4-Nitro-N-(3-nitro­phen­yl)benzamide

Dean H Johnston; Colin R Taylor

doi:10.1107/S1600536811038062

. 2011 Sep 30;67(Pt 10):o2735. doi: 10.1107/S1600536811038062

4-Nitro-N-(3-nitrophenyl)benzamide

Dean H Johnston ^a,^*, Colin R Taylor ^a

PMCID: PMC3201324 PMID: 22065512

Abstract

The title compound, C₁₃H₉N₃O₅, prepared as a solid derivative of 3-nitroanaline via reaction with 4-nitrobenzoyl chloride, crystallizes in a chiral space group. The molecule is non-planar with a dihedral angle of 26.1 (1)° between the two benzene rings. Both nitro groups are twisted slightly out of the plane of their corresponding benzene rings, making dihedral angles of 10.7 (4) and 13.5 (4)°. The molecules are stacked along the a axis with benzene ring centroid–centroid distances of 3.8878 (6) Å. In the crystal, intermolecular benzene C—H⋯O interactions involving one nitro group and the carbonyl group link the molecules, forming chains along [001]. An additional set of aromatic C—H⋯O interactions with the second nitro group form chains along [101], connecting adjacent chains to create layers perpendicular to the b axis.

Related literature

For the preparation, properties and applications of the title compound, see: Kichitaro (1954 ▶); Shchel’tsyn et al. (1972 ▶); Kang et al. (2008 ▶). For related structures, see: Hariharan & Srinivasan (1990 ▶); Adams et al. (2001 ▶); Novozhilova et al. (1986 ▶); Sun et al. (2009 ▶). The title compound represents a relatively unusual example of an achiral molecule in a chiral (Sohncke) space group with the conformational flexibility to convert to its mirror image (Pidcock, 2005 ▶).

Experimental

Crystal data

C₁₃H₉N₃O₅
M _r = 287.23
Monoclinic,
a = 3.8878 (6) Å
b = 21.686 (3) Å
c = 7.3919 (11) Å
β = 90.294 (11)°
V = 623.20 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 200 K
0.45 × 0.20 × 0.12 mm

Data collection

Bruker SMART X2S benchtop diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.737, T _max = 0.989
3940 measured reflections
1136 independent reflections
1008 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.083
S = 1.07
1136 reflections
190 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 and GIS (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and OLEX2 (Dolomanov et al., 2009 ▶); molecular graphics: PLATON (Spek, 2009 ▶), Mercury (Macrae et al., 2008 ▶), and POV-RAY (Cason, 2004 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811038062/zl2389sup1.cif

e-67-o2735-sup1.cif^{(20.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038062/zl2389Isup2.hkl

e-67-o2735-Isup2.hkl^{(56.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811038062/zl2389Isup3.mol

Supplementary material file. DOI: 10.1107/S1600536811038062/zl2389Isup4.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.95	2.50	3.375 (4)	153
C5—H5⋯O3ⁱⁱ	0.95	2.38	3.263 (4)	155
C13—H13⋯O5ⁱⁱⁱ	0.95	2.51	3.421 (4)	162

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

Acknowledgments

This work was supported in part by the National Science Foundation through grant CHE-0532510.

supplementary crystallographic information

Comment

The title compound was prepared as a solid derivative of 3-nitroanaline for a qualitative organic analysis laboratory course. The starting material was 3-nitroaniline, and reaction with 4-nitrobenzoyl chloride produced a p-nitrobenzamide derivative.

The title compound crystallizes in the chiral spacegroup P2₁ and represents a relatively unusual example of an achiral molecule in a chiral (Sohncke) space group with the conformational flexibility to convert to its mirror image (Pidcock, 2005).

The molecule (Fig. 1) is non-planar with a dihedral angle of approximately 26.1 (1)° between the two aromatic rings. Both nitro groups are twisted slightly out of the plane of their corresponding aromatic rings, with dihedral angles of 10.7 (4) (N1, O1, O2) and 13.5 (4) (N3, O4, O5) degrees.

In the unit cell, the molecules are stacked along the a axis (Fig. 2) with aromatic ring centroid-centroid distances of 3.8878 (6) Å, corresponding precisely to the length of the a axis. The ring numbered C1–C6 stacks with a plane-centroid distance of 3.392 (2) Å and a ring shift of 1.899 (4) Å. The ring numbered C8–C13 stacks with a plane-centroid distance of 3.483 (2) Å and a ring shift of 1.728 (4) Å.

The title compound forms hydrogen bonding interactions with adjacent molecules along two different axes to create layers perpendicular to the b axis. The C2—H2···O1ⁱ and C5—H5···O3ⁱⁱ interactions (Fig. 3, Fig. 4, Table 1) form chains along [001] (all symmetry operators as in Table 1). Additional C13—H13···O5ⁱⁱⁱ interactions also connect adjacent molecules, with the resulting chains running along [101] (Fig. 5). The position of the N—H in the molecule prevents it from forming a significant hydrogen bonding interaction (H2N···O4ⁱⁱⁱ distance of 2.65 Å, greater than the sum of the van der Waals radii).

Experimental

Approximately 1.0 g (7.24 mmol) of 3-nitroaniline was dissolved in 3.0 ml of pyridine in a small test tube. To this was added 0.5 g (2.70 mmol) of 4-nitrobenzoyl chloride. This mixture was warmed slightly with a water bath until homogeneous, allowed to cool to room temperature, and then poured into 10.0 ml of water. The solution was allowed to separate and the top layer was decanted. The residue was stirred with 5.0 ml of a 5% Na₂CO₃ solution, and then cooled in an ice bath to induce crystallization. The crude crystals were filtered, and then recrystallized from absolute ethanol to produce 4-nitro-N-(3-nitrophenyl)benzamide, mp = 502–503 K (lit = 500–501 K, Kang et al. (2008).)