Crystal structure of 2-{[2-(3-phenyl-allyl-idene)hydrazin-1-yl]thio-carbonyl-sulfanylmeth-yl}pyridinium chloride.

In the title salt of an S-substituted di-thio-carbazate, C16H16N3S2 (+)·Cl(-), the dihedral angles between the almost planar (r.m.s deviation = 0.005 Å) central CN2S2 residue and the terminal pyridinium and phenyl rings are 80.09 (11) and 3.82 (11)°, respectively, indicating the cation has an L-shape; the amine H and thione S atoms are syn. The conformation about each of the imine [1.376 (3) Å] and ethene [1.333 (4) Å] bonds is E. The shortened C-C bond [1.444 (4) Å] linking the double bonds is consistent with conjugation in this part of the mol-ecule. In the crystal, supra-molecular layers with a jagged topology are formed by charged-assisted amine-H⋯Cl(-) and pyridinium-N(+)-H⋯Cl(-) hydrogen bonds. The layers stack along the a axis with no specific directional inter-actions between them.

Related literature

For general background to related Schiff bases formed between S-substituted di­thio­carbaza­tes and cinnamaldehyde, see: Low et al. (2013 ▶). For the biological activity of similar sulfur/nitro­gen-containing Schiff base derivatives, see: Khoo et al. (2014 ▶). For the synthetic procedure, see: Crouse et al. (2004 ▶).

Experimental

Crystal data

C16H16N3S2 +·Cl−

M = 349.89

Orthorhombic,

a = 24.2206 (8) Å

b = 8.2838 (2) Å

c = 8.3206 (4) Å

V = 1669.43 (11) Å3

Z = 4

Cu Kα radiation

μ = 4.35 mm−1

T = 150 K

0.12 × 0.05 × 0.01 mm

Data collection

Agilent Xcaliber Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.80, T max = 0.96

5463 measured reflections

2460 independent reflections

2327 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.078

S = 1.04

2460 reflections

205 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.37 e Å−3

Δρmin = −0.23 e Å−3

Absolute structure: Flack (1983 ▶), 971 Friedel pairs

Absolute structure parameter: −0.009 (16)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814023228/hb7295sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814023228/hb7295Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814023228/hb7295Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814023228/hb7295fig1.tif

The mol­ecular structure of the title compound showing displacement ellipsoids at the 50% probability level.

Click here for additional data file.

bc . DOI: 10.1107/S1600536814023228/hb7295fig2.tif

A view of the supra­molecular layer in the bc plane mediated by charge-assisted N—H⋯Cl hydrogen bonds (orange dashed lines).

CCDC reference: 1030368

Additional supporting information: crystallographic information; 3D view; checkCIF report

C16H16N3S2+·Cl−	F(000) = 728
Mr = 349.89	Dx = 1.392 Mg m−3
Orthorhombic, Pna21	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2c -2n	Cell parameters from 3280 reflections
a = 24.2206 (8) Å	θ = 4–71°
b = 8.2838 (2) Å	µ = 4.35 mm−1
c = 8.3206 (4) Å	T = 150 K
V = 1669.43 (11) Å3	Plate, yellow
Z = 4	0.12 × 0.05 × 0.01 mm

Agilent Xcaliber Eos Gemini diffractometer	2460 independent reflections
Radiation source: fine-focus sealed tube	2327 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 16.1952 pixels mm-1	θmax = 67.7°, θmin = 3.7°
ω scans	h = −29→28
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −7→9
Tmin = 0.80, Tmax = 0.96	l = −8→8
5463 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078	w = 1/[σ2(Fo2) + (0.0531P)2 + 0.1085P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
2460 reflections	Δρmax = 0.37 e Å−3
205 parameters	Δρmin = −0.23 e Å−3
3 restraints	Absolute structure: Flack (1983), 971 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.009 (16)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cl1	0.63222 (3)	−0.05537 (7)	0.96332 (11)	0.03476 (18)
S1	0.69437 (3)	−0.37225 (7)	0.32589 (10)	0.02657 (17)
S2	0.71117 (3)	−0.11756 (6)	0.58644 (10)	0.02635 (17)
N1	0.65178 (9)	−0.0817 (2)	0.3311 (4)	0.0252 (5)
H1N	0.6375 (13)	−0.098 (4)	0.235 (2)	0.030*
N2	0.64340 (9)	0.0675 (2)	0.3995 (3)	0.0259 (5)
N3	0.67390 (9)	−0.3736 (2)	0.8473 (3)	0.0268 (5)
H3N	0.6674 (12)	−0.2714 (16)	0.869 (4)	0.032*
C1	0.68354 (9)	−0.1909 (3)	0.4053 (4)	0.0238 (6)
C2	0.74713 (11)	−0.2944 (3)	0.6613 (4)	0.0297 (7)
H2A	0.7679	−0.3442	0.5717	0.036*
H2B	0.7742	−0.2598	0.7434	0.036*
C3	0.70984 (10)	−0.4195 (3)	0.7339 (4)	0.0264 (6)
C4	0.64075 (12)	−0.4762 (3)	0.9260 (4)	0.0306 (7)
H4	0.6164	−0.4375	1.0068	0.037*
C5	0.64217 (12)	−0.6385 (3)	0.8889 (4)	0.0339 (7)
H5	0.6189	−0.7130	0.9432	0.041*
C6	0.67820 (12)	−0.6902 (3)	0.7709 (4)	0.0327 (7)
H6	0.6798	−0.8014	0.7435	0.039*
C7	0.71189 (12)	−0.5813 (3)	0.6926 (4)	0.0301 (7)
H7	0.7364	−0.6171	0.6108	0.036*
C8	0.60714 (9)	0.1556 (3)	0.3289 (4)	0.0241 (6)
H8	0.5884	0.1164	0.2365	0.029*
C9	0.59502 (10)	0.3146 (3)	0.3905 (4)	0.0257 (6)
H9	0.6141	0.3502	0.4837	0.031*
C10	0.55839 (10)	0.4140 (3)	0.3235 (4)	0.0272 (6)
H10	0.5403	0.3757	0.2297	0.033*
C11	0.54303 (10)	0.5752 (3)	0.3785 (4)	0.0276 (7)
C12	0.56395 (11)	0.6430 (3)	0.5201 (4)	0.0287 (7)
H12	0.5893	0.5831	0.5834	0.034*
C13	0.54828 (11)	0.7955 (3)	0.5692 (5)	0.0346 (7)
H13	0.5632	0.8404	0.6648	0.042*
C14	0.51043 (12)	0.8835 (3)	0.4779 (5)	0.0381 (8)
H14	0.4990	0.9877	0.5123	0.046*
C15	0.48967 (11)	0.8192 (3)	0.3381 (5)	0.0376 (8)
H15	0.4641	0.8793	0.2755	0.045*
C16	0.50597 (11)	0.6662 (4)	0.2882 (5)	0.0365 (8)
H16	0.4916	0.6231	0.1910	0.044*

	U11	U22	U33	U12	U13	U23
Cl1	0.0546 (4)	0.0238 (3)	0.0258 (4)	0.0111 (3)	0.0018 (4)	0.0001 (3)
S1	0.0320 (3)	0.0197 (3)	0.0279 (4)	0.0013 (2)	0.0003 (3)	−0.0026 (3)
S2	0.0362 (3)	0.0192 (3)	0.0237 (4)	0.0015 (2)	−0.0028 (3)	−0.0013 (3)
N1	0.0312 (10)	0.0209 (10)	0.0235 (15)	0.0022 (8)	0.0006 (12)	−0.0007 (10)
N2	0.0335 (11)	0.0199 (10)	0.0244 (15)	0.0009 (8)	0.0008 (11)	−0.0005 (9)
N3	0.0347 (10)	0.0189 (9)	0.0268 (16)	0.0051 (8)	−0.0042 (12)	−0.0023 (10)
C1	0.0244 (11)	0.0221 (11)	0.0250 (18)	−0.0015 (9)	0.0025 (12)	0.0017 (11)
C2	0.0318 (13)	0.0256 (13)	0.0316 (19)	0.0058 (10)	−0.0097 (14)	0.0018 (13)
C3	0.0304 (13)	0.0244 (12)	0.0244 (19)	0.0081 (10)	−0.0126 (13)	0.0018 (11)
C4	0.0357 (13)	0.0283 (12)	0.028 (2)	0.0021 (10)	−0.0020 (14)	0.0028 (12)
C5	0.0392 (14)	0.0296 (13)	0.033 (2)	−0.0011 (11)	−0.0098 (15)	0.0069 (13)
C6	0.0476 (15)	0.0196 (12)	0.031 (2)	0.0055 (11)	−0.0154 (16)	−0.0036 (11)
C7	0.0373 (14)	0.0263 (13)	0.027 (2)	0.0100 (10)	−0.0094 (14)	−0.0034 (12)
C8	0.0251 (10)	0.0237 (11)	0.0236 (16)	−0.0030 (9)	−0.0008 (14)	0.0022 (12)
C9	0.0282 (11)	0.0241 (12)	0.0247 (17)	−0.0007 (10)	0.0026 (13)	0.0017 (11)
C10	0.0261 (11)	0.0264 (12)	0.0291 (18)	−0.0005 (9)	−0.0006 (14)	−0.0011 (13)
C11	0.0240 (11)	0.0227 (12)	0.036 (2)	−0.0019 (9)	0.0002 (13)	0.0032 (11)
C12	0.0269 (12)	0.0258 (12)	0.033 (2)	0.0008 (10)	0.0037 (13)	0.0015 (12)
C13	0.0347 (13)	0.0286 (13)	0.041 (2)	−0.0020 (10)	0.0072 (16)	−0.0055 (14)
C14	0.0352 (14)	0.0214 (12)	0.058 (3)	0.0018 (10)	0.0138 (17)	−0.0036 (14)
C15	0.0345 (13)	0.0272 (13)	0.051 (2)	0.0053 (10)	0.0036 (16)	0.0082 (15)
C16	0.0339 (13)	0.0346 (15)	0.041 (2)	0.0037 (11)	−0.0025 (15)	0.0019 (13)

S1—C1	1.662 (3)	C6—H6	0.9500
S2—C1	1.757 (3)	C7—H7	0.9500
S2—C2	1.815 (3)	C8—C9	1.444 (4)
N1—C1	1.339 (3)	C8—H8	0.9500
N1—N2	1.376 (3)	C9—C10	1.333 (4)
N1—H1N	0.880 (10)	C9—H9	0.9500
N2—C8	1.284 (4)	C10—C11	1.460 (3)
N3—C3	1.339 (4)	C10—H10	0.9500
N3—C4	1.340 (4)	C11—C16	1.392 (4)
N3—H3N	0.880 (10)	C11—C12	1.400 (4)
C2—C3	1.502 (4)	C12—C13	1.381 (4)
C2—H2A	0.9900	C12—H12	0.9500
C2—H2B	0.9900	C13—C14	1.396 (5)
C3—C7	1.384 (4)	C13—H13	0.9500
C4—C5	1.380 (4)	C14—C15	1.375 (5)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.381 (4)	C15—C16	1.391 (4)
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.380 (4)	C16—H16	0.9500
C1—S2—C2	101.42 (13)	C6—C7—H7	120.2
C1—N1—N2	120.1 (3)	C3—C7—H7	120.2
C1—N1—H1N	123 (2)	N2—C8—C9	119.7 (3)
N2—N1—H1N	117 (2)	N2—C8—H8	120.2
C8—N2—N1	114.9 (3)	C9—C8—H8	120.2
C3—N3—C4	123.6 (2)	C10—C9—C8	123.4 (3)
C3—N3—H3N	122 (2)	C10—C9—H9	118.3
C4—N3—H3N	114 (2)	C8—C9—H9	118.3
N1—C1—S1	121.2 (2)	C9—C10—C11	127.1 (3)
N1—C1—S2	112.4 (2)	C9—C10—H10	116.4
S1—C1—S2	126.41 (16)	C11—C10—H10	116.4
C3—C2—S2	113.99 (18)	C16—C11—C12	118.1 (3)
C3—C2—H2A	108.8	C16—C11—C10	119.4 (3)
S2—C2—H2A	108.8	C12—C11—C10	122.6 (3)
C3—C2—H2B	108.8	C13—C12—C11	121.1 (3)
S2—C2—H2B	108.8	C13—C12—H12	119.5
H2A—C2—H2B	107.6	C11—C12—H12	119.5
N3—C3—C7	118.3 (3)	C12—C13—C14	119.8 (3)
N3—C3—C2	118.5 (2)	C12—C13—H13	120.1
C7—C3—C2	123.2 (3)	C14—C13—H13	120.1
N3—C4—C5	119.6 (3)	C15—C14—C13	119.9 (2)
N3—C4—H4	120.2	C15—C14—H14	120.1
C5—C4—H4	120.2	C13—C14—H14	120.1
C4—C5—C6	118.5 (3)	C14—C15—C16	120.1 (3)
C4—C5—H5	120.8	C14—C15—H15	119.9
C6—C5—H5	120.8	C16—C15—H15	119.9
C7—C6—C5	120.4 (3)	C15—C16—C11	121.0 (3)
C7—C6—H6	119.8	C15—C16—H16	119.5
C5—C6—H6	119.8	C11—C16—H16	119.5
C6—C7—C3	119.6 (3)
C1—N1—N2—C8	−171.9 (2)	C2—C3—C7—C6	176.6 (3)
N2—N1—C1—S1	179.90 (19)	N1—N2—C8—C9	180.0 (2)
N2—N1—C1—S2	−1.0 (3)	N2—C8—C9—C10	179.4 (3)
C2—S2—C1—N1	176.37 (19)	C8—C9—C10—C11	179.2 (3)
C2—S2—C1—S1	−4.5 (2)	C9—C10—C11—C16	176.5 (3)
C1—S2—C2—C3	−76.9 (2)	C9—C10—C11—C12	−3.8 (5)
C4—N3—C3—C7	1.7 (4)	C16—C11—C12—C13	0.1 (4)
C4—N3—C3—C2	−176.4 (3)	C10—C11—C12—C13	−179.6 (3)
S2—C2—C3—N3	−52.0 (3)	C11—C12—C13—C14	0.8 (4)
S2—C2—C3—C7	129.9 (3)	C12—C13—C14—C15	−1.1 (5)
C3—N3—C4—C5	−1.1 (4)	C13—C14—C15—C16	0.5 (5)
N3—C4—C5—C6	0.1 (4)	C14—C15—C16—C11	0.5 (5)
C4—C5—C6—C7	0.1 (4)	C12—C11—C16—C15	−0.8 (4)
C5—C6—C7—C3	0.6 (4)	C10—C11—C16—C15	178.9 (3)
N3—C3—C7—C6	−1.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1i	0.88 (2)	2.29 (2)	3.104 (3)	153 (3)
N3—H3N···Cl1	0.88 (2)	2.13 (2)	2.9833 (19)	163 (3)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1NCl1i	0.88(2)	2.29(2)	3.104(3)	153(3)
N3H3NCl1	0.88(2)	2.13(2)	2.9833(19)	163(3)

Symmetry code: (i) .