4-Thio-carbamoylpyridin-1-ium iodide.

The title salt, C6H7N2S(+)·I(-), crystallizes with two independent cations and two anions in the asymmetric unit. In one of the cations, the dihedral angle between the pyridinium ring and the thioamide group is 28.9 (2)°; in the other it is 33.5 (2)°. In the crystal, N-H⋯S and C-H⋯S hydrogen bonds link the independent cations into pairs. These pairs form a three-dimensional network through additional N-H⋯I and C-H⋯I hydrogen bonds to the anions.

Related literature

For details of the synthesis, see: Liebscher & Hartmann (1977 ▶). For related structures, see: Alléaume et al. (1973 ▶); Cardoso et al. (2008 ▶); Colleter & Gadret (1967 ▶, 1968a ▶,b ▶); Colleter et al. (1970 ▶, 1973 ▶); n class="Chemical">Gadret & Goursolle (1969 ▶); Gel’mbol’dt, et al. (2010 ▶); Kavitha et al. (2008 ▶); Revathi et al. (2009 ▶). For drug action, see: Vannelli et al. (2002 ▶). For a DFT computational study of the parent thio­amide and for vibrational spectroscopy data, see: Wysokińsky et al. (2006 ▶).

Experimental

Crystal data

C6H7N2S+·I−

M = 266.10

Monoclinic,

a = 18.7580 (11) Å

b = 7.7476 (4) Å

c = 24.1784 (14) Å

β = 101.165 (1)°

V = 3447.3 (3) Å3

Z = 16

Mo Kα radiation

μ = 3.89 mm−1

T = 173 K

0.31 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.541, T max = 0.746

19180 measured reflections

3923 independent reflections

3684 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.014

wR(F 2) = 0.034

S = 1.08

3923 reflections

199 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814003511/rn2122sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814003511/rn2122Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814003511/rn2122Isup3.cml

CCDC reference: 987377

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

C6H7N2S+·I−	F(000) = 2016
Mr = 266.10	Dx = 2.051 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.7580 (11) Å	Cell parameters from 9990 reflections
b = 7.7476 (4) Å	θ = 2.5–27.4°
c = 24.1784 (14) Å	µ = 3.89 mm−1
β = 101.165 (1)°	T = 173 K
V = 3447.3 (3) Å3	Block, orange
Z = 16	0.31 × 0.23 × 0.18 mm

Bruker APEXII CCD area-detector diffractometer	3923 independent reflections
Radiation source: fine-focus sealed tube, Bruker D8	3684 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 66.06 pixels mm-1	θmax = 27.4°, θmin = 1.7°
φ and ω scans	h = −24→24
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −10→10
Tmin = 0.541, Tmax = 0.746	l = −31→31
19180 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)] = 0.014	Hydrogen site location: difference Fourier map
wR(F2) = 0.034	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.014P)2 + 2.9155P] where P = (Fo2 + 2Fc2)/3
3923 reflections	(Δ/σ)max = 0.003
199 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Experimental. A crystal coated in Paratone (TM) oil was mounted on the end of a thin glass capillary and cooled in the gas stream of the diffractometer Kryoflex device.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Amine and pyridinium NH atoms freely refined in order to get H-bond s.u. data. The isotropic displacements were set to 1.2* values of attached N.

	x	y	z	Uiso*/Ueq
I1	0.73295 (2)	0.78676 (2)	0.40917 (2)	0.02306 (4)
I2	0.50416 (2)	−0.34932 (2)	0.65408 (2)	0.02433 (4)
S1	0.23724 (3)	0.15493 (7)	0.82498 (2)	0.03064 (11)
N1	0.32690 (10)	0.4190 (2)	0.83135 (8)	0.0322 (4)
H1A	0.3653 (13)	0.467 (3)	0.8274 (10)	0.039*
H1B	0.3022 (13)	0.473 (3)	0.8524 (10)	0.039*
N2	0.42894 (8)	0.0542 (2)	0.69703 (6)	0.0237 (3)
H2	0.4497 (11)	0.014 (3)	0.6721 (9)	0.028*
C1	0.30728 (10)	0.2657 (2)	0.81067 (7)	0.0221 (4)
C2	0.35203 (9)	0.1918 (2)	0.77127 (7)	0.0201 (3)
C3	0.38691 (10)	0.2986 (2)	0.73855 (8)	0.0226 (4)
H3	0.3849	0.4204	0.7424	0.027*
C4	0.42429 (10)	0.2264 (2)	0.70060 (8)	0.0238 (4)
H4	0.4467	0.2983	0.6771	0.029*
C5	0.39722 (10)	−0.0526 (2)	0.72831 (8)	0.0258 (4)
H5	0.4018	−0.1740	0.7247	0.031*
C6	0.35787 (10)	0.0139 (2)	0.76581 (8)	0.0253 (4)
H6	0.3348	−0.0613	0.7879	0.030*
S2	0.48535 (3)	0.15223 (6)	0.57798 (2)	0.02810 (10)
N3	0.59993 (10)	−0.0467 (2)	0.58319 (8)	0.0304 (4)
H3A	0.6393 (13)	−0.078 (3)	0.5779 (10)	0.036*
H3B	0.5804 (13)	−0.120 (3)	0.6025 (10)	0.036*
N4	0.66095 (9)	0.4143 (2)	0.45727 (7)	0.0294 (4)
H4A	0.6785 (12)	0.483 (3)	0.4351 (9)	0.035*
C7	0.56575 (10)	0.0956 (2)	0.56424 (7)	0.0209 (4)
C8	0.60102 (9)	0.2080 (2)	0.52709 (7)	0.0203 (4)
C9	0.64262 (10)	0.1370 (2)	0.49061 (8)	0.0244 (4)
H9	0.6511	0.0161	0.4904	0.029*
C10	0.67111 (11)	0.2439 (3)	0.45512 (8)	0.0287 (4)
H10	0.6979	0.1969	0.4291	0.034*
C11	0.62265 (11)	0.4872 (3)	0.49209 (8)	0.0299 (4)
H11	0.6173	0.6091	0.4926	0.036*
C12	0.59099 (10)	0.3860 (2)	0.52727 (8)	0.0259 (4)
H12	0.5626	0.4369	0.5514	0.031*

	U11	U22	U33	U12	U13	U23
I1	0.02298 (6)	0.02070 (6)	0.02617 (6)	−0.00052 (4)	0.00639 (5)	0.00397 (4)
I2	0.02670 (7)	0.01916 (6)	0.02859 (7)	0.00127 (5)	0.00896 (5)	0.00029 (5)
S1	0.0295 (3)	0.0312 (3)	0.0355 (3)	−0.0050 (2)	0.0170 (2)	−0.0023 (2)
N1	0.0314 (9)	0.0302 (10)	0.0400 (10)	−0.0058 (8)	0.0195 (8)	−0.0138 (8)
N2	0.0205 (8)	0.0296 (9)	0.0216 (8)	0.0028 (6)	0.0058 (6)	−0.0056 (6)
C1	0.0227 (9)	0.0233 (9)	0.0211 (8)	0.0025 (7)	0.0060 (7)	0.0004 (7)
C2	0.0185 (8)	0.0228 (9)	0.0186 (8)	0.0012 (7)	0.0029 (7)	−0.0017 (7)
C3	0.0246 (9)	0.0197 (9)	0.0235 (9)	−0.0001 (7)	0.0048 (7)	−0.0003 (7)
C4	0.0246 (9)	0.0248 (9)	0.0226 (9)	−0.0017 (7)	0.0056 (7)	0.0002 (7)
C5	0.0270 (10)	0.0198 (9)	0.0304 (10)	0.0022 (7)	0.0052 (8)	−0.0026 (7)
C6	0.0280 (10)	0.0206 (9)	0.0287 (9)	−0.0006 (8)	0.0086 (8)	0.0014 (7)
S2	0.0268 (2)	0.0295 (3)	0.0317 (2)	0.00596 (19)	0.0148 (2)	0.0049 (2)
N3	0.0259 (9)	0.0295 (9)	0.0392 (10)	0.0061 (7)	0.0150 (8)	0.0130 (8)
N4	0.0259 (8)	0.0325 (9)	0.0284 (8)	−0.0097 (7)	0.0017 (7)	0.0105 (7)
C7	0.0219 (9)	0.0219 (9)	0.0194 (8)	−0.0004 (7)	0.0053 (7)	−0.0006 (7)
C8	0.0185 (8)	0.0213 (9)	0.0204 (8)	−0.0016 (7)	0.0018 (7)	0.0005 (7)
C9	0.0229 (9)	0.0250 (10)	0.0263 (9)	−0.0019 (7)	0.0073 (7)	−0.0004 (7)
C10	0.0260 (10)	0.0353 (11)	0.0261 (9)	−0.0044 (8)	0.0082 (8)	0.0019 (8)
C11	0.0295 (10)	0.0212 (9)	0.0358 (11)	−0.0043 (8)	−0.0020 (8)	0.0061 (8)
C12	0.0278 (10)	0.0225 (9)	0.0267 (9)	−0.0002 (8)	0.0036 (8)	−0.0004 (7)

S1—C1	1.6608 (19)	S2—C7	1.6648 (18)
N1—C1	1.313 (3)	N3—C7	1.312 (2)
N1—H1A	0.83 (2)	N3—H3A	0.81 (2)
N1—H1B	0.86 (2)	N3—H3B	0.86 (2)
N2—C5	1.336 (2)	N4—C11	1.334 (3)
N2—C4	1.341 (2)	N4—C10	1.336 (3)
N2—H2	0.84 (2)	N4—H4A	0.86 (2)
C1—C2	1.500 (2)	C7—C8	1.494 (2)
C2—C6	1.391 (2)	C8—C12	1.392 (3)
C2—C3	1.392 (2)	C8—C9	1.399 (2)
C3—C4	1.377 (3)	C9—C10	1.373 (3)
C3—H3	0.9500	C9—H9	0.9500
C4—H4	0.9500	C10—H10	0.9500
C5—C6	1.376 (3)	C11—C12	1.374 (3)
C5—H5	0.9500	C11—H11	0.9500
C6—H6	0.9500	C12—H12	0.9500
C1—N1—H1A	123.0 (17)	C7—N3—H3A	126.7 (17)
C1—N1—H1B	121.3 (16)	C7—N3—H3B	120.9 (16)
H1A—N1—H1B	115 (2)	H3A—N3—H3B	112 (2)
C5—N2—C4	122.57 (16)	C11—N4—C10	122.80 (17)
C5—N2—H2	120.0 (15)	C11—N4—H4A	116.7 (15)
C4—N2—H2	117.2 (15)	C10—N4—H4A	120.5 (15)
N1—C1—C2	115.93 (16)	N3—C7—C8	117.14 (16)
N1—C1—S1	124.24 (14)	N3—C7—S2	123.51 (15)
C2—C1—S1	119.83 (14)	C8—C7—S2	119.32 (13)
C6—C2—C3	118.73 (16)	C12—C8—C9	118.95 (17)
C6—C2—C1	120.18 (16)	C12—C8—C7	119.98 (16)
C3—C2—C1	121.07 (16)	C9—C8—C7	121.04 (16)
C4—C3—C2	119.58 (17)	C10—C9—C8	119.26 (18)
C4—C3—H3	120.2	C10—C9—H9	120.4
C2—C3—H3	120.2	C8—C9—H9	120.4
N2—C4—C3	119.64 (17)	N4—C10—C9	119.73 (18)
N2—C4—H4	120.2	N4—C10—H10	120.1
C3—C4—H4	120.2	C9—C10—H10	120.1
N2—C5—C6	119.70 (17)	N4—C11—C12	119.95 (18)
N2—C5—H5	120.1	N4—C11—H11	120.0
C6—C5—H5	120.1	C12—C11—H11	120.0
C5—C6—C2	119.74 (17)	C11—C12—C8	119.26 (18)
C5—C6—H6	120.1	C11—C12—H12	120.4
C2—C6—H6	120.1	C8—C12—H12	120.4
N1—C1—C2—C6	152.73 (19)	N3—C7—C8—C12	−148.94 (18)
S1—C1—C2—C6	−28.0 (2)	S2—C7—C8—C12	32.8 (2)
N1—C1—C2—C3	−28.9 (3)	N3—C7—C8—C9	32.9 (3)
S1—C1—C2—C3	150.45 (15)	S2—C7—C8—C9	−145.37 (15)
C6—C2—C3—C4	1.9 (3)	C12—C8—C9—C10	−1.4 (3)
C1—C2—C3—C4	−176.50 (17)	C7—C8—C9—C10	176.76 (17)
C5—N2—C4—C3	1.4 (3)	C11—N4—C10—C9	−1.3 (3)
C2—C3—C4—N2	−2.4 (3)	C8—C9—C10—N4	2.3 (3)
C4—N2—C5—C6	0.2 (3)	C10—N4—C11—C12	−0.8 (3)
N2—C5—C6—C2	−0.6 (3)	N4—C11—C12—C8	1.7 (3)
C3—C2—C6—C5	−0.4 (3)	C9—C8—C12—C11	−0.6 (3)
C1—C2—C6—C5	178.03 (17)	C7—C8—C12—C11	−178.77 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I2i	0.83 (2)	2.79 (2)	3.5996 (18)	164 (2)
N1—H1B···I1ii	0.86 (2)	2.78 (3)	3.6232 (17)	167 (2)
N2—H2···I2	0.84 (2)	3.06 (2)	3.6622 (16)	131.0 (18)
N2—H2···S2	0.84 (2)	2.71 (2)	3.3410 (16)	133.2 (18)
N3—H3A···I1iii	0.81 (2)	2.86 (2)	3.6188 (17)	157 (2)
N3—H3B···I2	0.86 (2)	2.73 (3)	3.5854 (18)	173 (2)
N4—H4A···I1	0.86 (2)	2.69 (2)	3.4804 (17)	152.9 (19)
C4—H4···I2iv	0.95	3.03	3.8684 (19)	149
C4—H4···S2	0.95	2.87	3.4275 (19)	119

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯I2i	0.83 (2)	2.79 (2)	3.5996 (18)	164 (2)
N1—H1B⋯I1ii	0.86 (2)	2.78 (3)	3.6232 (17)	167 (2)
N2—H2⋯I2	0.84 (2)	3.06 (2)	3.6622 (16)	131.0 (18)
N2—H2⋯S2	0.84 (2)	2.71 (2)	3.3410 (16)	133.2 (18)
N3—H3A⋯I1iii	0.81 (2)	2.86 (2)	3.6188 (17)	157 (2)
N3—H3B⋯I2	0.86 (2)	2.73 (3)	3.5854 (18)	173 (2)
N4—H4A⋯I1	0.86 (2)	2.69 (2)	3.4804 (17)	152.9 (19)
C4—H4⋯I2iv	0.95	3.03	3.8684 (19)	149
C4—H4⋯S2	0.95	2.87	3.4275 (19)	119

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .