Acta Cryst. (2009). E65, o1257 [ doi:10.1107/S1600536809016651 ]
In the title compound, C12H11N3O3S·H2O, the pyridine ring makes a dihedral angle of 24.78 (14)° with the phenyl ring. Intramolecular N-H
O and intermolecular O-HO hydrogen bonds are observed and stabilize the packing in the crystal structure.
Solution of benzenesulfonyl chloride (0.04 mol) in ethanol was added to a stirred ethanol solution of isoniazid (0.02 mol) in the ice-bath, then the reaction was kept on for 2 h at room temperature. The solvent was removed by reduced pressure filter, the solid product was dissolved in 50 ml ethanol,. and then set aside for five days to obtain colourless crystals.
Water H atoms were located in a difference Fourier map and refined as riding in their as-found positions relative to O atoms with Uiso(H) = 1.5Ueq(O). All other H atoms were placed in calculated positions and refined as riding, with C—H = 0.93–0.97 Å, N—H = 0.86 Å, and Uiso(H) = 1.2–1.5 Ueq(C,N).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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: WinGX (Farrugia, 1999).
![[Figure 1]](./at2777fig1thm.gif)
| Fig. 1. The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. |
| C12H11N3O3S·H2O | F000 = 616 |
| Mr = 295.32 | Dx = 1.446 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2343 reflections |
| a = 7.3525 (5) Å | θ = 2.0–25.0º |
| b = 20.9324 (15) Å | µ = 0.26 mm−1 |
| c = 9.2443 (6) Å | T = 273 K |
| β = 107.565 (2)º | Block, colourless |
| V = 1356.41 (16) Å3 | 0.24 × 0.22 × 0.19 mm |
| Z = 4 |
| Bruker SMART APEX CCD area-detector diffractometer | 2343 independent reflections |
| Radiation source: fine-focus sealed tube | 1981 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.033 |
| T = 273 K | θmax = 25.0º |
| φ and ω scan | θmin = 2.0º |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −8→8 |
| Tmin = 0.833, Tmax = 0.864 | k = −24→24 |
| 10653 measured reflections | l = −10→10 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.0631P)2 + 0.5954P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.12 | (Δ/σ)max < 0.001 |
| 2343 reflections | Δρmax = 0.43 e Å−3 |
| 189 parameters | Δρmin = −0.53 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C12H11N3O3S·H2O | V = 1356.41 (16) Å3 |
| Mr = 295.32 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 7.3525 (5) Å | µ = 0.26 mm−1 |
| b = 20.9324 (15) Å | T = 273 K |
| c = 9.2443 (6) Å | 0.24 × 0.22 × 0.19 mm |
| β = 107.565 (2)º |
| Bruker SMART APEX CCD area-detector diffractometer | 2343 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1981 reflections with I > 2σ(I) |
| Tmin = 0.833, Tmax = 0.864 | Rint = 0.033 |
| 10653 measured reflections |
| R[F2 > 2σ(F2)] = 0.037 | 189 parameters |
| wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.12 | Δρmax = 0.43 e Å−3 |
| 2343 reflections | Δρmin = −0.53 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 > 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 | ||
| C1 | 0.5180 (5) | 0.38868 (12) | 0.1480 (3) | 0.0457 (7) | |
| H1 | 0.4780 | 0.3769 | 0.0463 | 0.055* | |
| C2 | 0.5608 (5) | 0.45147 (13) | 0.1899 (3) | 0.0598 (9) | |
| H2 | 0.5523 | 0.4810 | 0.1131 | 0.072* | |
| C3 | 0.6284 (4) | 0.42875 (11) | 0.4392 (3) | 0.0339 (6) | |
| H3 | 0.6653 | 0.4420 | 0.5399 | 0.041* | |
| C4 | 0.5927 (3) | 0.36459 (11) | 0.4100 (2) | 0.0297 (5) | |
| H4 | 0.6065 | 0.3359 | 0.4894 | 0.036* | |
| C5 | 0.5361 (3) | 0.34348 (10) | 0.2611 (2) | 0.0257 (5) | |
| C6 | 0.4884 (3) | 0.27532 (10) | 0.2125 (2) | 0.0253 (5) | |
| C7 | 0.4594 (3) | 0.13874 (10) | 0.5560 (3) | 0.0289 (5) | |
| C8 | 0.4371 (3) | 0.19677 (11) | 0.6218 (3) | 0.0322 (5) | |
| H8 | 0.3844 | 0.2317 | 0.5616 | 0.039* | |
| C9 | 0.4947 (4) | 0.20161 (12) | 0.7788 (3) | 0.0370 (6) | |
| H9 | 0.4826 | 0.2403 | 0.8246 | 0.044* | |
| C10 | 0.5702 (4) | 0.14896 (14) | 0.8673 (3) | 0.0424 (6) | |
| H10 | 0.6066 | 0.1523 | 0.9725 | 0.051* | |
| C11 | 0.5917 (4) | 0.09153 (13) | 0.8006 (3) | 0.0439 (7) | |
| H11 | 0.6426 | 0.0565 | 0.8611 | 0.053* | |
| C12 | 0.5379 (4) | 0.08587 (12) | 0.6439 (3) | 0.0359 (6) | |
| H12 | 0.5540 | 0.0475 | 0.5986 | 0.043* | |
| N1 | 0.6133 (3) | 0.47292 (9) | 0.3323 (2) | 0.0400 (5) | |
| N2 | 0.5685 (3) | 0.23082 (8) | 0.31946 (19) | 0.0258 (4) | |
| H2N | 0.6398 | 0.2425 | 0.4075 | 0.031* | |
| N3 | 0.5352 (3) | 0.16619 (9) | 0.2867 (2) | 0.0293 (5) | |
| H3N | 0.5925 | 0.1458 | 0.2324 | 0.035* | |
| O1 | 0.3873 (2) | 0.26165 (8) | 0.08506 (16) | 0.0340 (4) | |
| O2 | 0.2057 (2) | 0.16569 (8) | 0.30300 (19) | 0.0366 (4) | |
| O3 | 0.3881 (3) | 0.06518 (8) | 0.31658 (19) | 0.0421 (5) | |
| S1 | 0.38198 (8) | 0.13081 (3) | 0.35666 (6) | 0.0294 (2) | |
| H1E | 0.942 (6) | 0.1209 (16) | 0.248 (4) | 0.063 (12)* | |
| H1F | 0.849 (5) | 0.0671 (18) | 0.196 (4) | 0.063 (10)* | |
| O1W | 0.8432 (3) | 0.10382 (10) | 0.2345 (2) | 0.0421 (5) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.074 (2) | 0.0366 (14) | 0.0207 (12) | −0.0022 (13) | 0.0047 (12) | 0.0032 (10) |
| C2 | 0.109 (3) | 0.0334 (15) | 0.0298 (14) | −0.0045 (16) | 0.0109 (16) | 0.0109 (11) |
| C3 | 0.0439 (15) | 0.0309 (13) | 0.0245 (11) | 0.0031 (10) | 0.0068 (11) | −0.0011 (10) |
| C4 | 0.0356 (14) | 0.0298 (13) | 0.0210 (11) | 0.0041 (10) | 0.0047 (10) | 0.0035 (9) |
| C5 | 0.0239 (12) | 0.0290 (12) | 0.0223 (11) | 0.0043 (9) | 0.0042 (9) | 0.0018 (9) |
| C6 | 0.0226 (12) | 0.0323 (12) | 0.0192 (11) | 0.0027 (9) | 0.0037 (9) | 0.0000 (9) |
| C7 | 0.0306 (13) | 0.0260 (12) | 0.0285 (12) | −0.0040 (9) | 0.0064 (10) | −0.0012 (9) |
| C8 | 0.0360 (14) | 0.0282 (12) | 0.0348 (12) | −0.0019 (10) | 0.0144 (11) | 0.0008 (10) |
| C9 | 0.0384 (15) | 0.0392 (14) | 0.0378 (13) | −0.0110 (11) | 0.0181 (12) | −0.0107 (11) |
| C10 | 0.0422 (16) | 0.0572 (17) | 0.0273 (12) | −0.0089 (13) | 0.0096 (11) | −0.0029 (12) |
| C11 | 0.0493 (18) | 0.0434 (16) | 0.0350 (14) | 0.0029 (12) | 0.0068 (12) | 0.0098 (12) |
| C12 | 0.0393 (15) | 0.0298 (13) | 0.0341 (13) | 0.0012 (11) | 0.0044 (11) | 0.0001 (10) |
| N1 | 0.0537 (14) | 0.0300 (11) | 0.0331 (11) | 0.0006 (9) | 0.0084 (10) | 0.0014 (9) |
| N2 | 0.0283 (11) | 0.0243 (10) | 0.0191 (9) | −0.0005 (7) | −0.0015 (8) | −0.0017 (7) |
| N3 | 0.0354 (12) | 0.0252 (10) | 0.0259 (9) | 0.0027 (8) | 0.0073 (8) | −0.0044 (8) |
| O1 | 0.0341 (10) | 0.0392 (10) | 0.0205 (8) | 0.0009 (7) | −0.0041 (7) | −0.0024 (7) |
| O2 | 0.0273 (10) | 0.0362 (10) | 0.0401 (10) | −0.0004 (7) | 0.0008 (7) | 0.0024 (7) |
| O3 | 0.0606 (13) | 0.0233 (9) | 0.0349 (9) | −0.0036 (8) | 0.0031 (9) | −0.0048 (7) |
| S1 | 0.0332 (4) | 0.0227 (3) | 0.0273 (3) | −0.0019 (2) | 0.0014 (2) | −0.0017 (2) |
| O1W | 0.0352 (12) | 0.0344 (11) | 0.0582 (12) | −0.0005 (9) | 0.0161 (10) | −0.0123 (9) |
| C1—C2 | 1.379 (4) | C8—H8 | 0.9300 |
| C1—C5 | 1.386 (3) | C9—C10 | 1.385 (4) |
| C1—H1 | 0.9300 | C9—H9 | 0.9300 |
| C2—N1 | 1.333 (3) | C10—C11 | 1.382 (4) |
| C2—H2 | 0.9300 | C10—H10 | 0.9300 |
| C3—N1 | 1.333 (3) | C11—C12 | 1.386 (3) |
| C3—C4 | 1.379 (3) | C11—H11 | 0.9300 |
| C3—H3 | 0.9300 | C12—H12 | 0.9300 |
| C4—C5 | 1.385 (3) | N2—N3 | 1.392 (2) |
| C4—H4 | 0.9300 | N2—H2N | 0.8600 |
| C5—C6 | 1.505 (3) | N3—S1 | 1.635 (2) |
| C6—O1 | 1.223 (3) | N3—H3N | 0.8600 |
| C6—N2 | 1.356 (3) | O2—S1 | 1.4393 (17) |
| C7—C8 | 1.390 (3) | O3—S1 | 1.4272 (17) |
| C7—C12 | 1.392 (3) | O1W—H1E | 0.78 (4) |
| C7—S1 | 1.764 (2) | O1W—H1F | 0.86 (4) |
| C8—C9 | 1.387 (3) | ||
| C2—C1—C5 | 118.5 (2) | C10—C9—H9 | 120.0 |
| C2—C1—H1 | 120.8 | C8—C9—H9 | 120.0 |
| C5—C1—H1 | 120.8 | C11—C10—C9 | 120.5 (2) |
| N1—C2—C1 | 124.9 (2) | C11—C10—H10 | 119.7 |
| N1—C2—H2 | 117.6 | C9—C10—H10 | 119.7 |
| C1—C2—H2 | 117.6 | C10—C11—C12 | 120.4 (2) |
| N1—C3—C4 | 124.2 (2) | C10—C11—H11 | 119.8 |
| N1—C3—H3 | 117.9 | C12—C11—H11 | 119.8 |
| C4—C3—H3 | 117.9 | C11—C12—C7 | 118.7 (2) |
| C3—C4—C5 | 119.2 (2) | C11—C12—H12 | 120.7 |
| C3—C4—H4 | 120.4 | C7—C12—H12 | 120.7 |
| C5—C4—H4 | 120.4 | C2—N1—C3 | 115.6 (2) |
| C4—C5—C1 | 117.6 (2) | C6—N2—N3 | 120.00 (17) |
| C4—C5—C6 | 124.90 (19) | C6—N2—H2N | 120.0 |
| C1—C5—C6 | 117.5 (2) | N3—N2—H2N | 120.0 |
| O1—C6—N2 | 123.1 (2) | N2—N3—S1 | 116.82 (14) |
| O1—C6—C5 | 121.90 (19) | N2—N3—H3N | 121.6 |
| N2—C6—C5 | 115.02 (18) | S1—N3—H3N | 121.6 |
| C8—C7—C12 | 121.5 (2) | O3—S1—O2 | 119.65 (11) |
| C8—C7—S1 | 119.73 (18) | O3—S1—N3 | 104.70 (10) |
| C12—C7—S1 | 118.79 (17) | O2—S1—N3 | 106.88 (10) |
| C9—C8—C7 | 118.9 (2) | O3—S1—C7 | 109.64 (10) |
| C9—C8—H8 | 120.6 | O2—S1—C7 | 106.57 (11) |
| C7—C8—H8 | 120.6 | N3—S1—C7 | 109.05 (10) |
| C10—C9—C8 | 120.1 (2) | H1E—O1W—H1F | 108 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3N···O1W | 0.86 | 2.04 | 2.779 (3) | 144 |
| O1W—H1E···O2i | 0.78 (4) | 2.07 (4) | 2.857 (3) | 175 (4) |
| Symmetry codes: (i) x+1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3N···O1W | 0.86 | 2.04 | 2.779 (3) | 144 |
| O1W—H1E···O2i | 0.78 (4) | 2.07 (4) | 2.857 (3) | 175 (4) |
| Symmetry codes: (i) x+1, y, z. |
The authors gratefully acknowledge the Natural Science Foundation of China (No. 20767001), the International Collaborative Project of Guizhou Province and the Governor Foundation of Guizhou Province for financial support.
Bruker (2002). SMART and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA.
Bruker (2005). SADABS. Bruker AXS, Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Lemin, A. J. (1961). US Patent 2993829.
Shanbhag, A. V., Venkatesha, T. V., Prabhu, R. A., Kalkhambkar, R. G. & Kulkarni, G. M. (2008). J. Appl. Electrochem. 38, 279–287.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Zhen, X.-L. & Li, X.-L. (2008). Acta Cryst. E64, o2170.
Hydrazide derivatives investigated in the present work are non-toxic in nature, which play an important role in latex, plastic industry (Lemin et al., 1961; Zhen et al., 2008) and corrosion inhibition of mild steel in acidic medium (Shanbhag et al., 2008). In this paper, a substituted hydrazide, benzenesulfisoniazide, was synthesized in the solution of ethanol with benzenesulfonyl chloride and isoniazide in the ice-bath is reported.
The crystal of the title compound, (I), consists of N'-(phenylsulfinyl)isonicotinohydrazide and one water molecule, (Fig. 1). Pyridine ring makes a dihedral angle of 24.78 (14)° with the phenyl ring. The N—H···O hydrogen bonds are observed between N3 and the water molecule O1W, which the distance of the N3(H3N)···O1W hydrogen bonds is 2.779 (3) Å. In addition, there are O—H···O hydrogen bonds between O1W and O2 with distance of 2.857 (3) Å (Table 1). These hydrogen bonding interactions may help to establish the packing in the crystal structure.