Crystal structure of (E)-1-(2-nitro­benzyl­idene)-2,2-di­phenyl­hydrazine

Marcos Flores-Alamo; Ruth Meléndrez-Luévano; José A Ortiz Márquez; Estibaliz Sansinenea Royano; Blanca M Cabrera-Vivas

doi:10.1107/S1600536814016109

. 2014 Aug 1;70(Pt 9):o909–o910. doi: 10.1107/S1600536814016109

Crystal structure of (E)-1-(2-nitrobenzylidene)-2,2-diphenylhydrazine

Marcos Flores-Alamo ^a,^*, Ruth Meléndrez-Luévano ^b, José A Ortiz Márquez ^b, Estibaliz Sansinenea Royano ^b, Blanca M Cabrera-Vivas ^b

PMCID: PMC4186103 PMID: 25309247

Abstract

The title compound, C₁₉H₁₅N₃O₂, shows an E conformation of the imine bond. The dihedral angle between the planes of the phenyl rings in the diphenylhydrazine groups is 88.52 (4)°. The 2-nitrobenzene ring shows a torsion angle of 10.17 (8)° with the C=N—N plane. A short intramolecular C—H⋯O contact occurs. In the crystal, only van der Waals contacts occur between the molecules.

Keywords: crystal structure, hydrazine, hydrogen bonding

Related literature

For background to hydrazide–hydrazone derivatives and their various biological activities, see: Sztanke et al. (2007 ▶); Al-Macrosaur et al. (2007 ▶); Roma et al. (2000 ▶); Smalley et al. (2006 ▶). For a related structure, see: Mendoza et al. (2012 ▶).

Experimental

Crystal data

C₁₉H₁₅N₃O₂
M _r = 317.34
Monoclinic,
a = 11.8536 (5) Å
b = 12.4293 (3) Å
c = 11.9492 (5) Å
β = 118.584 (5)°
V = 1545.92 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 140 K
0.59 × 0.49 × 0.27 mm

Data collection

Agilent Xcalibur Atlas Gemini diffractometer
Absorption correction: analytical (CrysAlis RED; Agilent, 2012 ▶) T _min = 0.961, T _max = 0.977
12199 measured reflections
3757 independent reflections
3057 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.113
S = 1.03
3757 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis RED (Agilent, 2012 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global. DOI: 10.1107/S1600536814016109/hb7250sup1.cif

e-70-0o909-sup1.cif^{(23.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814016109/hb7250Isup2.hkl

e-70-0o909-Isup2.hkl^{(206.2KB, hkl)}

Click here for additional data file.^{(6.2KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814016109/hb7250Isup3.cml

Click here for additional data file.^{(1.8MB, tif)}

. DOI: 10.1107/S1600536814016109/hb7250fig1.tif

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as circles of arbitrary size.

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S1600536814016109/hb7250fig2.tif

The crystal packing in the title compound.

CCDC reference: 1013341

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O1	0.95	2.27	2.7822 (15)	113

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Acknowledgments

We are grateful for financial support from projects CAVB-NAT-14 G, VIEP, BUAP and MELR-NAT-14 G. MFA thanks Dr A. L. Maldonado-Hermenegildo for useful comments.

supplementary crystallographic information

S1. Comment

Hydrazides and hydrazones are present in many of the bioactive heterocyclic compounds that are of great interest because of their diverse biological and clinical applications, creating interest in researchers who have synthesized a variety of hydrazide-hydrazones derivatives and screened them for their various biological activities viz anticancer (Sztanke et al. 2007), anti-HIV (Al-Macrosaur et al. 2007), antimycobacterial, anti-inflammatory (Roma et al. 2000), antidiabetic, antimicrobial, as well antimalarial activities (Smalley et al. 2006). In the title compound C₁₉H₁₅N₃O₂, the discrete unit consist of one molecule showing an E configuration with respect to C=N for diphenylhydrazine group opposite to o-nitrophenyl ring (Fig. 1). The dihedral angle for the phenyl rings C1—C6 and C7—C12 is 88.52 (4)° very close to orthogonal form and this value is slightly higher than reported for positional isomer (E)-1-(4-nitrobenzylidene)-2,2-diphenylhydrazine (Mendoza et al. 2012). The dihedral angle for ortho-nitrophenyl ring and C=N—N plane is 10.17 (8) °, which evidences the coplanarity between these groups. The imine N2—C13, 1.2871 (15) Å bond distance is typical C=N bond. In the crystal array one intramolecular interaction C13—H13···O1 (2.27 Å) of type hydrogen bond is observed, and in the crystal packing intermolecular contacts of type van der Waals are observed growing along the a, b and c axes, resulting in a complex supramolecular array (Fig. 2).

S2. Experimental

228 mg (1.24 mmol) diphenylhydrazine were dissolved in ethanol and acetic acid (0.5 ml) was slowly added to this solution while stirring, 300 mg (1.24 mmol) of 2-nitrobenzaldehyde was added drop by drop into the above solution strongly stirring and the resulting mixture was kept at room temperature until it became orange transparent solution. After one and a half hours an orange solution precipitated. The reaction was monitored by TLC, aluminium Alugram Sil G/UV254. The mixture was separated with filtration in vacuo system and the precipitate was washed three times with cold methanol. Recrystallization was performed three times with ethanol, to obtain orange blocks (yield 91%, mp. 133–135°C). FT·IR (film): (cm^-1):3026 ν(C—H), 1577 ν(C=N), 1334,ν (NO2). ¹H NMR (400 MHz, (CD₃)₂CO: (d/ p.p.m., J/Hz):8.28 (dd,1H,C3), 7.91 (dd,1H,C5), 7.72 (m,1H,C4), 7.60 (s,1H,C=N),7.52(d, J = 1.44, 1H, C6),7.48 (m, 4H,C2') 7.25 (m,6H,C4', C2'). ¹³C NMR (400 MHz, (CD₃)₂CO): (d/ p.p.m.):143.16 (C2), 132.99 (C1'), 132.97 (C4), 130.41 (C=N), 130.13 (C6), 129.99 (C3'), 128.40 (C1), 127.72 (C3), 125.26 (C4'), 124.49 (C5), 122.41 (C2'). MS—EI: m/z 317.12.C₁₉H₁₅N₃O₂.