N-(4-Nitro­benzo­yl)-N'-phenyl­hydrazine: a three-dimensional hydrogen-bonded framework

In the title compound (systematic name: N-anilino-4-nitro­benzamide), C₁₃H₁₁N₃O₃, the mol­ecules are linked into a complex three-dimensional framework structure by a combination of two-centre N-H...O and C-H...O hydrogen bonds and a three-centre N-H...(O,N) hydrogen bond.

S1. Comment

As part of our continuing investigation of the supramolecular structures of acylhydrazines and acylhydrazones, we report here the structure of the title compound, (I) (Fig. 1), whose supramolecular structure we compare with that of the related compound N-(3,5-dinitrobenzoyl)-N'-phenylhydrazine, (II) (Wardell et al., 2006).

The configuration at each of the atoms N1 and N2 of (I) is almost co-planar. The central C—C(═O)—N—N unit adopts an almost planar trans conformation, and the remainder of the molecular conformation can be defined in terms of just four further torsion angles (Table 1). The large C7—N1—N2—C21 torsion angle reflects the tendency of the lone-pair orbitals on N1 and N2 to be nearly orthogonal, in order to minimize the corresponding overlap and resonance integrals. The molecules have no internal symmetry in the solid state and are thus conformationally chiral. The achiral space group ensures that each crystal contains only a single enantiomeric form.

The molecules of compound (I) are linked into a complex three-dimensional framework structure by a combination of one two-centre N—H···O hydrogen bond, one rather asymmetric three-centre N—H···(O,N) hydrogen bond and two independent two-centre C—H···O hydrogen bonds (Table 2). The formation of the sheet is readily analysed in terms of simple sub-structures.

In the first sub-structure, amide atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor to amide atom O7 in the molecule at (-1 + x, y, z), so generating by translation a C(4) (Bernstein et al., 1995) chain running parallel to the [100] direction (Fig. 2). In addition, atoms N2 and C26 in the molecule at (x, y, z) both act as hydrogen-bond donors to atom O7 in the molecule at (-1/2 + x, 1/2 - y, 1 - z), so forming a C(5)C(7)[R¹₂(6)] chain of rings running parallel to the [100] direction and generated by the 2₁ screw axis along (x, 1/4, 1/2) (Fig. 3). Atom N2 at (x, y, z) also forms a rather long and probably fairly weak interaction with atom N2 at (-1/2 + x, 1/2 - y, 1 - z), so that N2 can be regarded as the donor in an asymmetric but almost planar three-centre N—H···(O,N) hydrogen bond. The combination of all these interactions generates a complex chain of rings running parallel to the [100] direction (Fig. 2).

The second sub-structure is built from a single C—H···O hydrogen bond. Aryl atom C3 in the molecule at (x, y, z) acts as hydrogen-bond donor to nitro atom O42 in the molecule at (-x, -1/2 + y, 3/2 - z), so forming a C(5) chain running parallel to the [010] direction and generated by the 2₁ screw axis along (0, y, 3/4) (Fig. 3).

In combination, the N—H···O and C—H···O hydrogen bonds, which individually generate two independent C(5) helical chains running parallel to [100] and [010], respectively, together generate a C²₂(16) chain running parallel to the [001] direction (Fig. 4). The combined action of chains parallel to [100], [010] and [001] (Figs. 2–4) suffices to generate a single three-dimensional framework.

In the related 3,5-dinitro compound, (II) (Wardell et al., 2006), the molecules are again conformationally chiral, with a C7—N1—N2—C21 torsion angle of 84.2 (2)°, but the centrosymmetric space group P2₁/n accommodates equal numbers of the two enantiomeric forms. The molecules are linked into sheets by a combination of three independent two-centre hydrogen bonds, one each of N—H···O(carbonyl), N—H···O(nitro) and C—H···O(carbonyl) types.

Related literature

For related literature, see: Bernstein et al. (1995); Kornet et al. (1986); Wang et al. (2005); Wardell et al. (2006).

S2. Experimental

A solution of 4-nitrobenzoyl chloride (2 mmol) and phenylhydrazine (4 mmol) in 1,2-dichloroethane (25 ml) was heated under reflux for 3 h. The reaction mixture was cooled and the solvent was removed under reduced pressure. The solid product was then recrystallized from ethanol to give the title compound, (I) [m.p. 476–478 K; literature values: 476–478 K (Kornet et al., 1986); 471–473 K (Wang et al., 2005)].

S3. Refinement

The space group P2₁2₁2₁ was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 Å and N—H = 0.88 Å, and with U_iso(H) = 1.2U_eq(C,N). In the absence of significant resonant scattering, it was not possible to determine the absolute configuration of the molecules in the crystal selected for data collection. However, this has no chemical significance, and the Friedel-equivalent reflections were merged prior to the final refinements.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A molecule of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A stereoview of part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded chain of rings running parallel to the [100] direction. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 3. Part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded C(5) chain running parallel to the [010] direction. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (-x, -1/2 + y, 3/2 - z) and (-x,-1/2 + y, 3/2 - z), respectively. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded C^22(16) chain running parallel to the [001] direction. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

N-anilino-4-nitrobenzamide

Crystal data

C13H11N3O3	F(000) = 536
Mr = 257.25	Dx = 1.421 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1477 reflections
a = 4.6982 (6) Å	θ = 3.1–27.6°
b = 9.9532 (13) Å	µ = 0.10 mm^−1
c = 25.719 (4) Å	T = 120 K
V = 1202.7 (3) Å^3	Plate, yellow
Z = 4	0.32 × 0.16 × 0.07 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	1477 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1314 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 9.091 pixels mm^-1	θmax = 27.6°, θmin = 3.1°
ϕ and ω scans	h = −5→6
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→12
Tmin = 0.975, Tmax = 0.993	l = −32→33
4443 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 1.1588P] where P = (Fo^2 + 2Fc^2)/3
1477 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

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

	x	y	z	Uiso*/Ueq
C1	0.5301 (8)	0.4619 (4)	0.62844 (12)	0.0233 (8)
C2	0.3233 (8)	0.4257 (4)	0.66448 (13)	0.0281 (8)
C3	0.2294 (9)	0.5166 (4)	0.70126 (13)	0.0326 (9)
C4	0.3444 (9)	0.6445 (4)	0.70033 (13)	0.0303 (9)
N4	0.2407 (9)	0.7426 (4)	0.73870 (12)	0.0410 (9)
O41	0.0836 (10)	0.7033 (4)	0.77368 (12)	0.0619 (11)
O42	0.3102 (8)	0.8603 (3)	0.73315 (12)	0.0468 (9)
C5	0.5504 (9)	0.6830 (4)	0.66527 (13)	0.0292 (9)
C6	0.6447 (9)	0.5911 (4)	0.62919 (13)	0.0281 (8)
C7	0.6417 (8)	0.3675 (4)	0.58886 (13)	0.0242 (8)
O7	0.8892 (5)	0.3774 (3)	0.57235 (9)	0.0287 (6)
N1	0.4676 (7)	0.2685 (3)	0.57330 (10)	0.0249 (7)
N2	0.5636 (7)	0.1789 (3)	0.53576 (11)	0.0316 (8)
C21	0.7356 (8)	0.0726 (3)	0.55066 (13)	0.0225 (7)
C22	0.8580 (8)	0.0630 (4)	0.60011 (13)	0.0270 (8)
C23	1.0473 (9)	−0.0398 (4)	0.61098 (14)	0.0329 (9)
C24	1.1178 (9)	−0.1335 (4)	0.57367 (16)	0.0346 (9)
C25	0.9950 (8)	−0.1248 (4)	0.52475 (15)	0.0304 (8)
C26	0.8070 (8)	−0.0236 (4)	0.51305 (13)	0.0252 (8)
H2	0.2458	0.3376	0.6638	0.034*
H3	0.0904	0.4921	0.7264	0.039*
H5	0.6260	0.7714	0.6660	0.035*
H6	0.7876	0.6156	0.6048	0.034*
H1	0.2858	0.2666	0.5815	0.030*
H2A	0.4602	0.1733	0.5073	0.038*
H22	0.8113	0.1269	0.6262	0.032*
H23	1.1297	−0.0459	0.6446	0.040*
H24	1.2491	−0.2033	0.5814	0.042*
H25	1.0416	−0.1896	0.4990	0.036*
H26	0.7250	−0.0188	0.4793	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0196 (17)	0.0312 (18)	0.0191 (14)	0.0018 (16)	−0.0020 (13)	0.0014 (14)
C2	0.0269 (19)	0.0311 (19)	0.0263 (16)	0.0049 (18)	0.0015 (15)	0.0024 (15)
C3	0.032 (2)	0.043 (2)	0.0230 (16)	0.005 (2)	0.0036 (16)	0.0058 (17)
C4	0.032 (2)	0.036 (2)	0.0222 (15)	0.012 (2)	−0.0051 (16)	−0.0047 (15)
N4	0.048 (2)	0.046 (2)	0.0290 (16)	0.021 (2)	−0.0069 (17)	−0.0079 (16)
O41	0.089 (3)	0.059 (2)	0.0379 (15)	0.023 (2)	0.0232 (19)	−0.0037 (16)
O42	0.059 (2)	0.0384 (17)	0.0433 (16)	0.0102 (18)	−0.0075 (16)	−0.0153 (14)
C5	0.029 (2)	0.0303 (19)	0.0286 (16)	0.0048 (18)	−0.0044 (16)	−0.0005 (16)
C6	0.0222 (18)	0.0333 (19)	0.0287 (16)	0.0029 (18)	0.0004 (15)	0.0025 (15)
C7	0.0224 (18)	0.0278 (17)	0.0224 (14)	0.0046 (18)	0.0003 (14)	0.0044 (14)
O7	0.0194 (13)	0.0384 (15)	0.0284 (12)	0.0012 (13)	0.0056 (11)	0.0016 (12)
N1	0.0183 (15)	0.0331 (17)	0.0232 (12)	0.0031 (14)	0.0015 (12)	−0.0043 (13)
N2	0.0338 (18)	0.0382 (18)	0.0226 (13)	0.0157 (17)	−0.0069 (13)	−0.0061 (13)
C21	0.0188 (17)	0.0225 (17)	0.0263 (16)	−0.0009 (16)	−0.0003 (14)	0.0041 (14)
C22	0.0252 (19)	0.0279 (18)	0.0278 (17)	0.0003 (18)	−0.0024 (16)	−0.0033 (15)
C23	0.032 (2)	0.038 (2)	0.0286 (16)	−0.001 (2)	−0.0064 (17)	0.0099 (17)
C24	0.032 (2)	0.0260 (18)	0.046 (2)	0.005 (2)	−0.0067 (19)	0.0069 (18)
C25	0.029 (2)	0.0260 (18)	0.0362 (18)	0.0005 (18)	0.0005 (16)	−0.0027 (16)
C26	0.0236 (19)	0.0247 (17)	0.0273 (15)	−0.0036 (16)	0.0012 (15)	−0.0008 (14)

Geometric parameters (Å, º)

C1—C2	1.390 (5)	N1—N2	1.390 (4)
C1—C6	1.394 (5)	N1—H1	0.88
C1—C7	1.481 (5)	N2—C21	1.385 (5)
C2—C3	1.381 (5)	N2—H2A	0.88
C2—H2	0.95	C21—C22	1.399 (5)
C3—C4	1.383 (6)	C21—C26	1.402 (5)
C3—H3	0.95	C22—C23	1.385 (5)
C4—C5	1.377 (5)	C22—H22	0.95
C4—N4	1.472 (5)	C23—C24	1.379 (6)
N4—O42	1.224 (5)	C23—H23	0.95
N4—O41	1.228 (5)	C24—C25	1.387 (5)
C5—C6	1.376 (5)	C24—H24	0.95
C5—H5	0.95	C25—C26	1.373 (5)
C6—H6	0.95	C25—H25	0.95
C7—O7	1.242 (4)	C26—H26	0.95
C7—N1	1.342 (5)
C2—C1—C6	119.9 (3)	C7—N1—N2	118.7 (3)
C2—C1—C7	122.8 (3)	C7—N1—H1	122.4
C6—C1—C7	117.2 (3)	N2—N1—H1	117.9
C3—C2—C1	120.7 (4)	C21—N2—N1	119.2 (3)
C3—C2—H2	119.6	C21—N2—H2A	120.2
C1—C2—H2	119.6	N1—N2—H2A	116.1
C2—C3—C4	117.8 (4)	N2—C21—C22	122.9 (3)
C2—C3—H3	121.1	N2—C21—C26	118.1 (3)
C4—C3—H3	121.1	C22—C21—C26	118.8 (3)
C5—C4—C3	122.8 (4)	C23—C22—C21	119.9 (3)
C5—C4—N4	119.1 (4)	C23—C22—H22	120.1
C3—C4—N4	118.1 (4)	C21—C22—H22	120.1
O42—N4—O41	123.5 (4)	C24—C23—C22	120.9 (3)
O42—N4—C4	117.9 (4)	C24—C23—H23	119.5
O41—N4—C4	118.6 (4)	C22—C23—H23	119.5
C6—C5—C4	118.9 (4)	C23—C24—C25	119.3 (4)
C6—C5—H5	120.6	C23—C24—H24	120.4
C4—C5—H5	120.6	C25—C24—H24	120.4
C5—C6—C1	119.9 (4)	C26—C25—C24	120.8 (4)
C5—C6—H6	120.1	C26—C25—H25	119.6
C1—C6—H6	120.1	C24—C25—H25	119.6
O7—C7—N1	121.8 (3)	C25—C26—C21	120.3 (3)
O7—C7—C1	121.1 (4)	C25—C26—H26	119.9
N1—C7—C1	117.1 (3)	C21—C26—H26	119.9
C6—C1—C2—C3	0.0 (6)	C6—C1—C7—N1	−153.5 (3)
C7—C1—C2—C3	178.9 (3)	O7—C7—N1—N2	−3.3 (5)
C1—C2—C3—C4	1.0 (6)	C1—C7—N1—N2	179.3 (3)
C2—C3—C4—C5	−1.4 (6)	C7—N1—N2—C21	81.7 (4)
C2—C3—C4—N4	178.7 (3)	N1—N2—C21—C22	−11.2 (5)
C5—C4—N4—O42	10.7 (5)	C3—C4—N4—O41	8.7 (6)
C3—C4—N4—O42	−169.4 (4)	N1—N2—C21—C26	173.9 (3)
C5—C4—N4—O41	−171.2 (4)	N2—C21—C22—C23	−174.4 (3)
C3—C4—C5—C6	0.6 (6)	C26—C21—C22—C23	0.4 (5)
N4—C4—C5—C6	−179.4 (3)	C21—C22—C23—C24	0.0 (6)
C4—C5—C6—C1	0.4 (5)	C22—C23—C24—C25	−0.5 (6)
C2—C1—C6—C5	−0.7 (5)	C23—C24—C25—C26	0.6 (6)
C7—C1—C6—C5	−179.7 (3)	C24—C25—C26—C21	−0.1 (6)
C2—C1—C7—O7	−150.0 (4)	N2—C21—C26—C25	174.7 (3)
C6—C1—C7—O7	29.0 (5)	C22—C21—C26—C25	−0.3 (5)
C2—C1—C7—N1	27.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O7^i	0.88	2.18	2.926 (4)	143
N2—H2A···O7^ii	0.88	2.14	2.952 (4)	154
N2—H2A···N2^ii	0.88	2.62	3.302 (4)	135
C3—H3···O42^iii	0.95	2.52	3.419 (5)	158
C26—H26···O7^ii	0.95	2.50	3.285 (5)	140

Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+1/2, −z+1; (iii) −x, y−1/2, −z+3/2.