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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3163.
Published online 2010 November 13. doi:  10.1107/S1600536810045642
PMCID: PMC3011740

meso-Dimethyl 2,5-dibromo­hexa­ne­dioate

Abstract

The title compound, C8H12Br2O4, lies about a crystallographic center of inversion at the midpoint of the central C—C bond. The latter is also repsonsible for the observation of the meso form. There are no intra­molecular hydrogen bonds, but mol­ecules are connected by inter­molecular C—H(...)O inter­actions, forming a three-dimensional network.

Related literature

The title compound is an important intermediate in organic synthesis. For the synthetic procedure, see: McDonald & Reitz (1972 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-66-o3163-scheme1.jpg

Experimental

Crystal data

  • C8H12Br2O4
  • M r = 331.98
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3163-efi3.jpg
  • a = 4.5580 (9) Å
  • b = 12.134 (2) Å
  • c = 10.554 (2) Å
  • β = 90.36 (3)°
  • V = 583.7 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 6.93 mm−1
  • T = 293 K
  • 0.20 × 0.10 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.338, T max = 0.544
  • 1428 measured reflections
  • 1271 independent reflections
  • 639 reflections with I > 2σ(I)
  • R int = 0.071
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.072
  • S = 1.00
  • 1271 reflections
  • 64 parameters
  • 3 restraints
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1985 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810045642/im2243sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045642/im2243Isup2.hkl

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

Acknowledgments

This work was supported by the Science Fundamental Research Fund of the Education Department, Jiangsu Province (No. 09kjd150011). The authors also thank the Center of Testing and Analysis, Nanjing University, for the data collection.

supplementary crystallographic information

Comment

The tittle compound, meso-2,5-dibromo-hexanedioic acid dimethyl ester is an important intermediate for the synthesis of dimethyl cyclobut-1-ene-1,2-dicarboxylate. We herein report the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles are within normal ranges (Allen et al., 1987).

The central C4—C4A bond of the title compound, C8H12Br2O4, represents a crystallographic center of inversion. The latter is also repsonsible for the observation of the meso form. There are no intramolecular hydrogen bonds, but molecules of the title compound are connected by C—H···O intermolecular interactions to form a three dimensional network (Table 1).

Experimental

The title compound, (I) was prepared by a method reported in literature (McDonald & Reitz, 1972). Single crystals were obtained by dissolving (I) (0.5 g, 1.5 mmol) in ethanol (25 ml) and evaporating the solvent slowly at room temperature for about 3 d.

Refinement

H atoms were positioned geometrically, with C—H = 0.96 Å for alkyl H, and constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C).

Figures

Fig. 1.
Molecular structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Atoms labeled with the suffixes A are generated by the symmetry operation (1/2 - x, 3/2 - y, 1 - z). Hydrogen ...
Fig. 2.
Packing diagram for (I). C—H···O hydrogen bonds are shown as dashed lines.

Crystal data

C8H12Br2O4F(000) = 324
Mr = 331.98Dx = 1.889 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 4.5580 (9) Åθ = 9–13°
b = 12.134 (2) ŵ = 6.93 mm1
c = 10.554 (2) ÅT = 293 K
β = 90.36 (3)°Block, colourless
V = 583.7 (2) Å30.20 × 0.10 × 0.10 mm
Z = 2

Data collection

Enraf–Nonius CAD-4 diffractometer639 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.071
graphiteθmax = 27.1°, θmin = 2.6°
ω/2θ scansh = 0→5
Absorption correction: ψ scan (North et al., 1968)k = −15→0
Tmin = 0.338, Tmax = 0.544l = −13→13
1428 measured reflections3 standard reflections every 200 reflections
1271 independent reflections intensity decay: 1%

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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.022P)2] where P = (Fo2 + 2Fc2)/3
1271 reflections(Δ/σ)max < 0.001
64 parametersΔρmax = 0.33 e Å3
3 restraintsΔρmin = −0.37 e Å3

Special details

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.

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

xyzUiso*/Ueq
Br0.23822 (12)0.64074 (4)0.70596 (6)0.0813 (2)
O10.3762 (8)0.4221 (3)0.8857 (4)0.0888 (12)
O20.0821 (9)0.3620 (3)0.7400 (4)0.0980 (12)
C10.2255 (11)0.3583 (4)0.9715 (5)0.0872 (17)
H1A0.32630.35951.05160.131*
H1B0.21440.28390.94090.131*
H1C0.03100.38720.98170.131*
C20.2723 (12)0.4259 (4)0.7836 (5)0.0572 (12)
C30.4550 (10)0.4973 (3)0.6885 (4)0.0477 (11)
H3A0.65950.50440.71660.057*
C40.4369 (9)0.4614 (3)0.5570 (4)0.0475 (11)
H4A0.23150.44760.53840.057*
H4B0.53700.39110.55170.057*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.0997 (4)0.0232 (2)0.1214 (5)0.0072 (3)0.0337 (3)−0.0032 (4)
O10.111 (3)0.058 (2)0.098 (3)0.002 (2)0.007 (2)0.035 (2)
O20.119 (3)0.063 (3)0.112 (3)−0.028 (3)0.023 (2)0.020 (3)
C10.123 (5)0.061 (4)0.078 (3)0.014 (4)0.029 (3)0.022 (3)
C20.062 (3)0.040 (3)0.070 (3)0.006 (3)0.022 (2)0.025 (3)
C30.070 (3)0.029 (2)0.043 (2)−0.002 (2)−0.0005 (19)−0.0068 (19)
C40.063 (3)0.029 (2)0.050 (3)−0.004 (2)−0.006 (2)0.007 (2)

Geometric parameters (Å, °)

Br—C32.011 (4)C2—C31.569 (6)
O1—C21.175 (5)C3—C41.456 (5)
O1—C11.378 (5)C3—H3A0.9800
O2—C21.249 (6)C4—C4i1.632 (7)
C1—H1A0.9600C4—H4A0.9700
C1—H1B0.9600C4—H4B0.9700
C1—H1C0.9600
C2—O1—C1115.1 (5)C4—C3—Br108.7 (3)
O1—C1—H1A109.5C2—C3—Br99.0 (3)
O1—C1—H1B109.5C4—C3—H3A111.3
H1A—C1—H1B109.5C2—C3—H3A111.3
O1—C1—H1C109.5Br—C3—H3A111.3
H1A—C1—H1C109.5C3—C4—C4i120.9 (4)
H1B—C1—H1C109.5C3—C4—H4A107.1
O1—C2—O2126.0 (5)C4i—C4—H4A107.1
O1—C2—C3113.3 (5)C3—C4—H4B107.1
O2—C2—C3118.5 (5)C4i—C4—H4B107.1
C4—C3—C2114.7 (4)H4A—C4—H4B106.8
C1—O1—C2—O2−15.8 (8)O1—C2—C3—Br−95.3 (4)
C1—O1—C2—C3−178.7 (4)O2—C2—C3—Br100.4 (4)
O1—C2—C3—C4149.2 (4)C2—C3—C4—C4i168.8 (4)
O2—C2—C3—C4−15.1 (6)Br—C3—C4—C4i59.1 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3A···O2ii0.982.593.33 (1)132

Symmetry codes: (ii) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2243).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Enraf–Nonius (1985). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • McDonald, R. N. & Reitz, R. R. (1972). J. Org. Chem.37, 2418–2423.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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