Acta Cryst. (2007). E63, o4050 [ doi:10.1107/S160053680704398X ]
In the title molecule, C19H15NO9S2, the dihedral angle between the nitro group and the benzene ring to which it is attached is 11.68 (8)°. The N-C bond length of 1.466 (3) Å indicates that no conjugation exists between the nitro group and the benzene ring.
K2CO3 was charged into a solution of 2-hydroxy-5-nitrobenzene-1,3-diyl dibenzenesulfonate (4.66 g, 10 mmol) in anhydrous acetone (30 ml) with stirring. CH3I (0.66 ml, 13 mmol) was added dropwise to the reaction mixture at room temperature. The reaction mixture was then refluxed for 8 h. The residue was filtered and the cake washed with acetone. A shallow yellow solid was given in a yield of 85% after removal of the solvent. Recrystallization from acetone furnished volorless blocks for single-crystal structure determination.
All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) and C—H = 0.93 Å for the aromatic H atoms or Uiso(H) = 1.5Ueq(C) and C—H = 0.96 Å for methyl H atoms.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
![[Figure 1]](./lh2490fig1thm.gif)
| Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| C19H15NO9S2 | F000 = 960 |
| Mr = 465.44 | Dx = 1.562 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2407 reflections |
| a = 10.787 (2) Å | θ = 1.3–25.4º |
| b = 10.895 (2) Å | µ = 0.32 mm−1 |
| c = 16.876 (3) Å | T = 298 (2) K |
| β = 93.91 (3)º | Block, colorless |
| V = 1978.7 (6) Å3 | 0.30 × 0.20 × 0.20 mm |
| Z = 4 |
| Bruker SMART CCD diffractometer | 3872 independent reflections |
| Radiation source: fine-focus sealed tube | 2898 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.023 |
| T = 298(2) K | θmax = 26.0º |
| φ and ω scans | θmin = 1.9º |
| Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = 0→13 |
| Tmin = 0.909, Tmax = 0.938 | k = 0→13 |
| 4084 measured reflections | l = −20→20 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.0778P)2 + 0.2038P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.131 | (Δ/σ)max = 0.001 |
| S = 1.05 | Δρmax = 0.40 e Å−3 |
| 3872 reflections | Δρmin = −0.33 e Å−3 |
| 282 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.029 (2) |
| Secondary atom site location: difference Fourier map |
| C19H15NO9S2 | V = 1978.7 (6) Å3 |
| Mr = 465.44 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 10.787 (2) Å | µ = 0.32 mm−1 |
| b = 10.895 (2) Å | T = 298 (2) K |
| c = 16.876 (3) Å | 0.30 × 0.20 × 0.20 mm |
| β = 93.91 (3)º |
| Bruker SMART CCD diffractometer | 3872 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 1998) | 2898 reflections with I > 2σ(I) |
| Tmin = 0.909, Tmax = 0.938 | Rint = 0.023 |
| 4084 measured reflections |
| R[F2 > 2σ(F2)] = 0.044 | 282 parameters |
| wR(F2) = 0.131 | H-atom parameters constrained |
| S = 1.05 | Δρmax = 0.40 e Å−3 |
| 3872 reflections | Δρmin = −0.33 e Å−3 |
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 | ||
| S2 | −0.23217 (6) | 0.74187 (5) | 0.01047 (4) | 0.03603 (19) | |
| S1 | 0.37812 (6) | 0.76657 (6) | −0.11612 (4) | 0.0407 (2) | |
| O3 | 0.23769 (16) | 0.81284 (14) | −0.13794 (10) | 0.0410 (4) | |
| O7 | −0.09188 (15) | 0.68927 (15) | 0.02396 (9) | 0.0404 (4) | |
| O6 | 0.10742 (17) | 0.85730 (15) | −0.01565 (10) | 0.0461 (5) | |
| O9 | −0.30660 (17) | 0.64741 (17) | −0.02568 (10) | 0.0515 (5) | |
| O4 | 0.39210 (18) | 0.64822 (17) | −0.15073 (11) | 0.0524 (5) | |
| O8 | −0.22762 (19) | 0.85748 (16) | −0.02797 (11) | 0.0559 (5) | |
| O2 | −0.0900 (2) | 0.38064 (19) | −0.19229 (12) | 0.0659 (6) | |
| O5 | 0.44911 (18) | 0.86750 (18) | −0.14039 (12) | 0.0596 (5) | |
| C8 | 0.3875 (2) | 0.7536 (2) | −0.01236 (14) | 0.0377 (5) | |
| C3 | 0.1401 (2) | 0.7322 (2) | −0.12367 (14) | 0.0354 (5) | |
| C4 | 0.0728 (2) | 0.7565 (2) | −0.05757 (13) | 0.0347 (5) | |
| C5 | −0.0243 (2) | 0.6747 (2) | −0.04417 (13) | 0.0355 (5) | |
| C6 | −0.0520 (2) | 0.5758 (2) | −0.09344 (14) | 0.0379 (5) | |
| H6 | −0.1144 | 0.5208 | −0.0823 | 0.046* | |
| N1 | −0.0167 (2) | 0.4585 (2) | −0.21397 (14) | 0.0485 (5) | |
| C14 | −0.2601 (2) | 0.7581 (2) | 0.11059 (14) | 0.0367 (5) | |
| C2 | 0.1108 (2) | 0.6383 (2) | −0.17603 (14) | 0.0400 (6) | |
| H2 | 0.1544 | 0.6276 | −0.2212 | 0.048* | |
| C1 | 0.0152 (2) | 0.5605 (2) | −0.15972 (14) | 0.0383 (5) | |
| C13 | 0.3827 (3) | 0.6383 (2) | 0.02110 (16) | 0.0499 (7) | |
| H13 | 0.3757 | 0.5687 | −0.0108 | 0.060* | |
| O1 | 0.0290 (2) | 0.4572 (2) | −0.27821 (13) | 0.0733 (7) | |
| C9 | 0.3998 (3) | 0.8590 (3) | 0.03325 (17) | 0.0517 (7) | |
| H9 | 0.4035 | 0.9358 | 0.0096 | 0.062* | |
| C15 | −0.2564 (3) | 0.8751 (2) | 0.14369 (16) | 0.0486 (6) | |
| H15 | −0.2377 | 0.9433 | 0.1136 | 0.058* | |
| C19 | −0.2863 (3) | 0.6544 (3) | 0.15400 (16) | 0.0506 (7) | |
| H19 | −0.2893 | 0.5772 | 0.1305 | 0.061* | |
| C10 | 0.4065 (3) | 0.8469 (3) | 0.11472 (19) | 0.0673 (9) | |
| H10 | 0.4151 | 0.9161 | 0.1469 | 0.081* | |
| C7 | 0.0787 (3) | 0.8778 (3) | 0.06494 (15) | 0.0518 (7) | |
| H7A | −0.0060 | 0.9044 | 0.0661 | 0.078* | |
| H7B | 0.1329 | 0.9399 | 0.0882 | 0.078* | |
| H7C | 0.0900 | 0.8029 | 0.0945 | 0.078* | |
| C11 | 0.4003 (3) | 0.7318 (4) | 0.14827 (19) | 0.0696 (10) | |
| H11 | 0.4042 | 0.7244 | 0.2033 | 0.084* | |
| C17 | −0.3050 (3) | 0.7856 (4) | 0.26666 (18) | 0.0701 (10) | |
| H17 | −0.3195 | 0.7948 | 0.3200 | 0.084* | |
| C16 | −0.2811 (3) | 0.8871 (3) | 0.22228 (18) | 0.0628 (8) | |
| H16 | −0.2816 | 0.9645 | 0.2454 | 0.075* | |
| C18 | −0.3080 (3) | 0.6690 (3) | 0.23317 (17) | 0.0653 (9) | |
| H18 | −0.3246 | 0.6009 | 0.2640 | 0.078* | |
| C12 | 0.3885 (3) | 0.6280 (3) | 0.10238 (18) | 0.0689 (9) | |
| H12 | 0.3844 | 0.5513 | 0.1261 | 0.083* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S2 | 0.0391 (3) | 0.0318 (3) | 0.0376 (3) | −0.0018 (2) | 0.0057 (2) | 0.0007 (2) |
| S1 | 0.0459 (4) | 0.0375 (4) | 0.0401 (4) | −0.0039 (3) | 0.0134 (3) | 0.0019 (3) |
| O3 | 0.0488 (10) | 0.0323 (9) | 0.0428 (9) | −0.0041 (8) | 0.0098 (8) | 0.0080 (7) |
| O7 | 0.0427 (9) | 0.0417 (10) | 0.0376 (9) | 0.0011 (8) | 0.0080 (7) | 0.0017 (8) |
| O6 | 0.0589 (11) | 0.0347 (9) | 0.0461 (10) | −0.0088 (8) | 0.0137 (8) | −0.0080 (8) |
| O9 | 0.0499 (11) | 0.0551 (12) | 0.0494 (10) | −0.0125 (9) | 0.0030 (8) | −0.0120 (9) |
| O4 | 0.0617 (12) | 0.0487 (11) | 0.0481 (10) | 0.0066 (9) | 0.0134 (9) | −0.0091 (9) |
| O8 | 0.0721 (13) | 0.0399 (10) | 0.0565 (11) | 0.0052 (9) | 0.0100 (10) | 0.0157 (9) |
| O2 | 0.0823 (15) | 0.0460 (12) | 0.0691 (14) | −0.0170 (11) | 0.0038 (11) | −0.0126 (10) |
| O5 | 0.0583 (12) | 0.0552 (12) | 0.0678 (12) | −0.0132 (10) | 0.0235 (10) | 0.0135 (10) |
| C8 | 0.0370 (12) | 0.0383 (13) | 0.0381 (13) | −0.0048 (10) | 0.0049 (10) | −0.0025 (10) |
| C3 | 0.0409 (13) | 0.0303 (12) | 0.0351 (12) | −0.0017 (10) | 0.0041 (10) | 0.0057 (10) |
| C4 | 0.0413 (13) | 0.0277 (12) | 0.0353 (12) | 0.0032 (10) | 0.0032 (10) | 0.0016 (9) |
| C5 | 0.0390 (13) | 0.0327 (12) | 0.0352 (12) | 0.0018 (10) | 0.0047 (10) | 0.0028 (10) |
| C6 | 0.0424 (13) | 0.0290 (12) | 0.0421 (13) | −0.0011 (10) | 0.0007 (10) | 0.0053 (10) |
| N1 | 0.0511 (13) | 0.0431 (13) | 0.0506 (13) | −0.0002 (11) | −0.0025 (10) | −0.0088 (11) |
| C14 | 0.0365 (12) | 0.0347 (13) | 0.0395 (13) | −0.0006 (10) | 0.0063 (10) | −0.0025 (10) |
| C2 | 0.0463 (14) | 0.0392 (14) | 0.0351 (12) | 0.0051 (11) | 0.0060 (10) | −0.0007 (10) |
| C1 | 0.0444 (13) | 0.0315 (12) | 0.0383 (13) | 0.0013 (10) | −0.0024 (10) | −0.0031 (10) |
| C13 | 0.0646 (18) | 0.0391 (14) | 0.0456 (15) | −0.0090 (13) | 0.0021 (13) | 0.0040 (12) |
| O1 | 0.0871 (16) | 0.0800 (16) | 0.0545 (12) | −0.0138 (13) | 0.0181 (11) | −0.0297 (12) |
| C9 | 0.0532 (16) | 0.0452 (16) | 0.0569 (16) | −0.0068 (13) | 0.0041 (13) | −0.0136 (13) |
| C15 | 0.0517 (16) | 0.0411 (15) | 0.0532 (15) | −0.0022 (12) | 0.0057 (12) | −0.0095 (12) |
| C19 | 0.0578 (17) | 0.0437 (15) | 0.0515 (16) | −0.0002 (13) | 0.0131 (13) | 0.0071 (12) |
| C10 | 0.0559 (18) | 0.083 (2) | 0.0621 (19) | −0.0016 (17) | −0.0033 (15) | −0.0365 (18) |
| C7 | 0.0597 (17) | 0.0515 (16) | 0.0451 (14) | −0.0122 (14) | 0.0096 (12) | −0.0128 (13) |
| C11 | 0.0580 (19) | 0.109 (3) | 0.0413 (16) | −0.0024 (19) | 0.0005 (14) | −0.0044 (18) |
| C17 | 0.0575 (19) | 0.115 (3) | 0.0375 (15) | 0.0043 (19) | 0.0043 (13) | −0.0124 (18) |
| C16 | 0.0611 (19) | 0.069 (2) | 0.0582 (18) | −0.0009 (16) | 0.0040 (15) | −0.0286 (16) |
| C18 | 0.069 (2) | 0.078 (2) | 0.0500 (17) | 0.0014 (18) | 0.0142 (15) | 0.0166 (16) |
| C12 | 0.083 (2) | 0.075 (2) | 0.0475 (17) | −0.0125 (19) | 0.0011 (16) | 0.0149 (16) |
| S2—O9 | 1.4175 (18) | C14—C15 | 1.391 (3) |
| S2—O8 | 1.4192 (18) | C2—C1 | 1.377 (3) |
| S2—O7 | 1.6197 (18) | C2—H2 | 0.9300 |
| S2—C14 | 1.745 (2) | C13—C12 | 1.374 (4) |
| S1—O5 | 1.4164 (19) | C13—H13 | 0.9300 |
| S1—O4 | 1.4278 (19) | C9—C10 | 1.378 (4) |
| S1—O3 | 1.6150 (19) | C9—H9 | 0.9300 |
| S1—C8 | 1.753 (2) | C15—C16 | 1.377 (4) |
| O3—C3 | 1.405 (3) | C15—H15 | 0.9300 |
| O7—C5 | 1.411 (3) | C19—C18 | 1.381 (4) |
| O6—C4 | 1.345 (3) | C19—H19 | 0.9300 |
| O6—C7 | 1.433 (3) | C10—C11 | 1.380 (5) |
| O2—N1 | 1.232 (3) | C10—H10 | 0.9300 |
| C8—C13 | 1.379 (3) | C7—H7A | 0.9600 |
| C8—C9 | 1.384 (3) | C7—H7B | 0.9600 |
| C3—C2 | 1.375 (3) | C7—H7C | 0.9600 |
| C3—C4 | 1.397 (3) | C11—C12 | 1.371 (5) |
| C4—C5 | 1.406 (3) | C11—H11 | 0.9300 |
| C5—C6 | 1.381 (3) | C17—C16 | 1.370 (5) |
| C6—C1 | 1.384 (3) | C17—C18 | 1.390 (5) |
| C6—H6 | 0.9300 | C17—H17 | 0.9300 |
| N1—O1 | 1.221 (3) | C16—H16 | 0.9300 |
| N1—C1 | 1.466 (3) | C18—H18 | 0.9300 |
| C14—C19 | 1.387 (3) | C12—H12 | 0.9300 |
| O9—S2—O8 | 118.93 (12) | C2—C1—C6 | 121.9 (2) |
| O9—S2—O7 | 107.45 (11) | C2—C1—N1 | 119.3 (2) |
| O8—S2—O7 | 108.49 (11) | C6—C1—N1 | 118.9 (2) |
| O9—S2—C14 | 111.12 (11) | C12—C13—C8 | 118.8 (3) |
| O8—S2—C14 | 111.47 (12) | C12—C13—H13 | 120.6 |
| O7—S2—C14 | 96.97 (10) | C8—C13—H13 | 120.6 |
| O5—S1—O4 | 120.56 (12) | C10—C9—C8 | 118.2 (3) |
| O5—S1—O3 | 102.05 (11) | C10—C9—H9 | 120.9 |
| O4—S1—O3 | 108.19 (11) | C8—C9—H9 | 120.9 |
| O5—S1—C8 | 110.87 (12) | C16—C15—C14 | 118.1 (3) |
| O4—S1—C8 | 109.59 (11) | C16—C15—H15 | 120.9 |
| O3—S1—C8 | 104.02 (10) | C14—C15—H15 | 120.9 |
| C3—O3—S1 | 117.91 (14) | C18—C19—C14 | 118.1 (3) |
| C5—O7—S2 | 117.04 (14) | C18—C19—H19 | 120.9 |
| C4—O6—C7 | 123.80 (19) | C14—C19—H19 | 120.9 |
| C13—C8—C9 | 122.2 (2) | C9—C10—C11 | 119.7 (3) |
| C13—C8—S1 | 118.77 (19) | C9—C10—H10 | 120.2 |
| C9—C8—S1 | 119.0 (2) | C11—C10—H10 | 120.2 |
| C2—C3—C4 | 123.0 (2) | O6—C7—H7A | 109.5 |
| C2—C3—O3 | 119.8 (2) | O6—C7—H7B | 109.5 |
| C4—C3—O3 | 117.1 (2) | H7A—C7—H7B | 109.5 |
| O6—C4—C3 | 115.7 (2) | O6—C7—H7C | 109.5 |
| O6—C4—C5 | 128.0 (2) | H7A—C7—H7C | 109.5 |
| C3—C4—C5 | 116.2 (2) | H7B—C7—H7C | 109.5 |
| C6—C5—C4 | 122.0 (2) | C12—C11—C10 | 121.5 (3) |
| C6—C5—O7 | 118.4 (2) | C12—C11—H11 | 119.2 |
| C4—C5—O7 | 119.4 (2) | C10—C11—H11 | 119.2 |
| C5—C6—C1 | 118.5 (2) | C16—C17—C18 | 121.0 (3) |
| C5—C6—H6 | 120.7 | C16—C17—H17 | 119.5 |
| C1—C6—H6 | 120.7 | C18—C17—H17 | 119.5 |
| O1—N1—O2 | 124.2 (2) | C17—C16—C15 | 120.4 (3) |
| O1—N1—C1 | 118.1 (2) | C17—C16—H16 | 119.8 |
| O2—N1—C1 | 117.7 (2) | C15—C16—H16 | 119.8 |
| C19—C14—C15 | 122.4 (2) | C19—C18—C17 | 119.8 (3) |
| C19—C14—S2 | 118.91 (19) | C19—C18—H18 | 120.1 |
| C15—C14—S2 | 118.67 (19) | C17—C18—H18 | 120.1 |
| C3—C2—C1 | 118.2 (2) | C11—C12—C13 | 119.5 (3) |
| C3—C2—H2 | 120.9 | C11—C12—H12 | 120.2 |
| C1—C2—H2 | 120.9 | C13—C12—H12 | 120.2 |
The work was financed by grants (project 30672516) from the National Natural Science Foundation of China.
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.
Bruker (1998). SMART (Version 6.02a), SAINT (Version 6.02a) and SADABS (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA. Are all programs really the same version number?
Desai, D. G., Swami, S. S., Dabhade, S. K. & Ghagare, M. G. (2001). Synth. Commun. 31, 1249–1251.
Hoogenraad, M., van der Linden, J. B. & Smith, A. A. (2004). Org. Process Res. Dev. 8, 469–476.
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Sheldrick, G. M. (1997b). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Aromatic nitro compounds are potential intermediates for a variety of fine chemicals. They are easily reduced to the corresponding aromatic amines (Desai et al., 2001). Therefore, aromatic nitro compounds are frequently used in the synthesis of pharmaceuticals (Hoogenraad et al., 2004). We herein reported a crystal structure of 2-methoxy-5-nitrobenzene-1,3-diyl dibenzenesulfonate. As shown in Fig. 1, the nitro group (N1/O1/O2) makes a dihedral angle with the benzene ring (C1—C6) of 11.68 (8) °. In spite of the fact that the nitro group is almost coplanar with the benzene ring, no conjugation is observed as evidenced by the N1—C1 bond length of 1.466 (3) Å. This is an agreement with the standard values of single N—C bond (1.47–1.50 Å) and all other bonds distances are in the the normal ranges (Allen et al., 1987).