Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300014X/cv6161sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680300014X/cv6161Isup2.hkl |
CCDC reference: 204685
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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.
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.
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) Å3 | T = 293 K |
Z = 16 | Block, yellow |
F(000) = 1952 | 0.55 × 0.49 × 0.38 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0651P)2] where P = (Fo2 + 2Fc2)/3 |
2545 reflections | (Δ/σ)max < 0.001 |
135 parameters | Δρmax = 0.45 e Å−3 |
10 restraints | Δρmin = −0.15 e Å−3 |
C7H10N3S2+·Cl− | Z = 16 |
Mr = 235.75 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.72 mm−1 |
a = 16.5700 (8) Å | T = 293 K |
c = 15.3576 (7) Å | 0.55 × 0.49 × 0.38 mm |
V = 4216.7 (3) Å3 |
Bruker Smart APEX CCD area-detector diffractometer | 2545 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | 1920 reflections with I > 2s(I) |
Tmin = 0.694, Tmax = 0.773 | Rint = 0.023 |
12702 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 10 restraints |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.45 e Å−3 |
2545 reflections | Δρmin = −0.15 e Å−3 |
135 parameters |
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)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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···Cl1i | 0.83 (1) | 3.13 (2) | 3.580 (2) | 117 (2) |
N3—H3n1···Cl1i | 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···Cl1ii | 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. |
Experimental details
Crystal data | |
Chemical formula | C7H10N3S2+·Cl− |
Mr | 235.75 |
Crystal system, space group | Tetragonal, I41/a |
Temperature (K) | 293 |
a, c (Å) | 16.5700 (8), 15.3576 (7) |
V (Å3) | 4216.7 (3) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.55 × 0.49 × 0.38 |
Data collection | |
Diffractometer | Bruker Smart APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.694, 0.773 |
No. of measured, independent and observed [I > 2s(I)] reflections | 12702, 2545, 1920 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.096, 0.93 |
No. of reflections | 2545 |
No. of parameters | 135 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.45, −0.15 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
S1—C6 | 1.820 (2) | N1—C1 | 1.335 (2) |
S1—C7 | 1.764 (2) | N2—C7 | 1.296 (2) |
S2—C7 | 1.708 (2) | N2—N3 | 1.437 (2) |
N1—C5 | 1.337 (2) | ||
C6—S1—C7 | 103.9 (1) | N2—C7—S2 | 129.5 (1) |
C5—N1—C1 | 124.1 (2) | N2—C7—S1 | 116.7 (1) |
C7—N2—N3 | 112.2 (2) | S2—C7—S1 | 113.8 (1) |
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···Cl1i | 0.83 (1) | 3.13 (2) | 3.580 (2) | 117 (2) |
N3—H3n1···Cl1i | 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···Cl1ii | 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. |
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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)°.