Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024683/cf2106sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024683/cf2106Isup2.hkl |
CCDC reference: 654928
5-Bromothiophene-2-sulfonyl chloride (5 mmol, 1.304) in ethyl acetate (20 ml) was added dropwise to 3-nitroaniline (5 mmol, 1.38 g) in acetone (20 ml) at room temperature. The pure solid product was obtained after 24 h reaction and column chromatographic separation. Single crystals were obtained from 95% ethanol after 10 days.
All H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of Csp2—H = 0.93 Å with Uiso = 1.2Ueq(parent atom).
Some sulfonamide compounds exhibit germicidal activities (Gayathri et al., 2006; Krishnaiah et al., 1995; Yu, 2006). Some crystal structures involving sulfonamide groups have been published, including a recent report from our laboratory (Yan et al., 2007). As an extension of this research, we report here the synthesis and crystal structure of the title compound (I).
In (I) (Fig. 1), all bond lengths and angles show normal values (Allen et al., 1987) and are unremarkable when compared with those found in our previous report (Yan et al., 2007). The benzene ring (C5—C10) and the two thiophene groups (C1—C4/S1, C11—C14/S4) are essentially planar with r. m. s. deviations of 0.0025 Å, 0.0032 Å and 0.0036 Å each. The benzene ring and the two thiophene rings (C1—C4/S1, C11—C14/S4) make dihedral angles of 35.97 (15)° and 37.92 (19)°, respectively. The dihedral angle between the two thiophene rings is 62.47 (14)°.
For related literature, see Allen et al. (1987); Gayathri et al. (2006); Krishnaiah et al. (1995); Yan et al. (2007); Yu (2006).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.
Fig. 1. Molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level. |
C14H8Br2N2O6S4 | Z = 2 |
Mr = 588.30 | F(000) = 576 |
Triclinic, P1 | Dx = 1.963 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.5147 (7) Å | Cell parameters from 2347 reflections |
b = 9.3674 (7) Å | θ = 2.4–25.0° |
c = 13.7585 (11) Å | µ = 4.53 mm−1 |
α = 103.109 (1)° | T = 298 K |
β = 100.810 (1)° | Block, colorless |
γ = 105.155 (1)° | 0.29 × 0.26 × 0.21 mm |
V = 995.42 (14) Å3 |
Bruker APEX area-detector diffractometer | 3451 independent reflections |
Radiation source: fine-focus sealed tube | 2895 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.013 |
φ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −8→10 |
Tmin = 0.294, Tmax = 0.392 | k = −11→10 |
5264 measured reflections | l = −16→15 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0448P)2 + 1.0353P] where P = (Fo2 + 2Fc2)/3 |
3451 reflections | (Δ/σ)max = 0.001 |
253 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
C14H8Br2N2O6S4 | γ = 105.155 (1)° |
Mr = 588.30 | V = 995.42 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.5147 (7) Å | Mo Kα radiation |
b = 9.3674 (7) Å | µ = 4.53 mm−1 |
c = 13.7585 (11) Å | T = 298 K |
α = 103.109 (1)° | 0.29 × 0.26 × 0.21 mm |
β = 100.810 (1)° |
Bruker APEX area-detector diffractometer | 3451 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2895 reflections with I > 2σ(I) |
Tmin = 0.294, Tmax = 0.392 | Rint = 0.013 |
5264 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.57 e Å−3 |
3451 reflections | Δρmin = −0.50 e Å−3 |
253 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 | ||
Br1 | 0.80658 (6) | 0.57752 (6) | −0.01657 (3) | 0.06367 (16) | |
Br2 | 0.16643 (7) | 0.79432 (6) | 0.73552 (3) | 0.06776 (17) | |
S1 | 0.70495 (14) | 0.75108 (11) | 0.16962 (8) | 0.0508 (3) | |
S2 | 0.56667 (11) | 0.75343 (11) | 0.35446 (7) | 0.0415 (2) | |
S3 | 0.19996 (11) | 0.59462 (10) | 0.30359 (7) | 0.0402 (2) | |
S4 | 0.24634 (15) | 0.65019 (13) | 0.53339 (8) | 0.0549 (3) | |
O1 | 0.6610 (3) | 0.9124 (3) | 0.3806 (2) | 0.0577 (7) | |
O2 | 0.5703 (4) | 0.6730 (3) | 0.4300 (2) | 0.0583 (7) | |
O3 | 0.0704 (3) | 0.5875 (3) | 0.2195 (2) | 0.0554 (7) | |
O4 | 0.2608 (4) | 0.4679 (3) | 0.3058 (2) | 0.0553 (7) | |
O5 | 0.2349 (8) | 0.8484 (5) | −0.0312 (3) | 0.141 (2) | |
O6 | 0.2078 (12) | 1.0655 (7) | −0.0019 (4) | 0.220 (4) | |
N1 | 0.3660 (4) | 0.7446 (3) | 0.3097 (2) | 0.0377 (6) | |
N2 | 0.2335 (8) | 0.9620 (5) | 0.0268 (3) | 0.1021 (18) | |
C1 | 0.7121 (5) | 0.5809 (5) | 0.0948 (3) | 0.0462 (9) | |
C2 | 0.6533 (5) | 0.4597 (5) | 0.1300 (3) | 0.0544 (10) | |
H2 | 0.6492 | 0.3593 | 0.0987 | 0.065* | |
C3 | 0.5988 (5) | 0.5025 (5) | 0.2192 (3) | 0.0521 (10) | |
H3 | 0.5536 | 0.4337 | 0.2536 | 0.062* | |
C4 | 0.6197 (4) | 0.6552 (4) | 0.2491 (3) | 0.0412 (8) | |
C5 | 0.3332 (4) | 0.8701 (4) | 0.2738 (3) | 0.0389 (8) | |
C6 | 0.3002 (5) | 0.8562 (4) | 0.1699 (3) | 0.0489 (9) | |
H6 | 0.3000 | 0.7679 | 0.1224 | 0.059* | |
C7 | 0.2675 (7) | 0.9768 (5) | 0.1384 (3) | 0.0620 (12) | |
C8 | 0.2669 (6) | 1.1098 (5) | 0.2055 (3) | 0.0618 (12) | |
H8 | 0.2449 | 1.1897 | 0.1815 | 0.074* | |
C9 | 0.2998 (6) | 1.1209 (5) | 0.3093 (3) | 0.0565 (11) | |
H9 | 0.2993 | 1.2093 | 0.3564 | 0.068* | |
C10 | 0.3337 (5) | 1.0025 (4) | 0.3444 (3) | 0.0472 (9) | |
H10 | 0.3566 | 1.0112 | 0.4147 | 0.057* | |
C11 | 0.1428 (4) | 0.6570 (4) | 0.4158 (3) | 0.0408 (8) | |
C12 | 0.0271 (5) | 0.7303 (5) | 0.4243 (3) | 0.0580 (11) | |
H12 | −0.0394 | 0.7456 | 0.3683 | 0.070* | |
C13 | 0.0170 (5) | 0.7811 (6) | 0.5264 (3) | 0.0619 (11) | |
H13 | −0.0566 | 0.8329 | 0.5460 | 0.074* | |
C14 | 0.1281 (5) | 0.7448 (4) | 0.5924 (3) | 0.0482 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0770 (3) | 0.0778 (3) | 0.0497 (3) | 0.0413 (3) | 0.0284 (2) | 0.0152 (2) |
Br2 | 0.0943 (4) | 0.0683 (3) | 0.0411 (2) | 0.0204 (3) | 0.0258 (2) | 0.0162 (2) |
S1 | 0.0673 (7) | 0.0480 (5) | 0.0455 (6) | 0.0249 (5) | 0.0244 (5) | 0.0139 (4) |
S2 | 0.0417 (5) | 0.0467 (5) | 0.0323 (5) | 0.0134 (4) | 0.0067 (4) | 0.0076 (4) |
S3 | 0.0446 (5) | 0.0374 (5) | 0.0342 (5) | 0.0087 (4) | 0.0082 (4) | 0.0090 (4) |
S4 | 0.0752 (7) | 0.0623 (6) | 0.0394 (5) | 0.0343 (6) | 0.0164 (5) | 0.0224 (5) |
O1 | 0.0503 (16) | 0.0471 (15) | 0.0572 (18) | 0.0034 (13) | 0.0109 (13) | −0.0036 (13) |
O2 | 0.0656 (18) | 0.0781 (19) | 0.0389 (15) | 0.0320 (15) | 0.0112 (13) | 0.0234 (14) |
O3 | 0.0511 (16) | 0.0652 (18) | 0.0363 (14) | 0.0059 (13) | 0.0010 (12) | 0.0120 (13) |
O4 | 0.0740 (19) | 0.0354 (13) | 0.0612 (18) | 0.0190 (13) | 0.0255 (15) | 0.0147 (12) |
O5 | 0.312 (7) | 0.120 (3) | 0.044 (2) | 0.141 (4) | 0.060 (3) | 0.034 (2) |
O6 | 0.531 (14) | 0.148 (5) | 0.076 (3) | 0.213 (7) | 0.104 (6) | 0.073 (3) |
N1 | 0.0404 (16) | 0.0373 (15) | 0.0401 (16) | 0.0140 (13) | 0.0133 (13) | 0.0159 (13) |
N2 | 0.213 (6) | 0.078 (3) | 0.056 (3) | 0.085 (4) | 0.053 (3) | 0.041 (2) |
C1 | 0.045 (2) | 0.056 (2) | 0.040 (2) | 0.0260 (18) | 0.0100 (16) | 0.0075 (17) |
C2 | 0.062 (3) | 0.049 (2) | 0.057 (3) | 0.028 (2) | 0.019 (2) | 0.0085 (19) |
C3 | 0.053 (2) | 0.049 (2) | 0.063 (3) | 0.0225 (18) | 0.020 (2) | 0.0208 (19) |
C4 | 0.0401 (19) | 0.047 (2) | 0.0367 (19) | 0.0181 (16) | 0.0074 (15) | 0.0088 (16) |
C5 | 0.046 (2) | 0.0353 (18) | 0.0369 (19) | 0.0133 (15) | 0.0129 (15) | 0.0119 (15) |
C6 | 0.079 (3) | 0.0369 (19) | 0.038 (2) | 0.0264 (19) | 0.0231 (19) | 0.0102 (16) |
C7 | 0.108 (4) | 0.050 (2) | 0.041 (2) | 0.037 (2) | 0.024 (2) | 0.0197 (19) |
C8 | 0.102 (4) | 0.043 (2) | 0.052 (3) | 0.037 (2) | 0.024 (2) | 0.0185 (19) |
C9 | 0.084 (3) | 0.044 (2) | 0.049 (2) | 0.034 (2) | 0.025 (2) | 0.0085 (18) |
C10 | 0.061 (2) | 0.047 (2) | 0.0336 (19) | 0.0197 (18) | 0.0144 (17) | 0.0056 (16) |
C11 | 0.0413 (19) | 0.0407 (19) | 0.0367 (19) | 0.0057 (15) | 0.0104 (15) | 0.0126 (15) |
C12 | 0.041 (2) | 0.083 (3) | 0.051 (2) | 0.023 (2) | 0.0114 (18) | 0.021 (2) |
C13 | 0.052 (2) | 0.086 (3) | 0.052 (3) | 0.028 (2) | 0.022 (2) | 0.015 (2) |
C14 | 0.057 (2) | 0.041 (2) | 0.042 (2) | 0.0040 (17) | 0.0207 (18) | 0.0107 (17) |
Br1—C1 | 1.857 (4) | C2—C3 | 1.404 (6) |
Br2—C14 | 1.861 (4) | C2—H2 | 0.930 |
S1—C4 | 1.713 (4) | C3—C4 | 1.349 (5) |
S1—C1 | 1.713 (4) | C3—H3 | 0.930 |
S2—O2 | 1.415 (3) | C5—C6 | 1.374 (5) |
S2—O1 | 1.420 (3) | C5—C10 | 1.389 (5) |
S2—N1 | 1.677 (3) | C6—C7 | 1.372 (5) |
S2—C4 | 1.735 (4) | C6—H6 | 0.930 |
S3—O3 | 1.417 (3) | C7—C8 | 1.374 (6) |
S3—O4 | 1.417 (3) | C8—C9 | 1.378 (6) |
S3—N1 | 1.686 (3) | C8—H8 | 0.930 |
S3—C11 | 1.727 (4) | C9—C10 | 1.380 (5) |
S4—C14 | 1.704 (4) | C9—H9 | 0.930 |
S4—C11 | 1.715 (4) | C10—H10 | 0.930 |
O5—N2 | 1.181 (5) | C11—C12 | 1.348 (5) |
O6—N2 | 1.182 (5) | C12—C13 | 1.404 (6) |
N1—C5 | 1.444 (4) | C12—H12 | 0.930 |
N2—C7 | 1.475 (6) | C13—C14 | 1.349 (6) |
C1—C2 | 1.348 (6) | C13—H13 | 0.930 |
C4—S1—C1 | 89.88 (19) | S1—C4—S2 | 120.6 (2) |
O2—S2—O1 | 120.68 (18) | C6—C5—C10 | 120.7 (3) |
O2—S2—N1 | 107.56 (16) | C6—C5—N1 | 119.4 (3) |
O1—S2—N1 | 104.87 (16) | C10—C5—N1 | 119.9 (3) |
O2—S2—C4 | 109.33 (18) | C7—C6—C5 | 117.9 (3) |
O1—S2—C4 | 107.98 (18) | C7—C6—H6 | 121.1 |
N1—S2—C4 | 105.36 (16) | C5—C6—H6 | 121.1 |
O3—S3—O4 | 121.60 (18) | C6—C7—C8 | 123.3 (4) |
O3—S3—N1 | 105.18 (16) | C6—C7—N2 | 117.7 (4) |
O4—S3—N1 | 106.70 (16) | C8—C7—N2 | 119.0 (4) |
O3—S3—C11 | 107.58 (18) | C7—C8—C9 | 117.8 (4) |
O4—S3—C11 | 110.68 (17) | C7—C8—H8 | 121.1 |
N1—S3—C11 | 103.50 (16) | C9—C8—H8 | 121.1 |
C14—S4—C11 | 90.14 (19) | C8—C9—C10 | 120.8 (3) |
C5—N1—S2 | 118.8 (2) | C8—C9—H9 | 119.6 |
C5—N1—S3 | 118.3 (2) | C10—C9—H9 | 119.6 |
S2—N1—S3 | 122.91 (17) | C9—C10—C5 | 119.5 (4) |
O5—N2—O6 | 121.7 (5) | C9—C10—H10 | 120.3 |
O5—N2—C7 | 119.4 (4) | C5—C10—H10 | 120.3 |
O6—N2—C7 | 118.9 (4) | C12—C11—S4 | 112.0 (3) |
C2—C1—S1 | 112.9 (3) | C12—C11—S3 | 125.2 (3) |
C2—C1—Br1 | 126.3 (3) | S4—C11—S3 | 122.5 (2) |
S1—C1—Br1 | 120.7 (2) | C11—C12—C13 | 113.2 (4) |
C1—C2—C3 | 112.2 (4) | C11—C12—H12 | 123.4 |
C1—C2—H2 | 123.9 | C13—C12—H12 | 123.4 |
C3—C2—H2 | 123.9 | C14—C13—C12 | 111.1 (4) |
C4—C3—C2 | 112.0 (4) | C14—C13—H13 | 124.4 |
C4—C3—H3 | 124.0 | C12—C13—H13 | 124.4 |
C2—C3—H3 | 124.0 | C13—C14—S4 | 113.5 (3) |
C3—C4—S1 | 113.0 (3) | C13—C14—Br2 | 126.8 (3) |
C3—C4—S2 | 126.4 (3) | S4—C14—Br2 | 119.7 (2) |
O2—S2—N1—C5 | 149.9 (3) | S3—N1—C5—C10 | 97.3 (4) |
O1—S2—N1—C5 | 20.3 (3) | C10—C5—C6—C7 | −0.1 (6) |
C4—S2—N1—C5 | −93.5 (3) | N1—C5—C6—C7 | 179.2 (4) |
O2—S2—N1—S3 | −30.6 (3) | C5—C6—C7—C8 | 0.2 (7) |
O1—S2—N1—S3 | −160.2 (2) | C5—C6—C7—N2 | 179.5 (5) |
C4—S2—N1—S3 | 86.0 (2) | O5—N2—C7—C6 | 0.2 (9) |
O3—S3—N1—C5 | 28.7 (3) | O6—N2—C7—C6 | −178.8 (7) |
O4—S3—N1—C5 | 159.1 (3) | O5—N2—C7—C8 | 179.5 (6) |
C11—S3—N1—C5 | −84.1 (3) | O6—N2—C7—C8 | 0.5 (10) |
O3—S3—N1—S2 | −150.8 (2) | C6—C7—C8—C9 | −0.4 (8) |
O4—S3—N1—S2 | −20.4 (3) | N2—C7—C8—C9 | −179.7 (5) |
C11—S3—N1—S2 | 96.4 (2) | C7—C8—C9—C10 | 0.5 (7) |
C4—S1—C1—C2 | −0.3 (3) | C8—C9—C10—C5 | −0.4 (7) |
C4—S1—C1—Br1 | −176.5 (2) | C6—C5—C10—C9 | 0.2 (6) |
S1—C1—C2—C3 | 0.6 (5) | N1—C5—C10—C9 | −179.1 (4) |
Br1—C1—C2—C3 | 176.5 (3) | C14—S4—C11—C12 | 0.9 (3) |
C1—C2—C3—C4 | −0.6 (5) | C14—S4—C11—S3 | 174.4 (2) |
C2—C3—C4—S1 | 0.3 (4) | O3—S3—C11—C12 | −18.7 (4) |
C2—C3—C4—S2 | 179.4 (3) | O4—S3—C11—C12 | −153.7 (3) |
C1—S1—C4—C3 | 0.0 (3) | N1—S3—C11—C12 | 92.3 (4) |
C1—S1—C4—S2 | −179.1 (2) | O3—S3—C11—S4 | 168.6 (2) |
O2—S2—C4—C3 | 26.3 (4) | O4—S3—C11—S4 | 33.6 (3) |
O1—S2—C4—C3 | 159.3 (3) | N1—S3—C11—S4 | −80.4 (2) |
N1—S2—C4—C3 | −89.1 (4) | S4—C11—C12—C13 | −0.9 (5) |
O2—S2—C4—S1 | −154.7 (2) | S3—C11—C12—C13 | −174.2 (3) |
O1—S2—C4—S1 | −21.7 (3) | C11—C12—C13—C14 | 0.5 (6) |
N1—S2—C4—S1 | 90.0 (2) | C12—C13—C14—S4 | 0.2 (5) |
S2—N1—C5—C6 | 97.4 (4) | C12—C13—C14—Br2 | 177.6 (3) |
S3—N1—C5—C6 | −82.1 (4) | C11—S4—C14—C13 | −0.6 (3) |
S2—N1—C5—C10 | −83.2 (4) | C11—S4—C14—Br2 | −178.2 (2) |
Experimental details
Crystal data | |
Chemical formula | C14H8Br2N2O6S4 |
Mr | 588.30 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.5147 (7), 9.3674 (7), 13.7585 (11) |
α, β, γ (°) | 103.109 (1), 100.810 (1), 105.155 (1) |
V (Å3) | 995.42 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.53 |
Crystal size (mm) | 0.29 × 0.26 × 0.21 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.294, 0.392 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5264, 3451, 2895 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.095, 1.02 |
No. of reflections | 3451 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.50 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.
Some sulfonamide compounds exhibit germicidal activities (Gayathri et al., 2006; Krishnaiah et al., 1995; Yu, 2006). Some crystal structures involving sulfonamide groups have been published, including a recent report from our laboratory (Yan et al., 2007). As an extension of this research, we report here the synthesis and crystal structure of the title compound (I).
In (I) (Fig. 1), all bond lengths and angles show normal values (Allen et al., 1987) and are unremarkable when compared with those found in our previous report (Yan et al., 2007). The benzene ring (C5—C10) and the two thiophene groups (C1—C4/S1, C11—C14/S4) are essentially planar with r. m. s. deviations of 0.0025 Å, 0.0032 Å and 0.0036 Å each. The benzene ring and the two thiophene rings (C1—C4/S1, C11—C14/S4) make dihedral angles of 35.97 (15)° and 37.92 (19)°, respectively. The dihedral angle between the two thiophene rings is 62.47 (14)°.