Acta Cryst. (2009). E65, o107 [ doi:10.1107/S1600536808041792 ]
The molecule of the title compound, C9H8N4S, adopts an E configuration about both the C=N and C-NH bonds. In the crystal structure, adjacent molecules are linked by intermolecular N-H
S hydrogen-bonding interactions, forming chains running parallel to the b axis.
The title compound was synthesized by refluxing 4-cyanobenzaldehyde (1.05 g, 8 mmol) and thiosemicarbazide (0.73 g, 8 mmol) in absolute ethanol (40 ml) for 6 h. After cooling to room temperature, the white solid formed was isolated and dried under vacuum (1.47 g, yield 90%). Single crystals suitable for X-ray structure analysis were obtained by slow evaporation of a methanol solution.
H atoms were placed in calculated positions and refined using a riding model, with N—H = 0.86 Å, C—H = 0.93 Å and with Uiso(H) = 1.2 Ueq(C, N).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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]](./rz2264fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| C9H8N4S | F(000) = 424 |
| Mr = 204.26 | Dx = 1.339 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1740 reflections |
| a = 12.284 (6) Å | θ = 2.5–27.5° |
| b = 8.209 (4) Å | µ = 0.28 mm−1 |
| c = 10.058 (3) Å | T = 291 K |
| β = 92.20 (3)° | Block, colourless |
| V = 1013.5 (8) Å3 | 0.25 × 0.17 × 0.15 mm |
| Z = 4 |
| Rigaku Mercury2 diffractometer | 2309 independent reflections |
| Radiation source: fine-focus sealed tube | 1596 reflections with I > 2σ(I) |
| graphite | Rint = 0.055 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
| CCD_Profile_fitting scans | h = −15→15 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −10→10 |
| Tmin = 0.94, Tmax = 0.96 | l = −12→13 |
| 10019 measured reflections |
| 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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.109 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0258P)2 + 0.6908P] where P = (Fo2 + 2Fc2)/3 |
| 2309 reflections | (Δ/σ)max < 0.001 |
| 127 parameters | Δρmax = 0.17 e Å−3 |
| 0 restraints | Δρmin = −0.19 e Å−3 |
| C9H8N4S | V = 1013.5 (8) Å3 |
| Mr = 204.26 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 12.284 (6) Å | µ = 0.28 mm−1 |
| b = 8.209 (4) Å | T = 291 K |
| c = 10.058 (3) Å | 0.25 × 0.17 × 0.15 mm |
| β = 92.20 (3)° |
| Rigaku Mercury2 diffractometer | 2309 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1596 reflections with I > 2σ(I) |
| Tmin = 0.94, Tmax = 0.96 | Rint = 0.055 |
| 10019 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
| wR(F2) = 0.109 | Δρmax = 0.17 e Å−3 |
| S = 1.01 | Δρmin = −0.19 e Å−3 |
| 2309 reflections | Absolute structure: ? |
| 127 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.07786 (19) | 0.5792 (3) | 0.6753 (2) | 0.0446 (6) | |
| C2 | 0.18757 (19) | 0.2982 (3) | 0.4587 (2) | 0.0454 (6) | |
| H2 | 0.1575 | 0.2048 | 0.4946 | 0.054* | |
| C3 | 0.26310 (18) | 0.2841 (3) | 0.3506 (2) | 0.0426 (6) | |
| C4 | 0.30116 (19) | 0.1304 (3) | 0.3163 (2) | 0.0482 (6) | |
| H4 | 0.2748 | 0.0384 | 0.3583 | 0.058* | |
| C5 | 0.3781 (2) | 0.1135 (3) | 0.2198 (2) | 0.0532 (7) | |
| H5 | 0.4029 | 0.0108 | 0.1964 | 0.064* | |
| C6 | 0.4175 (2) | 0.2517 (3) | 0.1588 (2) | 0.0509 (6) | |
| C7 | 0.3777 (2) | 0.4058 (3) | 0.1891 (2) | 0.0541 (7) | |
| H7 | 0.4028 | 0.4973 | 0.1452 | 0.065* | |
| C8 | 0.3008 (2) | 0.4214 (3) | 0.2846 (2) | 0.0500 (6) | |
| H8 | 0.2740 | 0.5239 | 0.3052 | 0.060* | |
| C9 | 0.5021 (2) | 0.2377 (4) | 0.0632 (3) | 0.0616 (7) | |
| N1 | 0.1138 (2) | 0.7144 (3) | 0.6221 (2) | 0.0717 (8) | |
| H1A | 0.1485 | 0.7106 | 0.5496 | 0.086* | |
| H1B | 0.1026 | 0.8065 | 0.6600 | 0.086* | |
| N2 | 0.09749 (15) | 0.4384 (2) | 0.61235 (17) | 0.0436 (5) | |
| H2A | 0.0694 | 0.3490 | 0.6396 | 0.052* | |
| N3 | 0.16254 (15) | 0.4379 (2) | 0.50426 (18) | 0.0441 (5) | |
| N4 | 0.5709 (2) | 0.2293 (3) | −0.0102 (3) | 0.0853 (9) | |
| S1 | 0.01195 (6) | 0.57476 (8) | 0.81966 (6) | 0.0544 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0526 (14) | 0.0390 (12) | 0.0423 (12) | 0.0019 (12) | 0.0033 (11) | 0.0001 (11) |
| C2 | 0.0475 (14) | 0.0477 (14) | 0.0414 (13) | −0.0021 (12) | 0.0063 (11) | −0.0010 (11) |
| C3 | 0.0399 (13) | 0.0479 (14) | 0.0402 (12) | −0.0015 (11) | 0.0030 (10) | −0.0042 (10) |
| C4 | 0.0505 (14) | 0.0477 (14) | 0.0467 (13) | −0.0025 (12) | 0.0053 (12) | −0.0032 (11) |
| C5 | 0.0533 (15) | 0.0568 (17) | 0.0498 (14) | 0.0051 (13) | 0.0050 (12) | −0.0093 (12) |
| C6 | 0.0463 (14) | 0.0659 (17) | 0.0406 (13) | 0.0036 (14) | 0.0050 (11) | −0.0039 (13) |
| C7 | 0.0540 (15) | 0.0593 (17) | 0.0496 (14) | −0.0012 (14) | 0.0094 (12) | 0.0056 (13) |
| C8 | 0.0533 (15) | 0.0469 (14) | 0.0500 (14) | 0.0026 (13) | 0.0072 (11) | −0.0046 (12) |
| C9 | 0.0626 (17) | 0.0696 (19) | 0.0535 (15) | 0.0057 (15) | 0.0115 (14) | 0.0018 (14) |
| N1 | 0.112 (2) | 0.0411 (13) | 0.0645 (15) | −0.0058 (13) | 0.0407 (14) | −0.0043 (11) |
| N2 | 0.0546 (12) | 0.0375 (11) | 0.0396 (10) | 0.0007 (10) | 0.0111 (9) | −0.0008 (9) |
| N3 | 0.0492 (11) | 0.0464 (12) | 0.0372 (10) | 0.0016 (10) | 0.0068 (8) | −0.0027 (9) |
| N4 | 0.088 (2) | 0.091 (2) | 0.0797 (18) | 0.0167 (17) | 0.0398 (16) | 0.0100 (16) |
| S1 | 0.0765 (5) | 0.0431 (3) | 0.0448 (3) | 0.0083 (4) | 0.0184 (3) | 0.0010 (3) |
| C1—N1 | 1.316 (3) | C5—H5 | 0.9300 |
| C1—N2 | 1.344 (3) | C6—C7 | 1.394 (4) |
| C1—S1 | 1.689 (2) | C6—C9 | 1.447 (3) |
| C2—N3 | 1.277 (3) | C7—C8 | 1.378 (3) |
| C2—C3 | 1.461 (3) | C7—H7 | 0.9300 |
| C2—H2 | 0.9300 | C8—H8 | 0.9300 |
| C3—C4 | 1.394 (3) | C9—N4 | 1.146 (3) |
| C3—C8 | 1.396 (3) | N1—H1A | 0.8600 |
| C4—C5 | 1.387 (3) | N1—H1B | 0.8600 |
| C4—H4 | 0.9300 | N2—N3 | 1.374 (2) |
| C5—C6 | 1.385 (4) | N2—H2A | 0.8600 |
| N1—C1—N2 | 117.7 (2) | C5—C6—C9 | 120.1 (3) |
| N1—C1—S1 | 123.15 (19) | C7—C6—C9 | 118.9 (2) |
| N2—C1—S1 | 119.15 (18) | C8—C7—C6 | 119.4 (2) |
| N3—C2—C3 | 120.5 (2) | C8—C7—H7 | 120.3 |
| N3—C2—H2 | 119.8 | C6—C7—H7 | 120.3 |
| C3—C2—H2 | 119.8 | C7—C8—C3 | 120.4 (2) |
| C4—C3—C8 | 119.5 (2) | C7—C8—H8 | 119.8 |
| C4—C3—C2 | 119.0 (2) | C3—C8—H8 | 119.8 |
| C8—C3—C2 | 121.4 (2) | N4—C9—C6 | 178.1 (3) |
| C5—C4—C3 | 120.5 (2) | C1—N1—H1A | 120.0 |
| C5—C4—H4 | 119.7 | C1—N1—H1B | 120.0 |
| C3—C4—H4 | 119.7 | H1A—N1—H1B | 120.0 |
| C6—C5—C4 | 119.1 (2) | C1—N2—N3 | 119.73 (19) |
| C6—C5—H5 | 120.4 | C1—N2—H2A | 120.1 |
| C4—C5—H5 | 120.4 | N3—N2—H2A | 120.1 |
| C5—C6—C7 | 121.0 (2) | C2—N3—N2 | 116.2 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···S1i | 0.86 | 2.50 | 3.355 (2) | 171 |
| N1—H1B···S1ii | 0.86 | 2.63 | 3.399 (3) | 150 |
| Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···S1i | 0.86 | 2.50 | 3.355 (2) | 171 |
| N1—H1B···S1ii | 0.86 | 2.63 | 3.399 (3) | 150 |
| Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2. |
The authors thank the Start-up Projects for Postdoctoral Research Funds of Southeast University (grant No. 1112000048).
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Thiosemicarbazones constitute an important class of N,S donors due to their propensity to react with a wide range of metals (Casas et al., 2000). Schiff bases show potential as antimicrobial and anticancer agents (Tarafder et al., 2000; Deschamps et al., 2003) and so have biochemical and pharmacological applications. It has been postulated that extensive electron delocalization in the thiosemicarbazone moiety helps the free thiosemicarbazone ligands and their metal complexes to exhibit SHG (second harmonic generation) efficiency (Liu et al., 1999; Wu et al., 2000). As part of a research on non-linear optical materials, specifically thiosemicarbazones and their metal complexes, we report here the crystal structure of a new Schiff base compound derived from thiosemicarbazide and 4-cyanobenzaldehyde.
In the title compound (Fig. 1), the thiosemicarbazone moiety is nearly planar (maximum deviation 0.113 (2) Å for atom N2) and shows an E configuration about both the C1═N2 and C2═N3 bonds. The molecule is not strictly planar, the dihedral angle between the thiosemicarbazone moiety and the phenyl ring being 15.8 (6)°. The C—S bond distance of 1.689 (2) Å agrees well with similar bonds in related compounds, being intermediate between the value of 1.82Å for a C—S single bond and 1.56 Å for a C═S double bond (Sutton, 1965). The C1—N2 bond distance (1.344 (3)Å) is indicative of some double-bond character, suggesting extensive electron delocalization in the whole molecule. The C1—N1 bond distance of 1.316 (3)Å is also indicative of some double-bond character. All the bond distances except for the C6—C9 bond length (1.447 (3) Å) fall within the normal range. In the crystal packing, adjacent molecules are linked by N—H···S hydrogen bonds (Table 1) to form chains running parallel to the b axis.