Crystal structure of 4-bromo-N-(2-hydroxy­phen­yl)benzamide

Rodolfo Moreno-Fuquen; Vanessa Melo; Javier Ellena

doi:10.1107/S1600536814024696

. 2014 Nov 15;70(Pt 12):o1261–o1262. doi: 10.1107/S1600536814024696

Crystal structure of 4-bromo-N-(2-hydroxyphenyl)benzamide

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

PMCID: PMC4257397 PMID: 25553033

Abstract

In the title compound, C₁₃H₁₀BrNO₂, the mean plane of the non-H atoms of the central amide C—N—C(=O)—C fragment (r.m.s. deviation = 0.004 Å) forms a dihedral angle of 73.97 (12)° with the hydroxy-substituted benzene ring and 25.42 (19)° with the bromo-substituted benzene ring. The two aromatic rings are inclined to one another by 80.7 (2)°. In the crystal, molecules are linked by O—H⋯O and N—H⋯O hydrogen bonds, forming chains along [010]. The chains are linked by weak C—H⋯O hydrogen bonds, forming sheets parallel to (100), and enclosing R ³ ₃(17) and R ³ ₂(9) ring motifs.

Keywords: crystal structure, benzamide, hydroxyaniline, hydrogen bonding

Related literature

For the antiprotozoal and antimicrobial properties of phenylbenzamides, see: Ríos Martínez et al. (2014 ▶); Şener et al. (2000 ▶). For active metabolites of benzoxazoles, see: Mobinikhaledi et al. (2006 ▶). For studies of phenylbenzamides as inhibitors of tyrosine kinases, see: Capdeville et al. (2002 ▶). For studies of phenylbenzamides as inducers of apoptosis in biological processes, see: Olsson et al. (2002 ▶). For related structures, see: Fun et al. (2012 ▶); Hibbert et al. (1998 ▶).

Experimental

Crystal data

C₁₃H₁₀BrNO₂
M _r = 292.13
Monoclinic,
a = 23.4258 (10) Å
b = 5.6473 (1) Å
c = 9.2464 (3) Å
β = 93.008 (1)°
V = 1221.54 (7) Å³
Z = 4
Mo Kα radiation
μ = 3.35 mm⁻¹
T = 295 K
0.20 × 0.18 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.537, T _max = 0.662
21458 measured reflections
2490 independent reflections
1664 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.168
S = 0.99
2490 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; 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., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814024696/su5019sup1.cif

e-70-o1261-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814024696/su5019Isup2.hkl

e-70-o1261-Isup2.hkl^{(136.9KB, hkl)}

Click here for additional data file.^{(4.2KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814024696/su5019Isup3.cml

Click here for additional data file.^{(1MB, tif)}

. DOI: 10.1107/S1600536814024696/su5019fig1.tif

The molecular structure of the title compound (I), with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.5MB, tif)}

a 3 3 3 2 . DOI: 10.1107/S1600536814024696/su5019fig2.tif

Part of the crystal packing of the title compound (I) viewed along the a axis, showing the formation of R³ ₃(17) and R³ ₂(9) ring motifs within the two-dimensional hydrogen bonded network running parallel to (100). Hydrogen bonds are shown as dashed lines; see Table 1 for details [symmetry codes: (i) x, −y-3/2, z-1/2; (ii) x, −y-1/2, z-1/2; (iii) x, y+1, z].

CCDC reference: 1033535

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O2HO2O1ⁱ	0.82	2.00	2.682(3)	141
N1H1O1ⁱⁱ	0.86	2.02	2.824(3)	155
C6H6O2ⁱⁱⁱ	0.93	2.56	3.458(5)	164

Open in a new tab

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

Acknowledgments

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

supplementary crystallographic information

S1. Comment

The crystal structure determination of the title compound (I), is part of a study on phenylbenzamides carried out in our research group, and they are synthesized from the reaction of picryl benzoates with 2-hydroxy-aniline. These compounds have received extensive attention because of their antiprotozoal (Ríos Martínez et al., 2014) and anti-microbialactivity (Şener et al., 2000), and as active metabolites of benzoxazoles (Mobinikhaledi et al., 2006). They have also been studied as inhibitors of tyrosine kinases (Capdeville et al., 2002) and inducers of apoptosis in the tumor development process (Olsson et al., 2002). Similar compounds to (I) have been reported in the literature, viz. 4-bromo-N-phenylbenzamide (II) (Fun et al., 2012) and 2-hydroxy-N-benzoylaniline (III) (Hibbert et al., 1998).

The molecular structure of (I) is shown in Fig. 1. The central amide moiety, C8—N1-C7(═O1)—C1, is essentially planar (r.m.s. deviation for all non-H atoms = 0.0026 Å) and it forms dihedral angles of 73.97 (12)° with the hydroxy-substituted phenyl ring and 25.42 (19)° with the bromo-substituted benzene ring. The bond lengths and angles within the molecule of (I) are in a good agreement with those found in the related compounds (II) and (III), although the N1-C7 bond length in the central amide segment, is slightly increased in structure (II), [C1-C7= 1.361 (2)Å].

In the crystal of (I), molecules are linked by O-H···O and N-H···O hydrogen bonds of medium-strength and weak C-H···O intermolecular contacts forming sheets parallel to (100) (Table 1 and Fig. 2). The O2-HO2···O1 hydrogen bonds are responsible for crystal growth in the b direction. In this interaction, the hydroxy O2-HO2 group in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom O1 of the carbonyl group at (x ,-y-3/2, z-1/2). In turn, the N1-H1···O1 hydrogen bonds and weak C6-H6···O2 interactions, complement crystal growth in the c direction (see Fig. 2). The N1-H1 group of the amide moiety in the molecule at (x ,y, z) acts as hydrogen bond donor to carbonyl atom O1 in the molecule at (x, -y-1/2, z-1/2) and the C6-H6 group in the molecule at (x, y, z) acts as a hydrogen bond donor to atom O2 in the molecule at (x, y+1 ,z). Very likely, these interactions are responsible for the twist of the rings with respect to the central amide moiety. The combination of these interactions generate edge-fused R³₃(17) and R³₂(9) ring motifs.

S2. Experimental

4-bromobenzoate 2,4,6-trinitrophenyl (0.050 g, 0.117 mmol) and 2-hydroxyaniline (0.0254 g) in molar ratio 1:2, were dissolved in 15 mL of toluene and mixed for 6 h under reflux and constant stirring. On completion of the reaction part of the solvent was evaporated and a crystalline black solid was obtained. [m.p.: 454 (1) K].