Triethyl­ammonium N′-(benzyl­sulfanylthio­carbonyl)-2-hydroxy­benzohydrazidate

Mamata Singh; Ajay K Srivastava; N K Singh; Anuraag Shrivastav; R K Sharma

doi:10.1107/S1600536807067037

. 2007 Dec 21;64(Pt 1):o339. doi: 10.1107/S1600536807067037

Triethylammonium N′-(benzylsulfanylthiocarbonyl)-2-hydroxybenzohydrazidate

Mamata Singh ^a,^*, Ajay K Srivastava ^a, N K Singh ^a, Anuraag Shrivastav ^b, R K Sharma ^b

PMCID: PMC2915380 PMID: 21200900

Abstract

In the title compound, C₆H₁₆N⁺·C₁₅H₁₃N₂O₂S₂ ⁻, the thione S atom is in a cis configuration with respect to the phenyl and benzene rings, while it adopts a trans configuration with respect to the carbonyl group. The dihedral angle between the benzene and phenyl rings is 78.81 (2)°. The molecular conformation is stabilized by intramolecular O—H⋯O and N—H⋯S hydrogen bonds, while intermolecular N—H⋯O, N—H⋯N and weak C—H⋯O interactions help to stabilize the crystal structure.

Related literature

For related literature, see: Scovill et al. (1982 ▶, 1984 ▶); West et al. (1989 ▶); Gou et al. (1990 ▶); Abu-Raquabah et al. (1992 ▶); Marchi et al. (1990 ▶); Ali & Livingston, (1974 ▶); Wu et al. (2000); Boga et al. (1990 ▶).

Experimental

Crystal data

C₆H₁₆N⁺·C₁₅H₁₃N₂O₂S₂ ⁻
M _r = 419.59
Orthorhombic,
a = 10.7109 (4) Å
b = 18.6807 (6) Å
c = 22.1814 (7) Å
V = 4438.2 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 173 (2) K
0.08 × 0.08 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
26195 measured reflections
3928 independent reflections
2542 reflections with I > 2σ(I)
R _int = 0.138

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.118
S = 1.05
3928 reflections
257 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807067037/lh2550sup1.cif

e-64-0o339-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067037/lh2550Isup2.hkl

e-64-0o339-Isup2.hkl^{(192.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.84	1.79	2.538 (3)	147
N1—H1A⋯S2	0.88	2.39	2.855 (3)	114
N3—H3A⋯O2	0.93	2.18	2.929 (3)	137
N3—H3A⋯N2	0.93	2.27	3.094 (4)	148
C9—H9A⋯S2	0.99	2.59	3.200 (3)	120
C21—H21A⋯O1ⁱ	0.98	2.56	3.377 (5)	141

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Professor W. Quail, Saskatchewan Structural Sciences Centre, Canada, for the X-ray diffraction facility.

supplementary crystallographic information

Comment

Dithiocarbazates and their derivatives have attracted much attention as they have potential applications as antitumor, antibacterial and antifungal agents (Scovill et al., 1982,1984, West & Pannell, 1989, Gou et al., 1990). Interest in these systems is also stimulated by their unusual physico-chemical (Abu-Raquabah et al.1992, Marchi et al., 1990) and chemotherapeutic properties (Ali & Livingston, 1974). Although N'-acyl hydrazine carbodithioates are structurally similar to the derivatives of dithiocarbazates, little data is available on their synthesis and characterization. As part of our ongoing investigation, we report here the synthesis and structure determination of the title compound (I) which was obtained from the reaction of salicylic acid hydrazide, CS₂ and benzyl chloride in the presence of triethylamine.

The molecular structure of (I), together with atom labeling scheme is shown in Fig 1. The Hydrazinic H atom on N1 is trans with respect to the carbonyl group and cis with respect to the thione S atom. The C7—N1 distance of 1.329 (4) Å is intermediate between 1.47 Å for a C—N single bond and 1.29 Å for a double bond (Boga et al., 1999). The N1—N2 distance of 1.396 (3) Å [single bond (N—N) = 1.45 Å and double bond (N=N) = 1.25 Å] and the O2—C7 distance of 1.257 (4) Å suggest extensive delocalization in this part of the molecule. In the crystal structure, there is a weak C—H···π interaction (Fig 2) [C5—H5···Cg = 140.65°, H5···Cg = 2.976 Å and C5···Cg = 3.759 Å, where Cg is the centroid of the phenyl ring]. The molecular conformation is stabilized by intramolecular O—H···O and N—H···S hydrogen bonds while intermolecular N—H···O, N—H···N and weak C—H···O interactions help stabilize the crystal structure.

Experimental

The title compound was synthesized by the reaction of CS₂ (1.99 g, 26.29 mmol) with a solution of salicylic acid hydrazide (4 g, 24.09 mmol) in CHCl₃ (15 ml) in the presence of triethylamine (2 ml, 24.09 mmol). Benzyl chloride (3.5 ml, 26.30 mmol) was added dropwise to the above clear solution, which was stirred continuously for 2 h at room temperature. The product was obtained on evaporation of the solvent at room temperature. Colorless single crystals of (I) (m.p., 418 K) suitable for X-ray analysis were obtained by slow evaporation of a chloroform solution over a period of 10 days. (Yield 58%). Elemental analysis: Anal. Calcd (%): C, 60.11; H, 6.97; N, 10.01; S, 15.28; Found (%) for C₂₁H₂₉N₃O₂S₂ (419.59): C,60.01; H, 6.87; N, 10.30; S, 15.06. Spectroscopic analysis: ¹H NMR (CDCl₃, TMS, δ, p.p.m.) 11.66, 12.38 (s, 2H, NH), 7.92–6.9 (m, 4H, benzene ring), 7.18 - 6.89 (m, 5H, phenyl), 4.48 (s, 1H, OH), 4.25 (s, 2H, CH₂), 2.49 (s, 6H, CH₂ of Et₃NH⁺), 1.15 (s, 9H, CH₃ of Et₃NH⁺).¹³C NMR (CDCl₃, TMS, δ, p.p.m.): 117.25 (C1), 158.94 (C2), 116.30 (C3),134.06 (C4), 118.99 (C5), 128.42 (C6), 165.85 (C7), 174.23 (C8), 35.66 (C9), 139.52 (C10),127.60 (C11,C15), 129.09 (C12,C14),126.38 (C13),45.77 (C16,C18, C20), 8.59 (C17, C19, C21).