80 (1)°	T = 293 K
γ = 86.32 (1)°	Prism, colourless
V = 833.59 (17) Å³	0.36 × 0.14 × 0.08 mm

Data collection top

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	2688 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.018
Rotation method data acquisition using ω scans.	θ_max = 26.4°, θ_min = 2.6°
Absorption correction: multi-scan (CrysAlis RED, Oxford Diffraction, 2009)	h = −11→11
T_min = 0.831, T_max = 0.959	k = −12→12
5759 measured reflections	l = −13→12
3354 independent 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)] = 0.054	Hydrogen site location: mixed
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.22	w = 1/[σ²(F_o²) + (0.0148P)² + 1.1114P] where P = (F_o² + 2F_c²)/3
3354 reflections	(Δ/σ)_max = 0.002
223 parameters	Δρ_max = 0.27 e Å⁻³
2 restraints	Δρ_min = −0.39 e Å⁻³

Special details top

Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2009 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) 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
C1	0.2520 (3)	−0.1930 (3)	1.0295 (3)	0.0312 (6)
C2	0.1178 (3)	−0.2828 (3)	1.0900 (4)	0.0408 (7)
H2	0.0241	−0.2549	1.1415	0.049*
C3	0.1226 (4)	−0.4145 (4)	1.0739 (4)	0.0458 (8)
H3	0.0329	−0.4769	1.1166	0.055*
C4	0.2616 (4)	−0.4519 (3)	0.9939 (4)	0.0392 (7)
C5	0.3966 (4)	−0.3626 (3)	0.9327 (4)	0.0393 (7)
H5	0.4898	−0.3896	0.8789	0.047*
C6	0.3924 (3)	−0.2326 (3)	0.9519 (3)	0.0356 (7)
H6	0.4828	−0.1724	0.9131	0.043*
C7	0.2808 (3)	0.1427 (3)	0.7715 (3)	0.0356 (7)
H7A	0.2814	0.2480	0.7273	0.043*
H7B	0.1751	0.0995	0.8162	0.043*
C8	0.3771 (3)	0.0903 (3)	0.6490 (3)	0.0351 (7)
C9	0.1510 (4)	0.1675 (4)	0.4412 (3)	0.0414 (7)
H9	0.2108	0.1262	0.3740	0.050*
C10	0.0084 (4)	0.2250 (3)	0.4311 (3)	0.0400 (7)
C11	−0.0769 (4)	0.3041 (4)	0.5152 (4)	0.0469 (8)
H11	−0.0426	0.3245	0.5783	0.056*
C12	−0.2121 (4)	0.3515 (4)	0.5037 (4)	0.0540 (9)
C13	−0.2654 (4)	0.3247 (4)	0.4096 (5)	0.0600 (10)
H13	−0.3566	0.3589	0.4022	0.072*
C14	−0.1815 (5)	0.2467 (4)	0.3273 (5)	0.0603 (10)
H14	−0.2165	0.2274	0.2640	0.072*
C15	−0.0459 (4)	0.1966 (4)	0.3371 (4)	0.0497 (8)
H15	0.0097	0.1435	0.2808	0.060*
Cl1	0.26935 (11)	−0.61454 (10)	0.96808 (12)	0.0584 (3)
Cl2	−0.32203 (15)	0.44557 (16)	0.61290 (17)	0.0976 (5)
N1	0.3402 (3)	0.1031 (3)	0.8891 (3)	0.0318 (5)
H1N	0.436 (2)	0.101 (3)	0.860 (3)	0.038*
N2	0.3309 (3)	0.1124 (3)	0.5371 (3)	0.0436 (7)
H2N	0.378 (4)	0.072 (4)	0.474 (3)	0.052*
N3	0.1952 (3)	0.1727 (3)	0.5398 (3)	0.0394 (6)
O1	0.3340 (2)	−0.0350 (2)	1.1413 (2)	0.0411 (5)
O2	0.0898 (2)	0.0034 (2)	1.1055 (2)	0.0408 (5)
O3	0.4936 (2)	0.0311 (3)	0.6515 (2)	0.0475 (6)
S1	0.24739 (8)	−0.02589 (8)	1.05320 (8)	0.03071 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0333 (15)	0.0300 (15)	0.0385 (16)	0.0073 (12)	−0.0189 (13)	−0.0176 (13)
C2	0.0280 (16)	0.0415 (18)	0.057 (2)	0.0072 (13)	−0.0145 (15)	−0.0268 (16)
C3	0.0347 (17)	0.0386 (18)	0.069 (2)	0.0006 (14)	−0.0209 (17)	−0.0261 (17)
C4	0.0461 (19)	0.0299 (16)	0.0530 (19)	0.0096 (14)	−0.0279 (16)	−0.0204 (15)
C5	0.0347 (17)	0.0377 (17)	0.0496 (19)	0.0124 (13)	−0.0173 (15)	−0.0224 (15)
C6	0.0291 (15)	0.0343 (16)	0.0469 (18)	0.0061 (12)	−0.0159 (14)	−0.0192 (14)
C7	0.0354 (16)	0.0374 (17)	0.0375 (16)	0.0116 (13)	−0.0156 (14)	−0.0185 (14)
C8	0.0341 (16)	0.0371 (17)	0.0339 (16)	0.0086 (13)	−0.0129 (13)	−0.0153 (14)
C9	0.0435 (18)	0.050 (2)	0.0326 (16)	0.0112 (15)	−0.0145 (14)	−0.0195 (15)
C10	0.0422 (18)	0.0414 (18)	0.0329 (16)	0.0052 (14)	−0.0150 (14)	−0.0113 (14)
C11	0.047 (2)	0.054 (2)	0.0451 (19)	0.0126 (16)	−0.0246 (16)	−0.0199 (17)
C12	0.048 (2)	0.052 (2)	0.052 (2)	0.0109 (17)	−0.0181 (18)	−0.0131 (18)
C13	0.044 (2)	0.060 (2)	0.067 (3)	0.0048 (18)	−0.031 (2)	−0.006 (2)
C14	0.065 (3)	0.060 (2)	0.062 (2)	−0.004 (2)	−0.042 (2)	−0.011 (2)
C15	0.062 (2)	0.047 (2)	0.0440 (19)	0.0028 (17)	−0.0269 (18)	−0.0156 (16)
Cl1	0.0641 (6)	0.0405 (5)	0.0897 (7)	0.0132 (4)	−0.0367 (5)	−0.0401 (5)
Cl2	0.0847 (9)	0.1137 (11)	0.1072 (10)	0.0590 (8)	−0.0404 (8)	−0.0618 (9)
N1	0.0274 (12)	0.0354 (13)	0.0368 (14)	0.0033 (11)	−0.0109 (11)	−0.0205 (11)
N2	0.0416 (16)	0.0597 (18)	0.0408 (15)	0.0224 (13)	−0.0198 (13)	−0.0303 (14)
N3	0.0378 (14)	0.0457 (16)	0.0368 (14)	0.0134 (12)	−0.0165 (12)	−0.0183 (12)
O1	0.0400 (12)	0.0535 (14)	0.0406 (12)	0.0020 (10)	−0.0200 (10)	−0.0249 (11)
O2	0.0309 (11)	0.0474 (13)	0.0512 (13)	0.0071 (9)	−0.0115 (10)	−0.0320 (11)
O3	0.0404 (13)	0.0727 (16)	0.0418 (13)	0.0248 (12)	−0.0208 (11)	−0.0336 (12)
S1	0.0279 (4)	0.0352 (4)	0.0363 (4)	0.0050 (3)	−0.0127 (3)	−0.0219 (3)

Geometric parameters (Å, º) top

C1—C2	1.377 (4)	C9—C10	1.462 (4)
C1—C6	1.385 (4)	C9—H9	0.9300
C1—S1	1.773 (3)	C10—C15	1.394 (4)
C2—C3	1.384 (4)	C10—C11	1.394 (4)
C2—H2	0.9300	C11—C12	1.372 (5)
C3—C4	1.374 (4)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.381 (5)
C4—C5	1.380 (4)	C12—Cl2	1.743 (4)
C4—Cl1	1.737 (3)	C13—C14	1.370 (6)
C5—C6	1.382 (4)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.378 (5)
C6—H6	0.9300	C14—H14	0.9300
C7—N1	1.457 (4)	C15—H15	0.9300
C7—C8	1.510 (4)	N1—S1	1.618 (3)
C7—H7A	0.9700	N1—H1N	0.841 (17)
C7—H7B	0.9700	N2—N3	1.380 (3)
C8—O3	1.224 (3)	N2—H2N	0.863 (18)
C8—N2	1.342 (4)	O1—S1	1.433 (2)
C9—N3	1.275 (4)	O2—S1	1.430 (2)

C2—C1—C6	120.8 (3)	C15—C10—C9	118.8 (3)
C2—C1—S1	120.2 (2)	C11—C10—C9	122.2 (3)
C6—C1—S1	119.0 (2)	C12—C11—C10	119.3 (3)
C1—C2—C3	119.9 (3)	C12—C11—H11	120.4
C1—C2—H2	120.0	C10—C11—H11	120.4
C3—C2—H2	120.0	C11—C12—C13	121.9 (4)
C4—C3—C2	119.1 (3)	C11—C12—Cl2	119.4 (3)
C4—C3—H3	120.4	C13—C12—Cl2	118.7 (3)
C2—C3—H3	120.4	C14—C13—C12	118.7 (3)
C3—C4—C5	121.4 (3)	C14—C13—H13	120.6
C3—C4—Cl1	119.8 (2)	C12—C13—H13	120.6
C5—C4—Cl1	118.8 (2)	C13—C14—C15	120.9 (4)
C4—C5—C6	119.5 (3)	C13—C14—H14	119.6
C4—C5—H5	120.3	C15—C14—H14	119.6
C6—C5—H5	120.3	C14—C15—C10	120.3 (4)
C5—C6—C1	119.3 (3)	C14—C15—H15	119.9
C5—C6—H6	120.4	C10—C15—H15	119.9
C1—C6—H6	120.4	C7—N1—S1	119.9 (2)
N1—C7—C8	111.0 (2)	C7—N1—H1N	116 (2)
N1—C7—H7A	109.4	S1—N1—H1N	112 (2)
C8—C7—H7A	109.4	C8—N2—N3	120.8 (2)
N1—C7—H7B	109.4	C8—N2—H2N	117 (2)
C8—C7—H7B	109.4	N3—N2—H2N	121 (2)
H7A—C7—H7B	108.0	C9—N3—N2	115.1 (3)
O3—C8—N2	121.4 (3)	O2—S1—O1	119.53 (13)
O3—C8—C7	121.1 (3)	O2—S1—N1	107.80 (13)
N2—C8—C7	117.5 (3)	O1—S1—N1	105.65 (13)
N3—C9—C10	121.6 (3)	O2—S1—C1	107.23 (13)
N3—C9—H9	119.2	O1—S1—C1	107.84 (13)
C10—C9—H9	119.2	N1—S1—C1	108.40 (13)
C15—C10—C11	119.0 (3)

C6—C1—C2—C3	0.2 (5)	Cl2—C12—C13—C14	−178.0 (3)
S1—C1—C2—C3	−178.6 (3)	C12—C13—C14—C15	−0.4 (6)
C1—C2—C3—C4	−1.7 (5)	C13—C14—C15—C10	−0.2 (6)
C2—C3—C4—C5	1.5 (5)	C11—C10—C15—C14	0.3 (5)
C2—C3—C4—Cl1	−178.3 (3)	C9—C10—C15—C14	178.7 (3)
C3—C4—C5—C6	0.0 (5)	C8—C7—N1—S1	−107.2 (3)
Cl1—C4—C5—C6	179.8 (2)	O3—C8—N2—N3	176.8 (3)
C4—C5—C6—C1	−1.4 (5)	C7—C8—N2—N3	−3.8 (5)
C2—C1—C6—C5	1.3 (5)	C10—C9—N3—N2	179.1 (3)
S1—C1—C6—C5	−179.8 (2)	C8—N2—N3—C9	−169.5 (3)
N1—C7—C8—O3	−4.1 (4)	C7—N1—S1—O2	−50.2 (2)
N1—C7—C8—N2	176.5 (3)	C7—N1—S1—O1	−179.0 (2)
N3—C9—C10—C15	−170.4 (3)	C7—N1—S1—C1	65.6 (2)
N3—C9—C10—C11	8.0 (5)	C2—C1—S1—O2	−13.7 (3)
C15—C10—C11—C12	0.2 (5)	C6—C1—S1—O2	167.4 (2)
C9—C10—C11—C12	−178.2 (3)	C2—C1—S1—O1	116.3 (3)
C10—C11—C12—C13	−0.8 (6)	C6—C1—S1—O1	−62.6 (3)
C10—C11—C12—Cl2	178.1 (3)	C2—C1—S1—N1	−129.8 (3)
C11—C12—C13—C14	0.9 (6)	C6—C1—S1—N1	51.3 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (2)	2.23 (2)	3.041 (3)	161 (3)
N2—H2N···O3ⁱⁱ	0.86 (2)	1.97 (2)	2.828 (3)	171 (3)
C6—H6···O1ⁱ	0.93	2.53	3.422 (4)	161
C7—H7B···O2ⁱⁱⁱ	0.97	2.47	3.434 (4)	172
C15—H15···O2^iv	0.93	2.58	3.474 (4)	162
C14—H14···Cg^v	0.93	2.84	3.675 (5)	150

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

(E)-4-Chloro-N-{2-[2-(4-chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide (III) top

Crystal data top

C₁₅H₁₃Cl₂N₃O₃S	Z = 2
M_r = 386.24	F(000) = 396
Triclinic, P1	D_x = 1.459 Mg m⁻³
a = 6.7234 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.281 (1) Å	Cell parameters from 1746 reflections
c = 13.611 (2) Å	θ = 2.9–27.9°
α = 74.98 (1)°	µ = 0.51 mm⁻¹
β = 87.11 (1)°	T = 293 K
γ = 75.34 (1)°	Rod, colourless
V = 879.0 (2) Å³	0.46 × 0.42 × 0.20 mm

Data collection top

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	2600 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Rotation method data acquisition using ω scans.	θ_max = 26.4°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis RED, Oxford Diffraction, 2009)	h = −8→8
T_min = 0.801, T_max = 0.906	k = −12→12
5737 measured reflections	l = −13→16
3598 independent 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)] = 0.048	Hydrogen site location: mixed
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0407P)² + 0.5495P] where P = (F_o² + 2F_c²)/3
3598 reflections	(Δ/σ)_max < 0.001
223 parameters	Δρ_max = 0.33 e Å⁻³
2 restraints	Δρ_min = −0.30 e Å⁻³

Special details top

Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2009 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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

	x	y	z	U_iso*/U_eq
Cl1	−0.75370 (19)	0.81534 (16)	0.50474 (9)	0.1284 (5)
Cl2	1.20248 (15)	0.42711 (14)	0.39838 (7)	0.1119 (4)
S1	−0.27969 (10)	1.01993 (7)	0.11321 (5)	0.04891 (19)
O1	−0.1031 (3)	1.05461 (19)	0.14290 (15)	0.0609 (5)
O2	−0.4241 (3)	1.12132 (19)	0.04119 (15)	0.0628 (5)
O3	−0.1441 (3)	0.66440 (19)	0.00307 (15)	0.0601 (5)
N1	−0.1982 (3)	0.8899 (2)	0.06592 (17)	0.0518 (5)
H1N	−0.285 (4)	0.868 (3)	0.038 (2)	0.062*
N2	0.1718 (3)	0.5636 (2)	0.07085 (17)	0.0529 (5)
H2N	0.179 (4)	0.490 (2)	0.050 (2)	0.063*
N3	0.3257 (3)	0.5661 (2)	0.13326 (15)	0.0490 (5)
C1	−0.4154 (4)	0.9674 (3)	0.2247 (2)	0.0487 (6)
C2	−0.3286 (5)	0.9436 (4)	0.3189 (2)	0.0707 (8)
H2	−0.199533	0.958848	0.324412	0.085*
C3	−0.4330 (5)	0.8971 (4)	0.4049 (2)	0.0840 (10)
H3	−0.374571	0.880441	0.468907	0.101*
C4	−0.6231 (5)	0.8754 (4)	0.3961 (3)	0.0767 (9)
C5	−0.7090 (5)	0.8990 (4)	0.3026 (3)	0.0909 (11)
H5	−0.837854	0.883342	0.297257	0.109*
C6	−0.6066 (5)	0.9456 (4)	0.2165 (2)	0.0773 (9)
H6	−0.666116	0.962570	0.152735	0.093*
C7	−0.0149 (4)	0.7821 (3)	0.10526 (19)	0.0471 (6)
H7A	−0.022691	0.748572	0.178490	0.057*
H7B	0.105960	0.818535	0.089975	0.057*
C8	−0.0016 (4)	0.6659 (3)	0.05555 (18)	0.0466 (6)
C9	0.4825 (4)	0.4633 (3)	0.1450 (2)	0.0521 (6)
H9	0.486624	0.393537	0.112435	0.063*
C10	0.6568 (4)	0.4535 (3)	0.20951 (19)	0.0480 (6)
C11	0.6490 (4)	0.5479 (3)	0.2675 (2)	0.0606 (7)
H11	0.530130	0.618121	0.266545	0.073*
C12	0.8152 (5)	0.5385 (3)	0.3263 (2)	0.0682 (8)
H12	0.808568	0.601525	0.365387	0.082*
C13	0.9906 (4)	0.4354 (4)	0.3268 (2)	0.0648 (8)
C14	1.0018 (4)	0.3406 (3)	0.2719 (2)	0.0692 (8)
H14	1.120998	0.270324	0.273761	0.083*
C15	0.8334 (4)	0.3497 (3)	0.2128 (2)	0.0596 (7)
H15	0.840415	0.284985	0.175185	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1225 (9)	0.1721 (12)	0.0862 (7)	−0.0563 (9)	0.0375 (7)	−0.0130 (8)
Cl2	0.0737 (6)	0.1848 (12)	0.0779 (6)	−0.0439 (7)	−0.0247 (5)	−0.0185 (7)
S1	0.0460 (3)	0.0478 (4)	0.0565 (4)	−0.0123 (3)	−0.0034 (3)	−0.0181 (3)
O1	0.0516 (10)	0.0629 (12)	0.0799 (13)	−0.0225 (9)	−0.0016 (9)	−0.0303 (10)
O2	0.0616 (12)	0.0518 (11)	0.0695 (13)	−0.0097 (9)	−0.0111 (9)	−0.0076 (9)
O3	0.0520 (10)	0.0608 (11)	0.0742 (13)	−0.0063 (9)	−0.0165 (9)	−0.0329 (10)
N1	0.0454 (12)	0.0572 (13)	0.0591 (14)	−0.0092 (10)	−0.0070 (10)	−0.0277 (11)
N2	0.0500 (12)	0.0529 (13)	0.0604 (14)	−0.0070 (10)	−0.0122 (10)	−0.0258 (11)
N3	0.0473 (12)	0.0524 (13)	0.0495 (12)	−0.0115 (10)	−0.0077 (9)	−0.0161 (10)
C1	0.0438 (13)	0.0487 (14)	0.0566 (15)	−0.0078 (11)	−0.0012 (11)	−0.0215 (12)
C2	0.0552 (17)	0.103 (3)	0.0606 (18)	−0.0226 (16)	−0.0005 (14)	−0.0302 (18)
C3	0.076 (2)	0.119 (3)	0.0541 (19)	−0.019 (2)	−0.0019 (16)	−0.0212 (19)
C4	0.072 (2)	0.090 (2)	0.066 (2)	−0.0230 (18)	0.0196 (16)	−0.0157 (18)
C5	0.061 (2)	0.139 (3)	0.080 (2)	−0.044 (2)	0.0082 (17)	−0.023 (2)
C6	0.0577 (18)	0.118 (3)	0.0617 (19)	−0.0349 (18)	−0.0015 (15)	−0.0199 (19)
C7	0.0455 (13)	0.0516 (14)	0.0475 (14)	−0.0129 (11)	−0.0030 (11)	−0.0169 (12)
C8	0.0462 (13)	0.0511 (14)	0.0455 (14)	−0.0142 (11)	−0.0029 (11)	−0.0145 (11)
C9	0.0533 (15)	0.0527 (15)	0.0548 (15)	−0.0139 (12)	−0.0041 (12)	−0.0200 (12)
C10	0.0469 (13)	0.0483 (14)	0.0483 (14)	−0.0115 (11)	−0.0032 (11)	−0.0110 (11)
C11	0.0581 (16)	0.0583 (17)	0.0647 (18)	−0.0068 (13)	−0.0100 (13)	−0.0200 (14)
C12	0.075 (2)	0.077 (2)	0.0606 (18)	−0.0238 (17)	−0.0107 (15)	−0.0244 (16)
C13	0.0557 (17)	0.089 (2)	0.0481 (16)	−0.0261 (16)	−0.0076 (13)	−0.0056 (15)
C14	0.0499 (16)	0.075 (2)	0.0688 (19)	−0.0025 (14)	−0.0039 (14)	−0.0055 (16)
C15	0.0584 (16)	0.0557 (16)	0.0644 (18)	−0.0101 (13)	−0.0019 (13)	−0.0183 (14)

Geometric parameters (Å, º) top

Cl1—C4	1.735 (3)	C4—C5	1.362 (5)
Cl2—C13	1.738 (3)	C5—C6	1.368 (4)
S1—O1	1.4275 (18)	C5—H5	0.9300
S1—O2	1.4297 (19)	C6—H6	0.9300
S1—N1	1.594 (2)	C7—C8	1.500 (3)
S1—C1	1.764 (3)	C7—H7A	0.9700
O3—C8	1.229 (3)	C7—H7B	0.9700
N1—C7	1.450 (3)	C9—C10	1.467 (3)
N1—H1N	0.818 (17)	C9—H9	0.9300
N2—C8	1.341 (3)	C10—C15	1.375 (4)
N2—N3	1.380 (3)	C10—C11	1.390 (4)
N2—H2N	0.861 (17)	C11—C12	1.377 (4)
N3—C9	1.273 (3)	C11—H11	0.9300
C1—C2	1.373 (4)	C12—C13	1.371 (4)
C1—C6	1.374 (4)	C12—H12	0.9300
C2—C3	1.375 (4)	C13—C14	1.360 (4)
C2—H2	0.9300	C14—C15	1.392 (4)
C3—C4	1.369 (5)	C14—H14	0.9300
C3—H3	0.9300	C15—H15	0.9300

O1—S1—O2	119.70 (12)	N1—C7—C8	107.76 (19)
O1—S1—N1	107.02 (11)	N1—C7—H7A	110.2
O2—S1—N1	106.60 (12)	C8—C7—H7A	110.2
O1—S1—C1	107.38 (12)	N1—C7—H7B	110.2
O2—S1—C1	107.41 (12)	C8—C7—H7B	110.2
N1—S1—C1	108.32 (12)	H7A—C7—H7B	108.5
C7—N1—S1	121.73 (16)	O3—C8—N2	121.3 (2)
C7—N1—H1N	117 (2)	O3—C8—C7	121.3 (2)
S1—N1—H1N	116 (2)	N2—C8—C7	117.4 (2)
C8—N2—N3	119.7 (2)	N3—C9—C10	120.7 (2)
C8—N2—H2N	119.9 (19)	N3—C9—H9	119.7
N3—N2—H2N	119.6 (19)	C10—C9—H9	119.7
C9—N3—N2	115.3 (2)	C15—C10—C11	118.6 (2)
C2—C1—C6	120.1 (3)	C15—C10—C9	119.8 (2)
C2—C1—S1	120.5 (2)	C11—C10—C9	121.6 (2)
C6—C1—S1	119.3 (2)	C12—C11—C10	120.8 (3)
C1—C2—C3	119.8 (3)	C12—C11—H11	119.6
C1—C2—H2	120.1	C10—C11—H11	119.6
C3—C2—H2	120.1	C13—C12—C11	119.3 (3)
C4—C3—C2	119.7 (3)	C13—C12—H12	120.3
C4—C3—H3	120.1	C11—C12—H12	120.3
C2—C3—H3	120.1	C14—C13—C12	121.2 (3)
C5—C4—C3	120.4 (3)	C14—C13—Cl2	119.7 (3)
C5—C4—Cl1	119.9 (3)	C12—C13—Cl2	119.1 (2)
C3—C4—Cl1	119.7 (3)	C13—C14—C15	119.5 (3)
C4—C5—C6	120.3 (3)	C13—C14—H14	120.3
C4—C5—H5	119.8	C15—C14—H14	120.3
C6—C5—H5	119.8	C10—C15—C14	120.6 (3)
C5—C6—C1	119.7 (3)	C10—C15—H15	119.7
C5—C6—H6	120.2	C14—C15—H15	119.7
C1—C6—H6	120.2

O1—S1—N1—C7	35.4 (2)	S1—C1—C6—C5	177.1 (3)
O2—S1—N1—C7	164.6 (2)	S1—N1—C7—C8	171.09 (18)
C1—S1—N1—C7	−80.1 (2)	N3—N2—C8—O3	−177.6 (2)
C8—N2—N3—C9	178.5 (2)	N3—N2—C8—C7	2.2 (4)
O1—S1—C1—C2	−10.8 (3)	N1—C7—C8—O3	−9.0 (3)
O2—S1—C1—C2	−140.8 (2)	N1—C7—C8—N2	171.1 (2)
N1—S1—C1—C2	104.5 (2)	N2—N3—C9—C10	180.0 (2)
O1—S1—C1—C6	171.5 (2)	N3—C9—C10—C15	−173.1 (3)
O2—S1—C1—C6	41.5 (3)	N3—C9—C10—C11	6.4 (4)
N1—S1—C1—C6	−73.3 (3)	C15—C10—C11—C12	0.6 (4)
C6—C1—C2—C3	0.4 (5)	C9—C10—C11—C12	−179.0 (3)
S1—C1—C2—C3	−177.3 (3)	C10—C11—C12—C13	0.5 (5)
C1—C2—C3—C4	−0.2 (5)	C11—C12—C13—C14	−1.4 (5)
C2—C3—C4—C5	0.3 (6)	C11—C12—C13—Cl2	178.2 (2)
C2—C3—C4—Cl1	179.5 (3)	C12—C13—C14—C15	1.1 (5)
C3—C4—C5—C6	−0.5 (6)	Cl2—C13—C14—C15	−178.5 (2)
Cl1—C4—C5—C6	−179.7 (3)	C11—C10—C15—C14	−0.9 (4)
C4—C5—C6—C1	0.6 (6)	C9—C10—C15—C14	178.7 (3)
C2—C1—C6—C5	−0.6 (5)	C13—C14—C15—C10	0.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.82 (2)	2.25 (2)	3.032 (3)	162 (3)
N1—H1N···O3	0.82 (2)	2.23 (3)	2.609 (3)	109 (2)
N2—H2N···O3ⁱⁱ	0.86 (2)	1.98 (2)	2.829 (3)	170 (3)
C15—H15···O1ⁱⁱⁱ	0.93	2.45	3.330 (3)	157

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

Acknowledgements

The authors thank the SAIF, Panjab University, for providing the NMR facility.

Funding information

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

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc., Perkin Trans. 2, pp. S1–19. Google Scholar
Brouwer, E. B., Enright, G. D., Ratcliffe, C. I., Facey, G. A. & Ripmeester, J. A. (1999). J. Phys. Chem. B, 103, 10604–10616. Web of Science CSD CrossRef CAS Google Scholar
Cao, Y., Yu, T., Lai, W., Liu, Y. & Wang, B. (2020). Energetic Materials Frontiers, 1, 95–102. CrossRef Google Scholar
Jabłoński, M. (2020). Molecules, 25, 5512–5548. Google Scholar
Kim, K. S., Tarakeshwar, P. & Lee, J. Y. (2000). Chem. Rev. 100, 4145–4186. Web of Science CrossRef PubMed CAS Google Scholar
Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Purandara, H., Foro, S. & Thimme Gowda, B. (2017a). Acta Cryst. E73, 1683–1686. Web of Science CSD CrossRef IUCr Journals Google Scholar
Purandara, H., Foro, S. & Thimme Gowda, B. (2017b). Acta Cryst. E73, 1946–1951. Web of Science CSD CrossRef IUCr Journals Google Scholar
Purandara, H., Foro, S. & Thimme Gowda, B. (2018). Acta Cryst. C74, 1553–1560. Web of Science CSD CrossRef IUCr Journals Google Scholar
Seth, S. K., Sarkar, D., Jana, A. D. & Kar, T. (2011). Cryst. Growth Des. 11, 4837–4849. Web of Science CSD CrossRef CAS Google Scholar
Sharma, P., Sharma, S., Chawla, M. & Mitra, A. (2009). J. Mol. Model. 15, 633–649. Web of Science CrossRef PubMed CAS 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
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar

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Volume 77| Part 8| August 2021| Pages 780-784

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