Acta Cryst. (2009). E65, o958 [ doi:10.1107/S1600536809011519 ]
In the title compound, C15H13N3OS2, the pyridine ring and the benzo[d]thiazole unit subtend a dihedral angle of 57.7 (2)°. The length of the Csp2-S bond [1.7462 (17) Å] is significantly shorter than that of the Csp3-S bond [1.8133 (18) Å]. The crystal structure is stabilized by intramolecular N-H
N and intermolecular C-HO and C-HN hydrogen-bond interactions. Furthermore, C-H![[pi]](/logos/entities/pi_rmgif.gif)
interactions stabilize the crystal packing.
The title compound was synthesized by the reaction of from the benzo[d]thiazole-2-thiol with 6-methylpyridine carbamic chloride in the refluxing ethanol. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform/acetone.
The H atom attached to N atom was located in a different density map and the atomic coordinates allowed to refine freely. Other H atoms were positioned geometrically and refined as riding (C—H = 0.95–0.99 Å) and allowed to ride on their parent atoms, with Uiso(H) =1.2Ueq(parent) or 1.5Ueq(parent).
Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 1999); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 1999); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 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]](./at2753fig1thm.gif)
| Fig. 1. View of the molecule of (I) showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 35% probability level. |
| C15H13N3OS2 | Z = 2 |
| Mr = 315.40 | F(000) = 328 |
| Triclinic, P1 | Dx = 1.410 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.1919 (16) Å | Cell parameters from 2582 reflections |
| b = 9.0818 (18) Å | θ = 1.9–27.9° |
| c = 11.107 (2) Å | µ = 0.36 mm−1 |
| α = 74.78 (3)° | T = 113 K |
| β = 89.55 (3)° | Prism, colourless |
| γ = 69.34 (3)° | 0.16 × 0.14 × 0.10 mm |
| V = 742.8 (3) Å3 |
| Rigaku Saturn diffractometer | 3526 independent reflections |
| Radiation source: rotating anode | 2615 reflections with I > 2σ(I) |
| confocal | Rint = 0.048 |
| ω scans | θmax = 27.9°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
| Tmin = 0.945, Tmax = 0.965 | k = −11→11 |
| 9391 measured reflections | l = −14→14 |
| 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.99 | w = 1/[σ2(Fo2) + (0.0398P)2] where P = (Fo2 + 2Fc2)/3 |
| 3526 reflections | (Δ/σ)max = 0.001 |
| 195 parameters | Δρmax = 0.24 e Å−3 |
| 0 restraints | Δρmin = −0.38 e Å−3 |
| C15H13N3OS2 | γ = 69.34 (3)° |
| Mr = 315.40 | V = 742.8 (3) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.1919 (16) Å | Mo Kα radiation |
| b = 9.0818 (18) Å | µ = 0.36 mm−1 |
| c = 11.107 (2) Å | T = 113 K |
| α = 74.78 (3)° | 0.16 × 0.14 × 0.10 mm |
| β = 89.55 (3)° |
| Rigaku Saturn diffractometer | 2615 reflections with I > 2σ(I) |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | Rint = 0.048 |
| Tmin = 0.945, Tmax = 0.965 | θmax = 27.9° |
| 9391 measured reflections | Standard reflections: 0 |
| 3526 independent reflections |
| R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.092 | Δρmax = 0.24 e Å−3 |
| S = 0.99 | Δρmin = −0.38 e Å−3 |
| 3526 reflections | Absolute structure: ? |
| 195 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 | ||
| S1 | 0.08893 (5) | 1.05001 (5) | 0.25028 (4) | 0.02336 (13) | |
| S2 | 0.20597 (5) | 1.15671 (5) | 0.45732 (4) | 0.02242 (13) | |
| N1 | 0.74042 (17) | 0.74849 (16) | 0.19582 (13) | 0.0200 (3) | |
| N2 | 0.45173 (18) | 0.88209 (17) | 0.12486 (14) | 0.0210 (3) | |
| N3 | 0.37052 (17) | 1.13818 (15) | 0.25715 (13) | 0.0192 (3) | |
| O1 | 0.24938 (15) | 0.82797 (14) | 0.02096 (13) | 0.0320 (3) | |
| C1 | 0.6056 (2) | 0.74785 (18) | 0.12785 (15) | 0.0189 (4) | |
| C2 | 0.6186 (2) | 0.62959 (19) | 0.06672 (16) | 0.0217 (4) | |
| H2 | 0.5203 | 0.6332 | 0.0196 | 0.026* | |
| C3 | 0.7803 (2) | 0.50655 (19) | 0.07723 (16) | 0.0233 (4) | |
| H3 | 0.7949 | 0.4229 | 0.0371 | 0.028* | |
| C4 | 0.9210 (2) | 0.50511 (19) | 0.14621 (16) | 0.0217 (4) | |
| H4 | 1.0329 | 0.4214 | 0.1533 | 0.026* | |
| C5 | 0.8961 (2) | 0.62787 (19) | 0.20491 (16) | 0.0204 (4) | |
| C6 | 1.0426 (2) | 0.6313 (2) | 0.28327 (18) | 0.0300 (4) | |
| H6A | 1.0281 | 0.7452 | 0.2761 | 0.045* | |
| H6B | 1.1550 | 0.5765 | 0.2538 | 0.045* | |
| H6C | 1.0403 | 0.5745 | 0.3711 | 0.045* | |
| C7 | 0.2879 (2) | 0.9140 (2) | 0.07486 (16) | 0.0217 (4) | |
| C8 | 0.1511 (2) | 1.06990 (19) | 0.09143 (16) | 0.0222 (4) | |
| H8A | 0.0453 | 1.1009 | 0.0339 | 0.027* | |
| H8B | 0.1975 | 1.1594 | 0.0676 | 0.027* | |
| C9 | 0.2379 (2) | 1.11504 (18) | 0.31235 (16) | 0.0193 (4) | |
| C10 | 0.4590 (2) | 1.19559 (18) | 0.32980 (15) | 0.0184 (4) | |
| C11 | 0.3900 (2) | 1.21228 (18) | 0.44347 (16) | 0.0194 (4) | |
| C12 | 0.4660 (2) | 1.26537 (19) | 0.52672 (16) | 0.0239 (4) | |
| H12 | 0.4194 | 1.2750 | 0.6041 | 0.029* | |
| C13 | 0.6122 (2) | 1.3037 (2) | 0.49261 (17) | 0.0257 (4) | |
| H13 | 0.6667 | 1.3405 | 0.5476 | 0.031* | |
| C14 | 0.6811 (2) | 1.2894 (2) | 0.37940 (17) | 0.0255 (4) | |
| H14 | 0.7806 | 1.3181 | 0.3583 | 0.031* | |
| C15 | 0.6076 (2) | 1.23436 (19) | 0.29716 (16) | 0.0225 (4) | |
| H15 | 0.6563 | 1.2231 | 0.2207 | 0.027* | |
| H2A | 0.463 (2) | 0.951 (2) | 0.1624 (17) | 0.027 (5)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0181 (2) | 0.0224 (2) | 0.0319 (3) | −0.00785 (18) | 0.00497 (18) | −0.0107 (2) |
| S2 | 0.0215 (3) | 0.0227 (2) | 0.0215 (2) | −0.00602 (18) | 0.00643 (18) | −0.00652 (18) |
| N1 | 0.0180 (7) | 0.0194 (7) | 0.0224 (8) | −0.0055 (6) | 0.0019 (6) | −0.0072 (6) |
| N2 | 0.0166 (8) | 0.0207 (7) | 0.0274 (8) | −0.0035 (6) | −0.0001 (6) | −0.0139 (7) |
| N3 | 0.0175 (8) | 0.0178 (7) | 0.0215 (7) | −0.0049 (6) | 0.0015 (6) | −0.0062 (6) |
| O1 | 0.0229 (7) | 0.0330 (7) | 0.0440 (8) | −0.0057 (5) | −0.0046 (6) | −0.0229 (7) |
| C1 | 0.0186 (9) | 0.0183 (8) | 0.0186 (8) | −0.0054 (7) | 0.0036 (7) | −0.0052 (7) |
| C2 | 0.0220 (9) | 0.0220 (8) | 0.0237 (9) | −0.0086 (7) | 0.0046 (7) | −0.0095 (7) |
| C3 | 0.0281 (10) | 0.0191 (8) | 0.0246 (9) | −0.0088 (7) | 0.0078 (8) | −0.0094 (7) |
| C4 | 0.0206 (9) | 0.0156 (8) | 0.0250 (9) | −0.0032 (7) | 0.0070 (7) | −0.0042 (7) |
| C5 | 0.0187 (9) | 0.0191 (8) | 0.0207 (9) | −0.0056 (7) | 0.0046 (7) | −0.0030 (7) |
| C6 | 0.0215 (10) | 0.0271 (9) | 0.0374 (11) | −0.0034 (8) | −0.0007 (8) | −0.0097 (9) |
| C7 | 0.0178 (9) | 0.0236 (8) | 0.0230 (9) | −0.0056 (7) | 0.0016 (7) | −0.0082 (8) |
| C8 | 0.0179 (9) | 0.0229 (9) | 0.0252 (9) | −0.0046 (7) | −0.0016 (7) | −0.0096 (8) |
| C9 | 0.0185 (9) | 0.0137 (7) | 0.0211 (9) | −0.0005 (6) | 0.0015 (7) | −0.0047 (7) |
| C10 | 0.0198 (9) | 0.0142 (7) | 0.0188 (8) | −0.0036 (6) | −0.0017 (7) | −0.0041 (7) |
| C11 | 0.0194 (9) | 0.0147 (8) | 0.0199 (9) | −0.0023 (6) | 0.0010 (7) | −0.0033 (7) |
| C12 | 0.0284 (10) | 0.0212 (8) | 0.0178 (9) | −0.0029 (7) | −0.0002 (7) | −0.0068 (7) |
| C13 | 0.0289 (10) | 0.0201 (8) | 0.0270 (10) | −0.0068 (7) | −0.0042 (8) | −0.0076 (8) |
| C14 | 0.0255 (10) | 0.0233 (9) | 0.0284 (10) | −0.0115 (8) | −0.0009 (8) | −0.0046 (8) |
| C15 | 0.0216 (9) | 0.0241 (9) | 0.0208 (9) | −0.0081 (7) | 0.0043 (7) | −0.0049 (7) |
| S1—C9 | 1.7462 (17) | C4—H4 | 0.9500 |
| S1—C8 | 1.8133 (18) | C5—C6 | 1.502 (2) |
| S2—C11 | 1.7444 (17) | C6—H6A | 0.9800 |
| S2—C9 | 1.7459 (17) | C6—H6B | 0.9800 |
| N1—C5 | 1.340 (2) | C6—H6C | 0.9800 |
| N1—C1 | 1.345 (2) | C7—C8 | 1.519 (2) |
| N2—C7 | 1.359 (2) | C8—H8A | 0.9900 |
| N2—C1 | 1.404 (2) | C8—H8B | 0.9900 |
| N2—H2A | 0.863 (17) | C10—C11 | 1.402 (2) |
| N3—C9 | 1.297 (2) | C10—C15 | 1.402 (2) |
| N3—C10 | 1.395 (2) | C11—C12 | 1.389 (2) |
| O1—C7 | 1.2212 (19) | C12—C13 | 1.385 (2) |
| C1—C2 | 1.388 (2) | C12—H12 | 0.9500 |
| C2—C3 | 1.381 (2) | C13—C14 | 1.393 (3) |
| C2—H2 | 0.9500 | C13—H13 | 0.9500 |
| C3—C4 | 1.383 (2) | C14—C15 | 1.381 (2) |
| C3—H3 | 0.9500 | C14—H14 | 0.9500 |
| C4—C5 | 1.389 (2) | C15—H15 | 0.9500 |
| C9—S1—C8 | 100.19 (8) | O1—C7—C8 | 121.40 (15) |
| C11—S2—C9 | 88.51 (8) | N2—C7—C8 | 113.96 (14) |
| C5—N1—C1 | 117.98 (13) | C7—C8—S1 | 113.25 (12) |
| C7—N2—C1 | 128.33 (14) | C7—C8—H8A | 108.9 |
| C7—N2—H2A | 116.3 (12) | S1—C8—H8A | 108.9 |
| C1—N2—H2A | 115.3 (12) | C7—C8—H8B | 108.9 |
| C9—N3—C10 | 110.02 (14) | S1—C8—H8B | 108.9 |
| N1—C1—C2 | 123.80 (15) | H8A—C8—H8B | 107.7 |
| N1—C1—N2 | 111.89 (13) | N3—C9—S2 | 116.86 (12) |
| C2—C1—N2 | 124.31 (15) | N3—C9—S1 | 124.62 (13) |
| C3—C2—C1 | 117.24 (15) | S2—C9—S1 | 118.51 (10) |
| C3—C2—H2 | 121.4 | N3—C10—C11 | 115.18 (15) |
| C1—C2—H2 | 121.4 | N3—C10—C15 | 124.86 (16) |
| C2—C3—C4 | 119.97 (15) | C11—C10—C15 | 119.96 (15) |
| C2—C3—H3 | 120.0 | C12—C11—C10 | 121.74 (16) |
| C4—C3—H3 | 120.0 | C12—C11—S2 | 128.85 (14) |
| C3—C4—C5 | 119.00 (16) | C10—C11—S2 | 109.42 (12) |
| C3—C4—H4 | 120.5 | C13—C12—C11 | 117.45 (17) |
| C5—C4—H4 | 120.5 | C13—C12—H12 | 121.3 |
| N1—C5—C4 | 122.01 (15) | C11—C12—H12 | 121.3 |
| N1—C5—C6 | 116.40 (14) | C12—C13—C14 | 121.46 (16) |
| C4—C5—C6 | 121.59 (15) | C12—C13—H13 | 119.3 |
| C5—C6—H6A | 109.5 | C14—C13—H13 | 119.3 |
| C5—C6—H6B | 109.5 | C15—C14—C13 | 121.31 (17) |
| H6A—C6—H6B | 109.5 | C15—C14—H14 | 119.3 |
| C5—C6—H6C | 109.5 | C13—C14—H14 | 119.3 |
| H6A—C6—H6C | 109.5 | C14—C15—C10 | 118.07 (16) |
| H6B—C6—H6C | 109.5 | C14—C15—H15 | 121.0 |
| O1—C7—N2 | 124.63 (16) | C10—C15—H15 | 121.0 |
| C5—N1—C1—C2 | 0.0 (3) | C11—S2—C9—N3 | 0.20 (13) |
| C5—N1—C1—N2 | −179.13 (14) | C11—S2—C9—S1 | −178.48 (10) |
| C7—N2—C1—N1 | −173.97 (16) | C8—S1—C9—N3 | −10.77 (15) |
| C7—N2—C1—C2 | 6.9 (3) | C8—S1—C9—S2 | 167.80 (9) |
| N1—C1—C2—C3 | −0.1 (3) | C9—N3—C10—C11 | 1.10 (19) |
| N2—C1—C2—C3 | 178.95 (16) | C9—N3—C10—C15 | −179.48 (14) |
| C1—C2—C3—C4 | −0.2 (2) | N3—C10—C11—C12 | 178.84 (14) |
| C2—C3—C4—C5 | 0.5 (2) | C15—C10—C11—C12 | −0.6 (2) |
| C1—N1—C5—C4 | 0.3 (2) | N3—C10—C11—S2 | −0.95 (17) |
| C1—N1—C5—C6 | −179.05 (15) | C15—C10—C11—S2 | 179.60 (12) |
| C3—C4—C5—N1 | −0.6 (3) | C9—S2—C11—C12 | −179.36 (15) |
| C3—C4—C5—C6 | 178.74 (16) | C9—S2—C11—C10 | 0.42 (12) |
| C1—N2—C7—O1 | −1.3 (3) | C10—C11—C12—C13 | 0.8 (2) |
| C1—N2—C7—C8 | 178.66 (15) | S2—C11—C12—C13 | −179.40 (12) |
| O1—C7—C8—S1 | 105.85 (18) | C11—C12—C13—C14 | −0.1 (2) |
| N2—C7—C8—S1 | −74.11 (17) | C12—C13—C14—C15 | −0.8 (3) |
| C9—S1—C8—C7 | 91.58 (12) | C13—C14—C15—C10 | 1.1 (2) |
| C10—N3—C9—S2 | −0.76 (17) | N3—C10—C15—C14 | −179.76 (14) |
| C10—N3—C9—S1 | 177.84 (11) | C11—C10—C15—C14 | −0.4 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···N3 | 0.867 (18) | 2.142 (18) | 2.949 (2) | 154.6 (16) |
| C2—H2···O1 | 0.95 | 2.30 | 2.890 (2) | 119 |
| C8—H8A···O1i | 0.99 | 2.31 | 3.239 (2) | 156 |
| C8—H8B···N3 | 0.99 | 2.47 | 2.905 (2) | 106 |
| C12—H12···N1ii | 0.95 | 2.57 | 3.498 (2) | 166 |
| C8—H8B···Cg2iii | 0.99 | 2.68 | 3.494 (2) | 140 |
| Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+2, −z. |
| S1—C9 | 1.7462 (17) | S1—C8 | 1.8133 (18) |
| C1—N2—C7—C8 | 178.66 (15) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···N3 | 0.867 (18) | 2.142 (18) | 2.949 (2) | 154.6 (16) |
| C2—H2···O1 | 0.95 | 2.30 | 2.890 (2) | 119 |
| C8—H8A···O1i | 0.99 | 2.31 | 3.239 (2) | 156 |
| C8—H8B···N3 | 0.99 | 2.47 | 2.905 (2) | 106 |
| C12—H12···N1ii | 0.95 | 2.57 | 3.498 (2) | 166 |
| C8—H8B···Cg2iii | 0.99 | 2.68 | 3.494 (2) | 140 |
| Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+2, −z. |
The project was supported by the Initial Fund for Young Teachers of Qiqihar University (000203).
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Gao, Y., Liang, D., Gao, L.-X., Fang, G.-J. & Wang, W. (2007). Acta Cryst. E63, o4854.
Ladziata, U., Willging, J. & Zhdankin, V. V. (2006). Org. Lett. 8, 167–170.
Molecular Structure Corporation & Rigaku (1999). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany
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The acylamide compound is an important class of medical intermediate. Recently, many biological compounds containing acylamide have been reported (Ladziata et al., 2006; Bennasar et al., 2006). Now, we have synthesized the title compound, (I), from the benzo[d]thiazole-2-thiol with 6-methylpyridine carbamic chloride. Here, we report its crystal structure.
The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. The molecule contains a pyridine ring and a benzo[d]thiazole ring. The dihedral angle between the benzene ring and benzo[d]thiazole ring is 57.7 (2)°. The methyl carbon attached to the pyridine ring is coplanar to the pyridine ring with an r.m.s deviation of 0.0064 (3) Å. The C1—N1—C7—C8 torsion angle of 178.66 (15)° indicates that the acylamide group are nearly coplanar with the pyridine ring plane. As a result of π-π conjugation, the Csp2—S bond [S1—C9 = 1.7462 (17) Å] is significantly shorter than the Csp3—S bond [S1—C8 = 1.8133 (18) Å]. These values compare with the values of 1.772 (3) and 1.801 (2) Å reported in the literature (Gao et al., 2007). The crystal structure is stabilized by the intramolecular N—H···N and intermolecular C—H···O and C—H···N hydrogen bond interactions. Furthermore, C—H···π interactions stabilize the crystal packing (Table 1).