Hydrazine carbodi­thio­ic acid pyridinium-2-yl methyl ester chloride

The title compound, [C₇H₁₀N₃S₂]⁺·Cl^-, exists as an ionic compound of a di­thio­carb­aza­te system, with a zwitterionic ⁺H₃NNCS^- moiety and a protonated pyridine ring. The C-S thione bond distance of the zwitterionic moiety [1.708 (2) Å] is longer than the normal double bond and the C-N of the carb­aza­te moiety has double-bond character. The crystal packing is stabilized by intramolecular hydrogen bonds, which form a two-dimensional network perpendicular to b.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.037
• wR factor = 0.096
• Data-to-parameter ratio = 18.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Unlike many dithiocarbazate compounds such as S-methyldithiocarbazate (Mattes et al., 1980) and S-benzyldithiocarbazate (Shanmuga Sundara Raj et al., 2000) the title compound, (I), exists in ionic form, with a zwitterionic N3/N2/C7/S2 moiety, the protonated N1 as cation and a chloride anion (Fig.1). However, the organic cation maintains the preferred cis-trans configuration, where the ammonium and the pyiridiniummethylene groups lie relative to the thiono S atom across the C—N and C—S bonds, respectively. The C7—N2 bond length of 1.296 (2) Å indicates its double-bond character while C7—S2 [1.708 (2) Å] is longer than the normal C=S bond of between 1.65 and 1.68 Å for dithiocarbazate (Mattes et al., 1980; Shanmuga Sundara Raj et al., 2000; Tarafder et al., 2001) but close to the zwitterionic C—S bond length in dithiocarbamic acid [1.712 (2) Å; Yamin, et al., 2002]. Although the N2—N3 bond length of 1.437 (2) Å is within the normal range, it is longer than the normal N—N distance for a carbazate system [1.396 Å for S-benzyldithiocarbazate; Shanmuga Sundara Raj et al., 2000]. The bond lengths and angles of the picolyl group are in normal ranges (Allen et al., 1987).

All hydrogen atoms bonded to N atoms (one at N1 and three at N3) participate in hydrogen bonding (Table 2). Two of them are intramolecular (N1—H1n···N2 and N3-H3n2···S2). Intermolecular N—H···Cl hydrogen bonds connect the molecules into a two-dimensional network perpendicular to the b axis (Fig. 2).

The picolyl N1/C1/C2/C3/C4/C5/C6/C7 and zwitterionic N3/N2/S1/S2 moieties are planar, with maximum deviationa of 0.017 (2) Å at N1 and 0.034 (1) Å at S1, respectively. The two planes make a dihedral angle of 64.16 (6)°.

S2. Experimental

Potassium hydroxide (11.4 g, 0.2 mol) was completely dissolved in 70 ml of 90% ethanol and cooled in ice. To the cooled solution hydrazine hydrate (10 g, 0.2 mol) was added slowly with stirring. A solution of carbon disulfide (15.2 g, 0.2 mol) in ethanol (23 ml) was added dropwise from a burette, with constant stirring, for about 1 h. The temperature of the mixture was kept below 263 K during the addition. During this time, two layers formed. The yellow oil in the lower layer was then separated using a separation funnel, dissolved in 40% ethanol (100 ml) and cooled in ice. 2-Picolylchloride hydrochloride (32.8 g, 0.2 mol) was completely dissolved in 100 ml of 80% ethanol and added slowly to the above solution with vigorous mechanical stirring. The resulting light-green product was filtered, washed with distilled water and dried. The product was recrystallized from absolute ethanol.

S3. Refinement

The N—H distances were restrained to 0.85 (1) Å.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. ORTEPII (Johnson, 1976) view of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as circles of arbitrary radii.
	Fig. 2. Packing diagram of the title compound, viewed down the c axis. Dashed lines denote the N—H···Cl and N—H···S interactions.

Hydrazine carbodithioic acid pyridinium-2-yl methylester chloride

Crystal data

C7H10N3S2^+·Cl^−	Dx = 1.485 Mg m^−3
Mr = 235.75	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 6222 reflections
a = 16.5700 (8) Å	θ = 1.8–28.3°
c = 15.3576 (7) Å	µ = 0.72 mm^−1
V = 4216.7 (3) Å^3	T = 293 K
Z = 16	Block, yellow
F(000) = 1952	0.55 × 0.49 × 0.38 mm

Data collection

Bruker Smart APEX CCD area-detector diffractometer	2545 independent reflections
Radiation source: fine-focus sealed tube	1920 reflections with I > 2s(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 83.66 pixels mm^-1	θmax = 28.3°, θmin = 1.8°
ω scan	h = −21→21
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	k = −21→21
Tmin = 0.694, Tmax = 0.773	l = −10→19
12702 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ^2(Fo^2) + (0.0651P)^2] where P = (Fo^2 + 2Fc^2)/3
2545 reflections	(Δ/σ)max < 0.001
135 parameters	Δρmax = 0.45 e Å^−3
10 restraints	Δρmin = −0.15 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl1	0.31800 (3)	0.83881 (3)	0.18425 (3)	0.0512 (2)
S1	0.13595 (3)	0.72089 (3)	−0.05650 (3)	0.0568 (2)
S2	0.15969 (3)	0.54839 (3)	−0.03267 (3)	0.0586 (2)
N1	0.1273 (1)	0.8072 (1)	0.1543 (1)	0.0545 (4)
N2	0.2072 (1)	0.6639 (1)	0.0825 (1)	0.0486 (3)
N3	0.2360 (1)	0.5957 (1)	0.1313 (1)	0.0520 (4)
C1	0.0841 (1)	0.8243 (1)	0.2254 (1)	0.0595 (5)
C2	0.0164 (1)	0.8692 (1)	0.2182 (1)	0.0566 (5)
C3	−0.0061 (1)	0.8965 (1)	0.1373 (2)	0.0641 (5)
C4	0.0398 (1)	0.8782 (1)	0.0657 (1)	0.0583 (5)
C5	0.1086 (1)	0.8327 (1)	0.0743 (1)	0.0433 (4)
C6	0.1639 (1)	0.8125 (1)	0.0014 (1)	0.0521 (4)
C7	0.1745 (1)	0.6427 (1)	0.0094 (1)	0.0462 (4)
H1	0.1005	0.8053	0.2795	0.071*
H2	−0.0144	0.8814	0.2671	0.068*
H3	−0.0525	0.9275	0.1311	0.077*
H4	0.0242	0.8966	0.0111	0.070*
H6a	0.2181	0.8062	0.0243	0.063*
H6b	0.1646	0.8571	−0.0394	0.063*
H1n	0.170 (1)	0.781 (1)	0.159 (2)	0.082 (8)*
H3n1	0.231 (1)	0.604 (1)	0.186 (1)	0.063 (6)*
H3n2	0.210 (1)	0.555 (1)	0.108 (1)	0.051 (5)*
H3n3	0.286 (1)	0.589 (1)	0.120 (2)	0.084 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0542 (3)	0.0564 (3)	0.0432 (2)	−0.0037 (2)	−0.0015 (2)	0.0008 (2)
S1	0.0734 (3)	0.0615 (3)	0.0356 (2)	0.0058 (2)	−0.0086 (2)	−0.0047 (2)
S2	0.0671 (3)	0.0580 (3)	0.0508 (3)	−0.0042 (2)	−0.0025 (2)	−0.0122 (2)
N1	0.055 (1)	0.068 (1)	0.040 (1)	0.019 (1)	−0.002 (1)	−0.002 (1)
N2	0.055 (1)	0.053 (1)	0.039 (1)	0.002 (1)	−0.003 (1)	−0.003 (1)
N3	0.054 (1)	0.061 (1)	0.040 (1)	0.003 (1)	0.001 (1)	0.000 (1)
C1	0.071 (1)	0.068 (1)	0.039 (1)	0.011 (1)	0.003 (1)	−0.001 (1)
C2	0.053 (1)	0.061 (1)	0.057 (1)	−0.002 (1)	0.010 (1)	−0.011 (1)
C3	0.048 (1)	0.072 (1)	0.072 (1)	0.011 (1)	−0.007 (1)	−0.011 (1)
C4	0.060 (1)	0.063 (1)	0.052 (1)	0.004 (1)	−0.015 (1)	0.000 (1)
C5	0.048 (1)	0.042 (1)	0.040 (1)	−0.006 (1)	−0.004 (1)	−0.001 (1)
C6	0.062 (1)	0.053 (1)	0.041 (1)	−0.001 (1)	0.003 (1)	0.001 (1)
C7	0.047 (1)	0.055 (1)	0.037 (1)	0.000 (1)	0.004 (1)	−0.003 (1)

Geometric parameters (Å, º)

S1—C6	1.820 (2)	C5—C6	1.484 (2)
S1—C7	1.764 (2)	N1—H1n	0.83 (1)
S2—C7	1.708 (2)	N3—H3n1	0.86 (1)
N1—C5	1.337 (2)	N3—H3n2	0.88 (1)
N1—C1	1.335 (2)	N3—H3n3	0.86 (1)
N2—C7	1.296 (2)	C1—H1	0.9300
N2—N3	1.437 (2)	C2—H2	0.9300
C1—C2	1.351 (3)	C3—H3	0.9300
C2—C3	1.373 (3)	C4—H4	0.9300
C3—C4	1.371 (3)	C6—H6a	0.9700
C4—C5	1.373 (3)	C6—H6b	0.9700
C6—S1—C7	103.9 (1)	H3n1—N3—H3n2	119 (2)
C5—N1—C1	124.1 (2)	N2—N3—H3n3	109 (2)
C7—N2—N3	112.2 (2)	H3n1—N3—H3n3	108 (2)
N1—C1—C2	119.7 (2)	H3n2—N3—H3n3	107 (2)
C1—C2—C3	118.7 (2)	N1—C1—H1	120.2
C2—C3—C4	120.2 (2)	C2—C1—H1	120.2
C3—C4—C5	120.4 (2)	C1—C2—H2	120.6
N1—C5—C4	117.0 (2)	C3—C2—H2	120.6
N1—C5—C6	118.6 (2)	C4—C3—H3	119.9
C4—C5—C6	124.4 (2)	C2—C3—H3	119.9
C5—C6—S1	113.6 (1)	C3—C4—H4	119.8
N2—C7—S2	129.5 (1)	C5—C4—H4	119.8
N2—C7—S1	116.7 (1)	C5—C6—H6a	108.9
S2—C7—S1	113.8 (1)	S1—C6—H6a	108.9
C5—N1—H1n	116 (2)	C5—C6—H6b	108.9
C1—N1—H1n	120 (2)	S1—C6—H6B	108.9
N2—N3—H3n1	111 (2)	H6A—C6—H6B	107.7
N2—N3—H3n2	104 (1)
C5—N1—C1—C2	0.9 (3)	N1—C5—C6—S1	93.8 (2)
N1—C1—C2—C3	−0.2 (3)	C4—C5—C6—S1	−88.0 (2)
C1—C2—C3—C4	0.0 (3)	C7—S1—C6—C5	−81.0 (2)
C2—C3—C4—C5	−0.3 (3)	N3—N2—C7—S2	1.9 (2)
C1—N1—C5—C4	−1.1 (3)	N3—N2—C7—S1	179.5 (1)
C1—N1—C5—C6	177.2 (2)	C6—S1—C7—N2	4.3 (2)
C3—C4—C5—N1	0.8 (3)	C6—S1—C7—S2	−177.7 (1)
C3—C4—C5—C6	−177.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···N2	0.83 (1)	2.35 (2)	2.934 (2)	128 (2)
N1—H1n···Cl1	0.83 (1)	2.66 (2)	3.237 (2)	127 (2)
N1—H1n···Cl1^i	0.83 (1)	3.13 (2)	3.580 (2)	117 (2)
N3—H3n1···Cl1^i	0.86 (1)	2.35 (1)	3.162 (2)	158 (2)
N3—H3n2···S2	0.88 (1)	2.33 (2)	2.925 (2)	126 (2)
N3—H3n3···Cl1^ii	0.86 (1)	2.26 (1)	3.108 (2)	170 (2)

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1/2; (ii) −y+5/4, x+1/4, −z+1/4.