(E)-1-(4-Nitro­benzyl­idene)-2,2-diphenyl­hydrazine

Angel Mendoza; Ruth Meléndrez-Luevano; Blanca M Cabrera-Vivas; Claudia Acoltzi-X; Marcos Flores-Alamo

doi:10.1107/S1600536812043681

. 2012 Oct 31;68(Pt 11):o3238. doi: 10.1107/S1600536812043681

(E)-1-(4-Nitrobenzylidene)-2,2-diphenylhydrazine

Angel Mendoza ^a,^*, Ruth Meléndrez-Luevano ^b, Blanca M Cabrera-Vivas ^b, Claudia Acoltzi-X ^b, Marcos Flores-Alamo ^c

PMCID: PMC3515317 PMID: 23284537

Abstract

The asymmetric unit of the title compound, C₁₉H₁₅N₃O₂, contains two molecules, both of which show an E conformation of the imine bond. The dihedral angles between the phenyl rings in the phenylhydrazine groups are 86.09 (6) and 83.41 (5)° in the two molecules. The 4-nitrobenzene rings show torsion angles of 4.4 (2) and 10.9 (2)° from the two C=N—N planes. In the crystal, C—H⋯π interactions and C—H⋯O hydrogen bonds are observed growing along the a, b and c axes, resulting in a complex supramolecular array.

Related literature

For applications of hydrazones, see: Angell et al. (2006 ▶); Vicini et al. (2002 ▶); Rollas et al. (2002 ▶).

Experimental

Crystal data

C₁₉H₁₅N₃O₂
M _r = 317.34
Triclinic,
a = 10.8648 (6) Å
b = 11.1477 (6) Å
c = 16.2075 (7) Å
α = 72.084 (4)°
β = 89.037 (4)°
γ = 62.084 (6)°
V = 1631.47 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.6 × 0.36 × 0.29 mm

Data collection

Oxford Diffraction Xcalibur (Atlas, Gemini) diffractometer
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.963, T _max = 0.98
11850 measured reflections
6432 independent reflections
3566 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.100
S = 0.89
6432 reflections
434 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Click here for additional data file.^{(27.4KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812043681/bt6850sup1.cif

e-68-o3238-sup1.cif^{(27.4KB, cif)}

Click here for additional data file.^{(308.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043681/bt6850Isup2.hkl

e-68-o3238-Isup2.hkl^{(308.4KB, hkl)}

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

Supplementary material file. DOI: 10.1107/S1600536812043681/bt6850Isup3.cml

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

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

Cg1, Cg2 and Cg3 are the centroids of the C21–C26, C33–C38 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cg1ⁱ	0.93	2.92	3.4080 (18)	114
C29—H29⋯Cg2ⁱⁱ	0.93	2.80	3.6875 (18)	161
C7—H7⋯Cg2	0.93	2.83	3.4223 (16)	123
C30—H30⋯Cg3ⁱⁱⁱ	0.93	2.84	3.698 (2)	154
C6—H6⋯O2^iv	0.93	2.60	3.342 (3)	138

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

Acknowledgments

We are grateful for financial support (project No. CAVB-NAT11-I, VIEP-BUAP).

supplementary crystallographic information

Comment

Hydrazones have had diverse applications in pharmacology, microbiology and the industry; some of them are used in analytical tests, which serve to detect chemical and biological species (Angell, et al., 2006). Some hydrazones with functional groups like NO₂ and Cl, have been studied to have potential antimicrobial agents and were tested for their antibacterial and antifungal activities against (Vicini, et al., 2002 and Rollas et al., 2002). In the industry, hydrazones are used as plasticizing agents, polymerization initiators and antioxidants.

In the title compound C₁₉H₁₅N₃O₂, the ASU contains two molecules showing an E configuration on each of the C=N groups with diphenylhydrazine group opposite to p-nitrophenyl ring. The dihedral angle for phenyl rings C8—C13 and C14—C19 is 86.09 (6)° for molecule 1 and that between C27—C32 and C33—C38 rings is 83.41 (5)° for molecule 2. The dihedral angle for p-nitrophenyl rings and C=N—N planes are 10.89 (20) and 4.43 (23)° for molecule 1 and 2 respectively. The imine bond distances [N2—C1 1.2847 (18) Å and N5—C20 1.2774 (17) Å] are typical C=N bond. The crystal packing present four intermolecular interactions of the type C—H···π (table 1). Moreover, there is one intermolecular interaction of type hydrogen bond: C6—H6···O2, and an intramolecular interaction of type hydrogen bond, C15—H15···N2.

Experimental

Diphenylhydrazine was dissolved in ethanol (1.2 chemical equivalents), a chemical equivalent of aldehyde which was previously dissolved in the same solvent and it was added drop by drop stirring constantly. The reaction mixture was kept at room temperature and was monitored by TLC, and then vacuum filtered. The hydrazones were recrystallized by a continuous and controlled process until orange crystals with adequate size and purity were developed in order to obtain X-ray studies. Yield 90%. UV λ_max = 411.51 nm. FT IR (film): (cm^-1): 3031 ν(C—H), 1591, 1556 ν(C=N), 1508 ν(Ph—NO₂). ¹H NMR (400 MHz, (CD₃)₂CO: (d/p.p.m.): 8.20–8.18 (m, 2H), 7.88–7.86 (m, 2H), 7.51–7.47 (m, 4H), 7.29–7.22 (m, 7H). ¹³C NMR (400 MHz, (CD₃)₂CO): (d/p.p.m.): 143.02, 143.01, 142.80, 132.30, 130.03, 126.58, 125.35, 123.88, 122.43. MS—EI: m/z = 317 M⁺ C₁₉H₁₅N₃O₂.