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Acta Cryst. (2008). E64, o1946    [ doi:10.1107/S160053680802919X ]

2,3-Dibromo-3-phenylpropionic acid

P. Y. Thong, K. M. Lo and S. W. Ng

Abstract top

In the crystal of the title compound, C9H8Br2O2, inversion dimers linked by two O-H...O hydrogen bonds occur. All of the carbon and oxygen atoms are disordered over two sets of sites in a 2:1 ratio.

Comment top

The compound (Scheme I, Fig. 1) was obtained as a side-product from the reaction of cyclopentyldiphenyltin cinnamate and 4-dimethylaminopyridine hydrobromide perbromide. Possibly, bromine added across the double bond of the cinnamate group followed by cleavage of the tin–carbon bond. Only few dihalogenproponic acid derivatives have been characterized by X-ray crystallography. These are limited to, for example, threo-methyl 2,3-difluoropropionate (O'Hagan et al., 2006) and R-methyl 3-bromo-2-chloro-3-phenylpropionate (Shaw et al., 1995).

Related literature top

For threo-1,2-diphenyl-2,3-difluoropropionate, see: O'Hagan et al. (2006). For R-methyl 3-bromo-2-chloro-3-phenylpropionate, see: Shaw et al. (1995).

Experimental top

The compound was obtained as a side-product from the reaction of cyclopentyldiphenyltin cinnamate (0.3 g, 0.6 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (0.25 g) in a mixture of chloroform and ethanol.

Refinement top

The structure is disordered over two positions with respect of the non-bromide atoms. The Br1 atom is connected to the carbon atom in the 2-position in the major component but is connected to the carbon atom in the 3-position in the minor component. Conversely, the Br2 atom is connected to the carbon atom in the 3-position in the major component but is connected to the carbon atom in the 2-position in the minor component. All distances in the major component were restrained to within 0.01 Å of their equivalents in the minor component. The phenyl rings were restrained into rigid hexagons of 1.39 Å sides. Additionally, the four-atom carboxyl and seven-atom benzyl units were each restrained to be nearly flat. The anisotropic displacement parameters of the primed atoms were restrained to be equal to those of the unprimed atoms; these were also restrained to be nearly isotropic. In the inital stages of the refinement, the occupancy refined to an approximate 2:1 ratio. However, with the inclusion of hydrogen atoms, the refinement was unstable. Ratios that were either slightly smaller or slightly larger than 2:1 did not yield any significant differences in the final residual index. The ratio was then fixed to 2:1 Oxygen and carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 1.00 Å, O–H 0.84 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5Ueq(C,O).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-Seed (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. 70% Probability thermal ellipsoid plot (Barbour, 2001) of C9H8Br2O2. Hydrogen atoms are drawn as spheres of arbitrary radii. For clarity, the minor component is not shown.
2,3-Dibromo-3-phenylpropionic acid top
Crystal data top
C9H8Br2O2F(000) = 1184
Mr = 307.97Dx = 2.046 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 8127 reflections
a = 7.0278 (1) Åθ = 2.2–28.2°
b = 9.7105 (1) ŵ = 8.07 mm−1
c = 29.2970 (4) ÅT = 100 K
V = 1999.33 (4) Å3Block, colorless
Z = 80.28 × 0.22 × 0.14 mm
Data collection top
Bruker SMART APEX
diffractometer		2303 independent reflections
Radiation source: fine-focus sealed tube2056 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.211, Tmax = 0.398k = −12→12
17420 measured reflectionsl = −37→38
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0337P)2 + 3.2334P]
where P = (Fo2 + 2Fc2)/3
2303 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.61 e Å−3
83 restraintsΔρmin = −0.62 e Å−3
Crystal data top
C9H8Br2O2V = 1999.33 (4) Å3
Mr = 307.97Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.0278 (1) ŵ = 8.07 mm−1
b = 9.7105 (1) ÅT = 100 K
c = 29.2970 (4) Å0.28 × 0.22 × 0.14 mm
Data collection top
Bruker SMART APEX
diffractometer		2303 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2056 reflections with I > 2σ(I)
Tmin = 0.211, Tmax = 0.398Rint = 0.027
17420 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.066Δρmax = 0.61 e Å−3
S = 1.06Δρmin = −0.62 e Å−3
2303 reflectionsAbsolute structure: ?
127 parametersFlack parameter: ?
83 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.48392 (4)0.31033 (3)0.364350 (9)0.02208 (9)
Br2−0.06355 (4)0.45596 (3)0.436758 (9)0.03094 (10)
O10.4216 (6)0.3279 (4)0.48256 (13)0.0308 (10)0.67
H1O0.47650.35690.50610.046*0.67
O20.4214 (10)0.5338 (5)0.4476 (3)0.0209 (10)0.67
C10.3847 (4)0.4118 (4)0.44922 (12)0.0189 (8)0.67
C20.2859 (5)0.3388 (4)0.40959 (12)0.0176 (7)0.67
H20.23440.24800.42000.021*0.67
C30.1313 (5)0.4223 (4)0.38839 (12)0.0183 (7)0.67
H30.18590.51300.37900.022*0.67
C40.0358 (4)0.3575 (5)0.34721 (14)0.0133 (8)0.67
C5−0.0307 (8)0.2228 (5)0.3486 (3)0.0186 (11)0.67
H5−0.01670.16970.37560.022*0.67
C6−0.1176 (9)0.1657 (9)0.3104 (4)0.0224 (6)0.67
H6−0.16310.07360.31140.027*0.67
C7−0.1381 (9)0.2433 (15)0.2709 (3)0.0181 (8)0.67
H7−0.19760.20430.24480.022*0.67
C8−0.0716 (13)0.3781 (14)0.26947 (16)0.0206 (7)0.67
H8−0.08560.43110.24240.025*0.67
C90.0154 (11)0.4352 (8)0.3076 (2)0.0183 (9)0.67
H90.06080.52730.30670.022*0.67
O1'0.3463 (14)0.3474 (10)0.4912 (3)0.0308 (10)0.33
H1'O0.42020.37150.51220.046*0.33
O2'0.380 (2)0.5445 (11)0.4542 (7)0.0209 (10)0.33
C1'0.3118 (9)0.4305 (9)0.4576 (2)0.0189 (8)0.33
C2'0.1737 (9)0.3684 (7)0.4228 (2)0.0176 (7)0.33
H2'0.16330.26660.42740.021*0.33
C3'0.2239 (9)0.3993 (8)0.3748 (2)0.0183 (7)0.33
H3'0.23550.50120.37090.022*0.33
C4'0.0862 (9)0.3432 (12)0.3394 (3)0.0133 (8)0.33
C5'0.0090 (19)0.2117 (12)0.3425 (6)0.0186 (11)0.33
H5'0.04210.15360.36740.022*0.33
C6'−0.1164 (19)0.165 (2)0.3092 (8)0.0224 (6)0.33
H6'−0.16920.07540.31130.027*0.33
C7'−0.1648 (18)0.250 (3)0.2729 (6)0.0181 (8)0.33
H7'−0.25050.21850.25010.022*0.33
C8'−0.088 (3)0.382 (3)0.2698 (4)0.0206 (7)0.33
H8'−0.12070.43980.24490.025*0.33
C9'0.038 (2)0.4282 (17)0.3031 (5)0.0183 (9)0.33
H9'0.09060.51810.30100.022*0.33
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02081 (14)0.02271 (15)0.02272 (15)−0.00251 (10)−0.00187 (10)−0.00479 (10)
Br20.03118 (17)0.04015 (19)0.02150 (15)0.00134 (13)0.00331 (11)−0.00921 (12)
O10.055 (3)0.0188 (16)0.0182 (18)−0.0063 (19)−0.0143 (18)0.0006 (13)
O20.034 (3)0.0169 (12)0.012 (3)0.0006 (16)−0.0033 (18)−0.0032 (12)
C10.023 (2)0.0199 (18)0.0139 (17)−0.0030 (19)−0.0010 (16)−0.0003 (14)
C20.0211 (17)0.0149 (15)0.0166 (16)−0.0017 (14)0.0007 (13)−0.0010 (12)
C30.021 (2)0.0159 (16)0.0175 (17)−0.0033 (15)0.0002 (14)−0.0028 (13)
C40.007 (2)0.0153 (17)0.017 (2)0.0062 (19)0.0015 (16)−0.0077 (14)
C50.016 (3)0.0174 (16)0.023 (3)0.0023 (17)−0.002 (2)−0.0009 (15)
C60.0180 (12)0.0183 (13)0.0310 (15)−0.0018 (10)−0.0052 (11)−0.0067 (11)
C70.009 (2)0.0239 (19)0.0215 (14)0.006 (2)−0.0035 (16)−0.0106 (11)
C80.0169 (19)0.0259 (15)0.0190 (12)0.0082 (15)0.0007 (11)−0.0025 (10)
C90.017 (2)0.0167 (14)0.0211 (18)0.0027 (13)0.0015 (14)−0.0037 (14)
O1'0.055 (3)0.0188 (16)0.0182 (18)−0.0063 (19)−0.0143 (18)0.0006 (13)
O2'0.034 (3)0.0169 (12)0.012 (3)0.0006 (16)−0.0033 (18)−0.0032 (12)
C1'0.023 (2)0.0199 (18)0.0139 (17)−0.0030 (19)−0.0010 (16)−0.0003 (14)
C2'0.0211 (17)0.0149 (15)0.0166 (16)−0.0017 (14)0.0007 (13)−0.0010 (12)
C3'0.021 (2)0.0159 (16)0.0175 (17)−0.0033 (15)0.0002 (14)−0.0028 (13)
C4'0.007 (2)0.0153 (17)0.017 (2)0.0062 (19)0.0015 (16)−0.0077 (14)
C5'0.016 (3)0.0174 (16)0.023 (3)0.0023 (17)−0.002 (2)−0.0009 (15)
C6'0.0180 (12)0.0183 (13)0.0310 (15)−0.0018 (10)−0.0052 (11)−0.0067 (11)
C7'0.009 (2)0.0239 (19)0.0215 (14)0.006 (2)−0.0035 (16)−0.0106 (11)
C8'0.0169 (19)0.0259 (15)0.0190 (12)0.0082 (15)0.0007 (11)−0.0025 (10)
C9'0.017 (2)0.0167 (14)0.0211 (18)0.0027 (13)0.0015 (14)−0.0037 (14)
Geometric parameters (Å, °) top
Br1—C21.942 (4)C8—H80.9500
Br1—C3'2.044 (6)C9—H90.9500
Br2—C2'1.916 (6)O1'—C1'1.295 (8)
Br2—C31.997 (3)O1'—H1'O0.8400
O1—C11.298 (4)O2'—C1'1.212 (8)
O1—H1O0.8400C1'—C2'1.533 (8)
O2—C11.213 (5)C2'—C3'1.480 (7)
C1—C21.527 (5)C2'—H2'1.0000
C2—C31.491 (5)C3'—C4'1.518 (7)
C2—H21.0000C3'—H3'1.0000
C3—C41.517 (4)C4'—C5'1.3900
C3—H31.0000C4'—C9'1.3900
C4—C51.3900C5'—C6'1.3900
C4—C91.3900C5'—H5'0.9500
C5—C61.3900C6'—C7'1.3900
C5—H50.9500C6'—H6'0.9500
C6—C71.3900C7'—C8'1.3900
C6—H60.9500C7'—H7'0.9500
C7—C81.3900C8'—C9'1.3900
C7—H70.9500C8'—H8'0.9500
C8—C91.3900C9'—H9'0.9500
C1—O1—H1O120.0C1'—O1'—H1'O120.0
O2—C1—O1126.8 (6)O2'—C1'—O1'124.0 (13)
O2—C1—C2121.4 (6)O2'—C1'—C2'123.8 (13)
O1—C1—C2111.8 (4)O1'—C1'—C2'112.3 (8)
C3—C2—C1113.3 (3)C3'—C2'—C1'113.7 (6)
C3—C2—Br1108.4 (2)C3'—C2'—Br2108.7 (4)
C1—C2—Br1105.0 (2)C1'—C2'—Br2103.5 (4)
C3—C2—H2110.0C3'—C2'—H2'110.2
C1—C2—H2110.0C1'—C2'—H2'110.2
Br1—C2—H2110.0Br2—C2'—H2'110.2
C2—C3—C4115.4 (3)C2'—C3'—C4'115.0 (6)
C2—C3—Br2107.0 (2)C2'—C3'—Br1105.6 (4)
C4—C3—Br2109.20 (19)C4'—C3'—Br1108.5 (4)
C2—C3—H3108.3C2'—C3'—H3'109.2
C4—C3—H3108.3C4'—C3'—H3'109.2
Br2—C3—H3108.3Br1—C3'—H3'109.2
C5—C4—C9120.0C5'—C4'—C9'120.0
C5—C4—C3121.0 (5)C5'—C4'—C3'122.3 (11)
C9—C4—C3119.0 (5)C9'—C4'—C3'117.7 (11)
C4—C5—C6120.0C4'—C5'—C6'120.0
C4—C5—H5120.0C4'—C5'—H5'120.0
C6—C5—H5120.0C6'—C5'—H5'120.0
C7—C6—C5120.0C7'—C6'—C5'120.0
C7—C6—H6120.0C7'—C6'—H6'120.0
C5—C6—H6120.0C5'—C6'—H6'120.0
C6—C7—C8120.0C6'—C7'—C8'120.0
C6—C7—H7120.0C6'—C7'—H7'120.0
C8—C7—H7120.0C8'—C7'—H7'120.0
C7—C8—C9120.0C7'—C8'—C9'120.0
C7—C8—H8120.0C7'—C8'—H8'120.0
C9—C8—H8120.0C9'—C8'—H8'120.0
C8—C9—C4120.0C8'—C9'—C4'120.0
C8—C9—H9120.0C8'—C9'—H9'120.0
C4—C9—H9120.0C4'—C9'—H9'120.0
O2—C1—C2—C3−40.3 (4)O2'—C1'—C2'—Br2−77.8 (5)
O1—C1—C2—C3140.0 (3)O1'—C1'—C2'—Br2102.1 (5)
O2—C1—C2—Br177.8 (3)C3—Br2—C2'—C3'0.9 (4)
O1—C1—C2—Br1−101.9 (2)C3—Br2—C2'—C1'122.1 (7)
C1—C2—C3—C4176.8 (3)C1'—C2'—C3'—C4'−178.0 (6)
Br1—C2—C3—C460.7 (4)Br2—C2'—C3'—C4'−63.3 (7)
C1—C2—C3—Br2−61.5 (3)C1'—C2'—C3'—Br162.4 (6)
Br1—C2—C3—Br2−177.59 (16)Br2—C2'—C3'—Br1177.1 (3)
C2—C3—C4—C549.8 (4)C2—Br1—C3'—C2'0.1 (3)
Br2—C3—C4—C5−70.8 (3)C2—Br1—C3'—C4'−123.7 (8)
C2—C3—C4—C9−130.2 (4)C2'—C3'—C4'—C5'−42.3 (8)
Br2—C3—C4—C9109.2 (3)Br1—C3'—C4'—C5'75.6 (6)
C9—C4—C5—C60.0C2'—C3'—C4'—C9'137.7 (8)
C3—C4—C5—C6−179.99 (8)Br1—C3'—C4'—C9'−104.3 (6)
C4—C5—C6—C70.0C9'—C4'—C5'—C6'0.0
C5—C6—C7—C80.0C3'—C4'—C5'—C6'−179.96 (9)
C6—C7—C8—C90.0C4'—C5'—C6'—C7'0.0
C7—C8—C9—C40.0C5'—C6'—C7'—C8'0.0
C5—C4—C9—C80.0C6'—C7'—C8'—C9'0.0
C3—C4—C9—C8179.99 (8)C7'—C8'—C9'—C4'0.0
O2'—C1'—C2'—C3'40.0 (6)C5'—C4'—C9'—C8'0.0
O1'—C1'—C2'—C3'−140.1 (6)C3'—C4'—C9'—C8'179.96 (8)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···O2i0.841.862.68 (1)165
O1'—H1'o···O2i0.841.862.69 (1)166
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···O2i0.841.862.68 (1)165
O1'—H1'o···O2i0.841.862.69 (1)166
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

We thank the University of Malaya for funding this study (FR155/2007 A) and also for the purchase of the diffractometer.

references
References top

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Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

O'Hagan, D., Rzepa, H. S., Schüler, M. & Slawin, A. M. Z. (2006). Beilstein J. Org. Chem. 2, No. 19.

Shaw, J. P., Tan, E. W. & Blackman, A. G. (1995). Acta Cryst. C51, 134–135.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2008). publCIF. In preparation.