5-Bromo-2-hy­droxy­benzonitrile

Scott Oh; Joseph M Tanski

doi:10.1107/S1600536812031716

. 2012 Aug 1;68(Pt 9):o2617. doi: 10.1107/S1600536812031716

5-Bromo-2-hydroxybenzonitrile

Scott Oh ^a, Joseph M Tanski ^a,^*

PMCID: PMC3435646 PMID: 22969519

Abstract

The title compound, C₇H₄BrNO, crystallizes with two molecules in the asymmetric unit. The two molecules exhibit nearly linear C—C N nitrile bond angles of 179.1 (4) and 177.1 (4)°. In the crystal, the molecules are linked into a one-dimensional hydrogen-bonded chain by interactions between the phenol H atom and the nitrile N atom [N⋯O = 2.805 (4) and 2.810 (4) Å].

Related literature

For information on the synthesis of the title compound, see: Anwar & Hansen (2008 ▶); Bonnichon et al. (1999 ▶); Oberhauser (1997 ▶); Tamilselvan et al. (2009 ▶). For use as a synthetic reagent, see: Jiang et al. (2011 ▶); Tsuhako et al. (2012 ▶); Wetzel et al. (2011 ▶). For a related crystal structure, see: Beswick et al. (1996 ▶).

Experimental

Crystal data

C₇H₄BrNO
M _r = 198.01
Triclinic,
a = 3.8422 (3) Å
b = 8.5166 (7) Å
c = 21.6507 (18) Å
α = 97.074 (1)°
β = 91.991 (1)°
γ = 97.068 (1)°
V = 696.83 (10) Å³
Z = 4
Mo Kα radiation
μ = 5.82 mm⁻¹
T = 125 K
0.20 × 0.07 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.389, T _max = 0.845
11040 measured reflections
4213 independent reflections
3254 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.100
S = 1.03
4213 reflections
187 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.67 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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) I, global. DOI: 10.1107/S1600536812031716/rk2372sup1.cif

e-68-o2617-sup1.cif^{(15.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812031716/rk2372Isup2.hkl

e-68-o2617-Isup2.hkl^{(206.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812031716/rk2372Isup3.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
O1—H1⋯N2	0.83 (2)	1.98 (2)	2.805 (4)	170 (5)
O2—H2⋯N1ⁱ	0.84 (2)	1.98 (2)	2.810 (4)	175 (5)

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by Vassar College. X-ray facilities were provided by the US National Science Foundation (grant No. 0521237 to JMT).

supplementary crystallographic information

Comment

The title compound, 5-bromo-2-hydroxybenzonitrile, may be prepared by a variety of methods, including bromination of o-cyanophenol (Oberhauser, 1997), additon of nitrile to p-bromophenol (Anwar & Hansen, 2008), cobalt(II) catalyzed conversion of 5-bromo-2-hydroxyaldoxime to the nitrile (Tamilselvan et al., 2009), and photochemically from 5-chloro-2-hydroxybenzonitrile in the presence of bromide ions (Bonnichon et al., 1999). The 5-bromo-2-hydroxybenzonitrile is used as a synthetic reagent in the synthesis of biologically active compounds such as potential antiretroviral drugs (Jiang et al., 2011), cancer therapies (Tsuhako et al., 2012), and osteoporosis treatments (Wetzel et al., 2011).

The asymmetric unit contains two uniqe molecules of the title compound (Fig. 1) which are hydrogen bonded into an infinite one-dimensional chain (Fig. 2). The phenoxy group acts as the hydrogen donor and the nitrile group as the acceptor, with O···N distances of 2.805 (4)Å and 2.810 (4)Å, and O–H···N angles of 170 (5)° and 175 (5)°. The metrical parameters are similar to those found in the structure of o-cyanonitrile, which also crystallizes with two molecules in the asymmetric unit, and exhibts O···N distances of 2.795 (2)Å and 2.798 (2)Å, and O–H···N angles of 173 (2)° and 172 (2)° (Beswick et al., 1996). As in the structure of o-cyanonitrile, the molecules of the title compound are nearly planar, with a root mean square deviations from the plane of all atoms, excluding the aryl H atoms, of 0.0334Å and 0.2747Å. In each molecule in the asymmetric unit, the greatest deviation from the plane is the phenolic hydrogen atom, presumably to maximize the hydrogen bonding interaction between neighboring molecules, which make a dihedral angle between them of 12.6 (5)°.

Experimental

Crystalline 5-bromo-2-hydroxybenzonitrile was purchased from Aldrich Chemical Company, USA, and was recrystallized from chloroform.