Benzyl N′-[1-(3-pyrid­yl)ethyl­idene]­hydrazinecarbodithio­ate

The title compound, C₁₅H₅N₂S₂, crystallizes as a trans–cis 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.

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

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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

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S1. Comment

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

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).

S2. Experimental

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%

S3. Refinement

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 U_iso(H) (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints.

Computing details

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

	Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius.
	Fig. 2. A packing diagram of the molecules viewed along the b axis.
	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

Crystal data

C15H15N3S2	F(000) = 632
Mr = 301.44	Dx = 1.347 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3554 reflections
a = 11.7234 (2) Å	θ = 5–28°
b = 13.5577 (2) Å	µ = 0.35 mm^−1
c = 9.3637 (1) Å	T = 150 K
β = 93.2187 (7)°	Block, yellow
V = 1485.94 (4) Å^3	0.50 × 0.48 × 0.42 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3512 reflections with I > −3σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 27.9°, θmin = 5.3°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −15→15
Tmin = 0.58, Tmax = 0.86	k = −17→16
18346 measured reflections	l = −12→12
3512 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.074	Method = Modified Sheldrick w = 1/[σ^2(F^2) + ( 0.02P)^2 + 0.86P] , where P = (max(Fo^2,0) + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
3512 reflections	Δρmax = 0.30 e Å^−3
181 parameters	Δρmin = −0.26 e Å^−3
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.78782 (10)	0.50631 (9)	0.44621 (12)	0.0204
S2	0.75601 (3)	0.62579 (2)	0.38062 (3)	0.0260
C3	0.63081 (12)	0.65609 (10)	0.47897 (15)	0.0299
C4	0.57579 (10)	0.74496 (9)	0.40744 (13)	0.0245
C5	0.49029 (11)	0.73279 (10)	0.29964 (14)	0.0279
C6	0.43974 (11)	0.81421 (11)	0.23204 (14)	0.0303
C7	0.47496 (11)	0.90850 (10)	0.27085 (15)	0.0302
C8	0.56030 (12)	0.92152 (10)	0.37744 (15)	0.0309
C9	0.60965 (11)	0.83996 (10)	0.44638 (15)	0.0288
N10	0.88055 (9)	0.46646 (7)	0.38812 (11)	0.0219
N11	0.93938 (9)	0.52578 (7)	0.29861 (11)	0.0215
C12	1.02748 (10)	0.49194 (8)	0.23857 (12)	0.0197
C13	1.08339 (10)	0.56350 (8)	0.14515 (12)	0.0192
C14	1.06341 (11)	0.66496 (9)	0.15753 (13)	0.0248
N15	1.11066 (10)	0.73385 (8)	0.07742 (12)	0.0277
C16	1.18224 (11)	0.70228 (9)	−0.02079 (14)	0.0263
C17	1.20734 (11)	0.60399 (10)	−0.04110 (14)	0.0267
C18	1.15730 (10)	0.53334 (9)	0.04278 (14)	0.0238
C19	1.07337 (11)	0.38876 (9)	0.25203 (14)	0.0247
S20	0.71415 (3)	0.44675 (2)	0.56445 (3)	0.0232
H31	0.6542	0.6703	0.5772	0.0370*
H32	0.5808	0.5988	0.4735	0.0362*
H51	0.4672	0.6679	0.2716	0.0337*
H61	0.3812	0.8048	0.1577	0.0372*
H71	0.4403	0.9651	0.2234	0.0369*
H81	0.5850	0.9864	0.4052	0.0372*
H91	0.6661	0.8487	0.5191	0.0358*
H141	1.0131	0.6874	0.2285	0.0300*
H161	1.2152	0.7523	−0.0771	0.0315*
H171	1.2586	0.5850	−0.1096	0.0330*
H181	1.1733	0.4650	0.0300	0.0286*
H191	1.1552	0.3882	0.2461	0.0373*
H192	1.0426	0.3489	0.1756	0.0393*
H193	1.0549	0.3586	0.3418	0.0371*
H1	0.8966	0.4043	0.4024	0.0281*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0209 (5)	0.0197 (5)	0.0207 (5)	−0.0008 (4)	0.0013 (4)	−0.0012 (4)
S2	0.02711 (16)	0.02204 (16)	0.02971 (17)	0.00520 (11)	0.01023 (12)	0.00635 (11)
C3	0.0302 (6)	0.0279 (6)	0.0329 (7)	0.0080 (5)	0.0126 (5)	0.0075 (5)
C4	0.0229 (6)	0.0236 (6)	0.0278 (6)	0.0039 (5)	0.0103 (5)	0.0036 (5)
C5	0.0277 (6)	0.0248 (6)	0.0320 (6)	−0.0023 (5)	0.0085 (5)	−0.0010 (5)
C6	0.0239 (6)	0.0373 (7)	0.0299 (6)	0.0010 (5)	0.0036 (5)	0.0034 (6)
C7	0.0273 (6)	0.0287 (7)	0.0357 (7)	0.0076 (5)	0.0105 (5)	0.0076 (5)
C8	0.0333 (7)	0.0213 (6)	0.0390 (7)	0.0005 (5)	0.0089 (6)	−0.0007 (5)
C9	0.0264 (6)	0.0293 (7)	0.0309 (6)	0.0003 (5)	0.0023 (5)	0.0002 (5)
N10	0.0242 (5)	0.0179 (5)	0.0242 (5)	0.0007 (4)	0.0064 (4)	0.0018 (4)
N11	0.0229 (5)	0.0198 (5)	0.0221 (5)	−0.0012 (4)	0.0047 (4)	0.0011 (4)
C12	0.0206 (5)	0.0171 (5)	0.0213 (5)	−0.0004 (4)	0.0014 (4)	−0.0014 (4)
C13	0.0186 (5)	0.0180 (5)	0.0211 (5)	−0.0004 (4)	0.0005 (4)	−0.0010 (4)
C14	0.0300 (6)	0.0183 (5)	0.0268 (6)	0.0008 (5)	0.0085 (5)	−0.0018 (4)
N15	0.0345 (6)	0.0190 (5)	0.0302 (6)	−0.0018 (4)	0.0081 (5)	−0.0001 (4)
C16	0.0283 (6)	0.0240 (6)	0.0268 (6)	−0.0050 (5)	0.0051 (5)	0.0017 (5)
C17	0.0246 (6)	0.0275 (6)	0.0289 (6)	−0.0006 (5)	0.0093 (5)	−0.0011 (5)
C18	0.0230 (6)	0.0196 (5)	0.0291 (6)	0.0018 (4)	0.0052 (5)	−0.0013 (5)
C19	0.0251 (6)	0.0173 (5)	0.0322 (6)	0.0012 (4)	0.0052 (5)	0.0008 (5)
S20	0.02532 (16)	0.02044 (15)	0.02438 (15)	−0.00051 (11)	0.00682 (11)	0.00225 (11)

Geometric parameters (Å, º)

C1—S2	1.7647 (12)	N10—N11	1.3747 (13)
C1—N10	1.3550 (15)	N10—H1	0.872
C1—S20	1.6526 (12)	N11—C12	1.2879 (15)
S2—C3	1.8229 (13)	C12—C13	1.4834 (16)
C3—C4	1.5059 (17)	C12—C19	1.5014 (16)
C3—H31	0.965	C13—C14	1.4013 (16)
C3—H32	0.973	C13—C18	1.3892 (16)
C4—C5	1.3919 (19)	C14—N15	1.3374 (16)
C4—C9	1.3904 (18)	C14—H141	0.962
C5—C6	1.3886 (19)	N15—C16	1.3490 (16)
C5—H51	0.953	C16—C17	1.3802 (18)
C6—C7	1.386 (2)	C16—H161	0.954
C6—H61	0.958	C17—C18	1.3893 (17)
C7—C8	1.384 (2)	C17—H171	0.939
C7—H71	0.964	C18—H181	0.955
C8—C9	1.3900 (19)	C19—H191	0.964
C8—H81	0.957	C19—H192	0.951
C9—H91	0.930	C19—H193	0.970
S2—C1—N10	112.64 (8)	C1—N10—H1	119.7
S2—C1—S20	124.99 (7)	N11—N10—H1	123.2
N10—C1—S20	122.37 (9)	N10—N11—C12	119.99 (10)
C1—S2—C3	101.04 (6)	N11—C12—C13	114.59 (10)
S2—C3—C4	107.01 (8)	N11—C12—C19	125.99 (11)
S2—C3—H31	109.4	C13—C12—C19	119.39 (10)
C4—C3—H31	110.9	C12—C13—C14	120.78 (10)
S2—C3—H32	107.0	C12—C13—C18	121.86 (10)
C4—C3—H32	112.0	C14—C13—C18	117.36 (11)
H31—C3—H32	110.4	C13—C14—N15	124.25 (11)
C3—C4—C5	120.05 (12)	C13—C14—H141	118.6
C3—C4—C9	121.04 (12)	N15—C14—H141	117.1
C5—C4—C9	118.91 (12)	C14—N15—C16	116.99 (11)
C4—C5—C6	120.52 (12)	N15—C16—C17	123.09 (11)
C4—C5—H51	119.4	N15—C16—H161	116.0
C6—C5—H51	120.1	C17—C16—H161	121.0
C5—C6—C7	120.05 (12)	C16—C17—C18	119.19 (11)
C5—C6—H61	119.7	C16—C17—H171	120.6
C7—C6—H61	120.3	C18—C17—H171	120.2
C6—C7—C8	119.96 (12)	C17—C18—C13	119.13 (11)
C6—C7—H71	120.1	C17—C18—H181	120.4
C8—C7—H71	119.9	C13—C18—H181	120.4
C7—C8—C9	119.91 (13)	C12—C19—H191	110.9
C7—C8—H81	120.5	C12—C19—H192	110.3
C9—C8—H81	119.6	H191—C19—H192	106.8
C4—C9—C8	120.65 (12)	C12—C19—H193	111.6
C4—C9—H91	119.4	H191—C19—H193	108.5
C8—C9—H91	120.0	H192—C19—H193	108.6
C1—N10—N11	116.92 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H1···N15^i	0.87	2.32	3.171 (2)	165

Symmetry code: (i) −x+2, y−1/2, −z+1/2.