Crystal structure of 2-nitro-N-(2-nitro­phen­yl)benzamide

In the title compound, C₁₃H₉N₃O₅, the mean plane of the non-H atoms of the central amide fragment C—N—C(=O)—C [r.m.s. deviation = 0.0442 Å] forms dihedral angles of 71.76 (6) and 24.29 (10)° with the C-bonded and N-bonded benzene rings, respectively. In the crystal, mol­ecules are linked by N—H...O hydrogen bonds forming C(4) chains along [100]. Weak C—H...O contacts link the mol­ecules into (100) sheets containing edge-fused R₄⁴(30) rings. Together, the N—H...O and C—H...O hydrogen bonds generate a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.034
• wR factor = 0.088
• Data-to-parameter ratio = 12.1

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S1. Comment

The crystal structure determination of 2-nitro-N-(2-nitrophenyl)benzamide (I), is part of a study on phenylbenzamides carried out in our research group, and it was synthesized from the reaction between of 2-nitrobenzoic acid and 2-nitroaniline mediated by the presence of thionyl chloride. Benzanilides are versatile intermediate towards a diversity of heterocyclic compounds. Benzanilide systems as ameltolid, very similar to the molecule under study, have different properties ranging from anticonvulsant (Leander, 1992); antimicrobial drug (suramin) or as treatment in patients with prostate carcinoma (Alhes et al., 2004); as inhibitor of tyrosine-kinase, (imatinib) (Goldman et al., 2003) or a selective inhibitor of BCR-ABL, (nilotinib) (Weisberg et al., 2006). Similar compounds to (I) have been reported in the literature: N-(2,4-Dinitrophenyl)-4-nitrobenzamide (II) (Sun et al., 2009), N-(2-Nitrophenyl)benzamide (III) (Saed & Simpson, 2009) and 4-Bromo-N-(2-nitrophenyl)benzamide (IV) (Moreno-Fuquen et al., 2014). The molecular structure of (I) is shown in Fig. 1. The central amide moiety, C8—N1-C7(═O1)—C1, is essentially planar (r.m.s. deviation for all non-H atoms = 0.0442 Å) and it forms dihedral angles of 71.76 (6)° with the C1-C6 and 24.29 (10)° with the C8-C13 rings respectively. Bond lengths and bond angles in the molecule are in a good agreement with those found in the related compounds (II), (III) and (IV). A small lengthening of C7-N1 bond in (III) is observed [N1-C7= 1.3742 (11)Å], possibly caused by the formation of intramolecular S rings (6) in that structure. In the crystal structure (Fig. 2), molecules are linked by N-H···O hydrogen bonds of medium-strength and weak C-H···O intermolecular contacts (see Table 1). The N1-H1···O1 hydrogen bond interactions are responsible for crystal growth in [100]. In this interaction, the N-H in the molecule at (x,y,z) acts as a hydrogen-bond donor to O1 atom of the carbonyl group at (x-1/2,-y+3/2,-z+1). These interactions generate C(4) chains of molecules along [100]. Two C-H···O weak intermolecular contacts are further observed that run parallel to the bc plane in this structure (see Fig. 3). The group C5-H5 in the molecule at (x,y,z) acts as hydrogen bond donor to O5 atom of the nitro group in the molecule at (-x+3/2,-y+2,+z-1/2) and the C10-H10 group in the molecule at (x,y,z) acts as a hydrogen bond donor to O1 atom of the carbonyl group in the molecule at (-x+3/2,-y+1,+z-1/2). The combination of these interactions generate edge-fused R₄⁴(30) rings.

Related literature

For anticonvulsant and antimicrobial properties of benzanilide compounds, see: Leander (1992); Ahles et al. (2004). For studies as selective inhibitors of diverse enzymes, see: Goldman et al. (2003); Weisberg et al. (2006). For related structures, see: Sun et al. (2009); Saeed & Simpson (2009); Moreno-Fuquen et al. (2014).

S2. Experimental

A mass of 0.200 g (1.197 mmol) of 2-nitrobenzoic acid was refluxed with 2 ml of thionyl chloride for one hour. Then an equimolar amount of 2-nitroaniline was added and dissolved in 10 ml of acetonitrile and it was placed under reflux and constant stirring for 3 hours. Subsequently, the final solvent was slowly evaporated to obtain yellow needles of the title compound. [m.p. 431 (1)K].

S3. Refinement

All H-atoms were positioned in geometrically idealized positions, C—H = 0.95 Å, and were refined using a riding-model approximation with U_iso(H) constrained to 1.2 times U_eq of the respective parent atom. H1N atom was found from the Fourier maps and its coordinates were refined freely.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
	Fig. 2. Part of the crystal structure of (I), showing the formation of C(4) chains along [100] [symmetry code: (i) x - 1/2, -y + 3/2, -z + 1].
	Fig. 3. Part of the crystal structure of (I), showing the formation of R4^4(30) rings within a 2-D hydrogen-bonded network (dashed lines) running parallel to (100) [Symmetry codes: (ii) -x + 3/2, -y + 2, z - 1/2; (iii) -x + 3/2, -y + 1, z - 1/2].

2-Nitro-N-(2-nitrophenyl)benzamide

Crystal data

C13H9N3O5	Dx = 1.570 Mg m^−3
Mr = 287.23	Melting point: 431(1) K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54180 Å
a = 7.7564 (2) Å	Cell parameters from 2546 reflections
b = 12.1142 (4) Å	θ = 5.0–72.8°
c = 12.9355 (4) Å	µ = 1.06 mm^−1
V = 1215.45 (6) Å^3	T = 123 K
Z = 4	Needle, yellow
F(000) = 592	0.35 × 0.05 × 0.02 mm

Data collection

Oxford Diffraction Gemini S diffractometer	2367 independent reflections
Radiation source: fine-focus sealed tube	2259 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω scans	θmax = 72.9°, θmin = 6.8°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −7→9
Tmin = 0.657, Tmax = 1.000	k = −13→14
4952 measured reflections	l = −15→15

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0496P)^2 + 0.2131P] where P = (Fo^2 + 2Fc^2)/3
2367 reflections	(Δ/σ)max < 0.001
195 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.34.46 (release 25-11-2010 CrysAlis171 .NET) (compiled Nov 25 2010,17:55:46) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1	0.8757 (2)	0.69891 (13)	0.59755 (12)	0.0235 (4)
O2	0.6495 (2)	0.70531 (14)	0.25441 (12)	0.0304 (4)
O3	0.4638 (3)	0.58573 (16)	0.20009 (14)	0.0363 (5)
O4	0.5324 (2)	0.71871 (14)	0.68775 (13)	0.0297 (4)
O5	0.5249 (3)	0.84234 (16)	0.80856 (13)	0.0348 (5)
N1	0.6852 (2)	0.69018 (17)	0.46280 (14)	0.0215 (4)
N2	0.5754 (2)	0.61585 (17)	0.26036 (15)	0.0240 (4)
N3	0.5572 (2)	0.81237 (17)	0.71999 (15)	0.0248 (4)
C1	0.7127 (3)	0.85927 (19)	0.55862 (17)	0.0207 (5)
C2	0.6264 (3)	0.89486 (19)	0.64730 (17)	0.0212 (5)
C3	0.5993 (3)	1.0050 (2)	0.66891 (18)	0.0250 (5)
H3	0.5410	1.0265	0.7303	0.030*
C4	0.6585 (3)	1.0837 (2)	0.5998 (2)	0.0282 (5)
H4	0.6418	1.1600	0.6136	0.034*
C5	0.7424 (3)	1.0505 (2)	0.51017 (19)	0.0274 (5)
H5	0.7818	1.1045	0.4623	0.033*
C6	0.7695 (3)	0.9394 (2)	0.48978 (18)	0.0226 (5)
H6	0.8273	0.9180	0.4282	0.027*
H1N	0.607 (4)	0.734 (2)	0.427 (2)	0.030 (7)*
C7	0.7639 (3)	0.74034 (19)	0.54308 (17)	0.0202 (5)
C8	0.6909 (3)	0.57706 (19)	0.43817 (18)	0.0214 (5)
C9	0.6276 (3)	0.5389 (2)	0.34294 (17)	0.0223 (5)
C10	0.6114 (3)	0.4274 (2)	0.32093 (19)	0.0275 (5)
H10	0.5633	0.4042	0.2570	0.033*
C11	0.6657 (3)	0.3505 (2)	0.3926 (2)	0.0294 (5)
H11	0.6574	0.2738	0.3780	0.035*
C12	0.7325 (3)	0.3865 (2)	0.4863 (2)	0.0290 (5)
H12	0.7711	0.3338	0.5356	0.035*
C13	0.7437 (3)	0.4977 (2)	0.50897 (18)	0.0254 (5)
H13	0.7882	0.5203	0.5740	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0236 (8)	0.0239 (8)	0.0231 (8)	−0.0009 (7)	−0.0027 (6)	0.0021 (7)
O2	0.0379 (10)	0.0292 (9)	0.0242 (8)	−0.0038 (8)	0.0001 (7)	0.0028 (7)
O3	0.0408 (10)	0.0401 (11)	0.0278 (10)	−0.0036 (9)	−0.0132 (8)	−0.0007 (8)
O4	0.0346 (9)	0.0225 (9)	0.0321 (9)	−0.0046 (7)	0.0051 (7)	−0.0003 (8)
O5	0.0417 (10)	0.0421 (11)	0.0205 (9)	−0.0040 (8)	0.0053 (8)	−0.0024 (8)
N1	0.0251 (9)	0.0206 (10)	0.0188 (9)	0.0031 (8)	−0.0020 (8)	0.0000 (8)
N2	0.0258 (10)	0.0289 (10)	0.0173 (9)	0.0020 (8)	0.0012 (8)	−0.0017 (8)
N3	0.0228 (9)	0.0288 (11)	0.0227 (9)	−0.0009 (8)	0.0014 (8)	0.0017 (8)
C1	0.0198 (10)	0.0231 (12)	0.0191 (11)	−0.0015 (9)	−0.0041 (9)	0.0006 (9)
C2	0.0206 (10)	0.0243 (12)	0.0186 (11)	−0.0014 (9)	−0.0039 (9)	0.0005 (9)
C3	0.0246 (10)	0.0262 (12)	0.0241 (11)	−0.0001 (10)	−0.0020 (9)	−0.0047 (10)
C4	0.0292 (12)	0.0205 (11)	0.0347 (13)	0.0005 (10)	−0.0061 (11)	−0.0037 (10)
C5	0.0284 (12)	0.0254 (13)	0.0285 (12)	−0.0023 (10)	−0.0047 (10)	0.0056 (11)
C6	0.0229 (11)	0.0246 (13)	0.0204 (11)	−0.0002 (9)	0.0003 (9)	0.0001 (10)
C7	0.0205 (10)	0.0238 (12)	0.0164 (10)	−0.0024 (8)	0.0030 (9)	0.0015 (9)
C8	0.0195 (10)	0.0226 (11)	0.0221 (11)	−0.0004 (9)	0.0026 (9)	−0.0013 (9)
C9	0.0210 (11)	0.0255 (12)	0.0204 (11)	0.0027 (9)	0.0029 (9)	−0.0004 (9)
C10	0.0295 (11)	0.0288 (13)	0.0244 (12)	−0.0017 (10)	0.0019 (10)	−0.0052 (10)
C11	0.0354 (13)	0.0186 (11)	0.0341 (13)	0.0006 (10)	0.0024 (12)	−0.0052 (10)
C12	0.0326 (13)	0.0243 (13)	0.0300 (13)	0.0013 (10)	−0.0017 (10)	0.0032 (11)
C13	0.0287 (11)	0.0249 (13)	0.0225 (11)	0.0010 (9)	−0.0022 (10)	−0.0004 (10)

Geometric parameters (Å, º)

O1—C7	1.225 (3)	C4—C5	1.389 (4)
O2—N2	1.229 (3)	C4—H4	0.9500
O3—N2	1.221 (3)	C5—C6	1.388 (3)
O4—N3	1.224 (3)	C5—H5	0.9500
O5—N3	1.228 (3)	C6—H6	0.9500
N1—C7	1.349 (3)	C8—C13	1.389 (3)
N1—C8	1.408 (3)	C8—C9	1.405 (3)
N1—H1N	0.93 (3)	C9—C10	1.385 (3)
N2—C9	1.475 (3)	C10—C11	1.381 (4)
N3—C2	1.473 (3)	C10—H10	0.9500
C1—C6	1.389 (3)	C11—C12	1.388 (4)
C1—C2	1.396 (3)	C11—H11	0.9500
C1—C7	1.508 (3)	C12—C13	1.382 (4)
C2—C3	1.379 (3)	C12—H12	0.9500
C3—C4	1.386 (4)	C13—H13	0.9500
C3—H3	0.9500
C7—N1—C8	126.7 (2)	C5—C6—C1	120.5 (2)
C7—N1—H1N	115.1 (18)	C5—C6—H6	119.7
C8—N1—H1N	117.5 (17)	C1—C6—H6	119.7
O3—N2—O2	123.7 (2)	O1—C7—N1	125.4 (2)
O3—N2—C9	117.9 (2)	O1—C7—C1	120.1 (2)
O2—N2—C9	118.33 (19)	N1—C7—C1	114.4 (2)
O4—N3—O5	124.1 (2)	C13—C8—C9	117.0 (2)
O4—N3—C2	117.94 (19)	C13—C8—N1	122.2 (2)
O5—N3—C2	118.0 (2)	C9—C8—N1	120.5 (2)
C6—C1—C2	117.6 (2)	C10—C9—C8	122.2 (2)
C6—C1—C7	119.9 (2)	C10—C9—N2	116.3 (2)
C2—C1—C7	122.1 (2)	C8—C9—N2	121.5 (2)
C3—C2—C1	122.6 (2)	C11—C10—C9	119.5 (2)
C3—C2—N3	118.1 (2)	C11—C10—H10	120.3
C1—C2—N3	119.3 (2)	C9—C10—H10	120.3
C2—C3—C4	119.0 (2)	C10—C11—C12	119.2 (2)
C2—C3—H3	120.5	C10—C11—H11	120.4
C4—C3—H3	120.5	C12—C11—H11	120.4
C3—C4—C5	119.6 (2)	C13—C12—C11	121.0 (2)
C3—C4—H4	120.2	C13—C12—H12	119.5
C5—C4—H4	120.2	C11—C12—H12	119.5
C6—C5—C4	120.7 (2)	C12—C13—C8	121.1 (2)
C6—C5—H5	119.7	C12—C13—H13	119.5
C4—C5—H5	119.7	C8—C13—H13	119.5
C6—C1—C2—C3	−1.2 (3)	C6—C1—C7—N1	−72.2 (3)
C7—C1—C2—C3	171.1 (2)	C2—C1—C7—N1	115.7 (2)
C6—C1—C2—N3	177.28 (19)	C7—N1—C8—C13	16.9 (3)
C7—C1—C2—N3	−10.5 (3)	C7—N1—C8—C9	−169.1 (2)
O4—N3—C2—C3	157.7 (2)	C13—C8—C9—C10	2.5 (3)
O5—N3—C2—C3	−20.9 (3)	N1—C8—C9—C10	−171.9 (2)
O4—N3—C2—C1	−20.8 (3)	C13—C8—C9—N2	−177.2 (2)
O5—N3—C2—C1	160.5 (2)	N1—C8—C9—N2	8.4 (3)
C1—C2—C3—C4	0.6 (3)	O3—N2—C9—C10	28.9 (3)
N3—C2—C3—C4	−177.9 (2)	O2—N2—C9—C10	−149.3 (2)
C2—C3—C4—C5	0.4 (3)	O3—N2—C9—C8	−151.5 (2)
C3—C4—C5—C6	−0.8 (4)	O2—N2—C9—C8	30.4 (3)
C4—C5—C6—C1	0.1 (4)	C8—C9—C10—C11	−2.8 (3)
C2—C1—C6—C5	0.8 (3)	N2—C9—C10—C11	176.8 (2)
C7—C1—C6—C5	−171.6 (2)	C9—C10—C11—C12	1.2 (4)
C8—N1—C7—O1	12.8 (4)	C10—C11—C12—C13	0.7 (4)
C8—N1—C7—C1	−171.3 (2)	C11—C12—C13—C8	−1.0 (4)
C6—C1—C7—O1	103.9 (3)	C9—C8—C13—C12	−0.5 (3)
C2—C1—C7—O1	−68.2 (3)	N1—C8—C13—C12	173.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.93 (3)	2.00 (3)	2.859 (2)	154 (2)
C5—H5···O5^ii	0.95	2.57	3.427 (3)	150
C10—H10···O1^iii	0.95	2.46	3.271 (3)	144

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