PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o1946.
Published online 2008 September 17. doi:  10.1107/S160053680802919X
PMCID: PMC2959243

2,3-Dibromo-3-phenyl­propionic acid

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-o1946-scheme1.jpg

Experimental

Crystal data

  • C9H8Br2O2
  • M r = 307.97
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1946-efi1.jpg
  • a = 7.0278 (1) Å
  • b = 9.7105 (1) Å
  • c = 29.2970 (4) Å
  • V = 1999.33 (4) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 8.07 mm−1
  • T = 100 (2) K
  • 0.28 × 0.22 × 0.14 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.211, T max = 0.398 (expected range = 0.171–0.323)
  • 17420 measured reflections
  • 2303 independent reflections
  • 2056 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.066
  • S = 1.06
  • 2303 reflections
  • 127 parameters
  • 83 restraints
  • H-atom parameters constrained
  • Δρmax = 0.61 e Å−3
  • Δρmin = −0.62 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680802919X/tk2304sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802919X/tk2304Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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

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).

Figures

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.

Crystal data

C9H8Br2O2F(000) = 1184
Mr = 307.97Dx = 2.046 Mg m3
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 mm1
c = 29.2970 (4) ÅT = 100 K
V = 1999.33 (4) Å3Block, colorless
Z = 80.28 × 0.22 × 0.14 mm

Data collection

Bruker SMART APEX diffractometer2303 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

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 = 1.06w = 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 Å3
83 restraintsΔρmin = −0.62 e Å3

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

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2304).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • 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. [PMC free article] [PubMed]
  • 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. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography