Crystal structure of 3-bromo-2-hy-droxy-benzo-nitrile.

The crystal structure of the title compound, C7H4BrNO, has been determined, revealing a partial mol-ecular packing disorder such that a 180° rotation of the mol-ecule 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 intra-molecular O-H⋯Br contact occurs. In the crystal, O-H⋯Br/O-H⋯Nnitrile 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 mol-ecules also inter-act, forming offset face-to-face π-stacking inter-actions with plane-to-centroid distance of 3.487 (1) Å.

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 ▸).

Experimental

Crystal data

C7H4BrNO

M = 198.02

Monoclinic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.049

S = 1.08

1977 reflections

110 parameters

102 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.37 e Å−3

Δρmin = −0.45 e Å−3

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 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015011974/ld2134sup1.cif

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

Click here for additional data file.

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

Click here for additional data file.

. DOI: 10.1107/S2056989015011974/ld2134fig1.tif

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

Click here for additional data file.

O H O H nitrile . DOI: 10.1107/S2056989015011974/ld2134fig2.tif

A view of the inter­molecular O—H⋯Br/O—H⋯Nnitrile 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.

CCDC reference: 1408281

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

C7H4BrNO	F(000) = 384
Mr = 198.02	Dx = 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

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

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(Fo2) + (0.0241P)2 + 0.2328P] where P = (Fo2 + 2Fc2)/3
1977 reflections	(Δ/σ)max = 0.002
110 parameters	Δρmax = 0.37 e Å−3
102 restraints	Δρmin = −0.45 e Å−3

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.

	x	y	z	Uiso*/Ueq	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*

	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)

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)

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)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1H1N1i	0.81(2)	2.04(2)	2.810(3)	159(2)
O1H1Br1A	0.81(2)	2.82(2)	3.262(5)	116(2)
O1H1Br1A i	0.81(2)	2.62(2)	3.379(5)	156(2)

Symmetry code: (i) .