Acta Cryst. (2008). E64, o1730 [ doi:10.1107/S1600536808025105 ]
The title compound, C9H10N4O2S, was prepared by the reaction of 1-(4-nitrophenyl)ethanone and thiosemicarbazide in ethanol at 367 K. There are weak intermolecular N-H
S and N-HO hydrogen-bonding interactions in the crystal structure involving the amine and nitrile groups, respectively, as donors.
A mixture of hydrochloric acid 0.6 mL (0.02 mol) and thiosemicarbazide 1.8 g (0.02 mol) was stirred with ethanol (50 mL) at 293 K for 2 h, then add 1-(4-nitrophenyl)ethanone 3.3 g (0.02 mol), then afford the title compound [4.17 g, yield: 87.6%]. Single crystals suitable for X-ray measurements were obtained by recrystallization from acetone and ethanol(1:1) at room temperature.
H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H and N—H distances of 0.93–0.96 and 0.86 Å, and with Uiso=1.2 or 1.5Ueq.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./at2598fig1thm.gif)
| Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme. |
| C9H10N4O2S | Z = 2 |
| Mr = 238.27 | F000 = 248 |
| Triclinic, P1 | Dx = 1.475 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 7.4450 (15) Å | Cell parameters from 1776 reflections |
| b = 9.3180 (19) Å | θ = 2.5–27.0º |
| c = 9.4050 (19) Å | µ = 0.29 mm−1 |
| α = 62.08 (3)º | T = 293 (2) K |
| β = 76.41 (3)º | Block, yellow |
| γ = 69.02 (3)º | 0.20 × 0.15 × 0.10 mm |
| V = 536.5 (3) Å3 |
| Bruker SMART CCD area-detector diffractometer | 1776 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.026 |
| Monochromator: graphite | θmax = 27.0º |
| T = 293(2) K | θmin = 2.5º |
| φ and ω scans | h = 0→8 |
| Absorption correction: none | k = −11→11 |
| 2493 measured reflections | l = −11→11 |
| 2307 independent reflections |
| 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)] = 0.046 | H-atom parameters constrained |
| wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0802P)2 + 0.1605P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.08 | (Δ/σ)max < 0.001 |
| 2307 reflections | Δρmax = 0.39 e Å−3 |
| 145 parameters | Δρmin = −0.38 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C9H10N4O2S | γ = 69.02 (3)º |
| Mr = 238.27 | V = 536.5 (3) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.4450 (15) Å | Mo Kα |
| b = 9.3180 (19) Å | µ = 0.29 mm−1 |
| c = 9.4050 (19) Å | T = 293 (2) K |
| α = 62.08 (3)º | 0.20 × 0.15 × 0.10 mm |
| β = 76.41 (3)º |
| Bruker SMART CCD area-detector diffractometer | 2307 independent reflections |
| Absorption correction: none | 1776 reflections with I > 2σ(I) |
| 2493 measured reflections | Rint = 0.026 |
| R[F2 > 2σ(F2)] = 0.046 | 145 parameters |
| wR(F2) = 0.140 | H-atom parameters constrained |
| S = 1.08 | Δρmax = 0.39 e Å−3 |
| 2307 reflections | Δρmin = −0.38 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 | ||
| S1 | −0.18728 (10) | 0.97254 (7) | 0.38617 (7) | 0.0483 (2) | |
| O1 | 0.2761 (3) | −0.3046 (2) | 1.2287 (3) | 0.0697 (6) | |
| O2 | 0.4183 (3) | −0.2729 (2) | 1.3830 (2) | 0.0680 (6) | |
| N1 | 0.3337 (3) | −0.2167 (2) | 1.2626 (2) | 0.0472 (5) | |
| N2 | 0.0574 (3) | 0.5445 (2) | 0.7336 (2) | 0.0373 (4) | |
| N3 | 0.0128 (3) | 0.7117 (2) | 0.6222 (2) | 0.0394 (4) | |
| H3A | 0.0744 | 0.7778 | 0.6144 | 0.047* | |
| N4 | −0.2206 (3) | 0.6599 (2) | 0.5464 (2) | 0.0521 (5) | |
| H4A | −0.1876 | 0.5573 | 0.6190 | 0.063* | |
| H4B | −0.3121 | 0.6918 | 0.4873 | 0.063* | |
| C1 | 0.1766 (3) | 0.1958 (3) | 0.9090 (3) | 0.0392 (5) | |
| H1A | 0.1182 | 0.2381 | 0.8145 | 0.047* | |
| C2 | 0.2135 (3) | 0.0244 (3) | 1.0120 (3) | 0.0410 (5) | |
| H2B | 0.1813 | −0.0485 | 0.9871 | 0.049* | |
| C3 | 0.2990 (3) | −0.0353 (2) | 1.1521 (3) | 0.0364 (5) | |
| C4 | 0.3527 (3) | 0.0684 (3) | 1.1924 (3) | 0.0415 (5) | |
| H4C | 0.4109 | 0.0249 | 1.2873 | 0.050* | |
| C5 | 0.3167 (3) | 0.2400 (3) | 1.0864 (3) | 0.0397 (5) | |
| H5A | 0.3537 | 0.3112 | 1.1100 | 0.048* | |
| C6 | 0.2260 (3) | 0.3065 (2) | 0.9453 (2) | 0.0337 (4) | |
| C7 | 0.1848 (3) | 0.4909 (2) | 0.8317 (3) | 0.0371 (5) | |
| C8 | 0.2907 (4) | 0.5977 (3) | 0.8389 (4) | 0.0631 (8) | |
| H8A | 0.2478 | 0.7120 | 0.7589 | 0.095* | |
| H8B | 0.4268 | 0.5521 | 0.8185 | 0.095* | |
| H8C | 0.2649 | 0.5972 | 0.9441 | 0.095* | |
| C9 | −0.1299 (3) | 0.7696 (3) | 0.5255 (3) | 0.0384 (5) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0686 (4) | 0.0278 (3) | 0.0474 (4) | −0.0157 (3) | −0.0254 (3) | −0.0044 (2) |
| O1 | 0.0890 (15) | 0.0312 (9) | 0.0844 (14) | −0.0239 (9) | −0.0267 (11) | −0.0073 (9) |
| O2 | 0.0795 (14) | 0.0444 (10) | 0.0588 (11) | −0.0168 (9) | −0.0295 (10) | 0.0051 (9) |
| N1 | 0.0442 (11) | 0.0309 (9) | 0.0534 (12) | −0.0102 (8) | −0.0077 (9) | −0.0062 (8) |
| N2 | 0.0450 (10) | 0.0227 (8) | 0.0400 (9) | −0.0076 (7) | −0.0105 (8) | −0.0084 (7) |
| N3 | 0.0478 (10) | 0.0242 (8) | 0.0446 (10) | −0.0109 (7) | −0.0151 (8) | −0.0078 (7) |
| N4 | 0.0678 (14) | 0.0332 (10) | 0.0558 (12) | −0.0205 (9) | −0.0276 (10) | −0.0047 (9) |
| C1 | 0.0448 (12) | 0.0296 (10) | 0.0433 (11) | −0.0090 (8) | −0.0139 (9) | −0.0120 (9) |
| C2 | 0.0468 (12) | 0.0285 (10) | 0.0513 (13) | −0.0119 (9) | −0.0106 (10) | −0.0158 (9) |
| C3 | 0.0352 (11) | 0.0254 (9) | 0.0404 (11) | −0.0070 (8) | −0.0027 (8) | −0.0088 (8) |
| C4 | 0.0462 (12) | 0.0361 (11) | 0.0392 (11) | −0.0105 (9) | −0.0112 (9) | −0.0109 (9) |
| C5 | 0.0481 (12) | 0.0296 (10) | 0.0444 (12) | −0.0100 (9) | −0.0119 (9) | −0.0152 (9) |
| C6 | 0.0347 (10) | 0.0242 (9) | 0.0400 (11) | −0.0063 (8) | −0.0064 (8) | −0.0119 (8) |
| C7 | 0.0404 (11) | 0.0249 (9) | 0.0442 (11) | −0.0068 (8) | −0.0093 (9) | −0.0124 (9) |
| C8 | 0.0745 (18) | 0.0316 (11) | 0.0821 (19) | −0.0198 (12) | −0.0407 (15) | −0.0044 (12) |
| C9 | 0.0481 (12) | 0.0284 (10) | 0.0379 (11) | −0.0111 (9) | −0.0093 (9) | −0.0108 (8) |
| S1—C9 | 1.685 (2) | C1—H1A | 0.9300 |
| O1—N1 | 1.231 (3) | C2—C3 | 1.381 (3) |
| O2—N1 | 1.224 (3) | C2—H2B | 0.9300 |
| N1—C3 | 1.473 (3) | C3—C4 | 1.389 (3) |
| N2—C7 | 1.281 (3) | C4—C5 | 1.395 (3) |
| N2—N3 | 1.379 (2) | C4—H4C | 0.9300 |
| N3—C9 | 1.353 (3) | C5—C6 | 1.397 (3) |
| N3—H3A | 0.8600 | C5—H5A | 0.9300 |
| N4—C9 | 1.336 (3) | C6—C7 | 1.498 (3) |
| N4—H4A | 0.8600 | C7—C8 | 1.506 (3) |
| N4—H4B | 0.8600 | C8—H8A | 0.9600 |
| C1—C2 | 1.388 (3) | C8—H8B | 0.9600 |
| C1—C6 | 1.406 (3) | C8—H8C | 0.9600 |
| O2—N1—O1 | 123.1 (2) | C3—C4—H4C | 121.0 |
| O2—N1—C3 | 118.7 (2) | C5—C4—H4C | 121.0 |
| O1—N1—C3 | 118.15 (19) | C4—C5—C6 | 121.2 (2) |
| C7—N2—N3 | 119.08 (18) | C4—C5—H5A | 119.4 |
| C9—N3—N2 | 118.64 (17) | C6—C5—H5A | 119.4 |
| C9—N3—H3A | 120.7 | C5—C6—C1 | 118.60 (18) |
| N2—N3—H3A | 120.7 | C5—C6—C7 | 121.53 (18) |
| C9—N4—H4A | 120.0 | C1—C6—C7 | 119.86 (18) |
| C9—N4—H4B | 120.0 | N2—C7—C6 | 114.93 (18) |
| H4A—N4—H4B | 120.0 | N2—C7—C8 | 125.16 (19) |
| C2—C1—C6 | 121.03 (19) | C6—C7—C8 | 119.91 (18) |
| C2—C1—H1A | 119.5 | C7—C8—H8A | 109.5 |
| C6—C1—H1A | 119.5 | C7—C8—H8B | 109.5 |
| C3—C2—C1 | 118.5 (2) | H8A—C8—H8B | 109.5 |
| C3—C2—H2B | 120.8 | C7—C8—H8C | 109.5 |
| C1—C2—H2B | 120.8 | H8A—C8—H8C | 109.5 |
| C2—C3—C4 | 122.67 (19) | H8B—C8—H8C | 109.5 |
| C2—C3—N1 | 118.13 (19) | N4—C9—N3 | 117.19 (18) |
| C4—C3—N1 | 119.20 (19) | N4—C9—S1 | 122.63 (17) |
| C3—C4—C5 | 118.0 (2) | N3—C9—S1 | 120.19 (16) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···S1i | 0.86 | 2.74 | 3.581 (2) | 166 |
| N4—H4A···O1ii | 0.86 | 2.35 | 3.101 (3) | 146 |
| N4—H4B···O2iii | 0.86 | 2.29 | 3.133 (3) | 166 |
| Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y, −z+2; (iii) x−1, y+1, z−1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···S1i | 0.86 | 2.74 | 3.581 (2) | 166 |
| N4—H4A···O1ii | 0.86 | 2.35 | 3.101 (3) | 146 |
| N4—H4B···O2iii | 0.86 | 2.29 | 3.133 (3) | 166 |
| Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y, −z+2; (iii) x−1, y+1, z−1. |
Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Jian, F.-F., Zhuang, R.-R., Wang, K.-F., Zhao, P.-S. & Xiao, H.-L. (2006). Acta Cryst. E62, o3198–o3199.
Qin, Y.-Q., Ren, X.-Y., Liang, T.-L. & Jian, F.-F. (2006). Acta Cryst. E62, o5215–o5216.
Rozwadowski, Z., Majewski, E., Dziembowska, T. & Hansen, P. E. (1999). J. Chem. Soc. Perkin Trans. 2, pp. 2809–2817.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Schiff bases have been used extensively as ligands in the field of coordination chemistry (Jian et al., 2006). Schiff bases show biochemical and pharmacological applications. The growing interest in Schiff bases lately is also due to their ability to form intramolecular hydrogen bonds by electron coupling between acid-base centers (Rozwadowski et al.,1999). The title compound (I), was synthesized and we report here its crystal structure
In the crystal structure of (I) (Fig. 1). The C6–C9/N2/N3/S1 plane makes a dihedral angle of 19.78 (127)° with the benzene ring (C1—C6). The C═N bond length [1.281 (3) Å] and C═S bond length [1.685 (2) Å] are in agreement with those observed before (Jian et al., 2006; Qin et al., 2006). There are intermolecular N–H···S and N–H···O hydrogen-bond interactions to stabilize the crystal structure (Table 1).