Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053822/xu2352sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053822/xu2352Isup2.hkl |
CCDC reference: 672824
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C)= 0.002 Å
- R factor = 0.024
- wR factor = 0.064
- Data-to-parameter ratio = 16.4
checkCIF/PLATON results
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2,3,5,6-Tetrachlorobenzene-1,4-dicarbonitrile (26.5 g, 100 mmol) was mixed with concentrated sulfuric acid (240 ml) and water (60 ml) under reflux at 463 K for 36 h. Upon standing this solution yielded crystalline 2,3,5,6-tetrachlorobenzene-1,4-dicarboxylic acid, which was filtered, washed with water (2× 50 ml), and dried under vacuum for 24 h (19.2 g, 63.2% yield). Single crystals were obtained by slow evaporation of the aqueous solution.
H atom was placed in calculated position with O—H = 0.82 Å and refined in riding mode, Uiso(H) = 1.5Ueq(O).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
C8H2Cl4O4 | F(000) = 300.0 |
Mr = 303.90 | Dx = 1.920 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3424 reflections |
a = 5.9852 (9) Å | θ = 3.3–27.6° |
b = 7.0349 (10) Å | µ = 1.12 mm−1 |
c = 12.7012 (19) Å | T = 296 K |
β = 100.668 (2)° | Block, colorless |
V = 525.55 (13) Å3 | 0.30 × 0.22 × 0.20 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1213 independent reflections |
Radiation source: fine-focus sealed tube | 1145 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 27.6°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −7→7 |
Tmin = 0.734, Tmax = 0.800 | k = −9→8 |
4350 measured reflections | l = −16→16 |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.03P)2 + 0.2817P] where P = (Fo2 + 2Fc2)/3 |
1213 reflections | (Δ/σ)max < 0.001 |
74 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C8H2Cl4O4 | V = 525.55 (13) Å3 |
Mr = 303.90 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.9852 (9) Å | µ = 1.12 mm−1 |
b = 7.0349 (10) Å | T = 296 K |
c = 12.7012 (19) Å | 0.30 × 0.22 × 0.20 mm |
β = 100.668 (2)° |
Bruker SMART CCD area-detector diffractometer | 1213 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1145 reflections with I > 2σ(I) |
Tmin = 0.734, Tmax = 0.800 | Rint = 0.021 |
4350 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.32 e Å−3 |
1213 reflections | Δρmin = −0.23 e Å−3 |
74 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.27187 (7) | 1.04641 (6) | 0.19970 (3) | 0.04105 (13) | |
Cl2 | 0.10264 (7) | 0.73074 (6) | 0.02950 (3) | 0.03963 (13) | |
O1 | 0.4028 (2) | 0.53756 (15) | −0.12663 (9) | 0.0455 (3) | |
H1 | 0.3466 | 0.4605 | −0.1724 | 0.068* | |
O2 | 0.2347 (2) | 0.74573 (15) | −0.24712 (9) | 0.0395 (3) | |
C2 | 0.3240 (2) | 0.87853 (19) | 0.01385 (10) | 0.0272 (3) | |
C1 | 0.3983 (2) | 1.01943 (19) | 0.08955 (10) | 0.0270 (3) | |
C3 | 0.4255 (2) | 0.85885 (18) | −0.07583 (10) | 0.0265 (3) | |
C4 | 0.3431 (2) | 0.70930 (19) | −0.15941 (11) | 0.0289 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0506 (2) | 0.0444 (2) | 0.0328 (2) | −0.00380 (17) | 0.01984 (16) | −0.00767 (15) |
Cl2 | 0.0409 (2) | 0.0375 (2) | 0.0414 (2) | −0.01307 (15) | 0.00999 (16) | −0.00066 (15) |
O1 | 0.0733 (8) | 0.0230 (5) | 0.0330 (6) | 0.0063 (5) | −0.0091 (5) | −0.0043 (4) |
O2 | 0.0572 (7) | 0.0265 (5) | 0.0294 (5) | −0.0020 (5) | −0.0064 (5) | 0.0004 (4) |
C2 | 0.0303 (6) | 0.0229 (6) | 0.0280 (6) | −0.0014 (5) | 0.0044 (5) | 0.0008 (5) |
C1 | 0.0325 (7) | 0.0256 (6) | 0.0232 (6) | 0.0019 (5) | 0.0063 (5) | −0.0010 (5) |
C3 | 0.0340 (7) | 0.0207 (6) | 0.0234 (6) | 0.0017 (5) | 0.0015 (5) | −0.0012 (5) |
C4 | 0.0376 (7) | 0.0230 (6) | 0.0256 (6) | −0.0002 (5) | 0.0041 (5) | −0.0015 (5) |
Cl1—C1 | 1.7199 (14) | C2—C3 | 1.3936 (19) |
Cl2—C2 | 1.7243 (14) | C2—C1 | 1.3951 (18) |
O1—C4 | 1.3060 (17) | C1—C3i | 1.394 (2) |
O1—H1 | 0.8200 | C3—C4 | 1.5110 (18) |
O2—C4 | 1.2084 (18) | ||
C4—O1—H1 | 109.5 | C2—C3—C1i | 119.70 (12) |
C3—C2—C1 | 120.15 (12) | C2—C3—C4 | 120.56 (12) |
C3—C2—Cl2 | 119.66 (10) | C1i—C3—C4 | 119.73 (12) |
C1—C2—Cl2 | 120.18 (10) | O2—C4—O1 | 123.97 (13) |
C3i—C1—C2 | 120.15 (12) | O2—C4—C3 | 123.35 (12) |
C3i—C1—Cl1 | 119.39 (10) | O1—C4—C3 | 112.69 (11) |
C2—C1—Cl1 | 120.45 (11) | ||
Cl2—C2—C1—C3i | −178.81 (10) | Cl2—C2—C3—C4 | 0.05 (18) |
C3—C2—C1—Cl1 | 179.28 (10) | C2—C3—C4—O2 | 107.13 (17) |
Cl2—C2—C1—Cl1 | 0.47 (16) | C1i—C3—C4—O2 | −71.6 (2) |
Cl2—C2—C3—C1i | 178.82 (10) | C2—C3—C4—O1 | −73.18 (17) |
C1—C2—C3—C4 | −178.76 (12) | C1i—C3—C4—O1 | 108.05 (15) |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2ii | 0.82 | 1.84 | 2.6410 (15) | 166 |
Symmetry code: (ii) −x+1/2, y−1/2, −z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H2Cl4O4 |
Mr | 303.90 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 5.9852 (9), 7.0349 (10), 12.7012 (19) |
β (°) | 100.668 (2) |
V (Å3) | 525.55 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.12 |
Crystal size (mm) | 0.30 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.734, 0.800 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4350, 1213, 1145 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.064, 1.01 |
No. of reflections | 1213 |
No. of parameters | 74 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.23 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 1.84 | 2.6410 (15) | 166 |
Symmetry code: (i) −x+1/2, y−1/2, −z−1/2. |
2,3,5,6-Tetrachlorobenzene-1,4-dicarboxylic acid is an important intermediate which can be used for the synthesis of herbicides (Eufemia & Epel, 1998; Meazza et al., 2007). This paper presents the results of the single-crystal X-ray diffraction analysis of the title compound. A perspective view of the title compound is shown in Fig. 1. The bond lengths and angles are within normal ranges. In the molecule, the carboxyl group forms a dihedral angle of 72.42 (7)° with the central benzene ring. Classical intermolecular O—H···O hydrogen bonding occurs in the crystal structure (Table 1 and Fig. 2), which may be effective in the stabilization of the crystal structure. Short intermolecular Cl···Cl(1/2 - x,1/2 + y,1/2 - z) contact of 3.62 (8) Å is observed in the crystal structure.