2-Chloro-N-[2-(2-fluoro­benzo­yl)-4-nitro­phen­yl]-N-methyl­acetamide

B P Siddaraju; Jerry P Jasinski; James A Golen; H S Yathirajan; C R Raju

doi:10.1107/S1600536811034969

. 2011 Aug 31;67(Pt 9):o2537–o2538. doi: 10.1107/S1600536811034969

2-Chloro-N-[2-(2-fluorobenzoyl)-4-nitrophenyl]-N-methylacetamide

B P Siddaraju ^a, Jerry P Jasinski ^b,^*, James A Golen ^b, H S Yathirajan ^a, C R Raju ^c

PMCID: PMC3200782 PMID: 22064922

Abstract

The title compound, C₁₆H₁₂ClFN₂O₄, crystallizes with two molecules in the asymmetric unit in which the dihedral angles between the mean planes of the two benzene rings are 65.1 (7) and 65.6 (6)°. In each molecule, the nitro group displays rotational disorder over two orientations in a 0.503 (11):0.497 (11) ratio and the Cl atom is disordered in a 0.432 (5):0.568 (5) ratio. In one molecule, the F atoms is statistically disordered over two positions. The crystal packing features weak intermolecular C—H⋯O and C—H⋯Cl interactions, which form a layered network.

Related literature

For anti-anaphylactic and disease-related agents, see: Evans et al. (1987 ▶). For an intermediate in the synthesis of flunitrazepam (systematic name: 6-(2-fluorophenyl)-2-methyl-9-nitro-2,5-diazabicyclo[5.4.0]undeca-5,8,10,12-tetraen-3-one), see: Malanciuc et al. (2009 ▶). For related structures, see: Dutkiewicz et al. (2010 ▶); Jasinski et al. (2009 ▶); Khan et al. (2010 ▶); Malathy Sony et al. (2005a ▶,b ▶); Prasanna & Guru Row (2000 ▶). For standard bond lengths, see Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₆H₁₂ClFN₂O₄
M _r = 350.73
Triclinic,
a = 8.1339 (6) Å
b = 10.9639 (8) Å
c = 17.8690 (11) Å
α = 81.251 (6)°
β = 82.239 (6)°
γ = 87.937 (6)°
V = 1560.38 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 200 K
0.24 × 0.16 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.936, T _max = 0.967
13030 measured reflections
6373 independent reflections
3774 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.172
S = 1.03
6373 reflections
448 parameters
16 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811034969/im2312sup1.cif

e-67-o2537-sup1.cif^{(29.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034969/im2312Isup2.hkl

e-67-o2537-Isup2.hkl^{(311.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811034969/im2312Isup3.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
C32—H32A⋯O1	0.98	2.48	3.383 (4)	154
C29—H29⋯O5ⁱ	0.95	2.50	3.194 (5)	130
C28—H28⋯Cl1Aⁱⁱ	0.95	2.74	3.543 (6)	143
C17—H17A⋯O1	0.99	2.38	3.348 (4)	165
C16—H16B⋯O2ⁱⁱⁱ	0.98	2.47	3.45 (1)	176
C7—H7⋯O7^iv	0.95	2.37	3.31 (2)	173

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

Acknowledgments

BPS thanks the University of Mysore for access to their research facilities. HSY thanks R. L. Fine Chem, Bangalore, for the title compound. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

Benzophenone and related compounds have been reported to act as antiallergic, anti-inflammatory, antiasthmatic, antimalarial, antimicrobial and antianaphylactic agents (Evans et al., 1987). The title compound is an intermediate in the synthesis of certain anxiolytic, anticonvulsant and sedative drugs and is also used as an intermediate to synthesize flunitrazepam, which is used as a potent hypnotic and powerful sedative, anticonvulsant, anxiolytic, amnestic, and skeletal muscle relaxant drug (Malanciuc et al., 2009). The crystal structures of 2-chloroacetamido-5-chloro-2'-fluorobenzophenone (Prasanna & Guru Row, 2000), N-(2-benzoyl-4-chlorophenyl)-2- chloroacetamide (Malathy Sony et al., 2005a), 2-methoxy-5-methylphenyl phenyl ketone (Malathy Sony et al., 2005b), 2-amino-5-nitrophenyl 2-chlorophenyl ketone (Jasinski et al., 2009), N-[4-chloro-2-(2-chlorobenzoyl)phenyl]acetamide (Khan et al., 2010) and 2-chloro-N-[4-chloro-2-(2-chlorobenzoyl)phenyl]acetamide (Dutkiewicz et al., 2010) have been reported. In view of the importance of the title compound, C₁₆H₁₂N₂O₄ClF, the crystal structure of (I) is reported.

The title compound, C₁₆H₁₂N₂O₄ClF, crystallizes with two molecules in the asymmetric unit (Fig. 1). The dihedral angle between the mean planes of the two benzene rings is 65.1 (7)° and 65.6 (6)°, respectively. Bond lengths are in normal ranges (Allen et al., 1987). The two nitro groups display rotational disorder over two positions in a ratio of 0.503 (11) : 0.497 (11). In addition, disorder is observed concerning both chlorine atoms in a ratio of 0.432 (5) : 0.568 (5). One of the fluorine atoms (F2) is statistically disordered (0.50 (0)) over two positions (F2 and F2A). The crystal packing is realized by weak intermolecular C—H···O and C—H···Cl interactions forming a supermolecular 2-D network (Fig. 2).

Experimental

The title compound was obtained as a gift sample from R.L. Fine Chem., Bangalore, India. The compound was recrystallized from acetone (m.p.: 387–389 K).