Acta Cryst. (2007). E63, o2912 [ doi:10.1107/S1600536807022313 ]
The title compound, C20H19N3S2, crystallized as a cis-trans conformer in which the quinoline ring system is cis across the C-S bond but adopts a trans geometry with respect to the C-N bond. The compound exists in the thione form with the presence of a C=S bond.
S-quinolin-2-ylmethyldithiocarbazate (0.02 mol) [How, et al., 2007] was dissolved in hot absolute ethanol (30 ml) with dropwise addition of equimolar amount of 3-methylacetophenone. The mixture was left heated with stirring to reduce half the volume. Precipitate formed were filtered and washed with a little ice-cold ethanol. The crude yellow product was recrystallized from ethanol. Yellow single crystals were formed upon slow evaporation of an ethanol solution. (Yield = 70%, M.p = 437.7–438.5 K)
The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, N—H in the range 0.86–0.89 Å) and Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints. The other atoms were refined with anisotropic atomic displacement parameters.
Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.
![[Figure 1]](./lw2012fig1thm.gif)
| Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius. |
![[Figure 2]](./lw2012fig2thm.gif)
| Fig. 2. The packing diagram of the molecules viewed along the a axis. |
![[Figure 3]](./lw2012fig3thm.gif)
| Fig. 3. The quinoline rings are parallel to each other. |
![[Figure 4]](./lw2012fig4thm.gif)
| Fig. 4. The overlapping of the quinoline rings due to the π-π interaction. |
| C20H19N3S2 | F(000) = 384 |
| Mr = 365.52 | Dx = 1.385 Mg m−3 |
| Triclinic, P1 | Melting point: 438.5 K |
| a = 7.7423 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 8.2816 (2) Å | Cell parameters from 3785 reflections |
| c = 14.0409 (4) Å | θ = 5–28° |
| α = 81.2501 (13)° | µ = 0.31 mm−1 |
| β = 80.5729 (13)° | T = 150 K |
| γ = 85.7886 (13)° | Plate, yellow |
| V = 876.70 (4) Å3 | 0.48 × 0.12 × 0.06 mm |
| Z = 2 |
| Nonius KappaCCD diffractometer | 4155 reflections with I > −3σ(I) |
| graphite | Rint = 0.043 |
| ω scans | θmax = 27.9°, θmin = 5.1° |
| Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | h = −9→10 |
| Tmin = 0.79, Tmax = 0.98 | k = −10→10 |
| 14454 measured reflections | l = −18→18 |
| 4155 independent reflections |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.061 | H-atom parameters constrained |
| wR(F2) = 0.095 | Method = Modified Sheldrick
w = 1/[\s^2^(F^2^) + ( 0.04P)^2^ + 0.22P]
, where P = (max(Fo^2^,0) + 2Fc^2^)/3 |
| S = 0.93 | (Δ/σ)max = 0.0003 |
| 4155 reflections | Δρmax = 0.52 e Å−3 |
| 226 parameters | Δρmin = −0.45 e Å−3 |
| 0 restraints |
| C20H19N3S2 | γ = 85.7886 (13)° |
| Mr = 365.52 | V = 876.70 (4) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.7423 (2) Å | Mo Kα radiation |
| b = 8.2816 (2) Å | µ = 0.31 mm−1 |
| c = 14.0409 (4) Å | T = 150 K |
| α = 81.2501 (13)° | 0.48 × 0.12 × 0.06 mm |
| β = 80.5729 (13)° |
| Nonius KappaCCD diffractometer | 4155 independent reflections |
| Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | 4155 reflections with I > −3σ(I) |
| Tmin = 0.79, Tmax = 0.98 | Rint = 0.043 |
| 14454 measured reflections | θmax = 27.9° |
| R[F2 > 2σ(F2)] = 0.061 | H-atom parameters constrained |
| wR(F2) = 0.095 | Δρmax = 0.52 e Å−3 |
| S = 0.93 | Δρmin = −0.45 e Å−3 |
| 4155 reflections | Absolute structure: ? |
| 226 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| C1 | −0.0600 (2) | 0.1649 (2) | 0.37590 (12) | 0.0210 | |
| C2 | 0.0184 (2) | 0.2108 (2) | 0.45150 (12) | 0.0218 | |
| C3 | 0.1944 (2) | 0.1553 (2) | 0.45653 (13) | 0.0227 | |
| C4 | 0.2799 (2) | 0.0608 (2) | 0.39084 (12) | 0.0228 | |
| C5 | 0.1915 (2) | 0.0177 (2) | 0.31810 (12) | 0.0205 | |
| N6 | 0.02722 (17) | 0.06871 (17) | 0.30981 (10) | 0.0204 | |
| C7 | 0.2821 (2) | −0.0930 (2) | 0.24793 (13) | 0.0223 | |
| S8 | 0.45390 (5) | 0.00735 (5) | 0.15921 (3) | 0.0227 | |
| C9 | 0.6441 (2) | −0.0558 (2) | 0.21229 (12) | 0.0207 | |
| N10 | 0.78668 (17) | 0.02300 (17) | 0.16409 (10) | 0.0219 | |
| N11 | 0.76719 (18) | 0.12944 (17) | 0.08037 (10) | 0.0220 | |
| C12 | 0.8989 (2) | 0.2090 (2) | 0.03342 (12) | 0.0207 | |
| C13 | 0.8649 (2) | 0.3172 (2) | −0.05711 (12) | 0.0206 | |
| C14 | 0.6920 (2) | 0.3671 (2) | −0.07123 (13) | 0.0226 | |
| C15 | 0.6572 (2) | 0.4663 (2) | −0.15533 (13) | 0.0232 | |
| C16 | 0.7980 (2) | 0.5155 (2) | −0.22723 (13) | 0.0277 | |
| C17 | 0.9683 (2) | 0.4654 (2) | −0.21536 (13) | 0.0289 | |
| C18 | 1.0018 (2) | 0.3675 (2) | −0.13044 (13) | 0.0257 | |
| C19 | 0.4721 (2) | 0.5204 (2) | −0.17004 (14) | 0.0312 | |
| C20 | 1.0788 (2) | 0.1982 (2) | 0.06223 (13) | 0.0275 | |
| S21 | 0.65894 (5) | −0.19488 (5) | 0.30940 (3) | 0.0245 | |
| C22 | −0.0797 (2) | 0.3076 (2) | 0.51814 (13) | 0.0272 | |
| C23 | −0.2492 (2) | 0.3583 (2) | 0.50908 (14) | 0.0315 | |
| C24 | −0.3267 (2) | 0.3139 (2) | 0.43410 (14) | 0.0309 | |
| C25 | −0.2357 (2) | 0.2197 (2) | 0.36890 (14) | 0.0264 | |
| H31 | 0.2520 | 0.1821 | 0.5049 | 0.0288* | |
| H41 | 0.3961 | 0.0216 | 0.3934 | 0.0267* | |
| H71 | 0.3351 | −0.1901 | 0.2842 | 0.0269* | |
| H72 | 0.1962 | −0.1268 | 0.2120 | 0.0265* | |
| H141 | 0.5976 | 0.3328 | −0.0224 | 0.0273* | |
| H161 | 0.7761 | 0.5849 | −0.2840 | 0.0337* | |
| H171 | 1.0622 | 0.4989 | −0.2641 | 0.0341* | |
| H181 | 1.1171 | 0.3356 | −0.1222 | 0.0295* | |
| H191 | 0.4597 | 0.6381 | −0.1801 | 0.0469* | |
| H192 | 0.3907 | 0.4809 | −0.1141 | 0.0466* | |
| H193 | 0.4445 | 0.4798 | −0.2257 | 0.0463* | |
| H201 | 1.1334 | 0.3001 | 0.0399 | 0.0415* | |
| H202 | 1.0724 | 0.1749 | 0.1311 | 0.0415* | |
| H203 | 1.1508 | 0.1128 | 0.0336 | 0.0421* | |
| H221 | −0.0266 | 0.3374 | 0.5687 | 0.0329* | |
| H231 | −0.3129 | 0.4241 | 0.5535 | 0.0372* | |
| H241 | −0.4440 | 0.3492 | 0.4284 | 0.0361* | |
| H251 | −0.2890 | 0.1901 | 0.3188 | 0.0310* | |
| H1 | 0.8843 | 0.0107 | 0.1888 | 0.0281* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0220 (8) | 0.0180 (8) | 0.0207 (9) | −0.0026 (7) | −0.0008 (7) | 0.0026 (7) |
| C2 | 0.0249 (8) | 0.0184 (8) | 0.0203 (9) | −0.0055 (7) | −0.0004 (7) | 0.0018 (7) |
| C3 | 0.0238 (8) | 0.0237 (9) | 0.0208 (9) | −0.0049 (7) | −0.0045 (7) | −0.0011 (7) |
| C4 | 0.0189 (8) | 0.0255 (9) | 0.0232 (9) | −0.0019 (7) | −0.0042 (7) | 0.0007 (7) |
| C5 | 0.0192 (8) | 0.0205 (9) | 0.0205 (9) | −0.0055 (7) | −0.0012 (6) | 0.0011 (7) |
| N6 | 0.0177 (7) | 0.0213 (7) | 0.0209 (7) | −0.0029 (6) | −0.0015 (5) | 0.0001 (6) |
| C7 | 0.0173 (8) | 0.0245 (9) | 0.0253 (9) | −0.0015 (7) | −0.0026 (7) | −0.0041 (7) |
| S8 | 0.0171 (2) | 0.0292 (2) | 0.0207 (2) | −0.00164 (17) | −0.00296 (16) | 0.00023 (18) |
| C9 | 0.0187 (8) | 0.0211 (9) | 0.0226 (9) | 0.0015 (7) | −0.0019 (7) | −0.0066 (7) |
| N10 | 0.0178 (7) | 0.0264 (8) | 0.0201 (7) | −0.0009 (6) | −0.0039 (6) | 0.0022 (6) |
| N11 | 0.0210 (7) | 0.0237 (8) | 0.0199 (7) | −0.0006 (6) | −0.0022 (6) | 0.0000 (6) |
| C12 | 0.0177 (8) | 0.0222 (9) | 0.0229 (9) | 0.0002 (7) | −0.0026 (7) | −0.0068 (7) |
| C13 | 0.0203 (8) | 0.0201 (9) | 0.0214 (9) | −0.0018 (7) | −0.0015 (6) | −0.0043 (7) |
| C14 | 0.0212 (8) | 0.0242 (9) | 0.0224 (9) | −0.0030 (7) | −0.0019 (7) | −0.0047 (7) |
| C15 | 0.0278 (9) | 0.0197 (9) | 0.0240 (9) | −0.0002 (7) | −0.0074 (7) | −0.0062 (7) |
| C16 | 0.0369 (10) | 0.0226 (9) | 0.0220 (9) | −0.0012 (8) | −0.0047 (7) | 0.0014 (7) |
| C17 | 0.0301 (9) | 0.0250 (9) | 0.0272 (10) | −0.0050 (8) | 0.0054 (8) | 0.0012 (8) |
| C18 | 0.0220 (8) | 0.0256 (9) | 0.0280 (10) | −0.0021 (7) | −0.0016 (7) | −0.0010 (8) |
| C19 | 0.0308 (10) | 0.0322 (10) | 0.0324 (11) | 0.0019 (8) | −0.0125 (8) | −0.0037 (8) |
| C20 | 0.0204 (8) | 0.0351 (10) | 0.0266 (10) | −0.0039 (8) | −0.0058 (7) | 0.0001 (8) |
| S21 | 0.0228 (2) | 0.0262 (2) | 0.0226 (2) | −0.00006 (18) | −0.00369 (17) | 0.00191 (18) |
| C22 | 0.0316 (9) | 0.0247 (9) | 0.0242 (9) | −0.0053 (8) | 0.0018 (7) | −0.0051 (8) |
| C23 | 0.0338 (10) | 0.0221 (9) | 0.0353 (11) | −0.0001 (8) | 0.0055 (8) | −0.0061 (8) |
| C24 | 0.0231 (9) | 0.0284 (10) | 0.0377 (11) | 0.0025 (8) | 0.0004 (8) | −0.0014 (9) |
| C25 | 0.0227 (8) | 0.0254 (9) | 0.0299 (10) | −0.0009 (7) | −0.0034 (7) | −0.0010 (8) |
| C1—C2 | 1.417 (2) | C13—C18 | 1.390 (2) |
| C1—N6 | 1.375 (2) | C14—C15 | 1.386 (2) |
| C1—C25 | 1.416 (2) | C14—H141 | 0.944 |
| C2—C3 | 1.415 (2) | C15—C16 | 1.398 (3) |
| C2—C22 | 1.414 (3) | C15—C19 | 1.507 (2) |
| C3—C4 | 1.358 (2) | C16—C17 | 1.382 (3) |
| C3—H31 | 0.932 | C16—H161 | 0.941 |
| C4—C5 | 1.419 (2) | C17—C18 | 1.386 (2) |
| C4—H41 | 0.939 | C17—H171 | 0.940 |
| C5—N6 | 1.328 (2) | C18—H181 | 0.933 |
| C5—C7 | 1.503 (2) | C19—H191 | 0.963 |
| C7—S8 | 1.8210 (16) | C19—H192 | 0.954 |
| C7—H71 | 0.985 | C19—H193 | 0.957 |
| C7—H72 | 0.978 | C20—H201 | 0.958 |
| S8—C9 | 1.7679 (16) | C20—H202 | 0.951 |
| C9—N10 | 1.352 (2) | C20—H203 | 0.963 |
| C9—S21 | 1.6593 (17) | C22—C23 | 1.368 (3) |
| N10—N11 | 1.3803 (19) | C22—H221 | 0.948 |
| N10—H1 | 0.875 | C23—C24 | 1.400 (3) |
| N11—C12 | 1.287 (2) | C23—H231 | 0.945 |
| C12—C13 | 1.489 (2) | C24—C25 | 1.367 (3) |
| C12—C20 | 1.506 (2) | C24—H241 | 0.946 |
| C13—C14 | 1.408 (2) | C25—H251 | 0.942 |
| C2—C1—N6 | 122.67 (15) | C15—C14—H141 | 119.1 |
| C2—C1—C25 | 118.35 (17) | C14—C15—C16 | 118.53 (16) |
| N6—C1—C25 | 118.98 (15) | C14—C15—C19 | 121.25 (16) |
| C1—C2—C3 | 117.26 (16) | C16—C15—C19 | 120.21 (16) |
| C1—C2—C22 | 119.80 (16) | C15—C16—C17 | 120.91 (16) |
| C3—C2—C22 | 122.93 (16) | C15—C16—H161 | 119.3 |
| C2—C3—C4 | 119.72 (16) | C17—C16—H161 | 119.8 |
| C2—C3—H31 | 120.6 | C16—C17—C18 | 120.06 (16) |
| C4—C3—H31 | 119.6 | C16—C17—H171 | 120.3 |
| C3—C4—C5 | 119.71 (15) | C18—C17—H171 | 119.6 |
| C3—C4—H41 | 121.0 | C13—C18—C17 | 120.55 (16) |
| C5—C4—H41 | 119.2 | C13—C18—H181 | 119.6 |
| C4—C5—N6 | 122.65 (16) | C17—C18—H181 | 119.8 |
| C4—C5—C7 | 120.12 (15) | C15—C19—H191 | 109.8 |
| N6—C5—C7 | 117.21 (14) | C15—C19—H192 | 110.7 |
| C1—N6—C5 | 117.97 (14) | H191—C19—H192 | 108.1 |
| C5—C7—S8 | 112.42 (11) | C15—C19—H193 | 110.0 |
| C5—C7—H71 | 109.6 | H191—C19—H193 | 109.1 |
| S8—C7—H71 | 108.4 | H192—C19—H193 | 109.0 |
| C5—C7—H72 | 109.1 | C12—C20—H201 | 109.5 |
| S8—C7—H72 | 107.7 | C12—C20—H202 | 110.9 |
| H71—C7—H72 | 109.6 | H201—C20—H202 | 108.8 |
| C7—S8—C9 | 102.38 (8) | C12—C20—H203 | 110.5 |
| S8—C9—N10 | 112.31 (12) | H201—C20—H203 | 108.8 |
| S8—C9—S21 | 126.92 (10) | H202—C20—H203 | 108.2 |
| N10—C9—S21 | 120.76 (12) | C2—C22—C23 | 120.19 (17) |
| C9—N10—N11 | 117.61 (13) | C2—C22—H221 | 119.3 |
| C9—N10—H1 | 119.6 | C23—C22—H221 | 120.5 |
| N11—N10—H1 | 122.6 | C22—C23—C24 | 120.11 (18) |
| N10—N11—C12 | 119.50 (13) | C22—C23—H231 | 119.4 |
| N11—C12—C13 | 115.11 (14) | C24—C23—H231 | 120.5 |
| N11—C12—C20 | 125.40 (15) | C23—C24—C25 | 121.11 (17) |
| C13—C12—C20 | 119.48 (14) | C23—C24—H241 | 119.6 |
| C12—C13—C14 | 120.34 (15) | C25—C24—H241 | 119.3 |
| C12—C13—C18 | 121.04 (15) | C1—C25—C24 | 120.43 (17) |
| C14—C13—C18 | 118.60 (15) | C1—C25—H251 | 119.1 |
| C13—C14—C15 | 121.34 (16) | C24—C25—H251 | 120.5 |
| C13—C14—H141 | 119.6 |
| C9—N10 | 1.352 (2) | N10—N11 | 1.3803 (19) |
| C9—S21 | 1.6593 (17) | ||
| S8—C9—S21 | 126.92 (10) | C9—N10—N11 | 117.61 (13) |
| N10—C9—S21 | 120.76 (12) |
FNFH gratefully acknowledges MOSTI, Malaysia, for an attachment grant under an NSF scholarship and the Chemical Crystallography Laboratory, Oxford University, for instrumental facilities.
Altomare, A., Cascarano, G., Giacovazzo, G., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435–?.
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487–?.
Chan, M.-H. E., Crouse, K. A., Tarafder, M. T. H. & Yamin, B. M. (2003). Acta Cryst. E59, o628–o629.
How, F. N.-F., Watkin, D. J., Crouse, K. A. & Tahir, M. I. M. (2007). preparation. Any update?
Khoo, T.-J., Cowley, A. R., Watkin, D. J., Crouse, K. A. & Tarafder, M. T. H. (2005). Acta Cryst. E61, o2441–o2443.
Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON, Chemical Crystallography Laboratory, Oxford, England.
S-quinolin-2-ylmethyldithiocarbazate, a new dithiocarbazate derivative has been introduced. This dithiocarbazate derivative ligand contains a quinoline ring [How, et al., 2007]. This new ligand were used to synthesized new Schiff bases. It is likely that these compound will be of interest for further research.
The C9—N10 bond [1.352 (2) Å] is comparable with the literature value and showed a double-bond character. [1.342 (2) Å; Chan et al., 2003] and [1.343 (3) Å; Khoo et al., 2005]. The C=S bond is 1.6593 (17) Å, which is shorter than in S-quinolin-2-ylmethyldithiocarbazate [1.6804 (14) Å; How, et al., 2007] but comparable with Schiff bases derived from S-benzyldithiocarbazate. [1.6503 (17) Å; Chan et al., 2003] and [1.664 (2) Å; Khoo et al., 2005]
The molecule contains three planar fragments viz. the quinoline ring, dithiocarbazate moiety and the benzyl group. [Fig. 1.]. The dihedral angle between the planar quinoline ring and the dithiocarbazate moiety is 103.7°. The dihedral angle between the dithiocarbazate moiety with the benzyl group is 17.2°.
Bond angle N11—N10—C9 [117.61 (13)°] is slightly shorter than other Schiff bases. [119.20 (14)°; Chan et al., 2003] and [119.35 (17)°; Khoo et al., 2005]. However, S21—C9—S8 [126.92 (10)°] is slightly longer. [125.60 (10)°; Chan et al., 2003] and [125.22 (12)°; Khoo et al., 2005]. This is due to the twisting of both benzyl ring and the quinoline ring for stabilization.
The isolated molecule is L shaped [Fig. 2.]. Viewed along the a axis, the molecule packed in hearing-bone columns with pairs of quinoline rings residues lying parallel [Fig. 3.] and overlapping (mean separation 3.4 Å), corresponding to a reasonably strong π-π interaction between the quinoline rings. [Fig. 4.] Pairs of methyl benzyl residues are also almost parellel (mean separation 3.7 Å), but there is no overlap between the aromatic moieties. The moiety C7/S8/C9/N10/N11/C12/S21 behaves as a rigid group (TLS R-factor= 0.085).