Acta Cryst. (2008). E64, o722 [ doi:10.1107/S1600536808006752 ]
In the title compound, C8H9N3S2, the n-propyl chain is disordered over two orientations (site-occupancy ratio = 0.522:0.478) and is roughly perpendicular to the fused thiazolotriazine system. The angle between the fused ring and the propyl chain is 83.6 (1)° [ 82.2 (1)° for the disordered chain]. The structure is stabilized by C-H
N hydrogen bonds.
A mixture of ammonium thiocyanate (26 mmol) and butyryl chloride (26 mmol) in dry acetone (60 ml) was stirred for 30 min. Then 2-aminothiazole (26 mmol) was added and the reaction mixture was refluxed for 2 h. After cooling, the reaction mixture was poured into acidified cold water. The resulting yellow solid was filtered and washed with cold acetone. Single crystals of the title compound suitable for single-crystal x-ray analysis were obtained by recrystallization of the yellow solid from acetonitrile.
H atoms were found in difference Fourier maps and subsequently placed in idealized positions with constrained C—H distances of 0.98 Å (RCH3), 0.99 Å (R2CH2) and 0.95 Å (CArH) with Uiso(H) values set to either 1.5Ueq (RCH3) or 1.2Ueq of the attached C atom.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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]](./pk2086fig1thm.gif)
| Fig. 1. : A view of the molecular structure. Displacement ellipsoids are drawn at the 50% probability level. |
| C8H9N3S2 | F000 = 440 |
| Mr = 211.32 | Dx = 1.481 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 5571 reflections |
| a = 9.3240 (7) Å | θ = 2.6–28.3º |
| b = 14.9973 (11) Å | µ = 0.52 mm−1 |
| c = 6.8063 (5) Å | T = 173 (2) K |
| β = 95.505 (1)º | Block, pale yellow |
| V = 947.37 (12) Å3 | 0.32 × 0.25 × 0.22 mm |
| Z = 4 |
| Bruker SMART CCD diffractometer | 2254 independent reflections |
| Radiation source: fine-focus sealed tube | 2077 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.016 |
| T = 173(2) K | θmax = 28.3º |
| ω and φ scans | θmin = 2.6º |
| Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −12→12 |
| Tmin = 0.853, Tmax = 0.895 | k = −19→14 |
| 5571 measured reflections | l = −9→9 |
| 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)] = 0.024 | H-atom parameters constrained |
| wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.0392P)2 + 0.2601P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.001 |
| 2254 reflections | Δρmax = 0.32 e Å−3 |
| 161 parameters | Δρmin = −0.28 e Å−3 |
| 5 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0066 (12) |
| C8H9N3S2 | V = 947.37 (12) Å3 |
| Mr = 211.32 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 9.3240 (7) Å | µ = 0.52 mm−1 |
| b = 14.9973 (11) Å | T = 173 (2) K |
| c = 6.8063 (5) Å | 0.32 × 0.25 × 0.22 mm |
| β = 95.505 (1)º |
| Bruker SMART CCD diffractometer | 2254 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2077 reflections with I > 2σ(I) |
| Tmin = 0.853, Tmax = 0.895 | Rint = 0.016 |
| 5571 measured reflections |
| R[F2 > 2σ(F2)] = 0.024 | 5 restraints |
| wR(F2) = 0.068 | H-atom parameters constrained |
| S = 1.05 | Δρmax = 0.32 e Å−3 |
| 2254 reflections | Δρmin = −0.28 e Å−3 |
| 161 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 > 2σ(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 | Occ. (<1) | |
| S1 | 0.20093 (3) | 0.710163 (18) | 0.27470 (4) | 0.02095 (10) | |
| S2 | −0.15462 (3) | 0.443002 (19) | 0.21702 (4) | 0.02265 (10) | |
| N1 | 0.04853 (10) | 0.56884 (6) | 0.25767 (13) | 0.01739 (19) | |
| N2 | 0.12868 (11) | 0.42185 (7) | 0.29852 (15) | 0.0235 (2) | |
| N3 | 0.29929 (11) | 0.54164 (7) | 0.31895 (15) | 0.0231 (2) | |
| C1 | 0.01557 (13) | 0.71890 (8) | 0.23196 (17) | 0.0224 (2) | |
| H1 | −0.0344 | 0.7739 | 0.2143 | 0.027* | |
| C2 | −0.04951 (12) | 0.63902 (8) | 0.22664 (17) | 0.0211 (2) | |
| H2 | −0.1508 | 0.6311 | 0.2043 | 0.025* | |
| C3 | 0.18861 (12) | 0.59613 (7) | 0.28536 (15) | 0.0185 (2) | |
| C5 | 0.01588 (12) | 0.47711 (7) | 0.25939 (15) | 0.0187 (2) | |
| C4 | 0.26174 (14) | 0.45502 (8) | 0.32834 (18) | 0.0259 (3) | 0.522 (4) |
| C6 | 0.3713 (6) | 0.3883 (4) | 0.4050 (7) | 0.0221 (9) | 0.522 (4) |
| H6A | 0.3288 | 0.3278 | 0.4003 | 0.029 (8)* | 0.522 (4) |
| H6B | 0.4062 | 0.4022 | 0.5436 | 0.025 (7)* | 0.522 (4) |
| C7 | 0.4958 (2) | 0.39267 (16) | 0.2751 (4) | 0.0248 (6) | 0.522 (4) |
| H7A | 0.5357 | 0.4539 | 0.2799 | 0.021 (7)* | 0.522 (4) |
| H7B | 0.5730 | 0.3517 | 0.3292 | 0.036 (8)* | 0.522 (4) |
| C8 | 0.4516 (9) | 0.3679 (6) | 0.0614 (6) | 0.0357 (13) | 0.522 (4) |
| H8A | 0.5357 | 0.3714 | −0.0143 | 0.030 (8)* | 0.522 (4) |
| H8B | 0.3773 | 0.4093 | 0.0055 | 0.045 (10)* | 0.522 (4) |
| H8C | 0.4134 | 0.3070 | 0.0552 | 0.061 (12)* | 0.522 (4) |
| C4A | 0.26174 (14) | 0.45502 (8) | 0.32834 (18) | 0.0259 (3) | 0.478 (4) |
| C6A | 0.3938 (7) | 0.3911 (4) | 0.3487 (8) | 0.0255 (12) | 0.478 (4) |
| H6A1 | 0.4827 | 0.4276 | 0.3621 | 0.047 (11)* | 0.478 (4) |
| H6A2 | 0.3913 | 0.3565 | 0.4722 | 0.038 (11)* | 0.478 (4) |
| C7A | 0.4034 (3) | 0.32554 (16) | 0.1781 (4) | 0.0247 (7) | 0.478 (4) |
| H7A1 | 0.4736 | 0.2781 | 0.2199 | 0.036 (9)* | 0.478 (4) |
| H7A2 | 0.3083 | 0.2970 | 0.1461 | 0.037 (9)* | 0.478 (4) |
| C8A | 0.4491 (8) | 0.3709 (6) | −0.0056 (8) | 0.0320 (11) | 0.478 (4) |
| H8A1 | 0.4583 | 0.3263 | −0.1087 | 0.064 (14)* | 0.478 (4) |
| H8A2 | 0.5420 | 0.4007 | 0.0263 | 0.061 (13)* | 0.478 (4) |
| H8A3 | 0.3764 | 0.4152 | −0.0528 | 0.030 (9)* | 0.478 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.02618 (16) | 0.01417 (15) | 0.02233 (16) | −0.00294 (10) | 0.00150 (11) | 0.00001 (9) |
| S2 | 0.02469 (16) | 0.01845 (15) | 0.02542 (16) | −0.00432 (10) | 0.00559 (11) | −0.00188 (10) |
| N1 | 0.0225 (4) | 0.0139 (4) | 0.0155 (4) | −0.0004 (3) | 0.0008 (3) | 0.0001 (3) |
| N2 | 0.0307 (5) | 0.0151 (4) | 0.0231 (5) | 0.0010 (4) | −0.0059 (4) | −0.0003 (4) |
| N3 | 0.0254 (5) | 0.0183 (5) | 0.0243 (5) | 0.0009 (4) | −0.0051 (4) | −0.0020 (4) |
| C1 | 0.0273 (6) | 0.0166 (5) | 0.0236 (6) | 0.0020 (4) | 0.0037 (4) | −0.0001 (4) |
| C2 | 0.0235 (5) | 0.0172 (5) | 0.0226 (5) | 0.0024 (4) | 0.0029 (4) | 0.0003 (4) |
| C3 | 0.0247 (5) | 0.0157 (5) | 0.0147 (5) | −0.0022 (4) | 0.0000 (4) | −0.0010 (4) |
| C5 | 0.0280 (5) | 0.0148 (5) | 0.0130 (5) | −0.0015 (4) | 0.0010 (4) | −0.0015 (4) |
| C4 | 0.0301 (6) | 0.0183 (5) | 0.0266 (6) | 0.0025 (4) | −0.0106 (5) | −0.0023 (4) |
| C6 | 0.0217 (16) | 0.0211 (14) | 0.023 (2) | 0.0022 (11) | −0.0009 (16) | 0.0060 (18) |
| C7 | 0.0159 (11) | 0.0253 (12) | 0.0332 (13) | 0.0029 (8) | 0.0023 (9) | −0.0008 (9) |
| C8 | 0.0347 (17) | 0.039 (2) | 0.034 (3) | 0.0051 (15) | 0.006 (3) | −0.009 (3) |
| C4A | 0.0301 (6) | 0.0183 (5) | 0.0266 (6) | 0.0025 (4) | −0.0106 (5) | −0.0023 (4) |
| C6A | 0.032 (3) | 0.0196 (16) | 0.023 (3) | 0.0051 (16) | −0.0085 (19) | 0.0019 (19) |
| C7A | 0.0224 (11) | 0.0180 (12) | 0.0337 (15) | 0.0042 (9) | 0.0030 (10) | 0.0003 (10) |
| C8A | 0.0268 (16) | 0.0325 (18) | 0.038 (3) | −0.0014 (13) | 0.009 (3) | 0.004 (3) |
| S1—C3 | 1.7161 (11) | C6—H6B | 0.9900 |
| S1—C1 | 1.7299 (13) | C7—C8 | 1.519 (5) |
| S2—C5 | 1.6686 (12) | C7—H7A | 0.9900 |
| N1—C3 | 1.3644 (14) | C7—H7B | 0.9900 |
| N1—C2 | 1.3967 (14) | C8—H8A | 0.9800 |
| N1—C5 | 1.4093 (14) | C8—H8B | 0.9800 |
| N2—C4 | 1.3340 (16) | C8—H8C | 0.9800 |
| N2—C5 | 1.3455 (15) | C6A—C7A | 1.531 (6) |
| N3—C3 | 1.3191 (15) | C6A—H6A1 | 0.9900 |
| N3—C4 | 1.3485 (15) | C6A—H6A2 | 0.9900 |
| C1—C2 | 1.3418 (17) | C7A—C8A | 1.520 (6) |
| C1—H1 | 0.9500 | C7A—H7A1 | 0.9900 |
| C2—H2 | 0.9500 | C7A—H7A2 | 0.9900 |
| C4—C6 | 1.488 (6) | C8A—H8A1 | 0.9800 |
| C6—C7 | 1.526 (5) | C8A—H8A2 | 0.9800 |
| C6—H6A | 0.9900 | C8A—H8A3 | 0.9800 |
| C3—S1—C1 | 90.73 (6) | C8—C7—C6 | 113.1 (4) |
| C3—N1—C2 | 113.50 (9) | C8—C7—H7A | 109.0 |
| C3—N1—C5 | 119.76 (9) | C6—C7—H7A | 109.0 |
| C2—N1—C5 | 126.73 (10) | C8—C7—H7B | 109.0 |
| C4—N2—C5 | 119.89 (10) | C6—C7—H7B | 109.0 |
| C3—N3—C4 | 113.74 (10) | H7A—C7—H7B | 107.8 |
| C2—C1—S1 | 112.26 (9) | C7—C8—H8A | 109.5 |
| C2—C1—H1 | 123.9 | C7—C8—H8B | 109.5 |
| S1—C1—H1 | 123.9 | H8A—C8—H8B | 109.5 |
| C1—C2—N1 | 112.39 (10) | C7—C8—H8C | 109.5 |
| C1—C2—H2 | 123.8 | H8A—C8—H8C | 109.5 |
| N1—C2—H2 | 123.8 | H8B—C8—H8C | 109.5 |
| N3—C3—N1 | 124.11 (10) | C7A—C6A—H6A1 | 108.4 |
| N3—C3—S1 | 124.77 (9) | C7A—C6A—H6A2 | 108.4 |
| N1—C3—S1 | 111.11 (8) | H6A1—C6A—H6A2 | 107.5 |
| N2—C5—N1 | 115.95 (10) | C8A—C7A—C6A | 112.2 (4) |
| N2—C5—S2 | 123.99 (9) | C8A—C7A—H7A1 | 109.2 |
| N1—C5—S2 | 120.05 (8) | C6A—C7A—H7A1 | 109.2 |
| N2—C4—N3 | 126.44 (11) | C8A—C7A—H7A2 | 109.2 |
| N2—C4—C6 | 113.6 (3) | C6A—C7A—H7A2 | 109.2 |
| N3—C4—C6 | 119.4 (3) | H7A1—C7A—H7A2 | 107.9 |
| C4—C6—C7 | 107.7 (3) | C7A—C8A—H8A1 | 109.5 |
| C4—C6—H6A | 110.2 | C7A—C8A—H8A2 | 109.5 |
| C7—C6—H6A | 110.2 | H8A1—C8A—H8A2 | 109.5 |
| C4—C6—H6B | 110.2 | C7A—C8A—H8A3 | 109.5 |
| C7—C6—H6B | 110.2 | H8A1—C8A—H8A3 | 109.5 |
| H6A—C6—H6B | 108.5 | H8A2—C8A—H8A3 | 109.5 |
| C3—S1—C1—C2 | −0.03 (9) | C4—N2—C5—S2 | 179.23 (9) |
| S1—C1—C2—N1 | 0.23 (13) | C3—N1—C5—N2 | 3.03 (15) |
| C3—N1—C2—C1 | −0.38 (14) | C2—N1—C5—N2 | −178.04 (10) |
| C5—N1—C2—C1 | −179.36 (10) | C3—N1—C5—S2 | −177.64 (8) |
| C4—N3—C3—N1 | −1.45 (16) | C2—N1—C5—S2 | 1.28 (15) |
| C4—N3—C3—S1 | 177.43 (9) | C5—N2—C4—N3 | −1.78 (19) |
| C2—N1—C3—N3 | 179.37 (10) | C5—N2—C4—C6 | 169.6 (2) |
| C5—N1—C3—N3 | −1.58 (16) | C3—N3—C4—N2 | 3.24 (19) |
| C2—N1—C3—S1 | 0.35 (11) | C3—N3—C4—C6 | −167.7 (2) |
| C5—N1—C3—S1 | 179.41 (7) | N2—C4—C6—C7 | 129.4 (3) |
| C1—S1—C3—N3 | −179.19 (10) | N3—C4—C6—C7 | −58.6 (4) |
| C1—S1—C3—N1 | −0.19 (8) | C4—C6—C7—C8 | −62.5 (5) |
| C4—N2—C5—N1 | −1.48 (16) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1···N2i | 0.95 | 2.38 | 3.3261 (16) | 171 |
| Symmetry codes: (i) −x, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1···N2i | 0.95 | 2.38 | 3.3261 (16) | 171 |
| Symmetry codes: (i) −x, y+1/2, −z+1/2. |
The authors gratefully acknowledge Allama Iqbal Open University, Islamabad, Pakistan, for providing research facilities.
Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (1999). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Jiang, Y.-P., Qiu, T., Wang, L.-E. & Wang, J.-N. (2007). Acta Cryst. E63, o3096–?.
Pauling, L. (1960). The nature of the Chemical Bond, 3rd ed. Ithaca: Cornell University Press.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Yunus, U., Tahir, M. K., Bhatti, M. H., Ali, S. & Helliwell, M. (2007). Acta Cryst. E63, o3690–?.
We have previously reported the crystal structure of 2-phenyl-4H-thiazolo[3,2,-a]- [1,3,5]triazine-4-thione with a phenyl group attached to the 1,3,5-triazine ring (Yunus et al., 2007). The molecule was essentially planar. In contrast, in the title compound the pendant n-propyl group is almost perpendicular to the fused thiazolo[3,2,-a][1,3,5]triazine ring, which are themselves co-planar (maximum deviation from mean plane is 0.0437 (1) Å from atom C4). The n-propyl chain is disordered over two orientations with a site occupancy ratio of 0.522:0.478 (Jiang et al., 2007). The CN bond distances of the 1,3,5-triazine ring are in the range 1.3191 (15) to 1.4093 (14) Å, in which N1—C5 bond length is slightly longer than that of N2—C5. These values are intermediate between those expected for single and double C—N bonds (1.47 and 1.27 Å, respectively). The C=S bond length of 1.6686 (12) Å is similar to that of the phenyl analog (Yunus et al., 2007) but is slightly longer then the pure double bond distance (1.61 Å) (Pauling 1960). The bond angles and bond lengths in the thiazole ring are within the normal ranges. The crystal structure is stabilized by weak C—H···N hydrogen bonding interactions.