Acta Cryst. (2008). E64, o1378 [ doi:10.1107/S160053680801917X ]
The asymmetric unit of the title compound, C12H8N2O6S, an important diphenyl sulfone derivative, contains one half-molecule; a mirror plane passes through the SO2 group. The dihedral angle between the two symmetry-related benzene rings is 40.10 (13)°. An intramolecular C-H
O hydrogen bond results in the formation of a five-membered ring, which adopts an envelope conformation.
The title compound, (I), was prepared according to the literature method (Amer et al., 1989). Crystals suitable for X-ray analysis were obtained by dissolving (I) (0.2 g) in dichloroethane (25 ml) and evaporating the solvent slowly at room temperature for about 7 d.
H atoms were positioned geometrically, with C-H= 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./hk2478fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme [symmetry code: (') -x, y, z]. Hydrogen bonds are shown as dashed lines. |
| C12H8N2O6S | F000 = 316 |
| Mr = 308.27 | Dx = 1.583 Mg m−3 |
| Orthorhombic, Pmn21 | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: P 2ac -2 | Cell parameters from 25 reflections |
| a = 20.260 (4) Å | θ = 10–13º |
| b = 5.9380 (12) Å | µ = 0.28 mm−1 |
| c = 5.3770 (11) Å | T = 294 (2) K |
| V = 646.9 (2) Å3 | Block, light yellow |
| Z = 2 | 0.30 × 0.20 × 0.10 mm |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.028 |
| Radiation source: fine-focus sealed tube | θmax = 25.2º |
| Monochromator: graphite | θmin = 2.0º |
| T = 294(2) K | h = −24→24 |
| ω/2θ scans | k = −7→0 |
| Absorption correction: ψ scan (North et al., 1968) | l = 0→6 |
| Tmin = 0.920, Tmax = 0.972 | 3 standard reflections |
| 1304 measured reflections | every 120 min |
| 674 independent reflections | intensity decay: none |
| 624 reflections with I > 2σ(I) |
| Refinement on F2 | H-atom parameters constrained |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.06P)2 + 0.078P] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.032 | (Δ/σ)max < 0.001 |
| wR(F2) = 0.086 | Δρmax = 0.25 e Å−3 |
| S = 1.00 | Δρmin = −0.22 e Å−3 |
| 674 reflections | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 101 parameters | Extinction coefficient: 0.069 (8) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with no Friedel pairs |
| Secondary atom site location: difference Fourier map | Flack parameter: −0.11 (15) |
| Hydrogen site location: inferred from neighbouring sites |
| C12H8N2O6S | V = 646.9 (2) Å3 |
| Mr = 308.27 | Z = 2 |
| Orthorhombic, Pmn21 | Mo Kα |
| a = 20.260 (4) Å | µ = 0.28 mm−1 |
| b = 5.9380 (12) Å | T = 294 (2) K |
| c = 5.3770 (11) Å | 0.30 × 0.20 × 0.10 mm |
| Enraf–Nonius CAD-4 diffractometer | 624 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.028 |
| Tmin = 0.920, Tmax = 0.972 | 3 standard reflections |
| 1304 measured reflections | every 120 min |
| 674 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
| wR(F2) = 0.086 | Δρmax = 0.25 e Å−3 |
| S = 1.00 | Δρmin = −0.22 e Å−3 |
| 674 reflections | Absolute structure: Flack (1983), with no Friedel pairs |
| 101 parameters | Flack parameter: −0.11 (15) |
| ? restraints |
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 > 2sigma(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 | ||
| S | 0.5000 | 0.08254 (19) | 0.9607 (2) | 0.0438 (4) | |
| N | 0.68253 (13) | 0.0542 (4) | 0.2895 (5) | 0.0422 (6) | |
| O1 | 0.5000 | −0.1563 (5) | 0.9183 (9) | 0.0626 (12) | |
| O2 | 0.5000 | 0.1705 (7) | 1.2095 (7) | 0.0663 (11) | |
| O3 | 0.66204 (14) | −0.1343 (4) | 0.2403 (5) | 0.0660 (8) | |
| O4 | 0.72681 (13) | 0.1460 (4) | 0.1767 (5) | 0.0599 (7) | |
| C1 | 0.64732 (14) | 0.4956 (5) | 0.7589 (8) | 0.0451 (8) | |
| H1B | 0.6638 | 0.6351 | 0.8072 | 0.054* | |
| C2 | 0.59364 (14) | 0.4066 (5) | 0.8822 (7) | 0.0410 (7) | |
| H2B | 0.5741 | 0.4842 | 1.0131 | 0.049* | |
| C3 | 0.56929 (13) | 0.1978 (5) | 0.8063 (5) | 0.0347 (7) | |
| C4 | 0.59799 (14) | 0.0791 (4) | 0.6139 (6) | 0.0341 (6) | |
| H4A | 0.5816 | −0.0603 | 0.5648 | 0.041* | |
| C5 | 0.65163 (13) | 0.1743 (5) | 0.4973 (6) | 0.0356 (6) | |
| C6 | 0.67683 (14) | 0.3828 (4) | 0.5672 (7) | 0.0410 (7) | |
| H6A | 0.7130 | 0.4442 | 0.4852 | 0.049* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S | 0.0316 (5) | 0.0543 (6) | 0.0455 (7) | 0.000 | 0.000 | 0.0169 (6) |
| N | 0.0448 (13) | 0.0450 (14) | 0.0367 (14) | 0.0071 (11) | 0.0003 (12) | −0.0003 (11) |
| O1 | 0.0408 (17) | 0.0472 (16) | 0.100 (3) | 0.000 | 0.000 | 0.032 (2) |
| O2 | 0.049 (2) | 0.114 (3) | 0.0364 (18) | 0.000 | 0.000 | 0.016 (2) |
| O3 | 0.0784 (19) | 0.0580 (15) | 0.0615 (18) | −0.0025 (12) | 0.0081 (16) | −0.0211 (14) |
| O4 | 0.0545 (14) | 0.0738 (16) | 0.0512 (15) | 0.0009 (12) | 0.0190 (12) | 0.0005 (14) |
| C1 | 0.0374 (14) | 0.0341 (14) | 0.064 (2) | −0.0016 (12) | −0.0022 (16) | −0.0079 (16) |
| C2 | 0.0370 (15) | 0.0400 (15) | 0.0460 (17) | 0.0078 (12) | −0.0021 (14) | −0.0055 (14) |
| C3 | 0.0274 (12) | 0.0381 (14) | 0.0386 (16) | 0.0013 (11) | −0.0031 (12) | 0.0081 (13) |
| C4 | 0.0341 (13) | 0.0323 (12) | 0.0359 (16) | −0.0004 (11) | −0.0049 (13) | 0.0041 (14) |
| C5 | 0.0326 (13) | 0.0370 (13) | 0.0373 (14) | 0.0067 (10) | −0.0038 (13) | 0.0026 (13) |
| C6 | 0.0353 (14) | 0.0364 (14) | 0.0511 (19) | −0.0024 (12) | 0.0046 (15) | 0.0033 (14) |
| S—O2 | 1.436 (4) | C1—H1B | 0.9300 |
| S—O1 | 1.437 (3) | C2—C3 | 1.395 (4) |
| S—C3 | 1.769 (3) | C2—H2B | 0.9300 |
| S—C3i | 1.769 (3) | C3—C4 | 1.380 (4) |
| N—O4 | 1.212 (4) | C4—C5 | 1.376 (4) |
| N—O3 | 1.223 (3) | C4—H4A | 0.9300 |
| N—C5 | 1.466 (4) | C5—C6 | 1.391 (4) |
| C1—C6 | 1.367 (5) | C6—H6A | 0.9300 |
| C1—C2 | 1.379 (4) | ||
| O2—S—O1 | 120.5 (3) | C3—C2—H2B | 120.7 |
| O2—S—C3 | 107.24 (14) | C4—C3—C2 | 121.6 (3) |
| O1—S—C3 | 107.92 (15) | C4—C3—S | 119.2 (2) |
| O2—S—C3i | 107.24 (14) | C2—C3—S | 119.2 (3) |
| O1—S—C3i | 107.92 (15) | C5—C4—C3 | 117.7 (3) |
| C3—S—C3i | 105.06 (18) | C5—C4—H4A | 121.2 |
| O4—N—O3 | 123.7 (3) | C3—C4—H4A | 121.2 |
| O4—N—C5 | 118.6 (3) | C4—C5—C6 | 122.2 (3) |
| O3—N—C5 | 117.7 (3) | C4—C5—N | 119.0 (3) |
| C6—C1—C2 | 121.3 (3) | C6—C5—N | 118.8 (3) |
| C6—C1—H1B | 119.3 | C1—C6—C5 | 118.6 (3) |
| C2—C1—H1B | 119.3 | C1—C6—H6A | 120.7 |
| C1—C2—C3 | 118.6 (3) | C5—C6—H6A | 120.7 |
| C1—C2—H2B | 120.7 | ||
| C6—C1—C2—C3 | −0.4 (5) | S—C3—C4—C5 | 179.7 (2) |
| C1—C2—C3—C4 | 0.6 (5) | C3—C4—C5—C6 | −0.1 (4) |
| C1—C2—C3—S | −179.4 (2) | C3—C4—C5—N | −179.0 (2) |
| O2—S—C3—C4 | 152.5 (2) | O4—N—C5—C4 | 175.0 (3) |
| O1—S—C3—C4 | 21.3 (3) | O3—N—C5—C4 | −5.2 (4) |
| C3i—S—C3—C4 | −93.6 (2) | O4—N—C5—C6 | −3.9 (4) |
| O2—S—C3—C2 | −27.5 (3) | O3—N—C5—C6 | 175.9 (3) |
| O1—S—C3—C2 | −158.6 (3) | C2—C1—C6—C5 | 0.0 (5) |
| C3i—S—C3—C2 | 86.4 (3) | C4—C5—C6—C1 | 0.3 (5) |
| C2—C3—C4—C5 | −0.3 (4) | N—C5—C6—C1 | 179.2 (3) |
| Symmetry codes: (i) −x+1, y, z. |
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.
Amer, A., El-Massry, A. M. & Pittman, C. U. (1989). Chem. Scr. 29, 351–352.
Ayyangar, N. R., Lugade, A. G., Nikrad, P. V. & Sharma, V. K. (1981). Synthesis, pp. 640–643.
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
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.
The title compound, (I), is used for preparing 3,3'-diaminodiphenyl sulfone (Ayyangar et al., 1981). As part of our studies in this area, we report herein the synthesis and crystal structure of (I).
The asymmetric unit of (I) (Fig. 1) contains one half molecule. The bond lengths (Allen et al., 1987) and angles are within normal ranges. The dihedral angle between the two symmetry related bezene rings is 139.90 (13)°. The intramolecular C-H···O hydrogen bond (Table 1) results in the formation of a five-membered non-planar ring: (S/O1/C3/C4/H4A), in which it adopts envelope conformation, with O1 atom displaced by -0.494 (3) Å from the planes of the other ring atoms.