Single crystals of 2-bromofumaric acid, C
4H
3BrO
4, were obtained from an aqueous solution of racemic 2,3-dibromosuccinic acid and (−)-quinine. The title compound crystallizes with two molecules in the asymmetric unit. The structure is stabilized by O—H
O hydrogen bonds forming alternating chains.
Supporting information
CCDC reference: 621507
Key indicators
- Single-crystal X-ray study
- T = 299 K
- Mean (C-C) = 0.005 Å
- R factor = 0.037
- wR factor = 0.072
- Data-to-parameter ratio = 16.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.42
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.44
PLAT701_ALERT_1_C Bond Calc 1.865(3), Rep 1.861(3), Dev.. 1.33 Sigma
BR1 -C2 1.555 1.555
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg, 1992); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: maXus (Mackay et al., 1999).
Crystal data top
C4H3BrO4 | Z = 4 |
Mr = 194.97 | F(000) = 376 |
Triclinic, P1 | Dx = 2.188 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8290 (4) Å | Cell parameters from 60 reflections |
b = 8.3791 (4) Å | θ = 4.3–22.0° |
c = 10.2443 (3) Å | µ = 6.88 mm−1 |
α = 69.572 (4)° | T = 299 K |
β = 70.383 (3)° | Fragment, colourless |
γ = 79.963 (4)° | 0.30 × 0.30 × 0.30 mm |
V = 591.97 (5) Å3 | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 1821 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.052 |
φ and ω scans | θmax = 27.5°, θmin = 4.5° |
Absorption correction: numerical (Herrendorf & Bärnighausen, 1997) | h = −10→10 |
Tmin = 0.581, Tmax = 0.661 | k = −10→10 |
11936 measured reflections | l = −13→12 |
2701 independent reflections | |
Refinement top
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.0231P)2 + 0.495P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2701 reflections | Δρmax = 0.33 e Å−3 |
167 parameters | Δρmin = −0.44 e Å−3 |
0 restraints | |
Special details top
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) top | x | y | z | Uiso*/Ueq | |
Br2 | 0.65543 (6) | 0.05029 (6) | 0.59519 (4) | 0.06076 (16) | |
Br1 | 0.56894 (5) | 0.50250 (5) | 0.68940 (4) | 0.05132 (14) | |
O8 | 0.7533 (4) | 0.1438 (3) | 0.2636 (3) | 0.0534 (7) | |
C2 | 0.4980 (4) | 0.3307 (4) | 0.8676 (3) | 0.0342 (8) | |
C4 | 0.2319 (5) | 0.2437 (5) | 0.8299 (4) | 0.0372 (8) | |
O7 | 0.9082 (4) | 0.3746 (4) | 0.1279 (3) | 0.0559 (7) | |
C8 | 0.8514 (5) | 0.2514 (5) | 0.2480 (4) | 0.0402 (8) | |
C3 | 0.3572 (4) | 0.2377 (4) | 0.9116 (4) | 0.0358 (8) | |
O6 | 0.8979 (3) | 0.1258 (3) | 0.7387 (2) | 0.0482 (7) | |
O4 | 0.1034 (4) | 0.1408 (4) | 0.9054 (3) | 0.0553 (7) | |
O1 | 0.7273 (4) | 0.4053 (3) | 0.9363 (3) | 0.0523 (7) | |
C5 | 0.9442 (5) | 0.2002 (5) | 0.6086 (4) | 0.0369 (8) | |
C6 | 0.8569 (5) | 0.1816 (4) | 0.5055 (4) | 0.0369 (8) | |
O2 | 0.5820 (4) | 0.1726 (4) | 1.0752 (3) | 0.0620 (8) | |
C7 | 0.9219 (5) | 0.2552 (5) | 0.3632 (4) | 0.0393 (8) | |
O5 | 1.0728 (4) | 0.3031 (4) | 0.5434 (3) | 0.0639 (8) | |
C1 | 0.6154 (5) | 0.3058 (5) | 0.9637 (4) | 0.0376 (8) | |
O3 | 0.2492 (4) | 0.3336 (4) | 0.7044 (3) | 0.0615 (8) | |
H7O | 0.8624 | 0.3720 | 0.0675 | 0.084* | |
H3 | 0.3296 | 0.1537 | 1.0068 | 0.043* | |
H4 | 0.0409 | 0.1432 | 0.8545 | 0.083* | |
H2 | 0.6474 | 0.1655 | 1.1253 | 0.093* | |
H7 | 1.0273 | 0.3166 | 0.3377 | 0.047* | |
H5 | 1.1256 | 0.3006 | 0.6011 | 0.096* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br2 | 0.0524 (3) | 0.0857 (4) | 0.0506 (2) | −0.0289 (2) | −0.01035 (19) | −0.0224 (2) |
Br1 | 0.0495 (2) | 0.0573 (3) | 0.0433 (2) | −0.01669 (19) | −0.01746 (18) | −0.00144 (18) |
O8 | 0.0680 (18) | 0.0545 (17) | 0.0518 (15) | −0.0154 (15) | −0.0354 (14) | −0.0115 (13) |
C2 | 0.0372 (19) | 0.040 (2) | 0.0298 (16) | −0.0034 (16) | −0.0118 (15) | −0.0135 (15) |
C4 | 0.0379 (19) | 0.043 (2) | 0.0383 (19) | −0.0073 (17) | −0.0154 (16) | −0.0160 (17) |
O7 | 0.0632 (18) | 0.076 (2) | 0.0339 (13) | −0.0234 (15) | −0.0233 (13) | −0.0058 (14) |
C8 | 0.038 (2) | 0.050 (2) | 0.039 (2) | −0.0019 (18) | −0.0176 (16) | −0.0172 (18) |
C3 | 0.0385 (19) | 0.039 (2) | 0.0351 (17) | −0.0064 (16) | −0.0147 (15) | −0.0124 (15) |
O6 | 0.0477 (15) | 0.0671 (18) | 0.0335 (13) | −0.0155 (13) | −0.0165 (11) | −0.0104 (12) |
O4 | 0.0502 (16) | 0.0739 (19) | 0.0502 (15) | −0.0276 (15) | −0.0230 (13) | −0.0106 (14) |
O1 | 0.0561 (16) | 0.0621 (18) | 0.0481 (14) | −0.0235 (14) | −0.0271 (13) | −0.0080 (13) |
C5 | 0.0360 (19) | 0.044 (2) | 0.0365 (18) | −0.0016 (17) | −0.0176 (16) | −0.0139 (16) |
C6 | 0.0355 (19) | 0.040 (2) | 0.0421 (19) | −0.0028 (16) | −0.0172 (16) | −0.0158 (16) |
O2 | 0.084 (2) | 0.0598 (19) | 0.0561 (17) | −0.0280 (16) | −0.0477 (16) | 0.0023 (14) |
C7 | 0.040 (2) | 0.049 (2) | 0.0375 (19) | −0.0053 (17) | −0.0203 (16) | −0.0136 (17) |
O5 | 0.074 (2) | 0.087 (2) | 0.0383 (14) | −0.0440 (18) | −0.0270 (14) | −0.0014 (14) |
C1 | 0.040 (2) | 0.043 (2) | 0.0349 (18) | −0.0065 (17) | −0.0130 (15) | −0.0149 (16) |
O3 | 0.0688 (19) | 0.077 (2) | 0.0478 (16) | −0.0343 (16) | −0.0315 (14) | −0.0025 (15) |
Geometric parameters (Å, º) top
Br2—C6 | 1.860 (3) | O1—C1 | 1.210 (4) |
Br1—C2 | 1.861 (3) | C5—O5 | 1.284 (4) |
O8—C8 | 1.217 (4) | C5—C6 | 1.497 (4) |
C2—C3 | 1.320 (4) | C6—C7 | 1.321 (5) |
C2—C1 | 1.500 (4) | O2—C1 | 1.274 (4) |
C4—O3 | 1.216 (4) | O7—H7O | 0.8200 |
C4—O4 | 1.290 (4) | C3—H3 | 0.9600 |
C4—C3 | 1.472 (4) | O4—H4 | 0.8200 |
O7—C8 | 1.295 (4) | O2—H2 | 0.8200 |
C8—C7 | 1.472 (4) | C7—H7 | 0.9601 |
O6—C5 | 1.212 (4) | O5—H5 | 0.8200 |
| | | |
C3—C2—C1 | 120.9 (3) | C7—C6—Br2 | 124.7 (3) |
C3—C2—Br1 | 125.3 (2) | C5—C6—Br2 | 114.5 (2) |
C1—C2—Br1 | 113.8 (2) | C6—C7—C8 | 127.6 (3) |
O3—C4—O4 | 123.7 (3) | O1—C1—O2 | 124.9 (3) |
O3—C4—C3 | 123.8 (3) | O1—C1—C2 | 122.1 (3) |
O4—C4—C3 | 112.5 (3) | O2—C1—C2 | 112.9 (3) |
O8—C8—O7 | 124.3 (3) | C8—O7—H7O | 109.5 |
O8—C8—C7 | 123.9 (3) | C2—C3—H3 | 119.2 |
O7—C8—C7 | 111.9 (3) | C4—C3—H3 | 113.2 |
C2—C3—C4 | 127.5 (3) | C4—O4—H4 | 109.5 |
O6—C5—O5 | 124.3 (3) | C1—O2—H2 | 109.5 |
O6—C5—C6 | 123.3 (3) | C6—C7—H7 | 112.5 |
O5—C5—C6 | 112.4 (3) | C8—C7—H7 | 119.9 |
C7—C6—C5 | 120.8 (3) | C5—O5—H5 | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7O···O1i | 0.82 | 1.89 | 2.702 (3) | 168 |
O4—H4···O6ii | 0.82 | 1.93 | 2.752 (3) | 175 |
O2—H2···O8iii | 0.82 | 1.81 | 2.621 (3) | 169 |
O5—H5···O3iv | 0.82 | 1.76 | 2.574 (3) | 170 |
Symmetry codes: (i) x, y, z−1; (ii) x−1, y, z; (iii) x, y, z+1; (iv) x+1, y, z. |