N′-[Bis(benzyl­sulfan­yl)methyl­idene]-4-meth­oxy­benzohydrazide

Jerry P Jasinski; Ray J Butcher; S K Kushawaha; M K Bharty; N K Singh

doi:10.1107/S1600536810025389

. 2010 Jul 3;66(Pt 8):o1899. doi: 10.1107/S1600536810025389

N′-[Bis(benzylsulfanyl)methylidene]-4-methoxybenzohydrazide

Jerry P Jasinski ^a,^*, Ray J Butcher ^b, S K Kushawaha ^c, M K Bharty ^c, N K Singh ^c

PMCID: PMC3007250 PMID: 21588233

Abstract

In the title compound, C₂₃H₂₂N₂O₂S₂, the dihedral angles between the 4-methoxy-substituted phenyl ring and the other two phenyl rings are 84.4 (4) and 77.7 (1)°, respectively, while the dihedral angle between the two phenyl rings is 57.5 (2)°. The amino group is not involved in an N—H hydrogen bond. The crystal packing is established by intermolecular C—H⋯O packing interactions involving a relatively rare weak three-center hydrogen bond between the keto O atom and H atoms of the two nearby phenyl rings, which link the molecules into chains running along the a axis. Additional weak intermolecular hydrogen-bond interactions between the 4-methoxy O atom and one of the phenyl rings and provide added stability to the crystal packing.

Related literature

For radiopharmaceutical applications of dithiocarbazate derivatives, see: Boschi et al. (2003 ▶). For dithiocarbazate derivatives as anticancer and antimicrobial drugs, see: Bharti et al. (2000 ▶). For a related structure, see: Singh et al. (2007 ▶).

Experimental

Crystal data

C₂₃H₂₂N₂O₂S₂
M _r = 422.55
Triclinic,
a = 9.838 (2) Å
b = 9.845 (2) Å
c = 11.307 (2) Å
α = 70.25 (3)°
β = 90.00 (3)°
γ = 89.37 (3)°
V = 1030.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100 K
0.30 × 0.26 × 0.22 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.921, T _max = 0.941
12424 measured reflections
6210 independent reflections
5954 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.098
S = 1.06
6210 reflections
263 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810025389/bt5283sup1.cif

e-66-o1899-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025389/bt5283Isup2.hkl

e-66-o1899-Isup2.hkl^{(303.9KB, 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
C6A—H6AA⋯O1ⁱ	0.95	2.41	3.2516 (17)	147
C1B—H1BA⋯O1ⁱⁱ	0.99	2.35	3.2872 (16)	157
C3B—H3BA⋯O1ⁱⁱⁱ	0.95	2.67	3.5351 (18)	152
C6B—H6BA⋯O2^iv	0.95	2.47	3.4173 (17)	174

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

Acknowledgments

SKK thanks the DST, New Delhi, India, for the award of a Young Scientist Fellowship (No. SR/FTP/CS-35/2005). RJB acknowledges the Laboratory for the Structure of Matter at the Naval Research Laboratory for access to their diffractometers.

supplementary crystallographic information

Comment

Dithiocarbazate derivatives have been widely studied in radiopharmaceutical applications (Boschi et al., 2003) and have potential biological activity as anticancer and antimicrobial drugs (Bharti et al., 2000). This functional group is of particular interest and can coordinate to metals to give structures with different geometries and properties. As a part of our ongoing research on the dithio derivatives of acid hydrazides, we report here the crystal structure of the title compound, C₂₃H₂₂N₂O₂S₂, a new 4-methoxy benzoic acid bis benzyl sulfanyl methylene hydrazide with a relatively rare three-center donor hydrogen bond.

The sum of the angles around C1 (120.00 (8)°) and the S1A/C1/S1B bond angle of 117.52 (7)° indicated nearly planar sp² hybridized behavior (Fig. 1). The molecule can be divided into three distinct fragments with regard to their spatial orientation viz keto-amide, 4-methoxy benzene and bis benzyl sulfanyl methylene groups. Regarding the keto-amide group, all three rings including the 4-methoxy benzene, and two separate benzyl rings [A & B] have their mean planes twisted by 25,7(7)°, [B] 69.1 (6)° and [A] 76.5 (8)°, respectively. The dihedral angle between the 4-methoxy benzene group and two nearby benzyl groups is [B] 84.4 (4)° and [A] 77.7 (0)°, respectively. The mean plane between the two separate benzyl groups [A & B] is 57.5 (2)°. The torsion angles around the keto-amide linkage provides geometric support to these twist angles (C1/N1/N2/C2 = 154.32 (10)°; O1/C2/C3/C4 = 151.22 (11)°; N2/N1/C1/S1A = -173.64 (7)°; N/2/N/1/C1/S1B = 6.23 (13)°). The mean planes of the two sulfanyl groups are twisted nearly perpendicular to the dihedral planes of their adjacent benzyl rings with angles of [A] 70.6 (7)° and [B] 77.6 (4)° separating their groups to avoid steric hindrance. The N1 atom in the amide linkage possesses distorted tetrahedral geometry (C1/N1/N2 = 112.66 (10)°) while the N2 atom lies in a more planar fashion (N1/N2/C2/O1 = -1.25 (17)°). The C1—N1 and C2—N2 bond lengths (1.29253 (14)Å and 1.3574 (14) Å) lie between typical C—N and C═N values owing to the extensive delocalization of π electron density over the C2/N2/N1/C1 linkage.

A relatively rare weak three-center hydrogen bond configuration and additional weak C–H···O donor hydrogen bonds can be seen linking the molecules into chains along the (011) plane (Fig. 2). Additional hydrogen bonds between the 4-methoxy oxygen atom (O2) and one of the benzyl groups (C6B–H6BA···O2) help to stabilize crystal packing.

Experimental

The potassium salt of N'-(4-methoxy benzoyl) hydrazine carbodithioate was prepared by adding carbon disulfide (0.04 mol, 2.4 ml) to a solution of 4-methoxy benzoic acid hydrazide(0.02 mol, 3.32 g) and potassium hydroxide (0.02 mol, 1.12 g) in methanol (30 ml) then stirring the reaction mixture for 2 h. The solid separated was filtered off, washed with 10% (v/v) mixture of ethanol-ether and dried in vacuo. Yield 1.54 g, 55%, m.p. 518 K. The title compound was prepared by drop wise addition of benzyl chloride (0.02 mol, 2.53 g) to a suspension of potassium salt of N'-(4-methoxy benzoyl)hydrazine carbodithioate (0.01 mol, 2.80 g) in methanol (20 ml) and stirring the reaction mixture for a period of 5–6 h. The reaction mixture was filtered and the solution was evaporated almost to dryness. The solid was washed several times with carbon tetrachloride and then with chloroform and recrystallized from methanol. Transparent white shining crystals of (I) (m.p. 475 K), suitable for X-ray analysis were obtained by slow evaporation of the methanol solution over a period of 9–10 days (yield 2.53 g, 60%): Anal Calcd (%): C, 65.31; H, 5.20; N, 6.62; S, 15.17; Found(%) for C₂₃H₂₂N₂O₂S₂ (422.55): C, 65.52; H, 5.15; N, 6.75; S, 15.30.