4-Bromo-N-(2-nitro­phen­yl)benzamide

Rodolfo Moreno-Fuquen; Alexis Azcárate; Alan R Kennedy

doi:10.1107/S1600536814003298

. 2014 Feb 22;70(Pt 3):o344. doi: 10.1107/S1600536814003298

4-Bromo-N-(2-nitrophenyl)benzamide

Rodolfo Moreno-Fuquen ^a,^*, Alexis Azcárate ^a, Alan R Kennedy ^b

PMCID: PMC3998505 PMID: 24765035

Abstract

The title nitrophenyl benzamide, C₁₃H₉BrN₂O₃, with two molecules in the asymmetric unit, has dihedral angles of 16.78 (15) and 18.87 (14)° between the benzene rings. An intramolecular N—H⋯O hydrogen bond is observed in each molecule. In the crystal, the molecules are linked by weak C—H⋯O interactions; halogen–halogen interactions are also observed [Br⋯Br = 3.4976 (7) Å]. These interactions form R ² ₂(10), R ² ₂(15) and R ⁶ ₆(32) edge-fused rings along [010].

Related literature

For properties of amide compounds, see: Bisson et al. (2000 ▶). For the antibacterial and antifungal activity of amide compounds, see: Aytemir et al. (2003 ▶). For similar compounds, see: Moreno-Fuquen et al. (2013 ▶); Sripet et al. (2012 ▶). For halogen–halogen interactions, see: Awwadi et al. (2006 ▶); For hydrogen-bonding information, see: Nardelli (1995 ▶). For hydrogen-bond motifs, see: Etter (1990 ▶). graphic file with name e-70-0o344-scheme1.jpg

Experimental

Crystal data

C₁₃H₉BrN₂O₃
M _r = 321.13
Triclinic,
a = 3.8338 (4) Å
b = 12.6784 (13) Å
c = 24.918 (2) Å
α = 81.875 (8)°
β = 88.386 (7)°
γ = 85.460 (8)°
V = 1195.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 3.45 mm⁻¹
T = 123 K
0.49 × 0.05 × 0.03 mm

Data collection

Oxford Diffraction Xcalibur E diffractometer
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010 ▶; analytical numeric absorption correction using a multi-faceted crystal model (Clark & Reid, 1995 ▶)] T _min = 0.380, T _max = 0.914
9979 measured reflections
9979 independent reflections
7814 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.135
S = 1.04
9979 reflections
344 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); 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 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814003298/gg2134sup1.cif

e-70-0o344-sup1.cif^{(32.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814003298/gg2134Isup2.hkl

e-70-0o344-Isup2.hkl^{(478.9KB, hkl)}

Click here for additional data file.^{(4.6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814003298/gg2134Isup3.cml

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=986704

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O4ⁱ	0.95	2.65	3.378 (5)	134
C16—H16⋯O2ⁱⁱ	0.95	2.64	3.349 (5)	132
C19—H19⋯O1ⁱⁱⁱ	0.95	2.52	3.262 (5)	135
C3—H3⋯O5^iv	0.95	2.58	3.299 (5)	133
C23—H23⋯O6^v	0.95	2.56	3.334 (5)	139
N1—H1N⋯O2	0.88	1.92	2.615 (5)	134
N3—H3N⋯O5	0.88	1.92	2.628 (5)	136

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

Acknowledgments

RMF thanks the Universidad del Valle, Colombia, for partial financial support.

supplementary crystallographic information

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

The reagents and solvents for the synthesis were obtained from the Aldrich Chemical Co., and were used without additional purification. The title molecule was synthesized using equimolar quantities of 4-bromobenzoyl chloride (0.328 g., 1.495 mmol) and 2-nitroaniline (0.206 g). The reagents were dissolved in 10 mL of acetonitrile and the solution was taken to reflux in constant stirring for 1 hour. Yellow crystals of good quality were obtained after leaving the solvent to evaporate. Yellow crystals of good quality were obtained with m.p of 423 (1)K.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H-atoms were positioned at geometrically idealized positions with C—H distance of 0.95 Å and N—H distance of 0.88 Å and U_iso(H) = 1.2 times U_eq of the atoms to which they were bonded.

3. Results and discussion

The present compound forms part of a systematic work on N-aromatic amides. The formation of oligomers with properties of molecular zippers have been obtained using molecular templates which include amido ligands (Bisson et al., 2000). Antibacterial and antifungal activities of different carboxyamide derivatives have been reported (Aytemir et al., 2003). In the synthesis of amides in our group, the 2-nitroaniline is taken as a template, in order to study the structural changes and the supramolecular behavior by the reaction of different ligands with this precursor (Moreno-Fuquen et al., 2013). In the reactions involving the 2-nitroaniline, as precursor, we aimed to synthesize the N-(2-nitrophenyl)-4-bromobenzamide (I). A close structure, the 4-bromo-N-(4-methoxy-2-nitrophenyl)-benzamide, (4MNB), (Sripet et al., 2012), has been used as comparison with the structural parameters of the title compound. The title compound has two molecules (A and B) per asymmetric unit (see Fig. 1). The compound exhibits dihedral angles between the benzene rings, very similar: 16.78 (15)° and 18.87 (14)° for A and B molecules, respectively. These dihedral angles are somewhat different when compared with the related compound (4MNB) [2.90 (8)°]. In (I) the other bond lengths and bond angles agree closely with those values presented in its homologous amide (4MNB). The nitro groups form dihedral angles with the adjacent benzene ring of 6.7 (2)° and 9.9 (2)° for O2—N2—O3 and O5—N4—O6, respectively. The crystal packing shows no classical intermolecular hydrogen bonds and the molecules pack by forming weak C—H···O interactions that are propagated along [010] (see Fig. 2). According to the graph-set assignment, the intramolecular hydrogen-bond pattern generates a S(6) ring motif (Etter, 1990). The crystal packing is stabilized by weak C—H···O intermolecular interactions. The C6 and C3 atoms of the phenyl ring at (x,y,z) act as hydrogen-bond donors to carbonyl O4 atom at (x-1, +y, +z) and to nitro O5 atom at (x,+y+1,+z) respectively. The C16 and C19 atoms of the phenyl ring at (x, y, z) act as hydrogen-bond donors to nitro O2 atom at (x+1, y, z) and to carbonyl O1 atom at (x,y-1,z), respectively. Additionally the C23 atom at (x,y,z) acts as a hydrogen-bond donor to nitro O6 atom at (-x-1, -y, -z+1), (see Table 1; Nardelli, 1995). All these interactions form R²₂(10), R²₂(15) and R⁶₆(32) edge-fused rings along the [010] direction (see Fig. 2). Recent theoretical calculations show that halogen···halogen interactions are controlled by electrostatic forces and they display directional character (Awwadi et al., 2006). In the title structure, halogen···halogen interactions [Br···Br = 3.4976 (7) Å] within the chains stabilized by C—H···O interactions are observed. This Br···Br distance is much shorter than the sum of the van der Waals radii (3.70 Å).