Crystal structure of 2-bromo-benzoic acid at 120 K: a redetermination.

The crystal structure of the title compound, C7H5BrO2, was originally studied using photographic data at room temperature with Cu Kα radiation [Ferguson & Sim (1962 ▶). Acta Cryst. 15, 346-350]. The present study was undertaken at 120 K with a CCD diffractometer using Cu Kα radiation, and resulted in improved geometrical parameters. In the mol-ecule, the carb-oxy group is inclined to the benzene ring by 18.7 (2)° and there is a close intra-molecular Br⋯O contact of 3.009 (3) Å. In the crystal, mol-ecules are linked by pairs of O-H⋯O hydrogen bonds, forming inversion dimers with the classical R 2 (2)(8) ring motif for carb-oxy-lic acids. Neighbouring dimers are linked by weak C-H⋯O hydrogen bonds, forming tapes propagating in [1-10]. Adjacent tapes inter-act by slipped parallel π-π inter-actions [inter-centroid distance = 3.991 (2), inter-planar distance = 3.509 (2) Å, slippage = 1.900 Å] to form columns approximately along the b-axis direction. Neighbouring columns inter-act dispersively, forming a three-dimensional framework structure.

Related literature

For the original report of the unit-cell dimensions, space group and structure of the title compound, see: Ferguson & Sim (1962 ▶). For uses of the title compound in organic synthesis, see: Evano et al. (2008 ▶); Wolf et al. (2006 ▶), and for its physicochemical properties, see: Govindarajan et al. (2011 ▶); Sabbah & Aguilar (1996 ▶); Swaminathan et al. (2009 ▶). For related structures involving the title compound, see: Das et al. (2012 ▶); Wales et al. (2012 ▶). For reports on Br⋯O inter­actions, see: Jones & Lozano (2004 ▶); Saeed et al. (2013 ▶); Singh et al. (2009 ▶).

Experimental

Crystal data

C7H5BrO2

M = 201.01

Monoclinic,

a = 14.7955 (4) Å

b = 3.99062 (15) Å

c = 22.9240 (8) Å

β = 96.906 (3)°

V = 1343.69 (8) Å3

Z = 8

Cu Kα radiation

μ = 7.76 mm−1

T = 120 K

0.55 × 0.35 × 0.28 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.722, T max = 0.991

10883 measured reflections

1201 independent reflections

1172 reflections with I > 2σ(I)

R int = 0.067

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.091

S = 1.18

1201 reflections

95 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.82 e Å−3

Δρmin = −0.52 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Burnett & Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681402087X/su2783sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681402087X/su2783Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681402087X/su2783Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S160053681402087X/su2783fig1.tif

The mol­ecular structure of the title mol­ecule, with atom labeling. Displacement ellipsoids are drawn at the 25% probability level. The short intra­molecular Br⋯O contact [3.009 (3) Å] is shown as a dashed line.

Click here for additional data file.

ac x y z x y z x y z . DOI: 10.1107/S160053681402087X/su2783fig2.tif

A partial view perpendicular to the ac plane of the crystal packing of the title compound. The O–H⋯O and C–H⋯O hydrogen bonds are represented by dashed lines [see Table 1 for details; symmetry codes: (i) –x + 1, –y + 1, –z + 1; (ii) x–1/2, y + , z; (iii) –x + , –y + , –z + 1].

Click here for additional data file.

b x y z . DOI: 10.1107/S160053681402087X/su2783fig3.tif

A view along the b axis of the crystal packing of the title compound. The π–π inter­actions are represented by dashed lines [symmetry code: (iv) x, y + 1, z].

CCDC reference: 1024798

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

C7H5BrO2	F(000) = 784
Mr = 201.01	Dx = 1.987 Mg m−3
Monoclinic, C2/c	Melting point: 422.6 K
Hall symbol: -C 2yc	Cu Kα radiation, λ = 1.54184 Å
a = 14.7955 (4) Å	Cell parameters from 10883 reflections
b = 3.99062 (15) Å	θ = 3.9–67.3°
c = 22.9240 (8) Å	µ = 7.76 mm−1
β = 96.906 (3)°	T = 120 K
V = 1343.69 (8) Å3	Block, white
Z = 8	0.55 × 0.35 × 0.28 mm

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	1201 independent reflections
Radiation source: fine-focus sealed tube	1172 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
Detector resolution: 10.4002 pixels mm-1	θmax = 67.3°, θmin = 3.9°
ω scans	h = −17→17
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −4→4
Tmin = 0.722, Tmax = 0.991	l = −27→27
10883 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ2(Fo2) + (0.048P)2 + 4.6943P] where P = (Fo2 + 2Fc2)/3
1201 reflections	(Δ/σ)max < 0.001
95 parameters	Δρmax = 0.82 e Å−3
1 restraint	Δρmin = −0.52 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.3119 (2)	0.3168 (9)	0.40413 (14)	0.0222 (7)
C2	0.3109 (2)	0.1534 (9)	0.34999 (14)	0.0230 (7)
C3	0.2293 (2)	0.0629 (9)	0.31713 (16)	0.0268 (8)
H3	0.2296	−0.0469	0.2814	0.032*
C4	0.1473 (2)	0.1375 (10)	0.33802 (16)	0.0297 (8)
H4	0.0927	0.0740	0.3164	0.036*
C5	0.1463 (2)	0.3045 (10)	0.39040 (15)	0.0277 (8)
H5	0.0912	0.3580	0.4038	0.033*
C6	0.2278 (2)	0.3931 (10)	0.42318 (15)	0.0265 (8)
H6	0.2266	0.5057	0.4586	0.032*
C7	0.3963 (2)	0.4020 (9)	0.44374 (15)	0.0243 (7)
O8	0.47061 (15)	0.2776 (8)	0.44031 (11)	0.0337 (6)
O9	0.38191 (16)	0.6217 (8)	0.48460 (11)	0.0315 (6)
H9	0.427 (2)	0.659 (12)	0.5071 (15)	0.033 (11)*
Br10	0.41826 (2)	0.04521 (11)	0.315985 (15)	0.03005 (19)

	U11	U22	U33	U12	U13	U23
C1	0.0158 (15)	0.0262 (18)	0.0240 (16)	0.0011 (13)	−0.0009 (12)	0.0025 (14)
C2	0.0188 (15)	0.0263 (18)	0.0232 (16)	0.0026 (13)	−0.0001 (12)	0.0022 (14)
C3	0.0231 (18)	0.031 (2)	0.0248 (17)	0.0008 (14)	−0.0028 (14)	−0.0001 (14)
C4	0.0181 (16)	0.036 (2)	0.0326 (18)	−0.0030 (15)	−0.0053 (13)	0.0049 (16)
C5	0.0154 (15)	0.036 (2)	0.0308 (17)	0.0016 (14)	0.0007 (13)	0.0050 (16)
C6	0.0192 (17)	0.037 (2)	0.0225 (16)	0.0034 (15)	0.0012 (13)	0.0033 (15)
C7	0.0209 (17)	0.0309 (19)	0.0207 (16)	−0.0011 (14)	0.0009 (13)	0.0034 (14)
O8	0.0147 (12)	0.0520 (18)	0.0326 (13)	0.0064 (11)	−0.0052 (9)	−0.0121 (12)
O9	0.0183 (12)	0.0472 (17)	0.0277 (13)	0.0030 (12)	−0.0035 (10)	−0.0109 (12)
Br10	0.0190 (2)	0.0420 (3)	0.0286 (3)	0.00389 (14)	0.00077 (16)	−0.00733 (15)

C1—C2	1.400 (5)	C4—H4	0.9300
C1—C6	1.401 (5)	C5—C6	1.388 (5)
C1—C7	1.492 (5)	C5—H5	0.9300
C2—C3	1.392 (5)	C6—H6	0.9300
C2—Br10	1.901 (3)	C7—O8	1.217 (4)
C3—C4	1.389 (5)	C7—O9	1.319 (5)
C3—H3	0.9300	O9—H9	0.803 (19)
C4—C5	1.375 (5)
C2—C1—C6	117.5 (3)	C3—C4—H4	119.8
C2—C1—C7	124.4 (3)	C4—C5—C6	119.8 (3)
C6—C1—C7	118.1 (3)	C4—C5—H5	120.1
C3—C2—C1	121.1 (3)	C6—C5—H5	120.1
C3—C2—Br10	115.6 (3)	C5—C6—C1	121.5 (3)
C1—C2—Br10	123.3 (2)	C5—C6—H6	119.2
C4—C3—C2	119.7 (3)	C1—C6—H6	119.2
C4—C3—H3	120.2	O8—C7—O9	122.8 (3)
C2—C3—H3	120.2	O8—C7—C1	124.3 (3)
C5—C4—C3	120.4 (3)	O9—C7—C1	112.9 (3)
C5—C4—H4	119.8	C7—O9—H9	113 (3)
C6—C1—C2—C3	−1.6 (5)	C4—C5—C6—C1	0.1 (6)
C7—C1—C2—C3	175.8 (3)	C2—C1—C6—C5	1.3 (5)
C6—C1—C2—Br10	177.6 (3)	C7—C1—C6—C5	−176.3 (3)
C7—C1—C2—Br10	−4.9 (5)	C2—C1—C7—O8	−17.1 (6)
C1—C2—C3—C4	0.5 (6)	C6—C1—C7—O8	160.4 (4)
Br10—C2—C3—C4	−178.8 (3)	C2—C1—C7—O9	164.8 (3)
C2—C3—C4—C5	1.0 (6)	C6—C1—C7—O9	−17.7 (5)
C3—C4—C5—C6	−1.3 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O8i	0.81 (3)	1.84 (3)	2.643 (3)	177 (5)
C5—H5···O8ii	0.93	2.65	3.514 (3)	153
C6—H6···O9iii	0.93	2.64	3.417 (3)	141

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9⋯O8i	0.81 (3)	1.84 (3)	2.643 (3)	177 (5)
C5—H5⋯O8ii	0.93	2.65	3.514 (3)	153
C6—H6⋯O9iii	0.93	2.64	3.417 (3)	141

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