Acta Cryst. (2009). E65, o81-o82 [ doi:10.1107/S1600536808041123 ]
In the title compound, C14H12ClN3OS, the short exocyclic N-C bond lengths indicate resonance in the thiourea part of the molecule. The title compound is stabilized by an intramolecular N-H
N hydrogen bond, which results in the formation of a six-membered ring. In addition, it shows a synperiplanar conformation between the thiocarbonyl group and the pyridine group. Intermolecular N-HS and C-HO interactions are also present.
The compound was prepared with a procedure similar to that reported in the literature (Arslan et al., 2003b, 2006a). A solution of 4-chloro-benzoyl chloride (0.01 mol) in acetone (50 cm3) was added dropwise to a suspension of potassium thiocyanate (0.01 mol) in acetone (30 cm3). The reaction mixture was heated under reflux for 30 min, and then cooled to room temperature. A solution of 6-methylpyridin-2-amine (0.01 mol) in acetone (10 cm3) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 cm3) was added to the solution, which was then filtered. The solid product was washed with water and purifed by recrystalization from an ethanol:dichloromethane mixture (1:2). Anal. Calcd. for C14H12ClN3OS: C, 55.0; H, 4.0; N, 13.7. Found: C, 55.1; H, 3.9; N, 13.7%.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./hg2444fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. |
![[Figure 2]](./hg2444fig2thm.gif)
| Fig. 2. Packing diagram for (I) viewed along a-direction. Hydrogen bonds shown as dotted lines. |
| C14H12ClN3OS | Z = 2 |
| Mr = 305.78 | F(000) = 316 |
| Triclinic, P1 | Dx = 1.511 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.255 (3) Å | Cell parameters from 716 reflections |
| b = 9.030 (3) Å | θ = 2.3–26.3° |
| c = 9.957 (3) Å | µ = 0.44 mm−1 |
| α = 80.810 (7)° | T = 120 K |
| β = 66.552 (7)° | Prism, yellow |
| γ = 87.269 (7)° | 0.20 × 0.14 × 0.10 mm |
| V = 672.1 (4) Å3 |
| Bruker SMART CCD area-detector diffractometer | 2609 independent reflections |
| Radiation source: sealed tube | 1492 reflections with I > 2σ(I) |
| graphite | Rint = 0.100 |
| φ and ω scans | θmax = 26.4°, θmin = 2.3° |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −10→10 |
| Tmin = 0.918, Tmax = 0.958 | k = −11→5 |
| 3651 measured reflections | l = −12→10 |
| 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)] = 0.077 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.266 | H-atom parameters constrained |
| S = 0.98 | w = 1/[σ2(Fo2) + (0.1601P)2] where P = (Fo2 + 2Fc2)/3 |
| 2609 reflections | (Δ/σ)max < 0.001 |
| 182 parameters | Δρmax = 0.81 e Å−3 |
| 0 restraints | Δρmin = −0.50 e Å−3 |
| C14H12ClN3OS | γ = 87.269 (7)° |
| Mr = 305.78 | V = 672.1 (4) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.255 (3) Å | Mo Kα radiation |
| b = 9.030 (3) Å | µ = 0.44 mm−1 |
| c = 9.957 (3) Å | T = 120 K |
| α = 80.810 (7)° | 0.20 × 0.14 × 0.10 mm |
| β = 66.552 (7)° |
| Bruker SMART CCD area-detector diffractometer | 2609 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1492 reflections with I > 2σ(I) |
| Tmin = 0.918, Tmax = 0.958 | Rint = 0.100 |
| 3651 measured reflections | θmax = 26.4° |
| R[F2 > 2σ(F2)] = 0.077 | H-atom parameters constrained |
| wR(F2) = 0.266 | Δρmax = 0.81 e Å−3 |
| S = 0.98 | Δρmin = −0.50 e Å−3 |
| 2609 reflections | Absolute structure: ? |
| 182 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 | ||
| Cl1 | −0.0760 (2) | −0.08311 (16) | 0.24521 (19) | 0.0469 (5) | |
| S1 | 0.4068 (2) | 0.83271 (15) | 0.20068 (15) | 0.0316 (5) | |
| O1 | 0.2334 (6) | 0.5331 (4) | 0.3623 (4) | 0.0370 (10) | |
| N1 | 0.2869 (6) | 0.6040 (5) | 0.1158 (5) | 0.0296 (11) | |
| H1B | 0.2730 | 0.5725 | 0.0418 | 0.036* | |
| N2 | 0.4090 (6) | 0.8104 (5) | −0.0583 (5) | 0.0282 (11) | |
| H2B | 0.4462 | 0.9040 | −0.0760 | 0.034* | |
| N3 | 0.3162 (6) | 0.6306 (5) | −0.1620 (5) | 0.0253 (10) | |
| C1 | 0.0432 (8) | 0.2777 (6) | 0.3757 (6) | 0.0347 (14) | |
| H1A | 0.0183 | 0.3141 | 0.4662 | 0.042* | |
| C2 | −0.0314 (8) | 0.1427 (6) | 0.3760 (7) | 0.0394 (15) | |
| H2A | −0.1122 | 0.0888 | 0.4661 | 0.047* | |
| C3 | 0.0122 (8) | 0.0878 (6) | 0.2450 (6) | 0.0322 (13) | |
| C4 | 0.1259 (8) | 0.1664 (6) | 0.1110 (6) | 0.0365 (15) | |
| H4A | 0.1537 | 0.1280 | 0.0211 | 0.044* | |
| C5 | 0.1987 (7) | 0.3030 (6) | 0.1107 (6) | 0.0264 (12) | |
| H5A | 0.2783 | 0.3572 | 0.0201 | 0.032* | |
| C6 | 0.1558 (7) | 0.3597 (5) | 0.2407 (6) | 0.0258 (12) | |
| C7 | 0.2278 (7) | 0.5061 (6) | 0.2497 (6) | 0.0272 (12) | |
| C8 | 0.3644 (6) | 0.7438 (5) | 0.0850 (6) | 0.0208 (11) | |
| C9 | 0.4067 (7) | 0.7576 (6) | −0.1828 (6) | 0.0261 (12) | |
| C10 | 0.5010 (7) | 0.8375 (6) | −0.3213 (6) | 0.0291 (13) | |
| H10A | 0.5701 | 0.9232 | −0.3321 | 0.035* | |
| C11 | 0.4925 (8) | 0.7902 (6) | −0.4435 (6) | 0.0316 (13) | |
| H11A | 0.5503 | 0.8463 | −0.5394 | 0.038* | |
| C12 | 0.3987 (7) | 0.6598 (6) | −0.4245 (6) | 0.0287 (13) | |
| H12A | 0.3913 | 0.6251 | −0.5071 | 0.034* | |
| C13 | 0.3156 (7) | 0.5806 (6) | −0.2823 (6) | 0.0229 (12) | |
| C14 | 0.2159 (8) | 0.4360 (6) | −0.2553 (7) | 0.0322 (13) | |
| H14A | 0.2846 | 0.3515 | −0.2327 | 0.048* | |
| H14B | 0.1965 | 0.4249 | −0.3441 | 0.048* | |
| H14C | 0.1018 | 0.4375 | −0.1715 | 0.048* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0577 (11) | 0.0250 (8) | 0.0548 (11) | −0.0248 (7) | −0.0183 (9) | −0.0001 (7) |
| S1 | 0.0473 (10) | 0.0223 (7) | 0.0274 (8) | −0.0173 (6) | −0.0164 (7) | −0.0004 (6) |
| O1 | 0.053 (3) | 0.030 (2) | 0.029 (2) | −0.0182 (19) | −0.017 (2) | −0.0027 (17) |
| N1 | 0.043 (3) | 0.023 (2) | 0.022 (2) | −0.019 (2) | −0.009 (2) | −0.0055 (19) |
| N2 | 0.038 (3) | 0.020 (2) | 0.027 (2) | −0.0162 (19) | −0.013 (2) | −0.0017 (18) |
| N3 | 0.024 (2) | 0.022 (2) | 0.034 (3) | −0.0071 (18) | −0.015 (2) | −0.0014 (19) |
| C1 | 0.059 (4) | 0.022 (3) | 0.019 (3) | −0.015 (3) | −0.012 (3) | 0.004 (2) |
| C2 | 0.045 (4) | 0.027 (3) | 0.034 (3) | −0.022 (3) | −0.003 (3) | 0.003 (3) |
| C3 | 0.040 (3) | 0.022 (3) | 0.029 (3) | −0.019 (2) | −0.009 (3) | 0.005 (2) |
| C4 | 0.064 (4) | 0.021 (3) | 0.024 (3) | −0.014 (3) | −0.017 (3) | 0.001 (2) |
| C5 | 0.033 (3) | 0.020 (3) | 0.026 (3) | −0.013 (2) | −0.015 (2) | 0.007 (2) |
| C6 | 0.030 (3) | 0.017 (3) | 0.030 (3) | −0.008 (2) | −0.013 (3) | 0.004 (2) |
| C7 | 0.035 (3) | 0.020 (3) | 0.027 (3) | −0.009 (2) | −0.015 (3) | 0.002 (2) |
| C8 | 0.020 (3) | 0.017 (2) | 0.029 (3) | 0.000 (2) | −0.016 (2) | 0.004 (2) |
| C9 | 0.043 (3) | 0.017 (3) | 0.020 (3) | −0.009 (2) | −0.016 (3) | 0.004 (2) |
| C10 | 0.036 (3) | 0.020 (3) | 0.032 (3) | −0.013 (2) | −0.015 (3) | 0.003 (2) |
| C11 | 0.047 (4) | 0.020 (3) | 0.024 (3) | −0.013 (2) | −0.011 (3) | 0.001 (2) |
| C12 | 0.036 (3) | 0.025 (3) | 0.024 (3) | −0.014 (2) | −0.010 (2) | −0.004 (2) |
| C13 | 0.027 (3) | 0.021 (3) | 0.026 (3) | −0.004 (2) | −0.016 (2) | 0.001 (2) |
| C14 | 0.042 (3) | 0.024 (3) | 0.038 (3) | −0.011 (2) | −0.022 (3) | −0.006 (2) |
| Cl1—C3 | 1.737 (5) | C4—C5 | 1.396 (7) |
| S1—C8 | 1.655 (5) | C4—H4A | 0.9500 |
| O1—C7 | 1.203 (6) | C5—C6 | 1.376 (7) |
| N1—C8 | 1.376 (6) | C5—H5A | 0.9500 |
| N1—C7 | 1.395 (7) | C6—C7 | 1.504 (7) |
| N1—H1B | 0.8800 | C9—C10 | 1.382 (7) |
| N2—C8 | 1.364 (6) | C10—C11 | 1.379 (7) |
| N2—C9 | 1.405 (6) | C10—H10A | 0.9500 |
| N2—H2B | 0.8800 | C11—C12 | 1.386 (7) |
| N3—C9 | 1.341 (6) | C11—H11A | 0.9500 |
| N3—C13 | 1.347 (7) | C12—C13 | 1.392 (7) |
| C1—C2 | 1.391 (7) | C12—H12A | 0.9500 |
| C1—C6 | 1.405 (7) | C13—C14 | 1.506 (7) |
| C1—H1A | 0.9500 | C14—H14A | 0.9800 |
| C2—C3 | 1.375 (8) | C14—H14B | 0.9800 |
| C2—H2A | 0.9500 | C14—H14C | 0.9800 |
| C3—C4 | 1.390 (8) | ||
| C8—N1—C7 | 128.0 (4) | O1—C7—C6 | 122.3 (5) |
| C8—N1—H1B | 116.0 | N1—C7—C6 | 113.2 (4) |
| C7—N1—H1B | 116.0 | N2—C8—N1 | 113.5 (4) |
| C8—N2—C9 | 132.1 (4) | N2—C8—S1 | 119.5 (4) |
| C8—N2—H2B | 113.9 | N1—C8—S1 | 127.1 (4) |
| C9—N2—H2B | 113.9 | N3—C9—C10 | 123.1 (5) |
| C9—N3—C13 | 118.0 (5) | N3—C9—N2 | 118.5 (5) |
| C2—C1—C6 | 119.5 (5) | C10—C9—N2 | 118.3 (5) |
| C2—C1—H1A | 120.2 | C11—C10—C9 | 118.6 (5) |
| C6—C1—H1A | 120.2 | C11—C10—H10A | 120.7 |
| C3—C2—C1 | 119.7 (5) | C9—C10—H10A | 120.7 |
| C3—C2—H2A | 120.2 | C10—C11—C12 | 119.2 (5) |
| C1—C2—H2A | 120.2 | C10—C11—H11A | 120.4 |
| C2—C3—C4 | 121.4 (5) | C12—C11—H11A | 120.4 |
| C2—C3—Cl1 | 119.9 (4) | C11—C12—C13 | 118.8 (5) |
| C4—C3—Cl1 | 118.7 (4) | C11—C12—H12A | 120.6 |
| C3—C4—C5 | 118.8 (5) | C13—C12—H12A | 120.6 |
| C3—C4—H4A | 120.6 | N3—C13—C12 | 122.1 (5) |
| C5—C4—H4A | 120.6 | N3—C13—C14 | 116.7 (5) |
| C6—C5—C4 | 120.5 (5) | C12—C13—C14 | 121.2 (5) |
| C6—C5—H5A | 119.8 | C13—C14—H14A | 109.5 |
| C4—C5—H5A | 119.8 | C13—C14—H14B | 109.5 |
| C5—C6—C1 | 120.1 (5) | H14A—C14—H14B | 109.5 |
| C5—C6—C7 | 123.7 (5) | C13—C14—H14C | 109.5 |
| C1—C6—C7 | 116.2 (5) | H14A—C14—H14C | 109.5 |
| O1—C7—N1 | 124.4 (5) | H14B—C14—H14C | 109.5 |
| C6—C1—C2—C3 | 3.0 (10) | C9—N2—C8—N1 | −7.2 (8) |
| C1—C2—C3—C4 | −1.9 (10) | C9—N2—C8—S1 | 172.4 (5) |
| C1—C2—C3—Cl1 | 178.3 (5) | C7—N1—C8—N2 | 179.3 (5) |
| C2—C3—C4—C5 | 0.9 (10) | C7—N1—C8—S1 | −0.3 (8) |
| Cl1—C3—C4—C5 | −179.3 (4) | C13—N3—C9—C10 | −1.1 (8) |
| C3—C4—C5—C6 | −1.2 (9) | C13—N3—C9—N2 | −179.7 (4) |
| C4—C5—C6—C1 | 2.3 (9) | C8—N2—C9—N3 | 14.9 (9) |
| C4—C5—C6—C7 | −179.8 (5) | C8—N2—C9—C10 | −163.8 (5) |
| C2—C1—C6—C5 | −3.3 (9) | N3—C9—C10—C11 | 4.4 (9) |
| C2—C1—C6—C7 | 178.7 (5) | N2—C9—C10—C11 | −177.0 (5) |
| C8—N1—C7—O1 | 1.7 (9) | C9—C10—C11—C12 | −3.7 (8) |
| C8—N1—C7—C6 | −177.9 (5) | C10—C11—C12—C13 | 0.1 (9) |
| C5—C6—C7—O1 | −157.3 (6) | C9—N3—C13—C12 | −2.8 (8) |
| C1—C6—C7—O1 | 20.7 (8) | C9—N3—C13—C14 | 178.7 (5) |
| C5—C6—C7—N1 | 22.3 (8) | C11—C12—C13—N3 | 3.3 (8) |
| C1—C6—C7—N1 | −159.7 (5) | C11—C12—C13—C14 | −178.3 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C12—H12A···O1i | 0.95 | 2.42 | 3.303 (7) | 154 |
| N2—H2B···S1ii | 0.88 | 2.61 | 3.464 (5) | 165 |
| N1—H1B···N3 | 0.88 | 1.90 | 2.651 (7) | 142 |
| Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C12—H12A···O1i | 0.95 | 2.42 | 3.303 (7) | 154 |
| N2—H2B···S1ii | 0.88 | 2.61 | 3.464 (5) | 165 |
| N1—H1B···N3 | 0.88 | 1.90 | 2.651 (7) | 142 |
| Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+2, −z. |
This work was supported by Mersin University Research Fund (Project Nos. BAP-ECZ-F-TBB-(HA) 2004–3 and BAP-FEF-KB-(NK) 2006–3).
Arslan, H., Flörke, U. & Külcü, N. (2003a). J. Chem. Crystallogr. 33, 919–924.
Arslan, H., Flörke, U. & Külcü, N. (2007). Spectrochim. Acta A, 67, 936–943.
Arslan, H., Flörke, U., Külcü, N. & Emen, M. F. (2006a). J. Coord. Chem. 59, 223–228.
Arslan, H., Külcü, N. & Flörke, U. (2003b). Transition Met. Chem. 28, 816–819.
Arslan, H., Külcü, N. & Flörke, U. (2006b). Spectrochim. Acta A, 64, 1065–1071.
Binzet, G., Arslan, H., Flörke, U., Külcü, N. & Duran, N. (2006). J. Coord. Chem. 59, 1395–1406.
Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Dong, W.-K., Yan, H.-B., Chai, L.-Q., Lv, Z.-W. & Zhao, C.-Y. (2008). Acta Cryst. E64, o1097.
Duque, J., Estevez-Hernandez, O., Reguera, E., Corrêa, R. S. & Gutierrez Maria, P. (2008). Acta Cryst. E64, o1068.
Kemp, G., Roodt, A., Purcell, W. & Koch, K. R. (1997). J. Chem. Soc. Dalton Trans. 23, 4481–4483.
Koch, K. R., Sacht, C., Grimmbacher, T. & Bourne, S. (1995). S. Afr. J. Chem. 48, 71–77.
Mansuroğlu, D. S., Arslan, H., Flörke, U. & Külcü, N. (2008). J. Coord. Chem. 61, 3134–3146.
Nencki, M. (1873). Ber. Dtsch. Chem. Ges. 6, 598–600.
Özpozan, N., Arslan, H., Ozpozan, T., Ozdes, N. & Külcü, N. (2000). Thermochim. Acta, 343, 127–133.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Thiam, E. I., Diop, M., Gaye, M., Sall, A. S. & Barry, A. H. (2008). Acta Cryst. E64, o776.
Tutughamiarso, M. & Bolte, M. (2007). Acta Cryst. E63, o4682.
Uğur, D., Arslan, H. & Külcü, N. (2006). Russ. J. Coord. Chem. 32, 669–675.
Xian, L. (2008). Acta Cryst. E64, o1969.
Yue, H., Wang, Y., Xia, A., Luo, S. & Xu, D. (2008). Acta Cryst. E64, o858.
Yusof, M. S. M., Ayob, N. A. C., Kadir, M. A. & Yamin, B. M. (2008a). Acta Cryst. E64, o937.
Yusof, M. S. M., Muharam, S. H., Kassim, M. B. & Yamin, B. M. (2008b). Acta Cryst. E64, o1137.
Thiourea derivatives, first synthesized by Nencki, 1873, are very flexible ligands and able to coordinate to a range of metal centers as neutral ligands, monoanions or dianions (Mansuroğlu et al., 2008; Arslan et al., 2003b, 2006a; Binzet et al., 2006; Kemp et al., 1997; Koch et al., 1995). In addition, the oxygen, nitrogen and sulfur donors provide a multitude of bonding possibilities. The coordination chemistry of substituted thioureas has led to some interesting practical applications such as liquid–liquid extraction, pre-concentration and highly efficient chromatographic separation (Kemp et al., 1997; Koch et al., 1995).
Our team focused on the synthesis, characterization, crystal structure, thermal behavior and antimicrobial activity of new thiourea derivatives (Mansuroğlu et al., 2008; Arslan et al., 2003a, 2003b, 2006a, 2006b, 2007; Uğur et al., 2006; Özpozan et al., 2000). In this article, we report the preparation and characterization of a novel thiourea compound, 4-chloro-N-(6-methylpyridin-2-yl-carbamothioyl)benzamide (I), and its crystal structure. The title compound was purified by re-crystallization from ethanol:dichloromethane mixture (1:2) and characterized by elemental analysis. The analytical data is consistent with the proposed structure given in Scheme 1.
The molecular structure and packing diagram are depicted in Figure 1 and 2, respectively. The bond lengths and angles in the thiourea moiety are typical for thiourea derivatives; the C8—S1 and C7—O1 bonds both show a typical double-bond character with 1.655 (5) and 1.203 (6) Å, respectively. The short bond lengths of the N1—C7, 1.395 (7); N1—C8, 1.376 (6) and N2—C8, 1.364 (6) Å bonds indicate partial double bond character. These results can be explained by the existence of resonance in this part of the molecule. The other C—N bond length is within the expected range.
A lot of substitute benzoylthiourea derivatives have cis-trans configurations (Yusof, et al., 2008a, 2008b; Thiam, et al., 2008; Xian, 2008; Dong, et al., 2008; Duque, et al., 2008). However, the title compound shows an intramolecular N—H···N hydrogen bond (Table 1) which results in the formation of a six membered ring (N3—C9—N2—C8—N1—H1) and leads to a syn-periplanar conformation between the thiocarbonyl group carbon atom and the pyridine group nitrogen atom (Tutughamiarso & Bolte, 2007; Yue et al., 2008). The torsion angles in this region, C8—N2—C9—N3, 14.9 (9)° and C9—N2—C8—N1, -7.2 (8)° confirm this conformation. This formation forces the two amide hydrogen atoms to the opposite direction.
The carbonyl and thiocarbonyl part is essentially planar, as reflected by the torsional angles O1—C7—N1—C8, C7—N1—C8—S1 and C7—N1—C8—N2 of 1.7 (9), 0.3 (8) and 179.3 (5) °, respectively. O1, C7, N1, C8 and S1 fragment is also planar (maximum and mean deviations are 0.010 and 0.005 Å, respectively).
The crystal packing is shown in Fig. 2. There are two intermolecular, N—H···S and C—H···O, hydrogen bonds which connect molecules in chains parallel to [100].