N-(4-Nitro­benzyl­idene)-N'-phenyl­hydrazine

Molecules of the title compound (alternative name: p-nitro­benz­aldehyde phenyl­hydrazone), C₁₃H₁₁N₃O₂, adopt an E configuration about the azomethine C=N double bond. Molecules are approximately planar and the dihedral angle between the planes of the phenyl rings is 11.62 (9)°. Hydro­gen bonding links mol­ecules related by 4₂ screw axes to form helices with a pitch of 7.7186 (8) Å.

S1. Comment

Hydrazones are formed when hydrazines condense with aldehydes and ketones, e.g. by the condensation of aldehydes (or substituted aldehydes) with pheyl hydrazine at a pH of 4–5 (McMurry, 1999), and typically are crystalline compounds with sharp melting points. Hydrazones are frequently more suitable than oximes for this purpose, since the greater molecular weight of the hydrazones causes a lower solubility in most solvents,and they can therefore often be more easily isolated and recrystallized. Hydrazones have been widely studied as chelating ligants for the spectrophotometric and fluorimetric determination of trace metal ions (Katyal & Dutt, 1975; Galiano-Roth & Collum, 1988). Many of these compounds have found widespread application in medicine, technology and analytical chemistry (Kitaev, 1977).

Molecules of the title compound, (I), adopt an E configuration about the azomethine C═N double bond, with an N1—N2—C7—C8 torsion angle of 178.67 (11)°. The N1—N2 [1.348 (14) Å], O1—N3 [1.219 (15) Å] and O2—N3 bond lengths [1.219 (14) Å], which are consistent with those of 1.216 (8) and 1.214 (7) Å in the related compound 2-nitrobenzaldehyde methylhydrazone, indicate that these bonds correspond to double and single bonds. The dihedral angle between the planes of the phenyl rings is 11.62 (9)°, and the nitrophenyl and phenyl rings make dihedral angles with the central hydrazone bridge (N1/N2/C7) of 3.25 (11) and 9.47 (13)°, respectively. There is only slight asymmetry in the exocyclic angles at C11 [C12—C11—N3 = 119.68 (13)° and C10—C11—N3 = 118.40 (13)°], in contrast to the situation in 2-nitrobenzaldehyde phenylhydrazone (Tosi et al., 1988), where enhanced asymmetry is ascribed to steric contacts involving the 2-nitro group. The more pronounced asymmetry at C8 [C13—C8—C7 = 122.35 (12)° and C9—C8—C7 = 119.55 (12)°] is also seen in studies with a methoxy group on the phenyl ring (Shanmuga Sundara Raj et al., 1999, 2000; Tun˛c et al., 2003).

Intermolecular hydrogen bonding, between the H atom attached to the N atom of the hydrazone bridge (N1) and the O atom (O1) of a nitro group related by the 4₂ screw axis, link molecules into helices with a pitch of 7.7186 (8) Å running along the c axis (Fig. 2). The N—H···O and N···O distances are short compared with sum of the relevant van der Waals radii (Bondi,1964).

S2. Experimental

A solution of 4-nitrobenzaldehyde (3.02 g, 0.02 mol) in hot methanol (50 ml) was added dropwise to a solution of phenylhydrazine (2.16 g, 0.02 mol) in hot methanol (50 ml) at a pH of 5–6. The resulting red solid was filtered off, dried and recrystallized after refluxing in hot methanol for 3 h. The red crystals thus obtained were filtered off and dried in air.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXS97.

Figures

	Fig. 1. The molecular sructure and atomic labelling scheme of the title compound (ORTEP-3; Farrugia, 1997). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram showing the hydrogen bonding which links molecules related by 42 screw axes into helices.

(I)

Crystal data

C13H11N3O2	Dx = 1.355 Mg m^−3
Mr = 241.25	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/n	Cell parameters from 2629 reflections
Hall symbol: -P 4bc	θ = 1.7–27.2°
a = 17.5017 (17) Å	µ = 0.10 mm^−1
c = 7.7186 (8) Å	T = 293 K
V = 2364.3 (4) Å^3	Square prism, dark red
Z = 8	0.40 × 0.40 × 0.25 mm
F(000) = 1008

Data collection

Stoe IPDS2 diffractometer	2629 independent reflections
Radiation source: fine-focus sealed tube	1280 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 6.67 pixels mm^-1	θmax = 27.2°, θmin = 1.7°
rotation method scans	h = −22→22
Absorption correction: integration [Specify computer program used]	k = −22→22
Tmin = 0.963, Tmax = 0.977	l = −9→9
2636 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.070	w = 1/[σ^2(Fo^2) + (0.0254P)^2 + ] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
2629 reflections	Δρmax = 0.09 e Å^−3
164 parameters	Δρmin = −0.11 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.010 (2)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	−0.33210 (6)	0.57511 (7)	0.68510 (17)	0.1070 (4)
O2	−0.31395 (6)	0.68290 (7)	0.56216 (18)	0.1187 (5)
N1	0.08522 (6)	0.50860 (6)	0.13878 (14)	0.0694 (3)
N2	0.02088 (6)	0.54146 (6)	0.19933 (14)	0.0652 (3)
N3	−0.29504 (7)	0.61715 (8)	0.59140 (19)	0.0842 (4)
C1	0.13815 (7)	0.55098 (7)	0.04695 (18)	0.0658 (4)
C2	0.20855 (8)	0.51898 (9)	0.00835 (19)	0.0782 (4)
C3	0.26147 (9)	0.56013 (11)	−0.08280 (2)	0.0961 (5)
C4	0.24605 (11)	0.63237 (11)	−0.13760 (3)	0.1121 (7)
C5	0.17608 (11)	0.66349 (10)	−0.10090 (3)	0.1187 (8)
C6	0.12227 (9)	0.62350 (8)	−0.00900 (2)	0.0926 (5)
C7	−0.02552 (7)	0.49942 (8)	0.28568 (17)	0.0660 (4)
C8	−0.09519 (7)	0.53061 (7)	0.35850 (16)	0.0618 (3)
C9	−0.14244 (7)	0.48417 (8)	0.45634 (18)	0.0697 (4)
C10	−0.20768 (7)	0.51175 (8)	0.53237 (18)	0.0712 (4)
C11	−0.22577 (7)	0.58752 (8)	0.50909 (18)	0.0678 (4)
C12	−0.18095 (8)	0.63542 (8)	0.41120 (2)	0.0773 (4)
C13	−0.11606 (7)	0.60706 (8)	0.33716 (18)	0.0722 (4)
H1	0.0934	0.4609	0.1575	0.083*
H2	0.2198	0.4695	0.0444	0.094*
H3	0.3087	0.5384	−0.1078	0.115*
H4	0.2824	0.6602	−0.1989	0.145*
H5	0.1649	0.7126	−0.1391	0.154*
H6	0.0751	0.6456	0.0153	0.111*
H7	−0.0143	0.4480	0.3019	0.079*
H9	−0.1296	0.4330	0.4709	0.084*
H10	−0.2389	0.4800	0.5981	0.085*
H12	−0.1946	0.6863	0.3957	0.093*
H13	−0.0852	0.6392	0.2714	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.075 (7)	0.121 (9)	0.126 (1)	0.016 (8)	0.019 (7)	−0.006 (6)
O2	0.094 (8)	0.102 (9)	0.160 (1)	0.016 (8)	0.020 (8)	0.026 (7)
N1	0.074 (7)	0.064 (6)	0.070 (8)	−0.004 (6)	−0.001 (6)	0.008 (6)
N2	0.064 (7)	0.068 (7)	0.064 (8)	−0.006 (6)	−0.007 (6)	0.002 (6)
N3	0.063 (8)	0.092 (1)	0.097 (1)	0.000 (8)	−0.009 (7)	0.001 (7)
C1	0.066 (8)	0.065 (8)	0.067 (9)	−0.014 (7)	−0.006 (7)	−0.002 (7)
C2	0.074 (9)	0.081 (9)	0.080 (1)	−0.017 (8)	−0.006 (8)	0.008 (8)
C3	0.073 (1)	0.103 (1)	0.112 (1)	−0.037 (1)	0.009 (1)	−0.006 (9)
C4	0.106 (1)	0.086 (1)	0.171 (2)	−0.029 (1)	0.052 (1)	−0.027 (1)
C5	0.122 (2)	0.068 (1)	0.195 (2)	−0.001 (1)	0.062 (2)	−0.008 (1)
C6	0.085 (1)	0.063 (9)	0.113 (1)	−0.003 (9)	0.022 (1)	0.002 (7)
C7	0.072 (8)	0.063 (8)	0.063 (9)	−0.005 (7)	−0.010 (7)	0.000 (7)
C8	0.063 (8)	0.065 (8)	0.058 (8)	−0.003 (7)	−0.014 (7)	−0.005 (6)
C9	0.071 (9)	0.064 (8)	0.074 (1)	0.003 (7)	−0.010 (8)	−0.005 (7)
C10	0.067 (9)	0.074 (9)	0.072 (1)	0.007 (8)	−0.009 (7)	−0.013 (7)
C11	0.055 (7)	0.078 (9)	0.071 (9)	−0.001 (8)	−0.009 (7)	−0.001 (7)
C12	0.070 (9)	0.069 (9)	0.094 (1)	0.008 (8)	−0.004 (8)	0.002 (7)
C13	0.067 (8)	0.068 (8)	0.081 (1)	0.008 (8)	−0.002 (8)	−0.004 (7)

Geometric parameters (Å, º)

O1—N3	1.2188 (15)	C5—C6	1.371 (2)
O2—N3	1.2185 (14)	C5—H5	0.9300
N1—N2	1.3479 (14)	C6—H6	0.9300
N1—C1	1.3823 (16)	C7—C8	1.4494 (17)
N1—H1	0.8600	C7—H7	0.9300
N2—C7	1.2826 (15)	C8—C9	1.3837 (17)
N3—C11	1.4637 (17)	C8—C13	1.3967 (17)
C1—C6	1.3690 (19)	C9—C10	1.3714 (17)
C1—C2	1.3859 (18)	C9—H9	0.9300
C2—C3	1.368 (2)	C10—C11	1.3753 (18)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.360 (2)	C11—C12	1.3742 (17)
C3—H3	0.9300	C12—C13	1.3649 (17)
C4—C5	1.370 (2)	C12—H12	0.9300
C4—H4	0.9300	C13—H13	0.9300
N2—N1—C1	120.58 (11)	C1—C6—H6	120.1
N2—N1—H1	119.7	C5—C6—H6	120.1
C1—N1—H1	119.7	N2—C7—C8	121.21 (12)
C7—N2—N1	117.67 (11)	N2—C7—H7	119.4
O2—N3—O1	122.38 (14)	C8—C7—H7	119.4
O2—N3—C11	118.64 (14)	C9—C8—C13	118.09 (12)
O1—N3—C11	118.98 (13)	C9—C8—C7	119.55 (12)
C6—C1—N1	121.54 (12)	C13—C8—C7	122.35 (12)
C6—C1—C2	119.17 (14)	C10—C9—C8	121.62 (13)
N1—C1—C2	119.28 (13)	C10—C9—H9	119.2
C3—C2—C1	119.98 (15)	C8—C9—H9	119.2
C3—C2—H2	120.0	C9—C10—C11	118.37 (13)
C1—C2—H2	120.0	C9—C10—H10	120.8
C4—C3—C2	120.99 (16)	C11—C10—H10	120.8
C4—C3—H3	119.5	C12—C11—C10	121.91 (13)
C2—C3—H3	119.5	C12—C11—N3	119.68 (13)
C3—C4—C5	118.86 (17)	C10—C11—N3	118.40 (13)
C3—C4—H4	120.6	C13—C12—C11	118.91 (13)
C5—C4—H4	120.6	C13—C12—H12	120.5
C4—C5—C6	121.20 (17)	C11—C12—H12	120.5
C4—C5—H5	119.4	C12—C13—C8	121.09 (13)
C6—C5—H5	119.4	C12—C13—H13	119.5
C1—C6—C5	119.80 (15)	C8—C13—H13	119.5
C1—N1—N2—C7	−179.04 (11)	C13—C8—C9—C10	−0.62 (19)
N2—N1—C1—C6	−10.36 (19)	C7—C8—C9—C10	177.91 (12)
N2—N1—C1—C2	170.59 (11)	C8—C9—C10—C11	0.14 (19)
C6—C1—C2—C3	0.8 (2)	C9—C10—C11—C12	0.7 (2)
N1—C1—C2—C3	179.83 (13)	C9—C10—C11—N3	−179.49 (12)
C1—C2—C3—C4	−0.3 (3)	O2—N3—C11—C12	4.5 (2)
C2—C3—C4—C5	−0.4 (3)	O1—N3—C11—C12	−176.23 (14)
C3—C4—C5—C6	0.7 (3)	O2—N3—C11—C10	−175.35 (14)
N1—C1—C6—C5	−179.49 (15)	O1—N3—C11—C10	3.91 (19)
C2—C1—C6—C5	−0.4 (2)	C10—C11—C12—C13	−0.9 (2)
C4—C5—C6—C1	−0.3 (3)	N3—C11—C12—C13	179.20 (12)
N1—N2—C7—C8	178.67 (11)	C11—C12—C13—C8	0.4 (2)
N2—C7—C8—C9	−177.60 (12)	C9—C8—C13—C12	0.32 (19)
N2—C7—C8—C13	0.86 (19)	C7—C8—C13—C12	−178.16 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86	2.29	3.115 (2)	162

Symmetry code: (i) y−1/2, −x, z−1/2.