2-(3-Bromo-4-meth-oxy-phen-yl)acetic acid.

The title compound C(9)H(9)BrO(3), was synthesized by the regioselective bromination of 4-meth-oxy-phenyl-acetic acid using bromine in acetic acid in a 84% yield. In the mol-ecular structure, the meth-oxy group is almost coplanar with the phenyl ring within 0.06 Å; the acetic acid substituent is tilted by 78.15 (7)° relative to the ring. The C-C-C angles at the OMe, acetyl and Br substituents are 118.2 (2), 118.4 (2) and 121.5 (2)°, respectively, indicating that the Br atom is electron-withdrawing, whereas the other substituents possess electron-donating properties. In the crystal, the mol-ecules form centrosymmetric strongly O-H⋯O hydrogen-bonded dimers of the type R(2) (2)(8).

Related literature

For the use of the title compound in the synthesis of natural products such as Combretastatin A-4, see: Zou et al. (2008 ▶); for Verongamine, see: Wasserman & Wang (1998 ▶) and for model Vancomycin-type systems, see: Ghosh et al. (2009 ▶). The iodo-analogue featured in the synthesis of (+)-Phleichrome and (+)-Calphostin D, see: Morgan et al. (2010 ▶). For the synthesis of the title compound, see: Coutts et al., (1970 ▶); Morgan et al., (2007 ▶); Zou et al. (2008 ▶); Ghosh et al. (2009 ▶). For background for our program to introduce natural product synthesis, crystal growing techniques and single crystal X-ray diffraction data analysis into the undergraduate curriculum, see: Findlater et al., (2010 ▶); Guzei et al., (2010a ▶). For a discussion of hydrogen-bonding motif assignment, see: Guzei et al. (2010b ▶). Outlier reflections were omitted based on the statistics test described by Prince & Nicholson (1983 ▶) and Rollett (1988 ▶), and implemented in FCF_filter (Guzei, 2007 ▶).

Experimental

Crystal data

C9H9BrO3

M = 245.06

Monoclinic,

a = 12.5022 (4) Å

b = 8.2690 (2) Å

c = 9.0199 (3) Å

β = 93.573 (1)°

V = 930.67 (5) Å3

Z = 4

Cu Kα radiation

μ = 5.81 mm−1

T = 120 K

0.46 × 0.37 × 0.19 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: analytical (SADABS; Bruker, 2007 ▶) T min = 0.177, T max = 0.398

12598 measured reflections

1725 independent reflections

1708 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.073

S = 1.08

1725 reflections

120 parameters

H-atom parameters constrained

Δρmax = 0.86 e Å−3

Δρmin = −0.47 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ▶) and modiCIFer (Guzei, 2007 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020143/rk2206sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810020143/rk2206Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Enhanced figure: interactive version of Fig. 1

C9H9BrO3	F(000) = 488
Mr = 245.06	Dx = 1.749 Mg m−3
Monoclinic, P21/c	Melting point = 386.3–387.2 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 12.5022 (4) Å	Cell parameters from 9563 reflections
b = 8.2690 (2) Å	θ = 3.5–69.5°
c = 9.0199 (3) Å	µ = 5.81 mm−1
β = 93.573 (1)°	T = 120 K
V = 930.67 (5) Å3	Block, colourless
Z = 4	0.46 × 0.37 × 0.19 mm

Bruker SMART APEXII area-detector diffractometer	1725 independent reflections
Radiation source: fine-focus sealed tube	1708 reflections with I > 2σ(I)
graphite	Rint = 0.030
0.5° ω and 0.5° φ scans	θmax = 69.5°, θmin = 3.5°
Absorption correction: analytical (SADABS; Bruker, 2007)	h = −14→15
Tmin = 0.177, Tmax = 0.398	k = −9→10
12598 measured reflections	l = −10→10

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0442P)2 + 1.1574P] where P = (Fo2 + 2Fc2)/3
1725 reflections	(Δ/σ)max < 0.001
120 parameters	Δρmax = 0.86 e Å−3
0 restraints	Δρmin = −0.47 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Br1	0.253622 (18)	0.20274 (3)	0.38506 (3)	0.02281 (12)
O1	0.05071 (12)	0.0202 (2)	0.32075 (17)	0.0186 (3)
O2	0.40281 (14)	−0.3902 (2)	0.05910 (19)	0.0234 (4)
O3	0.50409 (14)	−0.3283 (2)	−0.12886 (19)	0.0229 (4)
H3	0.5326	−0.4178	−0.1071	0.034*
C1	0.12214 (17)	−0.0244 (3)	0.2209 (2)	0.0151 (4)
C2	0.22340 (18)	0.0476 (3)	0.2339 (2)	0.0148 (4)
C3	0.30189 (17)	0.0087 (3)	0.1381 (2)	0.0160 (4)
H3A	0.3701	0.0593	0.1493	0.019*
C4	0.28118 (18)	−0.1041 (3)	0.0255 (2)	0.0172 (5)
C5	0.1810 (2)	−0.1765 (3)	0.0129 (3)	0.0201 (5)
H5	0.1661	−0.2542	−0.0631	0.024*
C6	0.10183 (18)	−0.1383 (3)	0.1087 (3)	0.0181 (5)
H6	0.0339	−0.1898	0.0977	0.022*
C7	−0.05187 (18)	−0.0591 (3)	0.3100 (3)	0.0220 (5)
H7A	−0.0887	−0.0346	0.2135	0.033*
H7C	−0.0952	−0.0204	0.3896	0.033*
H7B	−0.0416	−0.1762	0.3195	0.033*
C8	0.3654 (2)	−0.1464 (3)	−0.0810 (3)	0.0209 (5)
H8A	0.4175	−0.0564	−0.0831	0.025*
H8B	0.3306	−0.1576	−0.1821	0.025*
C9	0.42502 (19)	−0.3007 (3)	−0.0408 (3)	0.0170 (5)

	U11	U22	U33	U12	U13	U23
Br1	0.02043 (17)	0.02308 (18)	0.02445 (17)	−0.00116 (9)	−0.00227 (11)	−0.00996 (9)
O1	0.0164 (7)	0.0206 (8)	0.0193 (8)	−0.0018 (6)	0.0047 (6)	−0.0044 (6)
O2	0.0309 (9)	0.0194 (8)	0.0214 (9)	0.0053 (7)	0.0119 (7)	0.0032 (7)
O3	0.0222 (9)	0.0241 (9)	0.0236 (9)	0.0068 (7)	0.0096 (7)	0.0059 (7)
C1	0.0169 (10)	0.0131 (10)	0.0152 (10)	0.0020 (8)	0.0009 (8)	0.0024 (8)
C2	0.0193 (10)	0.0110 (10)	0.0137 (10)	0.0010 (8)	−0.0029 (8)	−0.0009 (8)
C3	0.0163 (10)	0.0137 (10)	0.0180 (10)	0.0004 (8)	0.0005 (8)	0.0035 (8)
C4	0.0210 (11)	0.0152 (11)	0.0157 (11)	0.0040 (9)	0.0041 (8)	0.0040 (8)
C5	0.0252 (12)	0.0181 (11)	0.0169 (11)	0.0004 (9)	0.0013 (9)	−0.0035 (9)
C6	0.0189 (11)	0.0165 (11)	0.0188 (11)	−0.0030 (9)	0.0005 (9)	−0.0020 (9)
C7	0.0160 (11)	0.0241 (12)	0.0262 (12)	−0.0026 (9)	0.0028 (9)	−0.0010 (10)
C8	0.0246 (12)	0.0211 (12)	0.0176 (11)	0.0032 (10)	0.0072 (9)	0.0016 (9)
C9	0.0178 (11)	0.0188 (12)	0.0145 (11)	−0.0014 (8)	0.0019 (9)	−0.0039 (8)

Br1—C2	1.893 (2)	C4—C5	1.386 (3)
O1—C1	1.359 (3)	C4—C8	1.510 (3)
O1—C7	1.438 (3)	C5—C6	1.390 (3)
O2—C9	1.212 (3)	C5—H5	0.9500
O3—C9	1.326 (3)	C6—H6	0.9500
O3—H3	0.8400	C7—H7A	0.9800
C1—C6	1.394 (3)	C7—H7C	0.9800
C1—C2	1.397 (3)	C7—H7B	0.9800
C2—C3	1.385 (3)	C8—C9	1.510 (3)
C3—C4	1.392 (3)	C8—H8A	0.9900
C3—H3A	0.9500	C8—H8B	0.9900
C1—O1—C7	116.85 (18)	C5—C6—H6	120.0
C9—O3—H3	109.5	C1—C6—H6	120.0
O1—C1—C6	124.6 (2)	O1—C7—H7A	109.5
O1—C1—C2	117.3 (2)	O1—C7—H7C	109.5
C6—C1—C2	118.2 (2)	H7A—C7—H7C	109.5
C3—C2—C1	121.5 (2)	O1—C7—H7B	109.5
C3—C2—Br1	119.28 (17)	H7A—C7—H7B	109.5
C1—C2—Br1	119.23 (17)	H7C—C7—H7B	109.5
C2—C3—C4	120.3 (2)	C4—C8—C9	113.34 (19)
C2—C3—H3A	119.9	C4—C8—H8A	108.9
C4—C3—H3A	119.9	C9—C8—H8A	108.9
C5—C4—C3	118.4 (2)	C4—C8—H8B	108.9
C5—C4—C8	120.7 (2)	C9—C8—H8B	108.9
C3—C4—C8	120.9 (2)	H8A—C8—H8B	107.7
C4—C5—C6	121.7 (2)	O2—C9—O3	123.7 (2)
C4—C5—H5	119.2	O2—C9—C8	124.2 (2)
C6—C5—H5	119.2	O3—C9—C8	112.16 (19)
C5—C6—C1	120.0 (2)
C7—O1—C1—C6	1.2 (3)	C3—C4—C5—C6	0.4 (3)
C7—O1—C1—C2	−177.70 (19)	C8—C4—C5—C6	−179.3 (2)
O1—C1—C2—C3	179.39 (19)	C4—C5—C6—C1	0.1 (4)
C6—C1—C2—C3	0.4 (3)	O1—C1—C6—C5	−179.4 (2)
O1—C1—C2—Br1	−1.0 (3)	C2—C1—C6—C5	−0.5 (3)
C6—C1—C2—Br1	180.00 (17)	C5—C4—C8—C9	−81.5 (3)
C1—C2—C3—C4	0.1 (3)	C3—C4—C8—C9	98.8 (3)
Br1—C2—C3—C4	−179.53 (17)	C4—C8—C9—O2	5.8 (3)
C2—C3—C4—C5	−0.5 (3)	C4—C8—C9—O3	−175.0 (2)
C2—C3—C4—C8	179.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2i	0.84	1.82	2.661 (2)	179

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2i	0.84	1.82	2.661 (2)	179

Symmetry code: (i) .