The structures of three substituted arenesulfonamides have been solved from laboratory X-ray powder diffraction data, using a new direct-space structure solution method based on a differential evolution algorithm, and refined by the Rietveld method. In 2-toluenesulfonamide, C
7H
9NO
2S (I) (tetragonal
I4
1/
a,
Z = 16), the molecules are linked by N—H
O=S hydrogen bonds into a three-dimensional framework. In 3-nitrobenzenesulfonamide, C
6H
6N
2O
4S (II) (monoclinic
P2
1,
Z = 2), N—H
O=S hydrogen bonds produce molecular ladders, which are linked into sheets by C—H
O=S hydrogen bonds: the nitro group does not participate in the hydrogen bonding. Molecules of 4-nitrobenzenesulfonamide, C
6H
6N
2O
4S (III) (monoclinic
P2
1/
n,
Z = 4), are linked into sheets by four types of hydrogen bond, N—H
O=S, N—H
O(nitro), C—H
O=S and C—H
O(nitro), and the sheets are weakly linked by aromatic π
π stacking interactions.
Supporting information
CCDC references: 195799; 195800; 195801
For all compounds, data collection: Diffrac-AT (Siemens). Program(s) used to solve structure: POSSUM (Seaton et al. 2002) for otols; POSSUM (Tremayne, Seaton 2002) for 4NBS, 3NBS. For all compounds, program(s) used to refine structure: GSAS (Larson et al. 1994).
(otols)
ortho-toluenesulfonamide
top
Crystal data top
C7H9NO2S | Z = 16 |
Mr = 171.22 | Cu Kα1 radiation, λ = 1.54056 Å |
Tetragonal, I41/a | T = 273 K |
a = 18.7407 (8) Å | white |
c = 9.1004 (4) Å | plate, 30 × 0.5 mm |
V = 3196.2 (3) Å3 | |
Data collection top
Position sensitive detector diffractometer | Specimen mounting: disc |
Radiation source: sealed X-ray tube | Data collection mode: transmission |
Ge monochromator | 2θmin = 4.00°, 2θmax = 53.971°, 2θstep = 0.019° |
Refinement top
Rp = 0.077 | Profile function: pseudovoigt |
Rwp = 0.098 | 46 parameters |
Rexp = ? | 39 restraints |
R(F2) = 0.1078 | H-atom parameters constrained |
χ2 = 11.676 | |
? data points | Preferred orientation correction: none |
Crystal data top
C7H9NO2S | V = 3196.2 (3) Å3 |
Mr = 171.22 | Z = 16 |
Tetragonal, I41/a | Cu Kα1 radiation, λ = 1.54056 Å |
a = 18.7407 (8) Å | T = 273 K |
c = 9.1004 (4) Å | plate, 30 × 0.5 mm |
Data collection top
Position sensitive detector diffractometer | Data collection mode: transmission |
Specimen mounting: disc | 2θmin = 4.00°, 2θmax = 53.971°, 2θstep = 0.019° |
Refinement top
Rp = 0.077 | ? data points |
Rwp = 0.098 | 46 parameters |
Rexp = ? | 39 restraints |
R(F2) = 0.1078 | H-atom parameters constrained |
χ2 = 11.676 | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.3646 (4) | 0.6256 (4) | 0.7649 (7) | 0.028 (3)* | |
N1 | 0.4060 (7) | 0.5904 (7) | 0.629 (1) | 0.020 (9)* | |
O11 | 0.2905 (6) | 0.6025 (7) | 0.748 (1) | 0.064 (5)* | |
O12 | 0.3800 (9) | 0.7016 (5) | 0.758 (2) | 0.063 (5)* | |
C1 | 0.4016 (6) | 0.5867 (8) | 0.927 (1) | 0.020 (4)* | |
C2 | 0.4661 (8) | 0.609 (1) | 0.989 (2) | 0.020 (4)* | |
C3 | 0.4914 (8) | 0.579 (1) | 1.122 (2) | 0.020 (4)* | |
C4 | 0.4440 (9) | 0.541 (1) | 1.212 (1) | 0.020 (4)* | |
C5 | 0.375 (1) | 0.528 (1) | 1.154 (2) | 0.020 (4)* | |
C6 | 0.3519 (7) | 0.550 (1) | 1.014 (2) | 0.020 (4)* | |
C7 | 0.5200 (8) | 0.651 (1) | 0.902 (2) | 0.075 (1)* | |
H3 | 0.542 (3) | 0.598 (5) | 1.171 (6) | 0.05* | |
H4 | 0.464 (2) | 0.512 (5) | 1.307 (7) | 0.05* | |
H5 | 0.340 (3) | 0.494 (6) | 1.221 (7) | 0.05* | |
H6 | 0.2947 (8) | 0.561 (4) | 0.997 (6) | 0.05* | |
H11 | 0.3873 | 0.5427 | 0.5790 | 0.05* | |
H12 | 0.4540 | 0.6026 | 0.5809 | 0.05* | |
H71 | 0.4905 | 0.6749 | 0.8246 | 0.05* | |
H72 | 0.5400 | 0.6850 | 0.9758 | 0.05* | |
H73 | 0.5570 | 0.6174 | 0.8633 | 0.05* | |
Geometric parameters (Å, º) top
C1—C2 | 1.397 (8) | C4—C5 | 1.407 (8) |
C1—C6 | 1.406 (8) | C5—C6 | 1.410 (8) |
C1—S1 | 1.783 (7) | S1—N1 | 1.599 (7) |
C2—C3 | 1.418 (8) | S1—O11 | 1.463 (7) |
C2—C7 | 1.506 (8) | S1—O12 | 1.454 (7) |
C3—C4 | 1.397 (8) | | |
| | | |
C2—C1—C6 | 119 (1) | C4—C5—C6 | 125 (1) |
C2—C1—S1 | 123 (1) | C1—C6—C5 | 116 (1) |
C6—C1—S1 | 114 (1) | C1—S1—N1 | 106 (1) |
C1—C2—C3 | 121 (1) | C1—S1—O11 | 110 (1) |
C1—C2—C7 | 122 (1) | C1—S1—O12 | 111 (1) |
C3—C2—C7 | 116 (1) | N1—S1—O11 | 105 (1) |
C2—C3—C4 | 119 (1) | N1—S1—O12 | 106 (1) |
C3—C4—C5 | 117 (1) | O11—S1—O12 | 118 (1) |
(4NBS) "4-nitrobenzenesulfonamide"
top
Crystal data top
C6H6N2O4S | V = 829.9 (2) Å3 |
Mr = 202.20 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54056 Å |
a = 8.8424 (3) Å | T = 273 K |
b = 13.4933 (4) Å | orange |
c = 7.0732 (2) Å | plate, 30 × 0.5 mm |
β = 100.466 (2)° | |
Data collection top
Position sensitive detector diffractometer | Specimen mounting: disc |
Radiation source: sealed X-ray tube | Data collection mode: transmission |
Ge monochromator | 2θmin = 4.00°, 2θmax = 53.974°, 2θstep = 0.019° |
Refinement top
Rp = 0.072 | Profile function: pseudovoigt |
Rwp = 0.053 | 58 parameters |
Rexp = ? | 46 restraints |
R(F2) = 0.1646 | H-atom parameters constrained |
χ2 = 33.779 | |
? data points | Preferred orientation correction: none |
Crystal data top
C6H6N2O4S | β = 100.466 (2)° |
Mr = 202.20 | V = 829.9 (2) Å3 |
Monoclinic, P21/n | Z = 4 |
a = 8.8424 (3) Å | Cu Kα radiation, λ = 1.54056 Å |
b = 13.4933 (4) Å | T = 273 K |
c = 7.0732 (2) Å | plate, 30 × 0.5 mm |
Data collection top
Position sensitive detector diffractometer | Data collection mode: transmission |
Specimen mounting: disc | 2θmin = 4.00°, 2θmax = 53.974°, 2θstep = 0.019° |
Refinement top
Rp = 0.072 | ? data points |
Rwp = 0.053 | 58 parameters |
Rexp = ? | 46 restraints |
R(F2) = 0.1646 | H-atom parameters constrained |
χ2 = 33.779 | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.5590 (7) | 0.7705 (4) | 0.8930 (8) | 0.033 (3)* | |
N1 | 0.6911 (9) | 0.7149 (3) | 1.034 (1) | 0.010 (7)* | |
O11 | 0.587 (1) | 0.8316 (7) | 0.737 (1) | 0.028 (5)* | |
O12 | 0.466 (1) | 0.6857 (7) | 0.817 (1) | 0.028 (5)* | |
C1 | 0.448 (2) | 0.849 (1) | 1.022 (2) | 0.025 (4)* | |
C2 | 0.333 (2) | 0.910 (1) | 0.920 (2) | 0.025 (4)* | |
C3 | 0.257 (2) | 0.978 (1) | 1.022 (2) | 0.025 (4)* | |
C4 | 0.275 (2) | 0.967 (2) | 1.221 (2) | 0.025 (4)* | |
C5 | 0.396 (2) | 0.910 (2) | 1.325 (2) | 0.025 (4)* | |
C6 | 0.483 (2) | 0.851 (2) | 1.223 (2) | 0.025 (4)* | |
N4 | 0.176 (2) | 1.023 (1) | 1.337 (2) | 0.010 (8)* | |
O41 | 0.222 (1) | 1.0171 (9) | 1.506 (2) | 0.015 (5)* | |
O42 | 0.089 (1) | 1.0712 (9) | 1.225 (1) | 0.015 (5)* | |
H21 | 0.33 (1) | 0.919 (6) | 0.764 (3) | 0.05* | |
H31 | 0.22 (1) | 1.050 (3) | 0.957 (6) | 0.05* | |
H51 | 0.431 (9) | 0.921 (6) | 1.481 (3) | 0.05* | |
H61 | 0.57 (1) | 0.804 (8) | 1.302 (4) | 0.05* | |
H11 | 0.777 | 0.746 | 1.124 | 0.05* | |
H12 | 0.700 | 0.640 | 1.025 | 0.05* | |
Geometric parameters (Å, º) top
C1—C2 | 1.403 (4) | C5—C6 | 1.396 (4) |
C1—C6 | 1.401 (4) | S1—N1 | 1.579 (4) |
C1—S1 | 1.797 (4) | S1—O11 | 1.435 (4) |
C2—C3 | 1.408 (4) | S1—O12 | 1.453 (4) |
C3—C4 | 1.402 (4) | N4—O41 | 1.193 (4) |
C4—C5 | 1.403 (4) | N4—O42 | 1.192 (4) |
C4—N4 | 1.511 (4) | | |
| | | |
C2—C1—C6 | 120 (1) | C1—S1—N1 | 112 (1) |
C2—C1—S1 | 120 (1) | C1—S1—O11 | 104 (1) |
C6—C1—S1 | 119 (1) | C1—S1—O12 | 109 (1) |
C1—C2—C3 | 120 (1) | N1—S1—O11 | 123 (1) |
C2—C3—C4 | 118 (1) | N1—S1—O12 | 99 (1) |
C3—C4—C5 | 120 (1) | O11—S1—O12 | 109 (1) |
C3—C4—N4 | 121 (1) | C4—N4—O41 | 112 (1) |
C5—C4—N4 | 117 (1) | C4—N4—O42 | 107 (1) |
C4—C5—C6 | 118 (1) | O41—N4—O42 | 140 (1) |
C1—C6—C5 | 120 (1) | | |
(3NBS) "3-nitrobenzenesulfonamide"
top
Crystal data top
C6H6N2O4S | V = 409.93 (2) Å3 |
Mr = 202.20 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.5418 Å |
a = 7.7169 (2) Å | T = 273 K |
b = 8.0514 (2) Å | white |
c = 7.0334 (2) Å | plate, 30 × 0.5 mm |
β = 110.274 (1)° | |
Data collection top
Position sensitive detector diffractometer | Specimen mounting: capillary |
Radiation source: sealed X-ray tube | Data collection mode: transmission |
None monochromator | 2θmin = 8.00°, 2θmax = 50.021°, 2θstep = 0.019° |
Refinement top
Rp = 0.063 | Profile function: pseudovoigt |
Rwp = 0.047 | 59 parameters |
Rexp = ? | 46 restraints |
R(F2) = 0.0565 | H-atom parameters constrained |
χ2 = ? | |
? data points | Preferred orientation correction: none |
Crystal data top
C6H6N2O4S | β = 110.274 (1)° |
Mr = 202.20 | V = 409.93 (2) Å3 |
Monoclinic, P21 | Z = 2 |
a = 7.7169 (2) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 8.0514 (2) Å | T = 273 K |
c = 7.0334 (2) Å | plate, 30 × 0.5 mm |
Data collection top
Position sensitive detector diffractometer | Data collection mode: transmission |
Specimen mounting: capillary | 2θmin = 8.00°, 2θmax = 50.021°, 2θstep = 0.019° |
Refinement top
Rp = 0.063 | ? data points |
Rwp = 0.047 | 59 parameters |
Rexp = ? | 46 restraints |
R(F2) = 0.0565 | H-atom parameters constrained |
χ2 = ? | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 1.023 (1) | 0.645 (3) | 0.370 (1) | 0.070 (3)* | |
N1 | 0.935 (2) | 0.6586 (6) | 0.548 (2) | 0.013 (6)* | |
O11 | 1.133 (2) | 0.791 (3) | 0.384 (2) | 0.035 (4)* | |
O12 | 1.165 (2) | 0.522 (3) | 0.432 (2) | 0.035 (4)* | |
C1 | 0.875 (2) | 0.618 (4) | 0.121 (2) | 0.020 (4)* | |
C2 | 0.796 (3) | 0.463 (3) | 0.090 (2) | 0.020 (4)* | |
C3 | 0.658 (3) | 0.446 (3) | −0.099 (3) | 0.020 (4)* | |
C4 | 0.580 (3) | 0.581 (3) | −0.229 (2) | 0.020 (4)* | |
C5 | 0.650 (3) | 0.739 (3) | −0.150 (2) | 0.020 (4)* | |
C6 | 0.805 (3) | 0.767 (3) | 0.027 (2) | 0.020 (4)* | |
N3 | 0.627 (2) | 0.267 (3) | −0.179 (2) | 0.039 (9)* | |
O31 | 0.683 (1) | 0.144 (3) | −0.055 (2) | 0.049 (4)* | |
O32 | 0.464 (2) | 0.251 (3) | −0.313 (2) | 0.049 (4)* | |
H21 | 0.888 (8) | 0.354 (6) | 0.14 (1) | 0.05* | |
H41 | 0.49 (1) | 0.567 (6) | −0.388 (6) | 0.05* | |
H51 | 0.56 (1) | 0.845 (5) | −0.22 (1) | 0.05* | |
H61 | 0.906 (7) | 0.868 (6) | 0.053 (9) | 0.05* | |
H11 | 0.913 | 0.539 | 0.576 | 0.05* | |
H12 | 0.904 | 0.779 | 0.561 | 0.05* | |
Geometric parameters (Å, º) top
C1—C2 | 1.378 (6) | C5—C6 | 1.413 (6) |
C1—C6 | 1.384 (6) | S1—N1 | 1.619 (5) |
C1—S1 | 1.741 (6) | S1—O11 | 1.430 (6) |
C2—C3 | 1.394 (6) | S1—O12 | 1.433 (6) |
C3—C4 | 1.410 (6) | N3—O31 | 1.288 (6) |
C3—N3 | 1.540 (6) | N3—O32 | 1.292 (6) |
C4—C5 | 1.418 (6) | | |
| | | |
C2—C1—C6 | 129 (1) | C1—S1—N1 | 119 (1) |
C2—C1—S1 | 112 (1) | C1—S1—O11 | 110 (1) |
C6—C1—S1 | 112 (1) | C1—S1—O12 | 113 (1) |
C1—C2—C3 | 113 (1) | N1—S1—O11 | 107 (1) |
C2—C3—C4 | 124 (1) | N1—S1—O12 | 107 (1) |
C2—C3—N3 | 114 (1) | O11—S1—O12 | 100 (1) |
C4—C3—N3 | 121 (1) | C3—N3—O31 | 120 (1) |
C3—C4—C5 | 115 (1) | C3—N3—O32 | 110 (1) |
C4—C5—C6 | 125 (1) | O31—N3—O32 | 116 (1) |
C1—C6—C5 | 111 (1) | | |
Experimental details
| (otols) | (4NBS) | (3NBS) |
Crystal data |
Chemical formula | C7H9NO2S | C6H6N2O4S | C6H6N2O4S |
Mr | 171.22 | 202.20 | 202.20 |
Crystal system, space group | Tetragonal, I41/a | Monoclinic, P21/n | Monoclinic, P21 |
Temperature (K) | 273 | 273 | 273 |
a, b, c (Å) | 18.7407 (8), 18.7407 (8), 9.1004 (4) | 8.8424 (3), 13.4933 (4), 7.0732 (2) | 7.7169 (2), 8.0514 (2), 7.0334 (2) |
α, β, γ (°) | 90, 90, 90 | 90, 100.466 (2), 90 | 90, 110.274 (1), 90 |
V (Å3) | 3196.2 (3) | 829.9 (2) | 409.93 (2) |
Z | 16 | 4 | 2 |
Radiation type | Cu Kα1, λ = 1.54056 Å | Cu Kα, λ = 1.54056 Å | Cu Kα, λ = 1.5418 Å |
µ (mm−1) | ? | ? | ? |
Specimen shape, size (mm) | Plate, 30 × 0.5 | Plate, 30 × 0.5 | Plate, 30 × 0.5 |
|
Data collection |
Diffractometer | Position sensitive detector diffractometer | Position sensitive detector diffractometer | Position sensitive detector diffractometer |
Specimen mounting | Disc | Disc | Capillary |
Data collection mode | Transmission | Transmission | Transmission |
Scan method | ? | ? | ? |
2θ values (°) | 2θmin = 4.00 2θmax = 53.971 2θstep = 0.019 | 2θmin = 4.00 2θmax = 53.974 2θstep = 0.019 | 2θmin = 8.00 2θmax = 50.021 2θstep = 0.019 |
|
Refinement |
R factors and goodness of fit | Rp = 0.077, Rwp = 0.098, Rexp = ?, R(F2) = 0.1078, χ2 = 11.676 | Rp = 0.072, Rwp = 0.053, Rexp = ?, R(F2) = 0.1646, χ2 = 33.779 | Rp = 0.063, Rwp = 0.047, Rexp = ?, R(F2) = 0.0565, χ2 = ? |
No. of data points | ? | ? | ? |
No. of parameters | 46 | 58 | 59 |
No. of restraints | 39 | 46 | 46 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |