Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108009530/hj3069sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108009530/hj3069Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108009530/hj3069IIsup3.hkl |
CCDC references: 690200; 690201
A suspension of saccharin (1.0 g, 5.46 mmol,) and o- or p-chloroaniline (5 ml, in excess) was stirred first at room temperature (1.5 h) and then at high temperature (373 K, 2–4 h). The resulting light-brown solution was cooled to room temperature, diluted in chloroform, and washed with dilute hydrochloric acid (2M, 2 × 20 ml) and water. The organic layer was dried over magnesium sulfate and then evaporated at reduced pressure (11 Torr; 1 Torr = 133.322 Pa) to obtain light-pink and colourless solid products, (I) and (II), respectively. The products were crystallized from MeOH–CHCl3 (1:4 v/v) solutions by slow evaporation at 313 K.
Analysis for (I): IR (neat, νmax, cm-1): NH and NH2 3306 (br), CO 1662 (m), SO2 1342 and 1165 (s); 1H NMR (300 MHz, acetone-d6, δ, p.p.m.): 6.62 (s, 2H, NH2), 7.30 (ddd, 1H, J = 1.46, 7.68 and 9.14 Hz, H4'), 7.34 (m, 1H, H5'), 7.46 (dd, 1H, J = 1.47 and 8.05 Hz, H3'), 7.73–7.83 (m, 2H, H6' and H4), 7.93 (d, 1H, J = 7.1 Hz, H5), 8.09 (dd, 2H, J = 1.46 and 7.32 Hz, H3 and H6), 9.51 (s, 1H, NH); 13C NMR (Frequency?, Medium?, δ, p.p.m.): 206.2, 133.2, 131.6, 131.5, 130.4, 129.7, 128.5, 128.3, 127.8, 127.1; yield: 1.16 g, 3.77 mmol, 69%; m.p. 382–383 K.
Analysis for (II): IR (neat, νmax, cm-1): NH 3355 (m), NH2 3265, 3235 (m), CO 1636 (s), SO2 1349, 1157 (s); 1H NMR (300 MHz, DMSO-d6, δ, p.p.m.): 6.91–7.10 (4H, m, C6H4), 7.32–7.53 (4H, m, C6H4), 10.55 (1H, s, NH); 13C NMR (Frequency?, Medium?, δ, p.p.m.): 165.7, 140.1, 138.1, 133.8, 131.4, 129.9, 129.9, 129.2, 129.0, 128.6, 124.2, 121.0, 120.3; yield: 1.32 g, 4.26 mmol, 78%; m.p. 475–476 K.
For both structures, H atoms bonded to C atoms were included in the refinements at geometrically idealized positions, with C—H = 0.95 Å and with Uiso(H) = 1.2Ueq(C). H atoms bonded to N atoms were allowed to refine with Uiso(H) = 1.2Ueq(N). The final difference maps were free of chemically significant features. An absolute structure could not be established by the Flack method (Flack, 1983) as a twin refinement gave a 0.55 (8):0.45 (8) mixture. Friedel pairs were, therefore, merged.
For both compounds, data collection: COLLECT (Hooft, 1998); cell refinement: HKL DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C13H11ClN2O3S | F(000) = 640 |
Mr = 310.75 | Dx = 1.602 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 2709 reflections |
a = 15.734 (9) Å | θ = 2.3–27.5° |
b = 10.614 (6) Å | µ = 0.47 mm−1 |
c = 7.717 (3) Å | T = 173 K |
V = 1288.7 (12) Å3 | Prism, colourless |
Z = 4 | 0.18 × 0.12 × 0.07 mm |
Nonius KappaCCD diffractometer | 1571 independent reflections |
Radiation source: fine-focus sealed tube | 1353 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω and ϕ scans | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −20→20 |
Tmin = 0.921, Tmax = 0.968 | k = −13→13 |
2709 measured reflections | l = −9→9 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.047P)2 + 0.25P] where P = (Fo2 + 2Fc2)/3 |
1571 reflections | (Δ/σ)max = 0.001 |
191 parameters | Δρmax = 0.25 e Å−3 |
1 restraint | Δρmin = −0.33 e Å−3 |
C13H11ClN2O3S | V = 1288.7 (12) Å3 |
Mr = 310.75 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 15.734 (9) Å | µ = 0.47 mm−1 |
b = 10.614 (6) Å | T = 173 K |
c = 7.717 (3) Å | 0.18 × 0.12 × 0.07 mm |
Nonius KappaCCD diffractometer | 1571 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 1353 reflections with I > 2σ(I) |
Tmin = 0.921, Tmax = 0.968 | Rint = 0.030 |
2709 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 1 restraint |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.25 e Å−3 |
1571 reflections | Δρmin = −0.33 e Å−3 |
191 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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.08066 (5) | 0.81417 (7) | 0.19375 (18) | 0.0309 (2) | |
S1 | 0.02254 (4) | 0.18986 (6) | 0.19342 (12) | 0.02041 (18) | |
O1 | 0.06897 (13) | 0.3891 (2) | −0.1186 (3) | 0.0254 (5) | |
O2 | 0.08444 (13) | 0.2757 (2) | 0.2632 (3) | 0.0266 (5) | |
O3 | −0.00651 (16) | 0.0865 (2) | 0.2966 (3) | 0.0321 (6) | |
N1 | 0.06339 (17) | 0.1298 (3) | 0.0204 (4) | 0.0246 (6) | |
H1NA | 0.077 (2) | 0.190 (3) | −0.061 (5) | 0.030* | |
H1NB | 0.031 (2) | 0.069 (4) | −0.006 (5) | 0.030* | |
N2 | 0.06043 (17) | 0.5470 (2) | 0.0823 (4) | 0.0212 (6) | |
H2N | 0.032 (2) | 0.578 (3) | 0.152 (5) | 0.025* | |
C1 | −0.06698 (18) | 0.2832 (3) | 0.1383 (4) | 0.0194 (6) | |
C2 | −0.1471 (2) | 0.2402 (3) | 0.1813 (5) | 0.0261 (6) | |
H2 | −0.1535 | 0.1631 | 0.2423 | 0.031* | |
C3 | −0.2185 (2) | 0.3101 (3) | 0.1352 (5) | 0.0302 (8) | |
H3 | −0.2737 | 0.2801 | 0.1630 | 0.036* | |
C4 | −0.2088 (2) | 0.4231 (3) | 0.0488 (5) | 0.0261 (7) | |
H4 | −0.2576 | 0.4701 | 0.0159 | 0.031* | |
C5 | −0.12811 (19) | 0.4688 (3) | 0.0096 (5) | 0.0251 (7) | |
H5 | −0.1222 | 0.5476 | −0.0476 | 0.030* | |
C6 | −0.05605 (19) | 0.4000 (3) | 0.0533 (4) | 0.0189 (6) | |
C7 | 0.03036 (18) | 0.4440 (3) | −0.0020 (4) | 0.0200 (6) | |
C8 | 0.1456 (2) | 0.5914 (3) | 0.0788 (4) | 0.0208 (6) | |
C9 | 0.1629 (2) | 0.7139 (3) | 0.1360 (4) | 0.0237 (7) | |
C10 | 0.2461 (2) | 0.7571 (3) | 0.1498 (5) | 0.0301 (7) | |
H10 | 0.2570 | 0.8393 | 0.1935 | 0.036* | |
C11 | 0.3123 (2) | 0.6815 (4) | 0.1006 (5) | 0.0334 (8) | |
H11 | 0.3691 | 0.7111 | 0.1092 | 0.040* | |
C12 | 0.2962 (2) | 0.5612 (3) | 0.0379 (5) | 0.0302 (8) | |
H12 | 0.3420 | 0.5097 | 0.0004 | 0.036* | |
C13 | 0.21369 (19) | 0.5157 (3) | 0.0297 (5) | 0.0274 (7) | |
H13 | 0.2036 | 0.4322 | −0.0097 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0413 (4) | 0.0190 (3) | 0.0323 (4) | 0.0002 (3) | 0.0054 (4) | −0.0025 (4) |
S1 | 0.0229 (4) | 0.0181 (3) | 0.0202 (3) | 0.0010 (3) | 0.0000 (3) | 0.0007 (3) |
O1 | 0.0300 (12) | 0.0229 (11) | 0.0234 (11) | −0.0029 (9) | 0.0067 (9) | −0.0049 (9) |
O2 | 0.0253 (11) | 0.0250 (11) | 0.0296 (11) | 0.0013 (10) | −0.0077 (9) | −0.0052 (10) |
O3 | 0.0400 (14) | 0.0238 (11) | 0.0324 (13) | 0.0037 (11) | 0.0048 (11) | 0.0079 (11) |
N1 | 0.0262 (14) | 0.0218 (14) | 0.0259 (14) | −0.0004 (12) | 0.0007 (12) | −0.0051 (12) |
N2 | 0.0258 (14) | 0.0169 (13) | 0.0209 (13) | −0.0005 (11) | 0.0042 (10) | −0.0014 (11) |
C1 | 0.0229 (15) | 0.0159 (14) | 0.0195 (13) | −0.0007 (12) | −0.0006 (12) | −0.0038 (11) |
C2 | 0.0272 (15) | 0.0224 (14) | 0.0287 (16) | −0.0060 (13) | 0.0037 (14) | 0.0000 (16) |
C3 | 0.0206 (15) | 0.034 (2) | 0.0362 (19) | −0.0066 (15) | 0.0027 (14) | −0.0093 (15) |
C4 | 0.0225 (16) | 0.0239 (16) | 0.0318 (17) | 0.0047 (13) | −0.0033 (13) | −0.0047 (13) |
C5 | 0.0275 (16) | 0.0231 (16) | 0.0246 (15) | 0.0048 (13) | −0.0026 (13) | −0.0025 (13) |
C6 | 0.0243 (16) | 0.0164 (14) | 0.0159 (14) | −0.0021 (12) | −0.0002 (12) | −0.0024 (11) |
C7 | 0.0229 (15) | 0.0151 (14) | 0.0221 (14) | 0.0020 (12) | −0.0026 (13) | 0.0026 (12) |
C8 | 0.0250 (16) | 0.0191 (15) | 0.0184 (14) | −0.0034 (13) | 0.0002 (12) | 0.0010 (12) |
C9 | 0.0297 (17) | 0.0215 (15) | 0.0198 (14) | −0.0041 (13) | 0.0019 (13) | 0.0016 (12) |
C10 | 0.0388 (18) | 0.0242 (16) | 0.0272 (17) | −0.0125 (15) | −0.0015 (14) | 0.0031 (13) |
C11 | 0.0315 (19) | 0.041 (2) | 0.0273 (18) | −0.0127 (16) | −0.0028 (15) | 0.0058 (15) |
C12 | 0.0236 (16) | 0.0338 (18) | 0.0332 (19) | 0.0010 (15) | 0.0028 (14) | 0.0049 (15) |
C13 | 0.0279 (16) | 0.0215 (16) | 0.0327 (18) | −0.0012 (14) | 0.0018 (13) | 0.0045 (13) |
Cl1—C9 | 1.734 (3) | C3—H3 | 0.9500 |
S1—O3 | 1.431 (3) | C4—C5 | 1.392 (5) |
S1—O2 | 1.438 (2) | C4—H4 | 0.9500 |
S1—N1 | 1.613 (3) | C5—C6 | 1.390 (4) |
S1—C1 | 1.774 (3) | C5—H5 | 0.9500 |
O1—C7 | 1.232 (4) | C6—C7 | 1.499 (4) |
N1—H1NA | 0.93 (4) | C8—C13 | 1.393 (5) |
N1—H1NB | 0.85 (4) | C8—C9 | 1.400 (4) |
N2—C7 | 1.357 (4) | C9—C10 | 1.392 (5) |
N2—C8 | 1.420 (4) | C10—C11 | 1.369 (5) |
N2—H2N | 0.77 (4) | C10—H10 | 0.9500 |
C1—C2 | 1.381 (4) | C11—C12 | 1.388 (5) |
C1—C6 | 1.413 (4) | C11—H11 | 0.9500 |
C2—C3 | 1.392 (5) | C12—C13 | 1.387 (4) |
C2—H2 | 0.9500 | C12—H12 | 0.9500 |
C3—C4 | 1.381 (5) | C13—H13 | 0.9500 |
O3—S1—O2 | 119.58 (18) | C4—C5—H5 | 119.7 |
O3—S1—N1 | 106.54 (15) | C5—C6—C1 | 118.3 (3) |
O2—S1—N1 | 106.90 (15) | C5—C6—C7 | 120.4 (3) |
O3—S1—C1 | 107.95 (14) | C1—C6—C7 | 121.0 (3) |
O2—S1—C1 | 105.88 (14) | O1—C7—N2 | 124.0 (3) |
N1—S1—C1 | 109.80 (18) | O1—C7—C6 | 120.5 (3) |
S1—N1—H1NA | 113 (2) | N2—C7—C6 | 115.5 (3) |
S1—N1—H1NB | 105 (3) | C13—C8—C9 | 118.2 (3) |
H1NA—N1—H1NB | 120 (3) | C13—C8—N2 | 122.6 (3) |
C7—N2—C8 | 126.0 (3) | C9—C8—N2 | 119.1 (3) |
C7—N2—H2N | 118 (3) | C10—C9—C8 | 120.9 (3) |
C8—N2—H2N | 115 (3) | C10—C9—Cl1 | 118.7 (3) |
C2—C1—C6 | 120.8 (3) | C8—C9—Cl1 | 120.4 (3) |
C2—C1—S1 | 118.9 (2) | C11—C10—C9 | 120.1 (3) |
C6—C1—S1 | 120.3 (2) | C11—C10—H10 | 120.0 |
C1—C2—C3 | 119.9 (3) | C9—C10—H10 | 120.0 |
C1—C2—H2 | 120.0 | C10—C11—C12 | 119.8 (3) |
C3—C2—H2 | 120.0 | C10—C11—H11 | 120.1 |
C4—C3—C2 | 119.8 (3) | C12—C11—H11 | 120.1 |
C4—C3—H3 | 120.1 | C13—C12—C11 | 120.5 (3) |
C2—C3—H3 | 120.1 | C13—C12—H12 | 119.7 |
C3—C4—C5 | 120.5 (3) | C11—C12—H12 | 119.7 |
C3—C4—H4 | 119.7 | C12—C13—C8 | 120.5 (3) |
C5—C4—H4 | 119.7 | C12—C13—H13 | 119.8 |
C6—C5—C4 | 120.5 (3) | C8—C13—H13 | 119.8 |
C6—C5—H5 | 119.7 | ||
O3—S1—C1—C2 | −6.8 (3) | C8—N2—C7—C6 | 166.7 (3) |
O2—S1—C1—C2 | −135.9 (3) | C5—C6—C7—O1 | −106.9 (3) |
N1—S1—C1—C2 | 109.0 (3) | C1—C6—C7—O1 | 67.9 (4) |
O3—S1—C1—C6 | 172.7 (2) | C5—C6—C7—N2 | 72.0 (4) |
O2—S1—C1—C6 | 43.5 (3) | C1—C6—C7—N2 | −113.2 (3) |
N1—S1—C1—C6 | −71.6 (3) | C7—N2—C8—C13 | −19.2 (5) |
C6—C1—C2—C3 | 2.3 (5) | C7—N2—C8—C9 | 164.5 (3) |
S1—C1—C2—C3 | −178.2 (3) | C13—C8—C9—C10 | −2.5 (5) |
C1—C2—C3—C4 | −1.0 (5) | N2—C8—C9—C10 | 174.0 (3) |
C2—C3—C4—C5 | −0.9 (5) | C13—C8—C9—Cl1 | 178.4 (3) |
C3—C4—C5—C6 | 1.4 (5) | N2—C8—C9—Cl1 | −5.1 (4) |
C4—C5—C6—C1 | 0.0 (4) | C8—C9—C10—C11 | 2.7 (5) |
C4—C5—C6—C7 | 174.9 (3) | Cl1—C9—C10—C11 | −178.2 (3) |
C2—C1—C6—C5 | −1.8 (4) | C9—C10—C11—C12 | −0.4 (5) |
S1—C1—C6—C5 | 178.7 (2) | C10—C11—C12—C13 | −1.9 (5) |
C2—C1—C6—C7 | −176.7 (3) | C11—C12—C13—C8 | 2.1 (5) |
S1—C1—C6—C7 | 3.8 (4) | C9—C8—C13—C12 | 0.1 (5) |
C8—N2—C7—O1 | −14.5 (5) | N2—C8—C13—C12 | −176.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···Cl1 | 0.77 (4) | 2.64 (4) | 2.981 (3) | 109 (3) |
N1—H1NA···O1 | 0.93 (4) | 2.16 (4) | 2.955 (4) | 144 (3) |
N1—H1NB···O3i | 0.85 (4) | 2.28 (4) | 3.009 (4) | 144 (3) |
N2—H2N···O1ii | 0.77 (4) | 2.40 (4) | 3.152 (4) | 163 (3) |
C2—H2···O3 | 0.95 | 2.49 | 2.890 (4) | 106 |
C13—H13···O1 | 0.95 | 2.32 | 2.881 (4) | 117 |
C3—H3···O2iii | 0.95 | 2.44 | 3.380 (4) | 173 |
C5—H5···O2iv | 0.95 | 2.45 | 3.382 (4) | 167 |
Symmetry codes: (i) −x, −y, z−1/2; (ii) −x, −y+1, z+1/2; (iii) x−1/2, −y+1/2, z; (iv) −x, −y+1, z−1/2. |
C13H11ClN2O3S | F(000) = 1280 |
Mr = 310.75 | Dx = 1.572 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 9119 reflections |
a = 7.435 (2) Å | θ = 3.8–27.5° |
b = 16.006 (6) Å | µ = 0.46 mm−1 |
c = 22.061 (7) Å | T = 173 K |
V = 2625.4 (15) Å3 | Prism, colourless |
Z = 8 | 0.12 × 0.07 × 0.06 mm |
Nonius KappaCCD diffractometer | 3005 independent reflections |
Radiation source: fine-focus sealed tube | 2019 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
ω and ϕ scans | θmax = 27.5°, θmin = 3.8° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −9→9 |
Tmin = 0.947, Tmax = 0.973 | k = −19→20 |
9119 measured reflections | l = −28→28 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.061P)2 + 0.61P] where P = (Fo2 + 2Fc2)/3 |
3005 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
C13H11ClN2O3S | V = 2625.4 (15) Å3 |
Mr = 310.75 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.435 (2) Å | µ = 0.46 mm−1 |
b = 16.006 (6) Å | T = 173 K |
c = 22.061 (7) Å | 0.12 × 0.07 × 0.06 mm |
Nonius KappaCCD diffractometer | 3005 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 2019 reflections with I > 2σ(I) |
Tmin = 0.947, Tmax = 0.973 | Rint = 0.061 |
9119 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.26 e Å−3 |
3005 reflections | Δρmin = −0.44 e Å−3 |
190 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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.73145 (11) | −0.04552 (5) | −0.20202 (3) | 0.0473 (2) | |
S1 | 0.83054 (8) | 0.22246 (4) | 0.16281 (3) | 0.02399 (18) | |
O1 | 0.5441 (2) | 0.17758 (10) | 0.05808 (7) | 0.0264 (4) | |
O2 | 0.9182 (2) | 0.17305 (11) | 0.11770 (7) | 0.0297 (4) | |
O3 | 0.9267 (2) | 0.24784 (12) | 0.21619 (7) | 0.0327 (4) | |
N1 | 0.6573 (3) | 0.17113 (14) | 0.18574 (11) | 0.0282 (5) | |
H1NA | 0.591 (4) | 0.1568 (18) | 0.1589 (13) | 0.034* | |
H1NB | 0.608 (4) | 0.1932 (18) | 0.2160 (13) | 0.034* | |
N2 | 0.7105 (3) | 0.22676 (14) | −0.02088 (9) | 0.0244 (5) | |
H2N | 0.766 (4) | 0.2681 (19) | −0.0304 (12) | 0.029* | |
C1 | 0.7545 (3) | 0.31503 (15) | 0.12634 (10) | 0.0212 (5) | |
C2 | 0.7717 (3) | 0.39029 (16) | 0.15648 (11) | 0.0274 (6) | |
H2 | 0.8238 | 0.3918 | 0.1958 | 0.033* | |
C3 | 0.7130 (3) | 0.46374 (16) | 0.12940 (12) | 0.0314 (6) | |
H3 | 0.7208 | 0.5152 | 0.1507 | 0.038* | |
C4 | 0.6435 (3) | 0.46189 (16) | 0.07169 (11) | 0.0301 (6) | |
H4 | 0.6044 | 0.5122 | 0.0531 | 0.036* | |
C5 | 0.6302 (3) | 0.38739 (16) | 0.04059 (11) | 0.0270 (6) | |
H5 | 0.5855 | 0.3873 | 0.0003 | 0.032* | |
C6 | 0.6816 (3) | 0.31231 (15) | 0.06751 (10) | 0.0219 (5) | |
C7 | 0.6418 (3) | 0.23174 (15) | 0.03514 (10) | 0.0219 (5) | |
C8 | 0.7000 (3) | 0.15984 (16) | −0.06288 (10) | 0.0237 (5) | |
C9 | 0.7565 (3) | 0.17711 (17) | −0.12205 (10) | 0.0284 (6) | |
H9 | 0.7881 | 0.2326 | −0.1330 | 0.034* | |
C10 | 0.7668 (3) | 0.11454 (18) | −0.16439 (11) | 0.0326 (6) | |
H10 | 0.8072 | 0.1263 | −0.2043 | 0.039* | |
C11 | 0.7176 (3) | 0.03377 (18) | −0.14832 (11) | 0.0312 (6) | |
C12 | 0.6573 (3) | 0.01580 (17) | −0.09052 (11) | 0.0303 (6) | |
H12 | 0.6220 | −0.0395 | −0.0802 | 0.036* | |
C13 | 0.6485 (3) | 0.07950 (16) | −0.04747 (11) | 0.0274 (6) | |
H13 | 0.6073 | 0.0677 | −0.0076 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0590 (5) | 0.0457 (5) | 0.0372 (4) | −0.0022 (4) | 0.0049 (3) | −0.0178 (3) |
S1 | 0.0279 (3) | 0.0230 (3) | 0.0211 (3) | 0.0025 (3) | −0.0011 (2) | 0.0023 (2) |
O1 | 0.0300 (8) | 0.0260 (10) | 0.0231 (8) | −0.0036 (8) | 0.0022 (7) | 0.0000 (7) |
O2 | 0.0321 (9) | 0.0282 (10) | 0.0288 (9) | 0.0073 (8) | 0.0046 (7) | 0.0005 (8) |
O3 | 0.0398 (10) | 0.0333 (10) | 0.0250 (9) | 0.0010 (8) | −0.0099 (8) | 0.0030 (8) |
N1 | 0.0346 (12) | 0.0265 (13) | 0.0233 (11) | 0.0006 (10) | 0.0029 (9) | 0.0027 (9) |
N2 | 0.0279 (11) | 0.0226 (11) | 0.0226 (10) | −0.0045 (9) | 0.0012 (8) | −0.0003 (9) |
C1 | 0.0236 (11) | 0.0225 (13) | 0.0177 (11) | 0.0020 (10) | 0.0025 (9) | 0.0015 (10) |
C2 | 0.0336 (13) | 0.0249 (14) | 0.0235 (12) | −0.0014 (11) | 0.0006 (10) | −0.0006 (10) |
C3 | 0.0376 (13) | 0.0212 (13) | 0.0353 (14) | −0.0019 (11) | 0.0052 (11) | −0.0025 (11) |
C4 | 0.0306 (13) | 0.0235 (14) | 0.0361 (14) | 0.0031 (11) | 0.0016 (11) | 0.0091 (12) |
C5 | 0.0283 (12) | 0.0279 (14) | 0.0248 (12) | 0.0006 (11) | −0.0015 (10) | 0.0066 (11) |
C6 | 0.0215 (11) | 0.0219 (13) | 0.0223 (12) | −0.0015 (10) | 0.0030 (9) | 0.0026 (10) |
C7 | 0.0216 (11) | 0.0247 (14) | 0.0194 (11) | 0.0023 (10) | −0.0027 (9) | 0.0020 (10) |
C8 | 0.0208 (11) | 0.0297 (14) | 0.0205 (11) | 0.0010 (10) | −0.0007 (9) | −0.0011 (10) |
C9 | 0.0307 (13) | 0.0320 (14) | 0.0225 (12) | −0.0039 (11) | −0.0004 (10) | 0.0006 (11) |
C10 | 0.0352 (14) | 0.0435 (17) | 0.0190 (12) | −0.0019 (12) | 0.0025 (10) | −0.0028 (11) |
C11 | 0.0302 (12) | 0.0376 (16) | 0.0257 (13) | 0.0010 (12) | −0.0024 (10) | −0.0090 (11) |
C12 | 0.0331 (13) | 0.0272 (14) | 0.0305 (13) | −0.0034 (11) | 0.0003 (11) | −0.0034 (11) |
C13 | 0.0279 (12) | 0.0296 (14) | 0.0245 (12) | 0.0004 (11) | 0.0012 (10) | −0.0001 (11) |
Cl1—C11 | 1.739 (3) | C3—H3 | 0.9500 |
S1—O2 | 1.429 (2) | C4—C5 | 1.379 (4) |
S1—O3 | 1.436 (2) | C4—H4 | 0.9500 |
S1—N1 | 1.609 (2) | C5—C6 | 1.394 (3) |
S1—C1 | 1.778 (2) | C5—H5 | 0.9500 |
O1—C7 | 1.239 (3) | C6—C7 | 1.503 (3) |
N1—H1NA | 0.80 (3) | C8—C13 | 1.384 (3) |
N1—H1NB | 0.84 (3) | C8—C9 | 1.399 (3) |
N2—C7 | 1.340 (3) | C9—C10 | 1.372 (4) |
N2—C8 | 1.418 (3) | C9—H9 | 0.9500 |
N2—H2N | 0.81 (3) | C10—C11 | 1.390 (4) |
C1—C2 | 1.382 (3) | C10—H10 | 0.9500 |
C1—C6 | 1.407 (3) | C11—C12 | 1.382 (4) |
C2—C3 | 1.389 (4) | C12—C13 | 1.395 (3) |
C2—H2 | 0.9500 | C12—H12 | 0.9500 |
C3—C4 | 1.374 (4) | C13—H13 | 0.9500 |
O2—S1—O3 | 120.04 (11) | C6—C5—H5 | 119.5 |
O2—S1—N1 | 107.55 (12) | C5—C6—C1 | 118.2 (2) |
O3—S1—N1 | 106.55 (12) | C5—C6—C7 | 118.9 (2) |
O2—S1—C1 | 106.94 (10) | C1—C6—C7 | 122.7 (2) |
O3—S1—C1 | 107.08 (11) | O1—C7—N2 | 124.0 (2) |
N1—S1—C1 | 108.25 (11) | O1—C7—C6 | 121.4 (2) |
S1—N1—H1NA | 114 (2) | N2—C7—C6 | 114.5 (2) |
S1—N1—H1NB | 112 (2) | C13—C8—C9 | 119.7 (2) |
H1NA—N1—H1NB | 116 (3) | C13—C8—N2 | 123.8 (2) |
C7—N2—C8 | 128.8 (2) | C9—C8—N2 | 116.4 (2) |
C7—N2—H2N | 112.7 (19) | C10—C9—C8 | 120.5 (3) |
C8—N2—H2N | 118.4 (19) | C10—C9—H9 | 119.7 |
C2—C1—C6 | 120.4 (2) | C8—C9—H9 | 119.7 |
C2—C1—S1 | 118.63 (17) | C9—C10—C11 | 119.4 (2) |
C6—C1—S1 | 120.93 (18) | C9—C10—H10 | 120.3 |
C1—C2—C3 | 120.1 (2) | C11—C10—H10 | 120.3 |
C1—C2—H2 | 119.9 | C12—C11—C10 | 121.0 (2) |
C3—C2—H2 | 119.9 | C12—C11—Cl1 | 119.7 (2) |
C4—C3—C2 | 119.9 (2) | C10—C11—Cl1 | 119.32 (19) |
C4—C3—H3 | 120.1 | C11—C12—C13 | 119.4 (3) |
C2—C3—H3 | 120.1 | C11—C12—H12 | 120.3 |
C3—C4—C5 | 120.4 (2) | C13—C12—H12 | 120.3 |
C3—C4—H4 | 119.8 | C8—C13—C12 | 119.9 (2) |
C5—C4—H4 | 119.8 | C8—C13—H13 | 120.0 |
C4—C5—C6 | 120.9 (2) | C12—C13—H13 | 120.0 |
C4—C5—H5 | 119.5 | ||
O2—S1—C1—C2 | −139.24 (19) | C8—N2—C7—C6 | 179.1 (2) |
O3—S1—C1—C2 | −9.4 (2) | C5—C6—C7—O1 | −119.2 (2) |
N1—S1—C1—C2 | 105.1 (2) | C1—C6—C7—O1 | 55.1 (3) |
O2—S1—C1—C6 | 39.5 (2) | C5—C6—C7—N2 | 56.7 (3) |
O3—S1—C1—C6 | 169.33 (18) | C1—C6—C7—N2 | −129.0 (2) |
N1—S1—C1—C6 | −76.1 (2) | C7—N2—C8—C13 | −15.0 (4) |
C6—C1—C2—C3 | 1.6 (4) | C7—N2—C8—C9 | 169.0 (2) |
S1—C1—C2—C3 | −179.72 (18) | C13—C8—C9—C10 | −2.1 (4) |
C1—C2—C3—C4 | −2.3 (4) | N2—C8—C9—C10 | 174.1 (2) |
C2—C3—C4—C5 | 0.6 (4) | C8—C9—C10—C11 | 1.1 (4) |
C3—C4—C5—C6 | 2.0 (4) | C9—C10—C11—C12 | 0.5 (4) |
C4—C5—C6—C1 | −2.7 (3) | C9—C10—C11—Cl1 | −179.79 (19) |
C4—C5—C6—C7 | 171.9 (2) | C10—C11—C12—C13 | −1.1 (4) |
C2—C1—C6—C5 | 0.9 (3) | Cl1—C11—C12—C13 | 179.23 (18) |
S1—C1—C6—C5 | −177.79 (17) | C9—C8—C13—C12 | 1.5 (3) |
C2—C1—C6—C7 | −173.4 (2) | N2—C8—C13—C12 | −174.3 (2) |
S1—C1—C6—C7 | 7.9 (3) | C11—C12—C13—C8 | 0.0 (4) |
C8—N2—C7—O1 | −5.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.81 (3) | 2.32 (3) | 3.028 (3) | 146 (3) |
N1—H1NA···O1 | 0.80 (3) | 2.28 (3) | 2.941 (3) | 141 (3) |
N1—H1NB···O3ii | 0.84 (3) | 2.20 (3) | 3.021 (3) | 168 (3) |
C12—H12···O1iii | 0.95 | 2.58 | 3.512 (3) | 167 |
C2—H2···O3 | 0.95 | 2.47 | 2.874 (3) | 106 |
C13—H13···O1 | 0.95 | 2.33 | 2.914 (3) | 120 |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, y, −z+1/2; (iii) −x+1, −y, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C13H11ClN2O3S | C13H11ClN2O3S |
Mr | 310.75 | 310.75 |
Crystal system, space group | Orthorhombic, Pna21 | Orthorhombic, Pbca |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 15.734 (9), 10.614 (6), 7.717 (3) | 7.435 (2), 16.006 (6), 22.061 (7) |
V (Å3) | 1288.7 (12) | 2625.4 (15) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.47 | 0.46 |
Crystal size (mm) | 0.18 × 0.12 × 0.07 | 0.12 × 0.07 × 0.06 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.921, 0.968 | 0.947, 0.973 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2709, 1571, 1353 | 9119, 3005, 2019 |
Rint | 0.030 | 0.061 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.083, 1.01 | 0.045, 0.122, 1.04 |
No. of reflections | 1571 | 3005 |
No. of parameters | 191 | 190 |
No. of restraints | 1 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.33 | 0.26, −0.44 |
Computer programs: COLLECT (Hooft, 1998), HKL DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···Cl1 | 0.77 (4) | 2.64 (4) | 2.981 (3) | 109 (3) |
N1—H1NA···O1 | 0.93 (4) | 2.16 (4) | 2.955 (4) | 144 (3) |
N1—H1NB···O3i | 0.85 (4) | 2.28 (4) | 3.009 (4) | 144 (3) |
N2—H2N···O1ii | 0.77 (4) | 2.40 (4) | 3.152 (4) | 163 (3) |
C2—H2···O3 | 0.95 | 2.49 | 2.890 (4) | 106 |
C13—H13···O1 | 0.95 | 2.32 | 2.881 (4) | 117 |
C3—H3···O2iii | 0.95 | 2.44 | 3.380 (4) | 173 |
C5—H5···O2iv | 0.95 | 2.45 | 3.382 (4) | 167 |
Symmetry codes: (i) −x, −y, z−1/2; (ii) −x, −y+1, z+1/2; (iii) x−1/2, −y+1/2, z; (iv) −x, −y+1, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.81 (3) | 2.32 (3) | 3.028 (3) | 146 (3) |
N1—H1NA···O1 | 0.80 (3) | 2.28 (3) | 2.941 (3) | 141 (3) |
N1—H1NB···O3ii | 0.84 (3) | 2.20 (3) | 3.021 (3) | 168 (3) |
C12—H12···O1iii | 0.95 | 2.58 | 3.512 (3) | 167 |
C2—H2···O3 | 0.95 | 2.47 | 2.874 (3) | 106 |
C13—H13···O1 | 0.95 | 2.33 | 2.914 (3) | 120 |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, y, −z+1/2; (iii) −x+1, −y, −z. |
Benzenesulfonamide derivatives are well known in the biological sciences for their antibacterial, anticancer and anti-HIV activities (Brzozowski, 1996; Stawinski, 1997; Alovero et al., 2001). In the field of catalysis, their chloro-derivatives are particularly important for carrying out a huge number of oxidation reactions wherein the reaction kinetics are very important (Shashikala & Rangappa, 2002; Puttaswamy et al., 2001). The crystal structures of a number of interesting derivatives of benzenesulfonamide have been reported recently (Clark et al., 2003; Vyas et al., 2003; Singh et al., 2004; Bocelli et al., 1995; Sutton & Cody, 1989; Furuya et al., 1989). While continuing our research on the synthesis of biologically important 1,2-benzothiazine derivatives (Siddiqui et al., 2007, 2008), we have devised a simple and straightforward route for the synthesis of o-[(chlorophenyl)carbamoyl] benzene sulfonamide derivatives directly from saccharin as starting material. The syntheses of only two unsubstituted o-cyclohexyl and o-phenylcarbamoylbenzene sulfonamide derivatives have been reported to date, utilizing N-vinylsulfobenzimide as starting material (Kiyoshi, 1959). Here, we report the syntheses and crystal structures of two new benzenesulfonamides, the 2-chloro- and 4-chlorophenyl derivatives of the title compound, (I) and (II), respectively.
The molecular structure of (I) is presented in Fig. 1. The mean planes of the C1–C6 and C8–C13 phenyl rings are inclined at 48.83 (8)° with respect to each other, while the carbamoyl group, O1/N2/C7, is inclined at 70.51 (13) and 29.6 (2)°, respectively, with these phenyl rings. The structure contains two distinct patterns of hydrogen bonds involving N—H···O-type intermolecular interactions (Fig. 2). The sulfonamide groups are hydrogen bonded via atoms N1 and O3, forming chains of molecules. The carbamoyl groups are also hydrogen bonded, involving atoms O1 and N2, thus resulting in two parallel hydrogen-bonding patterns and affording stability to the polymeric chains running parallel to the c axis. There are two non-classical intermolecular C—H···O hydrogen bonds and the structure is further stabilized by four additional intramolecular interactions, N1—H1NA···O1, C13—H13···O1, C2—H2···O3 and N2—H2N···Cl1, resulting in seven-, six-, five- and five-membered rings, representing S(7), S(6), S(5) and S(5) motifs, respectively (Bernstein et al., 1994); details of the hydrogen-bonding geometry are given in Table 1.
The molecular structure of (II) is presented in Fig. 3. The mean planes of the C1–C6 and C8–C13 phenyl rings are inclined at 42.92 (6)° with respect to each other, while the carbamoyl group, O1/N2/C7, is inclined at 57.10 (11) and 17.96 (18)°, respectively, with these phenyl rings. The structure of (II) also contains two patterns of hydrogen bonds (Fig. 4), similar to those observed in (I). The sulfonamide groups in (II) are hydrogen bonded via atoms N1 and O3, forming chains of molecules. The carbamoyl groups are also hydrogen bonded, involving atoms O1 and N2, thus resulting in two parallel hydrogen-bonding patterns and affording stability to the polymeric chains running parallel to the a axis. There are two non-classical C—H···O hydrogen bonds and the structure is further stabilized by three additional intramolecular interactions, N1—H1NA···O1, C13—H13···O1 and C2—H2···O3, resulting in seven-, six- and five-membered rings, representing S(7), S(6) and S(5) motifs, respectively; details of the hydrogen-bonding geometry are given in Table 2.
In both molecules, the conformation about the S—N bond is in agreement with the conformation of a handful of structures containing an o-C-substituted benzenesulfonamide fragment; there were 14 hits in the Cambridge Structural Database (CSD, Version 5.29; Allen, 2002). The N1 atoms in both structures are tetrahedral, with angles at N1 in the ranges 105 (3)–120 (3)° (sum 338°) and 112 (2)–116 (3)° (sum 342°) for (I) and (II), respectively. The H atoms bonded to atom N1 and atoms O2 and O3 bonded to atom S1 are staggered, as observed in the compound with CSD refcode COYVER (Foresti et al., 1985). Several structures have been reported wherein the H and O atoms of the sulfonamide unit are eclipsed, e.g. refcodes ENIROI (Vyas et al., 2003), GUFQED01 (Clark et al., 2005) and ZZZULS01 (Tremayne et al., 2002). In a toluene sulfonamide (Helliwell et al., 1997), the C-substitents on N atom and the O atoms of the sulfonamide unit are also eclipsed. The N1—S1—C1—C6 torsion angles in (I) and (II) are -71.6 (3) and -76.1 (2)°, respectively. The corresponding angles in the structures quoted above vary between -18.95 (ZZZULS01) and -87.85° (ENIROI), depending on the substituents present on the benzene ring as well as on the inter- and intramolecular interactions between the substituents.
The molecular dimensions in the two structures are in agreement with the corresponding dimensions reported for similar structures quoted above (Clark et al., 2003; Vyas et al., 2003; Singh et al., 2004; Bocelli et al., 1995; Sutton & Cody, 1989; Furuya et al., 1989), with an average S═O distance of 1.435 (5) Å and S—N, S—C and Cl—C distances of 1.613 (3), 1.774 (3) and 1.734 (3) Å, respectively, in (I), and an average S═O distance of 1.433 (4) Å and S—N, S—C and Cl—C distances of 1.609 (2), 1.778 (2) and 1.739 (3) Å, respectively, in (II). The only minor difference in the bond lengths is observed for the N2—C7 bond [1.357 (4) and 1.340 (3) Å, in (I) and (II), respectively]. The bond angles at atoms N2 and C8 also reflect a slight influence of atom Cl1, which is bonded to atoms C9 and C11 in (I) and (II), respectively. Thus, the C7—N2—C8 bond angles are 126.0 (3) and 128.8 (2)° in (I) and (II), respectively, while the N2—C8—C9 and N2—C8—C13 bond angles have values of 119.1 (3) and 122.6 (3)° in (I), and 116.4 (2) and 123.8 (2)° in (II), respectively.