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Acta Cryst. (2007). E63, o2912
https://doi.org/10.1107/S1600536807022313
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2-Quinolylmethyl N'-[1-(m-tol­yl)ethyl­idene]hydrazinecarbodithio­ate

F. N.-F. How, D. J. Watkin, K. A. Crouse and M. I. M. Tahir
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.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022313/lw2012sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022313/lw2012Isup2.hkl
Contains datablock I

CCDC reference: 651446

checkCIF report

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.061
  • wR factor = 0.095
  • Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found




Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        130 Deg.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S21    -   C9      ..       6.24 su


   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check
Comment top

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).

Related literature top

The dithiocarbazate ligand used to prepared the title compound is S-quinolin-2-ylmethyldithiocarbazate. This compound was prepared as described by How et al. (2007). Interatomic parameters for similar compounds are reported by Chan et al. (2003), Khoo et al. (2005) and How et al. (2007).

Experimental top

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)

Refinement top

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.

Structure description top

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).

The dithiocarbazate ligand used to prepared the title compound is S-quinolin-2-ylmethyldithiocarbazate. This compound was prepared as described by How et al. (2007). Interatomic parameters for similar compounds are reported by Chan et al. (2003), Khoo et al. (2005) and How et al. (2007).

Computing details top

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.

Figures top
[Figure 1] 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] Fig. 2. The packing diagram of the molecules viewed along the a axis.
[Figure 3] Fig. 3. The quinoline rings are parallel to each other.
[Figure 4] Fig. 4. The overlapping of the quinoline rings due to the π-π interaction.
2-Quinolylmethyl N'-[1-(m-tolyl)ethylidene]hydrazinecarbodithioate top
Crystal data top
C20H19N3S2F(000) = 384
Mr = 365.52Dx = 1.385 Mg m−3
Triclinic, P1Melting point: 438.5 K
a = 7.7423 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.2816 (2) ÅCell parameters from 3785 reflections
c = 14.0409 (4) Åθ = 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) Å30.48 × 0.12 × 0.06 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer		4155 reflections with I > −3σ(I)
Graphite monochromatorRint = 0.043
ω scansθmax = 27.9°, θmin = 5.1°
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)		h = −9→10
Tmin = 0.79, Tmax = 0.98k = −10→10
14454 measured reflectionsl = −18→18
4155 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061H-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 = 0.000293
4155 reflectionsΔρmax = 0.52 e Å−3
226 parametersΔρmin = −0.45 e Å−3
0 restraints
Crystal data top
C20H19N3S2γ = 85.7886 (13)°
Mr = 365.52V = 876.70 (4) Å3
Triclinic, P1Z = 2
a = 7.7423 (2) ÅMo Kα radiation
b = 8.2816 (2) ŵ = 0.31 mm−1
c = 14.0409 (4) ÅT = 150 K
α = 81.2501 (13)°0.48 × 0.12 × 0.06 mm
β = 80.5729 (13)°
Data collection top
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 = 0.98Rint = 0.043
14454 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0610 restraints
wR(F2) = 0.095H-atom parameters constrained
S = 0.93Δρmax = 0.52 e Å−3
4155 reflectionsΔρmin = −0.45 e Å−3
226 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1−0.0600 (2)0.1649 (2)0.37590 (12)0.0210
C20.0184 (2)0.2108 (2)0.45150 (12)0.0218
C30.1944 (2)0.1553 (2)0.45653 (13)0.0227
C40.2799 (2)0.0608 (2)0.39084 (12)0.0228
C50.1915 (2)0.0177 (2)0.31810 (12)0.0205
N60.02722 (17)0.06871 (17)0.30981 (10)0.0204
C70.2821 (2)−0.0930 (2)0.24793 (13)0.0223
S80.45390 (5)0.00735 (5)0.15921 (3)0.0227
C90.6441 (2)−0.0558 (2)0.21229 (12)0.0207
N100.78668 (17)0.02300 (17)0.16409 (10)0.0219
N110.76719 (18)0.12944 (17)0.08037 (10)0.0220
C120.8989 (2)0.2090 (2)0.03342 (12)0.0207
C130.8649 (2)0.3172 (2)−0.05711 (12)0.0206
C140.6920 (2)0.3671 (2)−0.07123 (13)0.0226
C150.6572 (2)0.4663 (2)−0.15533 (13)0.0232
C160.7980 (2)0.5155 (2)−0.22723 (13)0.0277
C170.9683 (2)0.4654 (2)−0.21536 (13)0.0289
C181.0018 (2)0.3675 (2)−0.13044 (13)0.0257
C190.4721 (2)0.5204 (2)−0.17004 (14)0.0312
C201.0788 (2)0.1982 (2)0.06223 (13)0.0275
S210.65894 (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
H310.25200.18210.50490.0288*
H410.39610.02160.39340.0267*
H710.3351−0.19010.28420.0269*
H720.1962−0.12680.21200.0265*
H1410.59760.3328−0.02240.0273*
H1610.77610.5849−0.28400.0337*
H1711.06220.4989−0.26410.0341*
H1811.11710.3356−0.12220.0295*
H1910.45970.6381−0.18010.0469*
H1920.39070.4809−0.11410.0466*
H1930.44450.4798−0.22570.0463*
H2011.13340.30010.03990.0415*
H2021.07240.17490.13110.0415*
H2031.15080.11280.03360.0421*
H221−0.02660.33740.56870.0329*
H231−0.31290.42410.55350.0372*
H241−0.44400.34920.42840.0361*
H251−0.28900.19010.31880.0310*
H10.88430.01070.18880.0281*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0220 (8)0.0180 (8)0.0207 (9)−0.0026 (7)−0.0008 (7)0.0026 (7)
C20.0249 (8)0.0184 (8)0.0203 (9)−0.0055 (7)−0.0004 (7)0.0018 (7)
C30.0238 (8)0.0237 (9)0.0208 (9)−0.0049 (7)−0.0045 (7)−0.0011 (7)
C40.0189 (8)0.0255 (9)0.0232 (9)−0.0019 (7)−0.0042 (7)0.0007 (7)
C50.0192 (8)0.0205 (9)0.0205 (9)−0.0055 (7)−0.0012 (6)0.0011 (7)
N60.0177 (7)0.0213 (7)0.0209 (7)−0.0029 (6)−0.0015 (5)0.0001 (6)
C70.0173 (8)0.0245 (9)0.0253 (9)−0.0015 (7)−0.0026 (7)−0.0041 (7)
S80.0171 (2)0.0292 (2)0.0207 (2)−0.00164 (17)−0.00296 (16)0.00023 (18)
C90.0187 (8)0.0211 (9)0.0226 (9)0.0015 (7)−0.0019 (7)−0.0066 (7)
N100.0178 (7)0.0264 (8)0.0201 (7)−0.0009 (6)−0.0039 (6)0.0022 (6)
N110.0210 (7)0.0237 (8)0.0199 (7)−0.0006 (6)−0.0022 (6)0.0000 (6)
C120.0177 (8)0.0222 (9)0.0229 (9)0.0002 (7)−0.0026 (7)−0.0068 (7)
C130.0203 (8)0.0201 (9)0.0214 (9)−0.0018 (7)−0.0015 (6)−0.0043 (7)
C140.0212 (8)0.0242 (9)0.0224 (9)−0.0030 (7)−0.0019 (7)−0.0047 (7)
C150.0278 (9)0.0197 (9)0.0240 (9)−0.0002 (7)−0.0074 (7)−0.0062 (7)
C160.0369 (10)0.0226 (9)0.0220 (9)−0.0012 (8)−0.0047 (7)0.0014 (7)
C170.0301 (9)0.0250 (9)0.0272 (10)−0.0050 (8)0.0054 (8)0.0012 (8)
C180.0220 (8)0.0256 (9)0.0280 (10)−0.0021 (7)−0.0016 (7)−0.0010 (8)
C190.0308 (10)0.0322 (10)0.0324 (11)0.0019 (8)−0.0125 (8)−0.0037 (8)
C200.0204 (8)0.0351 (10)0.0266 (10)−0.0039 (8)−0.0058 (7)0.0001 (8)
S210.0228 (2)0.0262 (2)0.0226 (2)−0.00006 (18)−0.00369 (17)0.00191 (18)
C220.0316 (9)0.0247 (9)0.0242 (9)−0.0053 (8)0.0018 (7)−0.0051 (8)
C230.0338 (10)0.0221 (9)0.0353 (11)−0.0001 (8)0.0055 (8)−0.0061 (8)
C240.0231 (9)0.0284 (10)0.0377 (11)0.0025 (8)0.0004 (8)−0.0014 (9)
C250.0227 (8)0.0254 (9)0.0299 (10)−0.0009 (7)−0.0034 (7)−0.0010 (8)
Geometric parameters (Å, º) top
C1—C21.417 (2)C13—C181.390 (2)
C1—N61.375 (2)C14—C151.386 (2)
C1—C251.416 (2)C14—H1410.944
C2—C31.415 (2)C15—C161.398 (3)
C2—C221.414 (3)C15—C191.507 (2)
C3—C41.358 (2)C16—C171.382 (3)
C3—H310.932C16—H1610.941
C4—C51.419 (2)C17—C181.386 (2)
C4—H410.939C17—H1710.940
C5—N61.328 (2)C18—H1810.933
C5—C71.503 (2)C19—H1910.963
C7—S81.8210 (16)C19—H1920.954
C7—H710.985C19—H1930.957
C7—H720.978C20—H2010.958
S8—C91.7679 (16)C20—H2020.951
C9—N101.352 (2)C20—H2030.963
C9—S211.6593 (17)C22—C231.368 (3)
N10—N111.3803 (19)C22—H2210.948
N10—H10.875C23—C241.400 (3)
N11—C121.287 (2)C23—H2310.945
C12—C131.489 (2)C24—C251.367 (3)
C12—C201.506 (2)C24—H2410.946
C13—C141.408 (2)C25—H2510.942
C2—C1—N6122.67 (15)C15—C14—H141119.1
C2—C1—C25118.35 (17)C14—C15—C16118.53 (16)
N6—C1—C25118.98 (15)C14—C15—C19121.25 (16)
C1—C2—C3117.26 (16)C16—C15—C19120.21 (16)
C1—C2—C22119.80 (16)C15—C16—C17120.91 (16)
C3—C2—C22122.93 (16)C15—C16—H161119.3
C2—C3—C4119.72 (16)C17—C16—H161119.8
C2—C3—H31120.6C16—C17—C18120.06 (16)
C4—C3—H31119.6C16—C17—H171120.3
C3—C4—C5119.71 (15)C18—C17—H171119.6
C3—C4—H41121.0C13—C18—C17120.55 (16)
C5—C4—H41119.2C13—C18—H181119.6
C4—C5—N6122.65 (16)C17—C18—H181119.8
C4—C5—C7120.12 (15)C15—C19—H191109.8
N6—C5—C7117.21 (14)C15—C19—H192110.7
C1—N6—C5117.97 (14)H191—C19—H192108.1
C5—C7—S8112.42 (11)C15—C19—H193110.0
C5—C7—H71109.6H191—C19—H193109.1
S8—C7—H71108.4H192—C19—H193109.0
C5—C7—H72109.1C12—C20—H201109.5
S8—C7—H72107.7C12—C20—H202110.9
H71—C7—H72109.6H201—C20—H202108.8
C7—S8—C9102.38 (8)C12—C20—H203110.5
S8—C9—N10112.31 (12)H201—C20—H203108.8
S8—C9—S21126.92 (10)H202—C20—H203108.2
N10—C9—S21120.76 (12)C2—C22—C23120.19 (17)
C9—N10—N11117.61 (13)C2—C22—H221119.3
C9—N10—H1119.6C23—C22—H221120.5
N11—N10—H1122.6C22—C23—C24120.11 (18)
N10—N11—C12119.50 (13)C22—C23—H231119.4
N11—C12—C13115.11 (14)C24—C23—H231120.5
N11—C12—C20125.40 (15)C23—C24—C25121.11 (17)
C13—C12—C20119.48 (14)C23—C24—H241119.6
C12—C13—C14120.34 (15)C25—C24—H241119.3
C12—C13—C18121.04 (15)C1—C25—C24120.43 (17)
C14—C13—C18118.60 (15)C1—C25—H251119.1
C13—C14—C15121.34 (16)C24—C25—H251120.5
C13—C14—H141119.6

Experimental details

Crystal data
Chemical formulaC20H19N3S2
Mr365.52
Crystal system, space groupTriclinic, P1
Temperature (K)150
a, b, c (Å)7.7423 (2), 8.2816 (2), 14.0409 (4)
α, β, γ (°)81.2501 (13), 80.5729 (13), 85.7886 (13)
V (Å3)876.70 (4)
Z2
Radiation typeMo Kα
µ (mm−1)0.31
Crystal size (mm)0.48 × 0.12 × 0.06
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.79, 0.98
No. of measured, independent and
observed [I > −3σ(I)] reflections		14454, 4155, 4155
Rint0.043
(sin θ/λ)max (Å−1)0.659
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.095, 0.93
No. of reflections4155
No. of parameters226
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.52, −0.45

Computer programs: COLLECT (Nonius, 2001), DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996), CRYSTALS.

Selected geometric parameters (Å, º) top
C9—N101.352 (2)N10—N111.3803 (19)
C9—S211.6593 (17)
S8—C9—S21126.92 (10)C9—N10—N11117.61 (13)
N10—C9—S21120.76 (12)
 

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