Crystal structure of 2-(4-chloro­benzamido)­benzoic acid

Rodolfo Moreno-Fuquen; Vanessa Melo; Javier Ellena

doi:10.1107/S2056989015017879

. 2015 Oct 17;71(Pt 11):o856–o857. doi: 10.1107/S2056989015017879

Crystal structure of 2-(4-chlorobenzamido)benzoic acid

Rodolfo Moreno-Fuquen ^a,^*, Vanessa Melo ^a, Javier Ellena ^b

PMCID: PMC4645063 PMID: 26594563

Abstract

In the title molecule, C₁₄H₁₀ClNO₃, the amide C=O bond is anti to the o-carboxy substituent in the adjacent benzene ring, a conformation that facilitates the formation of an intramolecular amide-N—H⋯O(carbonyl) hydrogen bond that closes an S(6) loop. The central amide segment is twisted away from the carboxy- and chloro-substituted benzene rings by 13.93 (17) and 15.26 (15)°, respectively. The most prominent supramolecular interactions in the crystal packing are carboxylic acid-H⋯O(carboxyl) hydrogen bonds that lead to centrosymmetric dimeric aggregates connected by eight-membered {⋯HOC=O}₂ synthons.

Keywords: crystal structure, carboxylic acid, amide, hydrogen bonding

Related literature

For our studies on the effects of substituents on the structures of N-(aryl)-amides, see: Moreno-Fuquen et al. (2014 ▸, 2015 ▸). For benzanilide properties, see: Nuta et al. (2013 ▸); Leander (1992 ▸); Ahles et al. (2004 ▸). For related structures, see: Saeed et al. (2008 ▸, 2010 ▸); Rodrigues et al. (2011 ▸). For hydrogen bonding, see: Desiraju & Steiner (1999 ▸), Nardelli (1995 ▸). graphic file with name e-71-0o856-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₀ClNO₃
M _r = 275.69
Monoclinic
a = 26.8843 (10) Å
b = 5.0367 (2) Å
c = 20.9264 (12) Å
β = 117.489 (2)°
V = 2513.7 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 295 K
0.40 × 0.08 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer
4248 measured reflections
2295 independent reflections
1049 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.132
S = 0.92
2295 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▸); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 ▸); data reduction: HKL DENZO (Otwinowski & Minor, 1997 ▸) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2006 ▸); software used to prepare material for publication: SHELXL2014/7.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015017879/tk5391sup1.cif

e-71-0o856-sup1.cif^{(173KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017879/tk5391Isup2.hkl

e-71-0o856-Isup2.hkl^{(184.4KB, hkl)}

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

Supporting information file. DOI: 10.1107/S2056989015017879/tk5391Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015017879/tk5391fig1.tif

The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.

CCDC reference: 1427117

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1NH1O2	0.93(3)	1.96(3)	2.678(3)	133(3)
O3OH3O2ⁱ	0.82	1.83	2.645(3)	175

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Symmetry code: (i) Inline graphic .

Acknowledgments

RMF is grateful to the Universidad del Valle, Colombia, for partial financial support.

supplementary crystallographic information

S1. Comment

The crystal structure determination of 2-(4-chlorobenzamido)benzoic acid, (I), was investigated in a continuation of our studies on substituted N-phenyl benzamides which have been synthesized from picryl esters. This study was also performed to study the effect of substituents on the structures of benzanilides (Moreno-Fuquen et al., 2014, 2015). Benzanilide systems are used as antimicrobial drugs (Nuta et al., 2013), as anticonvulsants (Leander, 1992) or as treatment for patients with prostate carcinoma (Ahles et al., 2004). Structures of similar molecules were compared with (I), i.e. 4-chloro-N-(2-methoxyphenyl)benzamide (Saeed et al., 2010), 4-chloro-N-phenylbenzamide (Rodrigues et al., 2011) and 4-chloro-N-(o-tolyl)benzamide (Saeed et al., 2008). The molecular structure of (I) is shown in Fig. 1. The C═O bond is anti to the o-carboxy substituent in the benzoyl ring. The N—H and C=O bonds in the central amide group are also anti to each other. Comparing (I) with the three aforementioned structures reveals that significant differences in bond lengths and bond angles are not observed. The central amide segment (C1-C7(O1)-N1-C8) is twisted away from the carboxy- and chloro-substituted benzene rings by 13.93 (17) and 15.26 (15)°, respectively. Molecules of (I) are held together by intermolecular O—H···O hydrogen bonds of moderate strength (Desiraju & Steiner, 1999). The O3 atom is linked to O2ⁱ atom (i = -x+3/2, -y+3/2, -z+1) with O···O distances of 2.645 (2), (see Table 1, Nardelli, 1995). Except for the presence of hydrogen bonding in the formation of dimer, no other significant intermolecular interactions are observed in the structure.

S2. Experimental

2,4,6-Trinitrophenyl 4-chlorobenzoate (0.060 g, 0.163 mmol) and 2-carboxyaniline (0.045 g, 0.328 mmol) were dissolved in toluene (15 ml) and stirred for 6 h under reflux. On completion of the reaction part of the solvent was evaporated and a crystalline yellow solid was obtained; m.p. 470 (1) K.