(2E)-2-Benzyl­idene-N-phenyl­hydrazinecarboxamide

S R Layana; M Sithambaresan; V L Siji; M R Sudarsanakumar; S Suma

doi:10.1107/S1600536814008344

. 2014 Apr 26;70(Pt 5):o591. doi: 10.1107/S1600536814008344

(2E)-2-Benzylidene-N-phenylhydrazinecarboxamide

S R Layana ^a, M Sithambaresan ^b,^*, V L Siji ^c, M R Sudarsanakumar ^a, S Suma ^d

PMCID: PMC4011198 PMID: 24860389

Abstract

The molecule of the title compound, C₁₄H₁₃N₃O, adopts an E conformation with respect to the azomethine C=N bond, and is roughly planar, with an r.m.s. deviation of the non-H atoms from the least-squares plane of 0.100 (2) Å and a dihedral angle between the terminal benzene rings of 5.74 (12)°. An intramolecular N—H⋯N hydrogen bond closes an S(6) ring. In the crystal, molecules are linked by the pairs of N—H⋯O hydrogen bonds into centrosymmetric dimers. Dimers related by translation along [010] form slanted stacks, the shortest C⋯C intermolecular distance within the stack being 3.283 (3) Å. Weak C—H⋯π interactions link the stacks into a three-dimensional structure.

Related literature

For the synthesis of related compounds, see: Siji et al. (2010 ▶). For biological applications of hydrazinecarboxamide and its derivatives, see: Rivadeneira et al. (2009 ▶); Shalini et al. (2009 ▶). For related structures, see: Annie et al. (2012 ▶); Aravindakshan et al. (2013 ▶).

Experimental

Crystal data

C₁₄H₁₃N₃O
M _r = 239.27
Monoclinic,
a = 13.6308 (14) Å
b = 5.4023 (5) Å
c = 17.5751 (19) Å
β = 93.065 (4)°
V = 1292.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.29 × 0.24 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.977, T _max = 0.983
9857 measured reflections
2302 independent reflections
1655 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.146
S = 1.04
2300 reflections
171 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814008344/yk2104sup1.cif

e-70-0o591-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008344/yk2104Isup2.hkl

e-70-0o591-Isup2.hkl^{(113.1KB, hkl)}

Click here for additional data file.^{(4.7KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814008344/yk2104Isup3.cml

CCDC reference: 997059

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

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

Cg1 is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3′⋯N1	0.88 (1)	2.20 (2)	2.634 (2)	110 (2)
N2—H2′⋯O1ⁱ	0.88 (1)	2.00 (1)	2.860 (2)	167 (2)
C3—H3⋯Cg1ⁱⁱ	0.93	2.99	3.800 (3)	146

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

Acknowledgments

We thank the Indian Institute for Science Education and Research (IISER), Thiruvananthapuram, for the diffraction measurements. LSR thanks the CSIR, New Delhi, for the award of a Junior Research Fellowship.

supplementary crystallographic information

1. Comment

Hydrazinecarboxamides with versatile structural features are good ligands for both the neutral and anionic complexes (Rivadeneira et al., 2009). The aryl hydrazinecarboxamides were found to be devoid of sedative hypnotic activity and exhibited anticonvulsant activity with less neurotoxicity (Shalini et al., 2009).

The title compound (Scheme 1, Fig. 1) crystallizes in the monoclinic space group P2/c. The molecule adopts an E configuration with respect to C7═N1 bond and the N3–C8–N2–N1 torsion angle of 4.3 (3)° reveals that N1 and N3 atoms are cis to each other with respect to C8—N2 bond. The central fragment N3–C8(O1)–N2–N1 is almost planar and forms diherdal angles with two benzene rings of 13.24 (11)° (C1—C6) and of 7.60 (12)° (C9—C14).

The C7—N1 (1.273 (2) Å) and C8—O1 (1.225 (2) Å) bond distances are very close to the reported bond lengths of azomethine and keto groups, respectively, in similar structures (Annie et al., 2012), confirming the azomethine bond formation and existence of semicarbazone in amido form. A five-membered ring is formed by N1/N2/C8/N3 and H3' through an intramolecular H-bonding interaction with a D···A distance of 2.634 Å. In the crystal, a centrosymmetric dimer (Aravindakshan et al., 2013) is formed by means of a classical intermolecular N—H···O hydrogen bond (Fig. 2) with a D···A distance of 2.860 (2) Å. A C—H···π interaction (Fig. 3) is present in the crystal between the hydrogen attached to the carbon C3 and the C9—C14 benzene ring with H···π distance of 2.99 Å, interconnects the adjacent centrosymmetric dimers to build a three-dimensional supramolecular architecture in the system. Fig. 4 shows the packing diagram of the title compound along b axis.

2. Experimental

The title compound was prepared by adapting a reported procedure (Siji et al., 2010). Hot methanolic solutions (25 ml) of equimolar amounts of benzaldehyde (0.106 g, 1 mmol) and N-phenylhydrazinecarboxamide (0.151 g, 1 mmol) were mixed and refluxed for 3 h after adding a few drops of dilute acetic acid. The resulting solution was cooled to room temperature. The colourless block shaped crystals were collected, washed with few drops of methanol and dried over P₄O₁₀in vacuo. Single crystals suitable for X-ray analysis were obtained by slow evaporation of solution in air for few days.

IR (KBr, υ in cm^-1): 3356, 2959, 1684, 1540, 1024. ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 9.51 (s, 1H), 8.13 (s, 1H), 7.85 (s, 1H), 7.09–7.58 (m, 5H), 7.09–7.67 (m, 10H). ¹³C NMR (400 MHz, CDCl₃, δ, p.p.m.): 153.61, 141.78, 137.84, 133.66, 130.02, 129.02, 128.79, 126.94, 123.54, 119.68.