Crystal structure of 3-bromo-2-hy­droxy­benzo­nitrile

Dickinson, S.R.; Müller, P.; Tanski, J.M.

doi:10.1107/S2056989015011974

organic compounds

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Volume 71| Part 7| July 2015| Pages o523-o524

doi:10.1107/S2056989015011974

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Crystal structure of 3-bromo-2-hydroxybenzonitrile

Sean R. Dickinson,^a Peter Müller ^b and Joseph M. Tanski ^a ^*

^aDepartment of Chemistry, Vassar College, Poughkeepsie, NY 12604, USA, and ^bX-Ray Diffraction Facility, MIT Department of Chemistry, 77 Massachusetts Avenue, Building 2, Room 325, Cambridge, MA, 02139-4307, USA
^*Correspondence e-mail: jotanski@vassar.edu

Edited by S. V. Lindeman, Marquette University, USA (Received 18 June 2015; accepted 22 June 2015; online 27 June 2015)

The crystal structure of the title compound, C₇H₄BrNO, has been determined, revealing a partial molecular packing disorder such that a 180° rotation of the molecule about the phenol C—O bond results in disorder of the bromine and nitrile groups. The disorder has been parameterized as a disorder of only the bromine and nitrile substituents on a unique phenol ring. An intramolecular O—H⋯Br contact occurs. In the crystal, O—H⋯Br/O—H⋯N_nitrile hydrogen bonding is present between the disordered bromine and nitrile substituents and the phenol group, forming a spiral chain about a twofold screw axis extending parallel to the b-axis direction. Within this spiral chain, the molecules also interact, forming offset face-to-face π-stacking interactions with plane-to-centroid distance of 3.487 (1) Å.

Keywords: crystal structure; disorder; hydrogen bonding; π-stacking.

CCDC reference: 1408281

1. Related literature

For syntheses of the title compound, see: Anwar & Hansen (2008 ); Nakai et al. (2014 ); Whiting et al. (2015 ). For its use as a synthetic reagent, see: Li & Chua (2011 ); Mulzer & Coates (2011 ). For related crystal structures, see: Beswick et al. (1996 ); Oh & Tanski (2012 ). For information on π-stacking, see: Hunter & Sanders (1990 ); Lueckheide et al. (2013 ). For information on the refinement of disordered crystal structures, see: Müller (2009 ); Thorn et al. (2012 ).

2. Experimental

2.1. Crystal data

C₇H₄BrNO
M_r = 198.02
Monoclinic, P 2₁ /c
a = 13.0171 (7) Å
b = 3.8488 (2) Å
c = 13.5989 (7) Å
β = 96.062 (1)°
V = 677.50 (6) Å³
Z = 4
Mo Kα radiation
μ = 5.98 mm⁻¹
T = 125 K
0.22 × 0.10 × 0.04 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.57, T_max = 0.80
9903 measured reflections
1977 independent reflections
1776 reflections with I > 2σ(I)
R_int = 0.025

2.3. Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.049
S = 1.08
1977 reflections
110 parameters
102 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.81 (2)	2.04 (2)	2.810 (3)	159 (2)
O1—H1⋯Br1A	0.81 (2)	2.82 (2)	3.262 (5)	116 (2)
O1—H1⋯Br1Aⁱ	0.81 (2)	2.62 (2)	3.379 (5)	156 (2)
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ); molecular graphics: SHELXTL2014; software used to prepare material for publication: SHELXTL2014, OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1408281

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015011974/ld2134sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015011974/ld2134Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015011974/ld2134Isup3.cml

checkCIF report

Structural commentary top

The title compound, 3-bromo-2-hydroxybenzonitrile, may be prepared by the addition of a cyano group to o-bromophenol (Anwar & Hansen, 2008; Nakai et al. 2014). It has also recently been synthesized by the one-pot conversion of the salicylaldoxime, (E)-3-bromo-2-hydroxybenzaldehyde oxime, directly to 3-bromo-2-hydroxybenzonitrile (Whiting et al., 2015). 3-Bromo-2-hydroxybenzonitrile is used as a synthetic reagent in the synthesis of 3,4-fused isoquinolin-1(2H)-one analogs (Li & Chua, 2011) and ampakine heterocycles which are a promising as a therapy for neurodegenerative diseases (Mulzer & Coates, 2011). The crystal structure of an isomer of the title compound which differs only in the position of the bromine substituent, 5-bromo-2-hydroxybenzonitrile, has previously been published (Oh & Tanski, 2012).

3-Bromo-2-hydroxybenzonitrile, (Fig. 1), crystallizes with a partial molecular packing disorder, where the bromine and nitrile substituents ortho to the phenol group are disordered with one another via a 180° rotation of the molecule about the carbon-oxygen bond of the phenol moiety. The disorder has been modeled as a disorder of only the bromine and nitrile substituents on a unique phenol ring, where the phenolic hydroxyl itself is not disordered, and the model has been refined with the help of similarity and advanced rigid bond restraints (Thorn et al., 2012). Although the accuracy of the observed metrical parameters for the disordered groups is impacted by the refinement of the disorder, the bond lengths are nevertheless comparable to those found in related structures. The nitrile bond lengths C7—N1 and C7A—N1A of 1.161 (4) and 1.14 (2) Å, respectively, are similar to those seen in the related structures 5-bromo-2-hydroxybenzonitrile, with nitrile C≡N distance 1.142 (4) Å (Oh & Tanski, 2012), and the unbrominated analog, o-cyanophenol, with C≡N distance 1.136 (2) Å (Beswick et al., 1996). The aromatic bromine bond lengths C1—Br1A and C3—Br1 of 1.988 (5) Å and 1.907 (2) Å, respectively, are also similar to those seen in the related structure 5-bromo-2-hydroxybenzonitrile, with C—Br length 1.897 (3) Å (Oh & Tanski, 2012).

The molecules of the title compound pack together in the solid state with intermolecular O—H···Br/O—H···N_nitrile hydrogen bonding (Fig. 2, Table 2). The hydrogen bonding is disordered with respect to the disordered bromine and nitrile substituents, not with respect to the phenol hydroxyl, which is found to have only one orientation. This hydrogen bonding forms a one-dimensional spiral chain extending parallel to the crystallographic b-axis, about the two-fold screw axis in P2₁/c with direction [0,1,0] at 1/2, y, 1/4. Within the chains, the molecules also interact via an offset face-to-face π-stacking interaction. This π-stacking is characterized by a centroid-to-centroid distance of 3.8488 (2) Å, a plane-to-centroid distance of 3.487 (1) Å, and a ring offset or ring-slippage distance of 1.630 (2) Å (Hunter & Saunders, 1990; Lueckheide et al., 2013).

Synthesis and crystallization top

3-Bromo-2-hydroxybenzonitrile (97%) was purchased from Aldrich Chemical Company, USA, and was recrystallized from acetone.

Refinement top

The structure was refined against F² using all data with SHELXL2014 (Sheldrick, 2015), employing established refinement strategies (Müller, 2009). All non-hydrogen atoms were refined anisotropically. Hydrogen atoms on carbon were included in calculated positions and refined using a riding model at C–H = 0.95 Å and U_iso(H) = 1.2 × U_eq(C) of the aryl C-atoms. Coordinates for the hydrogen atom on oxygen were taken from the difference Fourier synthesis and the hydrogen atom was subsequently refined semi-freely with the help of an O—H distance restraint (target value 0.84 (2) Å) while constraining its U_iso to 1.5 times the U_eq of the oxygen atom. The extinction parameter refined to zero and was removed from the refinement. The structure exhibits a partial molecular disorder. The disorder was successfully modeled and refined with the help of similarity restraints on 1,2- and 1,3-distances and displacement parameters as well as advanced rigid-bond restraints (Thorn et al., 2012) for anisotropic displacement parameters, and interatomic distance restraints.

Related literature top

For syntheses of the title compound, see: Anwar & Hansen (2008); Nakai et al. (2014); Whiting et al. (2015). For its use as a synthetic reagent, see: Li & Chua (2011); Mulzer & Coates (2011). For related crystal structures, see: Beswick et al. (1996); Oh & Tanski (2012). For information on π-stacking, see: Hunter & Sanders (1990); Lueckheide et al. (2013). For information on the refinement of disordered crystal structures, see: Müller (2009); Thorn et al. (2012).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL2014 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL2014 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008).

Figures top

Fig. 1. : A view of the title compound showing the disordered nitrile and bromine substituents, with displacement ellipsoids shown at the 50% probability level.

Fig. 2. : A view of the intermolecular O—H···Br/O—H···N_nitrile hydrogen bonding interactions (dashed lines) forming a helical one-dimensional chain, with displacement ellipsoids shown at the 50% probability level. See Table 1 for symmetry code (i). A thin solid line indicates an intramolecular O—H···Br hydrogen bond, and a thick solid line indicates a π-stacking centroid-to-centroid interaction.

3-Bromo-2-hydroxybenzonitrile top

Crystal data top

C₇H₄BrNO	F(000) = 384
M_r = 198.02	D_x = 1.941 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.0171 (7) Å	Cell parameters from 6401 reflections
b = 3.8488 (2) Å	θ = 3.0–30.5°
c = 13.5989 (7) Å	µ = 5.98 mm⁻¹
β = 96.062 (1)°	T = 125 K
V = 677.50 (6) Å³	Needle, colourless
Z = 4	0.22 × 0.10 × 0.04 mm

Data collection top

Bruker APEXII CCD diffractometer	1977 independent reflections
Radiation source: fine-focus sealed tube	1776 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.0°, θ_min = 3.0°
ϕ and ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −5→5
T_min = 0.57, T_max = 0.80	l = −19→19
9903 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.020	Hydrogen site location: mixed
wR(F²) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0241P)² + 0.2328P] where P = (F_o² + 2F_c²)/3
1977 reflections	(Δ/σ)_max = 0.002
110 parameters	Δρ_max = 0.37 e Å⁻³
102 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₇H₄BrNO	V = 677.50 (6) Å³
M_r = 198.02	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.0171 (7) Å	µ = 5.98 mm⁻¹
b = 3.8488 (2) Å	T = 125 K
c = 13.5989 (7) Å	0.22 × 0.10 × 0.04 mm
β = 96.062 (1)°

Data collection top

Bruker APEXII CCD diffractometer	1977 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1776 reflections with I > 2σ(I)
T_min = 0.57, T_max = 0.80	R_int = 0.025
9903 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	102 restraints
wR(F²) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.37 e Å⁻³
1977 reflections	Δρ_min = −0.45 e Å⁻³
110 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.70927 (9)	0.4093 (4)	0.76425 (9)	0.0264 (3)
H1	0.6483 (13)	0.420 (6)	0.7450 (18)	0.04*
C1	0.66122 (12)	0.6091 (4)	0.92251 (12)	0.0195 (3)
C7	0.5648 (2)	0.7338 (8)	0.8786 (2)	0.0225 (6)	0.9272 (13)
N1	0.4862 (2)	0.8421 (7)	0.84343 (18)	0.0281 (5)	0.9272 (13)
Br1A	0.5216 (4)	0.7707 (10)	0.8684 (3)	0.0332 (13)	0.0728 (13)
C2	0.73013 (11)	0.4575 (4)	0.86256 (11)	0.0185 (3)
C3	0.82692 (11)	0.3564 (4)	0.90818 (11)	0.0186 (3)
Br1	0.92397 (2)	0.15982 (5)	0.82834 (2)	0.02008 (6)	0.9272 (13)
C7A	0.8979 (14)	0.192 (6)	0.8577 (15)	0.02008 (6)	0.0728 (13)
N1A	0.9658 (13)	0.131 (5)	0.8138 (13)	0.02008 (6)	0.0728 (13)
C4	0.85334 (13)	0.3982 (4)	1.00854 (12)	0.0234 (3)
H4	0.9194	0.3259	1.0376	0.028*
C5	0.78350 (14)	0.5460 (5)	1.06728 (12)	0.0267 (3)
H5	0.8017	0.5739	1.1363	0.032*
C6	0.68739 (13)	0.6519 (4)	1.02446 (12)	0.0237 (3)
H6	0.6394	0.7532	1.064	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0175 (5)	0.0414 (7)	0.0194 (5)	0.0021 (5)	−0.0026 (4)	−0.0046 (5)
C1	0.0174 (7)	0.0191 (7)	0.0216 (7)	−0.0012 (5)	0.0008 (6)	0.0021 (6)
C7	0.0186 (12)	0.0255 (11)	0.0237 (10)	0.0015 (11)	0.0044 (11)	−0.0002 (7)
N1	0.0217 (12)	0.0369 (13)	0.0253 (11)	0.0038 (9)	0.0012 (8)	0.0005 (9)
Br1A	0.029 (3)	0.031 (2)	0.040 (2)	0.001 (2)	0.003 (2)	−0.0004 (15)
C2	0.0173 (7)	0.0186 (7)	0.0190 (7)	−0.0024 (6)	−0.0007 (5)	0.0016 (6)
C3	0.0161 (6)	0.0173 (7)	0.0224 (7)	−0.0009 (6)	0.0012 (5)	0.0015 (6)
Br1	0.01502 (9)	0.02106 (9)	0.02437 (10)	0.00176 (7)	0.00305 (6)	−0.00176 (7)
C7A	0.01502 (9)	0.02106 (9)	0.02437 (10)	0.00176 (7)	0.00305 (6)	−0.00176 (7)
N1A	0.01502 (9)	0.02106 (9)	0.02437 (10)	0.00176 (7)	0.00305 (6)	−0.00176 (7)
C4	0.0198 (7)	0.0252 (8)	0.0241 (8)	−0.0006 (6)	−0.0037 (6)	0.0047 (6)
C5	0.0290 (8)	0.0325 (9)	0.0176 (7)	−0.0004 (7)	−0.0023 (6)	0.0027 (7)
C6	0.0236 (8)	0.0265 (8)	0.0215 (7)	−0.0004 (6)	0.0043 (6)	0.0003 (7)

Geometric parameters (Å, º) top

O1—C2	1.3487 (19)	C3—C4	1.381 (2)
O1—H1	0.810 (16)	C3—Br1	1.9071 (16)
C1—C2	1.401 (2)	C7A—N1A	1.143 (16)
C1—C6	1.402 (2)	C4—C5	1.393 (2)
C1—C7	1.416 (3)	C4—H4	0.95
C1—Br1A	1.988 (5)	C5—C6	1.384 (2)
C7—N1	1.161 (4)	C5—H5	0.95
C2—C3	1.400 (2)	C6—H6	0.95
C3—C7A	1.363 (14)

C2—O1—H1	113.7 (18)	C4—C3—Br1	119.86 (12)
C2—C1—C6	121.38 (14)	C2—C3—Br1	118.52 (11)
C2—C1—C7	119.29 (17)	N1A—C7A—C3	164 (3)
C6—C1—C7	119.28 (17)	C3—C4—C5	120.30 (15)
C2—C1—Br1A	122.09 (17)	C3—C4—H4	119.9
C6—C1—Br1A	116.52 (16)	C5—C4—H4	119.9
N1—C7—C1	178.7 (4)	C6—C5—C4	119.63 (15)
O1—C2—C3	118.60 (14)	C6—C5—H5	120.2
O1—C2—C1	124.04 (14)	C4—C5—H5	120.2
C3—C2—C1	117.35 (14)	C5—C6—C1	119.71 (16)
C7A—C3—C4	116.1 (9)	C5—C6—H6	120.1
C7A—C3—C2	122.2 (9)	C1—C6—H6	120.1
C4—C3—C2	121.62 (15)

C6—C1—C2—O1	179.94 (15)	C1—C2—C3—Br1	−178.46 (11)
C7—C1—C2—O1	−2.6 (3)	C4—C3—C7A—N1A	−88 (8)
Br1A—C1—C2—O1	0.4 (3)	C2—C3—C7A—N1A	96 (8)
C6—C1—C2—C3	−1.2 (2)	C7A—C3—C4—C5	−176.5 (12)
C7—C1—C2—C3	176.33 (18)	C2—C3—C4—C5	−0.4 (2)
Br1A—C1—C2—C3	179.33 (18)	Br1—C3—C4—C5	179.11 (13)
O1—C2—C3—C7A	−4.1 (13)	C3—C4—C5—C6	−0.2 (3)
C1—C2—C3—C7A	176.9 (13)	C4—C5—C6—C1	0.1 (3)
O1—C2—C3—C4	−179.97 (15)	C2—C1—C6—C5	0.6 (2)
C1—C2—C3—C4	1.1 (2)	C7—C1—C6—C5	−176.89 (19)
O1—C2—C3—Br1	0.5 (2)	Br1A—C1—C6—C5	−179.86 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.81 (2)	2.04 (2)	2.810 (3)	159 (2)
O1—H1···Br1A	0.81 (2)	2.82 (2)	3.262 (5)	116 (2)
O1—H1···Br1Aⁱ	0.81 (2)	2.62 (2)	3.379 (5)	156 (2)

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.810 (16)	2.038 (18)	2.810 (3)	159.(2)
O1—H1···Br1A	0.810 (16)	2.82 (2)	3.262 (5)	116.(2)
O1—H1···Br1Aⁱ	0.810 (16)	2.621 (19)	3.379 (5)	156.(2)

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Acknowledgements

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

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