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The title compound, C15H5N2S2, crystallizes as a transcis conformer. The thione sulfur is in a trans position with the methyl pyridyl fragment with respect to the C—N bond but adopts a cis position with the benzyl ring across the C—S bond. The dihedral angle between the planar quinoline ring and the dithio­carbazate unit is 103.70 (1)°. The inclination of the dithio­carbazate unit with the benzyl group is 17.20 (1)°. There are strong π–π stacking inter­actions between pairs of dithio­carbazate units and also pairs of pyridine rings [3.27 (5) and 3.28 (5) Å, respectively]. A long-distance inter­molecular N—H...N hydrogen bond [3.171 (2) Å] also stabilizes the structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025056/pk2024sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025056/pk2024Isup2.hkl
Contains datablock I

CCDC reference: 651517

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.034
  • wR factor = 0.074
  • Data-to-parameter ratio = 19.4

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT940_ALERT_3_A F   2 Refinement with I .GT. n * Sigma(I) only .. ?
Author Response: This "A" alert is generated by an omission in PLATON, which currently fails to identify a negative I/sigma(I) threshold. This is because the data-item is held as a text string, not a numeric value. Prof Ton SpeK has been informed about this problem, and will fix it in the next release of PLATON.

Alert level B ABSTM02_ALERT_3_B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.580 0.860 Tmin(prime) and Tmax expected: 0.835 0.863 RR(prime) = 0.697 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ............. 0.69
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for S20 - C1 .. 6.34 su
1 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 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 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Many Schiff bases and metal complexes have been derived from S-benzyldithiocarbazate (SBDTC) because these compounds are often biologically active. [Ali et al., 2005, Tarafder et al., 2002 and Ali et al., 2002]. Our attempt to synthesize Schiff bases with different pyridyl isomers led to the title compound [Fig. 1].

The C1—N10 bond [1.3549 (15) Å] is comparable with the literature value and shows some 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 1.6526 (12) Å, 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 bond angle N11—N10—C1 [116.92 (10)°] is slightly smaller than in Schiff bases derived from S-benzyldithiocarbazate [119.20 (14)°; Chan et al., 2003] and [119.35 (17)°; Khoo et al., 2005], but comparable with Schiff base derived from S-quinolin-2-ylmethyldithiocarbazate [117.61 (13)°; How et al., 2007]. Bond angle of S20—C1—S2 [124.99 (7)°] is comparable with other literature values. [125.60 (10)°; Chan et al., 2003] and [125.22 (12)°; Khoo et al., 2005].

Viewed along the b axis [Fig. 2], the molecules form columnar stacks with overlapping benzyl fragments and overlapping π-π stacked pyridine [mean separation of 3.28 (5) Å] and dithiocarabazate [mean separation of 3.27 (5) Å] groups. There is also a long N—H···N [3.171 (2) Å] hydrogen bond [Fig 3.]

Related literature top

The dithiocarbazate ligand, S-benzyldithiocarbazate (SBDTC), was prepared as described by Shanmuga Sundara Raj et al. (2000). Interatomic parameters for the crystal structure are comparable with those reported by Chan et al. (2003), Khoo et al. (2005) and How et al. (2007). For related literature, see: Ali et al. (2002, 2005); Görbitz (1999); Tarafder et al. (2002).

Experimental top

S-benzyldithiocarbazate(SBDTC) (1.98 g, 0.01 mol), prepared as previously described (Shanmuga Sundara Raj et al., 2000), was dissolved in hot absolute ethanol (35 ml). Equimolar amount of 3-acetylpyridine was added dropwise into the dissolved SBDTC (in ethanol). The mixture was left heated with stirring to reduce to half the volume and allowed to stand until precipitates formed. Products were filtered, washed with ethanol and dried in vacuo over P2O5. Crystals suitable for X-ray analysis were obtained by upon slow evaporation of ethanol. Yield: 72.6%

Refinement top

The relatively large ratio of minimum to maximum corrections applied in the multiscan process (1:1.48) reflect effects in addition to absorption, and were taken into account (Görbitz, 1999) by the multi-scan inter-frame scaling (DENZO/SCALEPACK, Otwinowski & Minor, 1997).

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 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.

Structure description top

Many Schiff bases and metal complexes have been derived from S-benzyldithiocarbazate (SBDTC) because these compounds are often biologically active. [Ali et al., 2005, Tarafder et al., 2002 and Ali et al., 2002]. Our attempt to synthesize Schiff bases with different pyridyl isomers led to the title compound [Fig. 1].

The C1—N10 bond [1.3549 (15) Å] is comparable with the literature value and shows some 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 1.6526 (12) Å, 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 bond angle N11—N10—C1 [116.92 (10)°] is slightly smaller than in Schiff bases derived from S-benzyldithiocarbazate [119.20 (14)°; Chan et al., 2003] and [119.35 (17)°; Khoo et al., 2005], but comparable with Schiff base derived from S-quinolin-2-ylmethyldithiocarbazate [117.61 (13)°; How et al., 2007]. Bond angle of S20—C1—S2 [124.99 (7)°] is comparable with other literature values. [125.60 (10)°; Chan et al., 2003] and [125.22 (12)°; Khoo et al., 2005].

Viewed along the b axis [Fig. 2], the molecules form columnar stacks with overlapping benzyl fragments and overlapping π-π stacked pyridine [mean separation of 3.28 (5) Å] and dithiocarabazate [mean separation of 3.27 (5) Å] groups. There is also a long N—H···N [3.171 (2) Å] hydrogen bond [Fig 3.]

The dithiocarbazate ligand, S-benzyldithiocarbazate (SBDTC), was prepared as described by Shanmuga Sundara Raj et al. (2000). Interatomic parameters for the crystal structure are comparable with those reported by Chan et al. (2003), Khoo et al. (2005) and How et al. (2007). For related literature, see: Ali et al. (2002, 2005); Görbitz (1999); Tarafder et al. (2002).

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. A packing diagram of the molecules viewed along the b axis.
[Figure 3] Fig. 3. Weak intermolecular N10—H1···N15 hydrogen bond stabilize the molecules, while pairs of dithiocarbazate moieties overlap each other.
Benzyl N'-[1-(3-pyridyl)ethylidene]hydrazinecarbodithioate top
Crystal data top
C15H15N3S2F(000) = 632
Mr = 301.44Dx = 1.347 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3554 reflections
a = 11.7234 (2) Åθ = 5–28°
b = 13.5577 (2) ŵ = 0.35 mm1
c = 9.3637 (1) ÅT = 150 K
β = 93.2187 (7)°Block, yellow
V = 1485.94 (4) Å30.50 × 0.48 × 0.42 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
3512 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.023
ω scansθmax = 27.9°, θmin = 5.3°
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
h = 1515
Tmin = 0.58, Tmax = 0.86k = 1716
18346 measured reflectionsl = 1212
3512 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)] = 0.034H-atom parameters constrained
wR(F2) = 0.074 Method = Modified Sheldrick w = 1/[σ2(F2) + ( 0.02P)2 + 0.86P] ,
where P = (max(Fo2,0) + 2Fc2)/3
S = 0.98(Δ/σ)max = 0.001
3512 reflectionsΔρmax = 0.30 e Å3
181 parametersΔρmin = 0.26 e Å3
0 restraints
Crystal data top
C15H15N3S2V = 1485.94 (4) Å3
Mr = 301.44Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.7234 (2) ŵ = 0.35 mm1
b = 13.5577 (2) ÅT = 150 K
c = 9.3637 (1) Å0.50 × 0.48 × 0.42 mm
β = 93.2187 (7)°
Data collection top
Nonius KappaCCD
diffractometer
3512 independent reflections
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
3512 reflections with I > 3σ(I)
Tmin = 0.58, Tmax = 0.86Rint = 0.023
18346 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.074H-atom parameters constrained
S = 0.98Δρmax = 0.30 e Å3
3512 reflectionsΔρmin = 0.26 e Å3
181 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.78782 (10)0.50631 (9)0.44621 (12)0.0204
S20.75601 (3)0.62579 (2)0.38062 (3)0.0260
C30.63081 (12)0.65609 (10)0.47897 (15)0.0299
C40.57579 (10)0.74496 (9)0.40744 (13)0.0245
C50.49029 (11)0.73279 (10)0.29964 (14)0.0279
C60.43974 (11)0.81421 (11)0.23204 (14)0.0303
C70.47496 (11)0.90850 (10)0.27085 (15)0.0302
C80.56030 (12)0.92152 (10)0.37744 (15)0.0309
C90.60965 (11)0.83996 (10)0.44638 (15)0.0288
N100.88055 (9)0.46646 (7)0.38812 (11)0.0219
N110.93938 (9)0.52578 (7)0.29861 (11)0.0215
C121.02748 (10)0.49194 (8)0.23857 (12)0.0197
C131.08339 (10)0.56350 (8)0.14515 (12)0.0192
C141.06341 (11)0.66496 (9)0.15753 (13)0.0248
N151.11066 (10)0.73385 (8)0.07742 (12)0.0277
C161.18224 (11)0.70228 (9)0.02079 (14)0.0263
C171.20734 (11)0.60399 (10)0.04110 (14)0.0267
C181.15730 (10)0.53334 (9)0.04278 (14)0.0238
C191.07337 (11)0.38876 (9)0.25203 (14)0.0247
S200.71415 (3)0.44675 (2)0.56445 (3)0.0232
H310.65420.67030.57720.0370*
H320.58080.59880.47350.0362*
H510.46720.66790.27160.0337*
H610.38120.80480.15770.0372*
H710.44030.96510.22340.0369*
H810.58500.98640.40520.0372*
H910.66610.84870.51910.0358*
H1411.01310.68740.22850.0300*
H1611.21520.75230.07710.0315*
H1711.25860.58500.10960.0330*
H1811.17330.46500.03000.0286*
H1911.15520.38820.24610.0373*
H1921.04260.34890.17560.0393*
H1931.05490.35860.34180.0371*
H10.89660.40430.40240.0281*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0209 (5)0.0197 (5)0.0207 (5)0.0008 (4)0.0013 (4)0.0012 (4)
S20.02711 (16)0.02204 (16)0.02971 (17)0.00520 (11)0.01023 (12)0.00635 (11)
C30.0302 (6)0.0279 (6)0.0329 (7)0.0080 (5)0.0126 (5)0.0075 (5)
C40.0229 (6)0.0236 (6)0.0278 (6)0.0039 (5)0.0103 (5)0.0036 (5)
C50.0277 (6)0.0248 (6)0.0320 (6)0.0023 (5)0.0085 (5)0.0010 (5)
C60.0239 (6)0.0373 (7)0.0299 (6)0.0010 (5)0.0036 (5)0.0034 (6)
C70.0273 (6)0.0287 (7)0.0357 (7)0.0076 (5)0.0105 (5)0.0076 (5)
C80.0333 (7)0.0213 (6)0.0390 (7)0.0005 (5)0.0089 (6)0.0007 (5)
C90.0264 (6)0.0293 (7)0.0309 (6)0.0003 (5)0.0023 (5)0.0002 (5)
N100.0242 (5)0.0179 (5)0.0242 (5)0.0007 (4)0.0064 (4)0.0018 (4)
N110.0229 (5)0.0198 (5)0.0221 (5)0.0012 (4)0.0047 (4)0.0011 (4)
C120.0206 (5)0.0171 (5)0.0213 (5)0.0004 (4)0.0014 (4)0.0014 (4)
C130.0186 (5)0.0180 (5)0.0211 (5)0.0004 (4)0.0005 (4)0.0010 (4)
C140.0300 (6)0.0183 (5)0.0268 (6)0.0008 (5)0.0085 (5)0.0018 (4)
N150.0345 (6)0.0190 (5)0.0302 (6)0.0018 (4)0.0081 (5)0.0001 (4)
C160.0283 (6)0.0240 (6)0.0268 (6)0.0050 (5)0.0051 (5)0.0017 (5)
C170.0246 (6)0.0275 (6)0.0289 (6)0.0006 (5)0.0093 (5)0.0011 (5)
C180.0230 (6)0.0196 (5)0.0291 (6)0.0018 (4)0.0052 (5)0.0013 (5)
C190.0251 (6)0.0173 (5)0.0322 (6)0.0012 (4)0.0052 (5)0.0008 (5)
S200.02532 (16)0.02044 (15)0.02438 (15)0.00051 (11)0.00682 (11)0.00225 (11)
Geometric parameters (Å, º) top
C1—S21.7647 (12)N10—N111.3747 (13)
C1—N101.3550 (15)N10—H10.872
C1—S201.6526 (12)N11—C121.2879 (15)
S2—C31.8229 (13)C12—C131.4834 (16)
C3—C41.5059 (17)C12—C191.5014 (16)
C3—H310.965C13—C141.4013 (16)
C3—H320.973C13—C181.3892 (16)
C4—C51.3919 (19)C14—N151.3374 (16)
C4—C91.3904 (18)C14—H1410.962
C5—C61.3886 (19)N15—C161.3490 (16)
C5—H510.953C16—C171.3802 (18)
C6—C71.386 (2)C16—H1610.954
C6—H610.958C17—C181.3893 (17)
C7—C81.384 (2)C17—H1710.939
C7—H710.964C18—H1810.955
C8—C91.3900 (19)C19—H1910.964
C8—H810.957C19—H1920.951
C9—H910.930C19—H1930.970
S2—C1—N10112.64 (8)C1—N10—H1119.7
S2—C1—S20124.99 (7)N11—N10—H1123.2
N10—C1—S20122.37 (9)N10—N11—C12119.99 (10)
C1—S2—C3101.04 (6)N11—C12—C13114.59 (10)
S2—C3—C4107.01 (8)N11—C12—C19125.99 (11)
S2—C3—H31109.4C13—C12—C19119.39 (10)
C4—C3—H31110.9C12—C13—C14120.78 (10)
S2—C3—H32107.0C12—C13—C18121.86 (10)
C4—C3—H32112.0C14—C13—C18117.36 (11)
H31—C3—H32110.4C13—C14—N15124.25 (11)
C3—C4—C5120.05 (12)C13—C14—H141118.6
C3—C4—C9121.04 (12)N15—C14—H141117.1
C5—C4—C9118.91 (12)C14—N15—C16116.99 (11)
C4—C5—C6120.52 (12)N15—C16—C17123.09 (11)
C4—C5—H51119.4N15—C16—H161116.0
C6—C5—H51120.1C17—C16—H161121.0
C5—C6—C7120.05 (12)C16—C17—C18119.19 (11)
C5—C6—H61119.7C16—C17—H171120.6
C7—C6—H61120.3C18—C17—H171120.2
C6—C7—C8119.96 (12)C17—C18—C13119.13 (11)
C6—C7—H71120.1C17—C18—H181120.4
C8—C7—H71119.9C13—C18—H181120.4
C7—C8—C9119.91 (13)C12—C19—H191110.9
C7—C8—H81120.5C12—C19—H192110.3
C9—C8—H81119.6H191—C19—H192106.8
C4—C9—C8120.65 (12)C12—C19—H193111.6
C4—C9—H91119.4H191—C19—H193108.5
C8—C9—H91120.0H192—C19—H193108.6
C1—N10—N11116.92 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N10—H1···N15i0.872.323.171 (2)165
Symmetry code: (i) x+2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC15H15N3S2
Mr301.44
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)11.7234 (2), 13.5577 (2), 9.3637 (1)
β (°) 93.2187 (7)
V3)1485.94 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.35
Crystal size (mm)0.50 × 0.48 × 0.42
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.58, 0.86
No. of measured, independent and
observed [I > 3σ(I)] reflections
18346, 3512, 3512
Rint0.023
(sin θ/λ)max1)0.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.074, 0.98
No. of reflections3512
No. of parameters181
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.26

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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N10—H1···N15i0.872.323.171 (2)165
Symmetry code: (i) x+2, y1/2, z+1/2.
 

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