Acta Cryst. (2007). E63, o3696 [ doi:10.1107/S1600536807037518 ]
Redetermination of the structure of the title compound, alternatively called 4-methylbenzenesulfonohydrazide, C7H10N2O2S, at 100 K reveals that both H atoms of the NH2 group form intermolecular N-H
O hydrogen bonds, which together with an N-HO hydrogen bond from the NH group form a sheet-like structure in the ab plane.
Single crystals of 4-tosylhydrazine (Friedman et al., 1973) were obtained by recrystallization from ethanol.
Atoms H2A and H2B of the NH2 group were located in difference Fourier maps and refined isotropically without restraint. Atom H1 was also located in a difference Fourier map and refined with the N—H distance restrained to be 1.01 (2) Å. All other H atoms were visible in difference Fourier maps but were placed at calculated positions and allowed to ride with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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, 2000); software used to prepare material for publication: SHELXTL and X-SEED (Barbour, 2001).
![[Figure 1]](./bi2204fig1thm.gif)
| Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level for non-H atoms. |
![[Figure 2]](./bi2204fig2thm.gif)
| Fig. 2. N—H···O hydrogen bonds connect the molecules into double chains along the b axis. |
| C7H10N2O2S | F000 = 392 |
| Mr = 186.23 | Dx = 1.484 Mg m−3 |
| Monoclinic, P21/c | Melting point: 382 K |
| Hall symbol: -P 2ybc | Mo Kα radiation λ = 0.71073 Å |
| a = 8.4166 (8) Å | Cell parameters from 5282 reflections |
| b = 5.6056 (5) Å | θ = 2.3–26.0º |
| c = 17.9484 (17) Å | µ = 0.35 mm−1 |
| β = 100.260 (1)º | T = 100 (2) K |
| V = 833.27 (13) Å3 | Block, colourless |
| Z = 4 | 0.30 × 0.18 × 0.10 mm |
| Bruker APEX CCD diffractometer | 1641 independent reflections |
| Radiation source: fine-focus sealed tube | 1584 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.034 |
| T = 100(2) K | θmax = 26.0º |
| φ and ω scans | θmin = 2.3º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
| Tmin = 0.903, Tmax = 0.966 | k = −6→6 |
| 8195 measured reflections | l = −22→22 |
| 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)] = 0.060 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0212P)2 + 1.9226P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.30 | (Δ/σ)max = 0.001 |
| 1641 reflections | Δρmax = 0.65 e Å−3 |
| 122 parameters | Δρmin = −0.31 e Å−3 |
| 1 restraint | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| C7H10N2O2S | V = 833.27 (13) Å3 |
| Mr = 186.23 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 8.4166 (8) Å | µ = 0.35 mm−1 |
| b = 5.6056 (5) Å | T = 100 (2) K |
| c = 17.9484 (17) Å | 0.30 × 0.18 × 0.10 mm |
| β = 100.260 (1)º |
| Bruker APEX CCD diffractometer | 1641 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1584 reflections with I > 2σ(I) |
| Tmin = 0.903, Tmax = 0.966 | Rint = 0.034 |
| 8195 measured reflections |
| R[F2 > 2σ(F2)] = 0.060 | 1 restraint |
| wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.30 | Δρmax = 0.65 e Å−3 |
| 1641 reflections | Δρmin = −0.31 e Å−3 |
| 122 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 > 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 | ||
| S1 | 0.27606 (8) | 0.14178 (13) | 0.17916 (4) | 0.0144 (2) | |
| O1 | 0.4359 (2) | 0.0492 (4) | 0.20362 (12) | 0.0207 (5) | |
| O2 | 0.1440 (2) | −0.0239 (4) | 0.16470 (12) | 0.0184 (5) | |
| N1 | 0.2469 (3) | 0.3220 (5) | 0.24704 (14) | 0.0173 (6) | |
| H1 | 0.346 (3) | 0.402 (5) | 0.2665 (17) | 0.015 (8)* | |
| N2 | 0.1052 (3) | 0.4620 (5) | 0.22597 (16) | 0.0191 (6) | |
| H2A | 0.130 (4) | 0.605 (7) | 0.215 (2) | 0.026 (10)* | |
| H2B | 0.056 (4) | 0.467 (7) | 0.266 (2) | 0.027 (10)* | |
| C1 | 0.2708 (3) | 0.3161 (5) | 0.09705 (16) | 0.0149 (6) | |
| C2 | 0.3625 (4) | 0.5216 (6) | 0.10103 (17) | 0.0179 (6) | |
| H2 | 0.4279 | 0.5681 | 0.1475 | 0.021* | |
| C3 | 0.3581 (4) | 0.6590 (6) | 0.03662 (17) | 0.0204 (7) | |
| H3 | 0.4215 | 0.8001 | 0.0392 | 0.024* | |
| C4 | 0.2624 (4) | 0.5941 (6) | −0.03207 (17) | 0.0182 (6) | |
| C5 | 0.1721 (4) | 0.3860 (6) | −0.03418 (18) | 0.0252 (7) | |
| H5 | 0.1070 | 0.3383 | −0.0806 | 0.030* | |
| C6 | 0.1747 (4) | 0.2466 (6) | 0.02964 (17) | 0.0207 (7) | |
| H6 | 0.1116 | 0.1053 | 0.0273 | 0.025* | |
| C7 | 0.2553 (4) | 0.7451 (7) | −0.10152 (18) | 0.0256 (7) | |
| H7A | 0.2719 | 0.6444 | −0.1441 | 0.038* | |
| H7B | 0.3400 | 0.8671 | −0.0923 | 0.038* | |
| H7C | 0.1495 | 0.8225 | −0.1136 | 0.038* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0148 (4) | 0.0132 (4) | 0.0152 (4) | 0.0006 (3) | 0.0022 (3) | 0.0006 (3) |
| O1 | 0.0182 (11) | 0.0210 (11) | 0.0221 (12) | 0.0033 (9) | 0.0017 (9) | 0.0038 (9) |
| O2 | 0.0199 (11) | 0.0146 (11) | 0.0210 (11) | 0.0003 (9) | 0.0045 (9) | 0.0008 (9) |
| C5 | 0.0239 (16) | 0.0307 (19) | 0.0185 (16) | 0.0005 (14) | −0.0029 (13) | −0.0018 (14) |
| C1 | 0.0130 (13) | 0.0165 (15) | 0.0148 (14) | 0.0025 (11) | 0.0017 (11) | 0.0025 (12) |
| N1 | 0.0162 (12) | 0.0191 (14) | 0.0159 (12) | −0.0016 (11) | 0.0008 (10) | −0.0001 (10) |
| N2 | 0.0186 (13) | 0.0181 (14) | 0.0216 (14) | 0.0017 (11) | 0.0058 (11) | −0.0009 (12) |
| C2 | 0.0168 (14) | 0.0209 (16) | 0.0155 (14) | −0.0011 (12) | 0.0015 (12) | −0.0037 (12) |
| C6 | 0.0198 (15) | 0.0197 (16) | 0.0213 (16) | −0.0022 (13) | −0.0002 (12) | −0.0004 (13) |
| C3 | 0.0197 (15) | 0.0192 (16) | 0.0229 (16) | −0.0009 (13) | 0.0053 (12) | 0.0015 (13) |
| C7 | 0.0247 (17) | 0.0330 (19) | 0.0193 (16) | 0.0039 (15) | 0.0042 (13) | 0.0066 (14) |
| C4 | 0.0171 (14) | 0.0201 (16) | 0.0182 (15) | 0.0070 (12) | 0.0054 (12) | 0.0022 (12) |
| S1—O1 | 1.436 (2) | N2—H2A | 0.86 (4) |
| S1—O2 | 1.436 (2) | N2—H2B | 0.89 (4) |
| S1—N1 | 1.635 (3) | C2—C3 | 1.384 (4) |
| S1—C1 | 1.762 (3) | C2—H2 | 0.950 |
| C5—C6 | 1.384 (4) | C6—H6 | 0.950 |
| C5—C4 | 1.389 (5) | C3—C4 | 1.395 (4) |
| C5—H5 | 0.950 | C3—H3 | 0.950 |
| C1—C2 | 1.381 (4) | C7—C4 | 1.499 (4) |
| C1—C6 | 1.386 (4) | C7—H7A | 0.980 |
| N1—N2 | 1.422 (4) | C7—H7B | 0.980 |
| N1—H1 | 0.96 (2) | C7—H7C | 0.980 |
| O1—S1—O2 | 118.33 (13) | C1—C2—C3 | 119.3 (3) |
| O1—S1—N1 | 104.61 (13) | C1—C2—H2 | 120.3 |
| O2—S1—N1 | 108.68 (13) | C3—C2—H2 | 120.3 |
| O1—S1—C1 | 109.81 (13) | C5—C6—C1 | 119.0 (3) |
| O2—S1—C1 | 107.70 (13) | C5—C6—H6 | 120.5 |
| N1—S1—C1 | 107.22 (14) | C1—C6—H6 | 120.5 |
| C6—C5—C4 | 121.6 (3) | C2—C3—C4 | 121.2 (3) |
| C6—C5—H5 | 119.2 | C2—C3—H3 | 119.4 |
| C4—C5—H5 | 119.2 | C4—C3—H3 | 119.4 |
| C2—C1—C6 | 120.9 (3) | C4—C7—H7A | 109.5 |
| C2—C1—S1 | 119.2 (2) | C4—C7—H7B | 109.5 |
| C6—C1—S1 | 119.9 (2) | H7A—C7—H7B | 109.5 |
| N2—N1—S1 | 111.91 (19) | C4—C7—H7C | 109.5 |
| N2—N1—H1 | 118 (2) | H7A—C7—H7C | 109.5 |
| S1—N1—H1 | 108.8 (19) | H7B—C7—H7C | 109.5 |
| N1—N2—H2A | 110 (2) | C5—C4—C3 | 118.0 (3) |
| N1—N2—H2B | 107 (2) | C5—C4—C7 | 120.7 (3) |
| H2A—N2—H2B | 109 (3) | C3—C4—C7 | 121.3 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1i | 0.96 (2) | 2.00 (2) | 2.948 (3) | 173 (3) |
| N2—H2A···O2ii | 0.86 (4) | 2.28 (4) | 3.122 (4) | 167 (3) |
| N2—H2B···O2iii | 0.89 (4) | 2.27 (4) | 3.118 (3) | 160 (3) |
| Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1i | 0.96 (2) | 2.00 (2) | 2.948 (3) | 173 (3) |
| N2—H2A···O2ii | 0.86 (4) | 2.28 (4) | 3.122 (4) | 167 (3) |
| N2—H2B···O2iii | 0.89 (4) | 2.27 (4) | 3.118 (3) | 160 (3) |
| Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1/2. |
AN thanks DST (SR/S5/OC-02/2002) for financial assistance. SR thanks the UGC for a fellowship.
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Bruker (1997). SMART (Version 5.054) and SAINT (Version ?). Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2000). SHELXTL. Versions 6.10 and 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.
Friedman, L., Litle, R. L. & Reichle, W. R. (1973). Org. Synth. Coll. Vol. V, pp. 1055–1057.
Lightfoot, P., Tremayne, M., Glidewell, C., Harris, K. D. M. & Bruce, P. G. (1993). J. Chem. Soc. Perkin Trans. 2, pp. 1625–1630.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.
The structure of the title compound, C7H10N2O2S (Figure 1), has been determined previously by Lightfoot et al. (1993) from powder X-ray diffraction data. However, H atoms could not be located using that technique and the authors assumed the presence of an intramolecular N—H···O hydrogen bond (graph-set motif S(5)). Re-determination of the structure using single-crystal X-ray diffraction reveals that the H atoms of the NH2 group actually make intermolecular N—H···O hydrogen bonds, with O1 and O2 acting as acceptors (Table 1). The N1—H1···O1 and N2—H2A···O2 hydrogen bonds link the molecules into double chains along the b axis, and these chains are linked via N2—H2B···O2 hydrogen bonds to form a sheet-like structure in the ab planes.