N-(4-Chloro­phen­yl)-4-nitro­benzamide

Ghulam Waris; Humaira Masood Siddiqi; Ulrich Flörke; MSaeed Butt; Rizwan Hussain

doi:10.1107/S1600536812036082

. 2012 Aug 25;68(Pt 9):o2768. doi: 10.1107/S1600536812036082

N-(4-Chlorophenyl)-4-nitrobenzamide

Ghulam Waris ^a, Humaira Masood Siddiqi ^a,^*, Ulrich Flörke ^b, MSaeed Butt ^a, Rizwan Hussain ^c

PMCID: PMC3435803 PMID: 22969649

Abstract

The title compound, C₁₃H₉ClN₂O₃, is almost planar, showing a dihedral angle of 4.63 (6)° between the aromatic ring planes. The nitro group also lies in the plane, the C—C—N—O torsion angle being 6.7 (2)°. There is an intamolecular C—H⋯O hydrogen bond. The crystal structure features N—H⋯O(nitro) hydrogen bonds that link the molecules into zigzag chains extending along [010].

Related literature

For background information on aromatic polyimides, see: Yang et al. (1999 ▶); More et al. (2010 ▶); Litvinov et al., (2010 ▶); Sheng et al. (2009 ▶); Choi et al. (1992 ▶); Hsiao & Lin (2004 ▶); Li et al. (2007 ▶); Liaw et al. (2005 ▶). For related structures, see Saeed et al. (2011 ▶); Wardell et al. (2006 ▶).

Experimental

Crystal data

C₁₃H₉ClN₂O₃
M _r = 276.67
Monoclinic,
a = 9.6019 (7) Å
b = 13.0688 (10) Å
c = 9.6412 (7) Å
β = 103.853 (1)°
V = 1174.64 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 130 K
0.49 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.855, T _max = 0.943
10822 measured reflections
2808 independent reflections
2557 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.116
S = 1.08
2808 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812036082/bt6822sup1.cif

e-68-o2768-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036082/bt6822Isup2.hkl

e-68-o2768-Isup2.hkl^{(137.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812036082/bt6822Isup3.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
C13—H13A⋯O1	0.95	2.26	2.859 (2)	120
N1—H1A⋯O3ⁱ	0.88	2.29	3.1312 (17)	159

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge financial assistance for this project from the Higher Education Commission of Pakistan.

supplementary crystallographic information

Comment

Aromatic polyimides are distinguished as high performance polymers owing to excellent thermal, mechanical, and chemical properties (Yang et al., 1999, More et al., 2010). They are not only used as beneficial substitutes for metals or ceramics in presently used goods but also as new materials in novel technological applications (Litvinov et al., 2010). Nevertheless, infusibility and insolubility are some of the shortcomings due to the highly regular and rigid polymer backbones and the formation of intermolecular hydrogen bonding, causing deterioration in processability and applications (Sheng et al., 2009, Choi et al., 1992). In order to improve upon these drawbacks, recent research has aimed at improving their processability and solubility without an intense loss in the chemical, thermal, and mechanical properties. For this, improvement of solubility is targeted through diminishing the cohesive energy by lowering the interchain interactions. To achieve this, designing and synthesizing new diamines or dicarboxylic acids is proposed to produce a great variety of soluble and processable polyimides (Hsiao et al., 2004). Incorporating substituted pendant groups which reduce dense chain packing and interchain interactions increases the solubility of resulting polyimides (Liaw et al., 2005, Li et al., 2007). As part of our enduring interest in solubility of aromatic polyimides by structural modification, we are reporting a chloro substituted pendant group having inbuilt amide functionality, which enhances the solubility of polyimides without worsening the inherent properties of polyimides. The molecular structure of the title compound (Figure 1) is closely related to that of the bromo- (Saeed et al., 2011) and iodo-compound (Wardell et al., 2006). The two aromatic rings are almost coplanar with a dihedral angle of 4.63 (6)°, and the nitro group is also coplanar, the associated C4–C5–N2–O2 torsion angle is 6.7 (2)°. The molecular conformation is stabilized by a rather strong intramolecular C13–H···O1 bond. Crystal packing shows a strong intermolecular N1–H···O3(-x + 0.5, y - 0.5, -z + 1.5) hydrogen interaction with H···O3 2.29 Å and N–H···O 159.1° that links molecules into endless zigzag chains extended along the b axis (Figure 2).

Experimental

All the chemicals were of analytical grade and no further purification was carried out before their usage. 1.275 g (0.01 mole) of 4-chloroaniline, 25 ml dichloromethane and 1.39 ml of triethylamine were charged in 100 ml, three-necked, round-bottomed flask fitted with a condenser, a nitrogen inlet tube, a thermometer and a magnetic stirrer. The mixture was stirred at 273-278K for 30 minutes. A solution of 1.85 g (0.01mole) of 4-nitrobenzoyl chloride in 25 ml dichloromethane was added dropwise and stirring was continued for further 45 minutes under same conditions. The temperature was then raised to room temperature along with stirring for further 30 minutes. Product was precipitated by pouring the flask content into water. The product was filtered, washed with 5% NaOH solution, further washing with hot water was carried out and solid product was dried overnight under vacuum at 343K. The product was recrystallized from an ethanol-tetrahydrofuran(1:1)