1-Methyl-4-thio­carbamoylpyridin-1-ium iodide

Shotonwa, I.O.; Boeré, R.T.

doi:10.1107/S2414314618014918

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 11| November 2018| x181491

https://doi.org/10.1107/S2414314618014918

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1-Methyl-4-thiocarbamoylpyridin-1-ium iodide

Ibukun O. Shotonwa ^b,^a and René T. Boeré ^b ^*

^aDepartment of Chemistry, Lagos State University, Ojo, Lagos, Nigeria, and ^bDepartment of Chemistry and Biochemistry, University of Lethbridge, 4401 University Drive West, Lethbridge, Alberta, T1K3M4, Canada
^*Correspondence e-mail: boere@uleth.ca

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 4 September 2018; accepted 22 October 2018; online 6 November 2018)

In the title compound, C₇H₉N₂S⁺·I⁻, the thioamide moiety is twisted out of the aromatic plane by 38.98 (4)° and forms N—H⋯I hydrogen bonds. In the crystal, hydrogen-bonded centrosymmetric dimers [C₇H₉N₂S⁺·I⁻]₂ are linked via additional short contacts from an aromatic CH group to the iodide anion into ribbons parallel to the (010) plane.

Keywords: crystal structure; hydrogen bonds; heteroelements.

CCDC reference: 1874701

Structure description

Methylation at the pyridine nitrogen was used as a protecting group in synthetic attempts to prepare the corresponding 3,5-dipyridyl-1,2,4-dithiazolium salts. In the title compound (I), the cation and anion are linked pairwise in a centrosymmetric hydrogen-bonded dimer (N1, I1, N1ⁱ and I1ⁱ; see Table 1 for symmetry code, and Fig. 1). The pyridine ring is planar (r.m.s. deviation = 0.0054 Å), as is the thioamide functional group (r.m.s. deviation = 0.0020 Å), and the two planes make a dihedral angle of 38.98 (4)°. The N1/I1/N1ⁱ/I1ⁱ plane makes a dihedral angle of 26.67 (2)° with the thioamide moiety, and the H1A and H1B hydrogen atoms deviate from this plane by −0.39 (2) and 0.12 (2) Å, respectively. The cation structure is closely related to that of the protonated analogue, C₆H₇N₂S⁺·I⁻ (Shotonwa & Boeré, 2014 ) and all comparable intramolecular distances are indistinguishable within standard uncertainties [Cambridge Structural Database (CSD) Version 5.39, with updates to November 2017 (Groom et al., 2016 ), refcode: TODDAT].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯I1	0.83 (2)	2.79 (2)	3.6037 (16)	166 (2)
N1—H1A⋯I1ⁱ	0.86 (2)	2.93 (2)	3.6367 (16)	141 (2)
C5—H5⋯I1ⁱⁱ	0.95	2.96	3.8642 (17)	160
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the ion pair with the labelling scheme and 50% displacement ellipsoids.

In the crystal (Fig. 2), the only significant intermolecular contacts are non-classical hydrogen bonds between H5 and I1ⁱⁱ, with a separation 0.22 Å shorter than the sum of van der Waals radii (Table 1, entry 3). These link the dimers of ion pairs into ribbons parallel to the (010) plane.

Figure 2
Packing viewed along the b-axis direction with classical and non-classical hydrogen bonds to the iodide anion shown as dashed lines.

Synthesis and crystallization

The title salt was prepared by a modification of a literature method for related compounds (Kosower, 1955 ): methyl iodide (0.57 g, 4 mmol) was added dropwise to 4-pyridine-thioamide (0.50 g, 4 mmol) in 5.00 ml of dry CH₃CN, with a colour change from yellow to deep orange. The mixture was stirred for 30 min. at room temperature, followed by reflux for 10 min., cooled, filtered and washed three times with cold CH₃CN. Recrystallization from boiling 99% ethanol afforded 0.21 g (35% yield) of (I) [CAS registry 749784–54-1]. The crystals are hygroscopic and were stored in a well sealed flask. ¹H NMR, (D₂O, δ/p.p.m.): 8.84 (d, 2H Ar, J = 6.9 Hz), 8.23 (d, 2H Ar, J = 6.9 Hz), 4.38 (s, 3H, N—CH₃). mp = 219.3–220.9°C (lit. 220°C; Christ et al., 1974 ).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₉N₂S⁺·I⁻
M_r	280.12
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	19.6249 (16), 7.2198 (6), 14.9117 (12)
β (°)	108.592 (1)
V (Å³)	2002.5 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	3.35
Crystal size (mm)	0.27 × 0.15 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.610, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	13927, 2294, 2121
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.014, 0.032, 1.07
No. of reflections	2294
No. of parameters	107
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.27
Computer programs: APEX2 and SAINT-Plus (Bruker, 2008), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1874701

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618014918/bh4040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618014918/bh4040Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618014918/bh4040Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S2414314618014918/bh4040Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Mercury CSD (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

1-Methyl-4-thiocarbamoylpyridin-1-ium iodide top

Crystal data top

C₇H₉N₂S⁺·I⁻	D_x = 1.858 Mg m⁻³
M_r = 280.12	Melting point: 493 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.6249 (16) Å	Cell parameters from 13927 reflections
b = 7.2198 (6) Å	θ = 2.2–27.5°
c = 14.9117 (12) Å	µ = 3.35 mm⁻¹
β = 108.592 (1)°	T = 173 K
V = 2002.5 (3) Å³	Prism, clear orange
Z = 8	0.27 × 0.15 × 0.08 mm
F(000) = 1072

Data collection top

Bruker APEXII CCD area-detector diffractometer	2294 independent reflections
Radiation source: sealed tube	2121 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 8 pixels mm^-1	θ_max = 27.5°, θ_min = 2.2°
ω and φ scans	h = −25→25
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −9→9
T_min = 0.610, T_max = 0.746	l = −19→19
13927 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.014	Hydrogen site location: mixed
wR(F²) = 0.032	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0118P)² + 2.1492P] where P = (F_o² + 2F_c²)/3
2294 reflections	(Δ/σ)_max = 0.001
107 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Special details top

Refinement. 1. Fixed Uiso At 1.2 times of: All C(H) groups, All N(H,H) groups At 1.5 times of: All C(H,H,H) groups 2.a Aromatic/amide H refined with riding coordinates: C5(H5), C3(H3), C4(H4), C6(H6) 2.b Idealised Me refined as rotating group: C7(H7A,H7B,H7C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.11514 (2)	0.17323 (2)	0.42525 (2)	0.02707 (4)
S1	0.14565 (2)	0.31395 (7)	0.75400 (3)	0.03144 (10)
N1	0.23622 (9)	0.2254 (2)	0.66302 (11)	0.0301 (3)
H1A	0.2776 (12)	0.196 (3)	0.6589 (15)	0.036*
H1B	0.2037 (12)	0.228 (3)	0.6114 (16)	0.036*
N2	0.40862 (7)	0.20871 (19)	0.98789 (10)	0.0241 (3)
C5	0.41537 (9)	0.2872 (2)	0.90990 (12)	0.0269 (4)
H5	0.461071	0.330808	0.910006	0.032*
C3	0.28424 (9)	0.1655 (2)	0.91256 (12)	0.0235 (3)
H3	0.238945	0.124022	0.915043	0.028*
C4	0.34445 (9)	0.1489 (2)	0.99079 (12)	0.0256 (3)
H4	0.340682	0.095014	1.047130	0.031*
C7	0.47204 (10)	0.1918 (3)	1.07418 (13)	0.0333 (4)
H7A	0.516062	0.208892	1.057507	0.050*
H7B	0.472432	0.068642	1.102007	0.050*
H7C	0.469549	0.286572	1.120068	0.050*
C6	0.35692 (9)	0.3056 (2)	0.82953 (12)	0.0263 (4)
H6	0.362264	0.360346	0.774227	0.032*
C2	0.28980 (8)	0.2431 (2)	0.82991 (11)	0.0207 (3)
C1	0.22502 (8)	0.2579 (2)	0.74402 (12)	0.0227 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02370 (6)	0.03292 (7)	0.02592 (6)	−0.00189 (5)	0.00981 (4)	−0.00090 (5)
S1	0.01959 (19)	0.0456 (3)	0.0283 (2)	0.00281 (19)	0.00643 (16)	−0.0004 (2)
N1	0.0238 (7)	0.0447 (10)	0.0210 (7)	0.0019 (7)	0.0058 (6)	0.0001 (7)
N2	0.0204 (7)	0.0245 (8)	0.0247 (7)	0.0037 (6)	0.0032 (5)	−0.0017 (6)
C5	0.0213 (8)	0.0293 (9)	0.0301 (9)	−0.0016 (7)	0.0081 (7)	−0.0004 (7)
C3	0.0202 (7)	0.0248 (9)	0.0267 (8)	0.0003 (7)	0.0090 (6)	0.0009 (7)
C4	0.0254 (8)	0.0273 (9)	0.0250 (8)	0.0028 (7)	0.0094 (7)	0.0025 (7)
C7	0.0250 (9)	0.0398 (11)	0.0279 (9)	0.0039 (8)	−0.0018 (7)	−0.0002 (8)
C6	0.0243 (8)	0.0307 (10)	0.0249 (8)	−0.0020 (7)	0.0093 (7)	0.0014 (7)
C2	0.0207 (8)	0.0197 (8)	0.0221 (8)	0.0013 (6)	0.0074 (6)	−0.0028 (6)
C1	0.0219 (8)	0.0205 (8)	0.0251 (8)	−0.0021 (6)	0.0068 (6)	0.0012 (6)

Geometric parameters (Å, º) top

S1—C1	1.6615 (17)	C3—C2	1.389 (2)
N1—C1	1.316 (2)	C3—H3	0.9500
N1—H1A	0.86 (2)	C4—H4	0.9500
N1—H1B	0.83 (2)	C7—H7A	0.9800
N2—C5	1.338 (2)	C7—H7B	0.9800
N2—C4	1.345 (2)	C7—H7C	0.9800
N2—C7	1.483 (2)	C6—C2	1.394 (2)
C5—C6	1.376 (2)	C6—H6	0.9500
C5—H5	0.9500	C2—C1	1.493 (2)
C3—C4	1.376 (2)

C1—N1—H1A	123.2 (14)	N2—C7—H7A	109.5
C1—N1—H1B	123.0 (15)	N2—C7—H7B	109.5
H1A—N1—H1B	114 (2)	H7A—C7—H7B	109.5
C5—N2—C4	121.14 (14)	N2—C7—H7C	109.5
C5—N2—C7	120.07 (15)	H7A—C7—H7C	109.5
C4—N2—C7	118.76 (15)	H7B—C7—H7C	109.5
N2—C5—C6	120.80 (16)	C5—C6—C2	119.45 (16)
N2—C5—H5	119.6	C5—C6—H6	120.3
C6—C5—H5	119.6	C2—C6—H6	120.3
C4—C3—C2	119.89 (15)	C3—C2—C6	118.39 (15)
C4—C3—H3	120.1	C3—C2—C1	120.23 (14)
C2—C3—H3	120.1	C6—C2—C1	121.37 (15)
N2—C4—C3	120.31 (15)	N1—C1—C2	115.41 (14)
N2—C4—H4	119.8	N1—C1—S1	124.14 (13)
C3—C4—H4	119.8	C2—C1—S1	120.44 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···I1	0.83 (2)	2.79 (2)	3.6037 (16)	166 (2)
N1—H1A···I1ⁱ	0.86 (2)	2.93 (2)	3.6367 (16)	141 (2)
C5—H5···I1ⁱⁱ	0.95	2.96	3.8642 (17)	160

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

Funding information

The Natural Sciences and Engineering Research Council of Canada is gratefully acknowledged for Discovery Grants (RTB). The APEXII diffractometer was purchased with the help of the NSERC and the University of Lethbridge.

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