Crystal structure of 3-carbamo­thio­yl­pyridinium thio­cyanate

In the cation of the title salt, C₆H₇N₂S⁺·SCN⁻, the C=S bond is oriented trans with respect to the C—C=N fragment in the pyridine ring. The planes of the aromatic ring and the thio­amide fragment of the cation make a dihedral angle of 38.31 (4)°. In the crystal, the components are linked by N—H...S and N—H...N, hydrogen bonds, forming a two-dimensional network parallel to (10-1).

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.045
• wR factor = 0.140
• Data-to-parameter ratio = 30.4

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PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1 Note

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S1. Comment

There are three isomeric thionicotinamides of general formula C₆H₆N₂S, 2-thioamidopyridine (Downie et al., 1972), 3-thioamidopyridine (Form et al., 1973) and 4-thioamidopyridine (Colleter & Gadret, 1967), then three possible coordination sites. The structural interest to these compounds has centered on the parameters of the thioamide group and the consequent electron arrangement within the group (Fonari et al., 2007). The thioamide group and the pyridine ring are not coplanar.

In the title compound, (I), the asymmetric unit contains one 3-3-carbamothioylpyridinium and one thiocyanate ions. The molecular geometry and the atom-numbering scheme are shown in Fig 1. In the cation moiety, the C=S bond is oriented trans with respect to the C—C—N fragment in the pyridine ring. The aromatic ring and the thioamide fragment of the thionicotinamide molecule make a dihedral angle of 38.31 (4)° similar to that found in 3-carbamothioylpyridinium iodide (trans) (30.02 (3)°) (Sharif et al., 2009) and 3-thioamido-pyridine (cis) (33.76 (7)°) (Form et al. 1973). The crystal packing is stabilized by weak N—H···N and N—H···S hydrogen bonds forming a two-dimensional network (Fig. 2).

Related literature

For isomeric thionicotinamide structures, see: Downie et al. (1972); Form et al. (1973); Colleter & Gadret (1967). For a related structure, see: Sharif et al. (2009). For the structural interest of thionicotinamides, see: Fonari et al. (2007).

S2. Experimental

3-Thionicotinamide (690 mg, 0.5 mmol) was added dropwise to a solution of KSCN (48.6 mg, 0.5 mmol) in water/ethanol (10 ml/10 ml). The mixture was then refluxed with stirring for 3 h and the resulting solution was left to stand at room temperature. After several days, single crystals suitable for X-ray diffraction were obtained.

S3. Refinement

Approximate positions for all H atoms were first obtained from the difference electron density map. However, the H atoms were situated into idealized positions and the H-atoms have been refined within the riding atom approximation. The applied constraints were as follow: C—H = 0.93 Å and N—H = 0.86 Å with U_iso = 1.2U_eq(C or N).

Computing details

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures

	Fig. 1. The molecular structure of, (I), with displacement ellipsoids drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Packing diagram of (I) viewed along the b axis showing hydrogen bond as dashed lines [N—H···S in red and N—H···N in black]

3-Carbamothioylpyridinium thiocyanate

Crystal data

C6H7N2S^+·CNS^−	F(000) = 408
Mr = 197.28	Dx = 1.422 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.2495 (2) Å	Cell parameters from 5267 reflections
b = 9.3759 (3) Å	θ = 2.6–32.1°
c = 13.5949 (3) Å	µ = 0.52 mm^−1
β = 94.454 (1)°	T = 295 K
V = 921.26 (4) Å^3	Prism, colorless
Z = 4	0.2 × 0.16 × 0.1 mm

Data collection

Bruker APEXII diffractometer	3313 independent reflections
Radiation source: sealed tube	2563 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 32.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −10→10
Tmin = 0.679, Tmax = 0.746	k = −14→14
12686 measured reflections	l = −20→20

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0808P)^2 + 0.1946P] where P = (Fo^2 + 2Fc^2)/3
3313 reflections	(Δ/σ)max < 0.001
109 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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. 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 > σ(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.

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

	x	y	z	Uiso*/Ueq
C1	0.9430 (2)	0.08889 (15)	0.83615 (10)	0.0351 (3)
C2	0.91545 (18)	0.13467 (15)	0.73124 (9)	0.0322 (3)
C3	0.9619 (2)	0.27153 (17)	0.70337 (11)	0.0401 (3)
H3	1.0114	0.336	0.7503	0.048*
C4	0.9342 (3)	0.3117 (2)	0.60509 (13)	0.0536 (4)
H4	0.9675	0.4025	0.5854	0.064*
C5	0.8576 (3)	0.2168 (2)	0.53738 (12)	0.0552 (5)
H5	0.8365	0.2434	0.4716	0.066*
C6	0.8395 (2)	0.04215 (18)	0.65938 (10)	0.0392 (3)
H6	0.8072	−0.0501	0.6764	0.047*
C11	0.3607 (2)	0.10281 (16)	0.67580 (11)	0.0383 (3)
N1	0.9976 (2)	−0.04356 (15)	0.85163 (10)	0.0492 (3)
H1A	1.0153	−0.0983	0.8025	0.059*
H1B	1.0156	−0.0754	0.9109	0.059*
N2	0.81305 (19)	0.08559 (17)	0.56595 (9)	0.0464 (3)
H2	0.7655	0.027	0.5224	0.056*
N11	0.3114 (3)	0.0569 (2)	0.59942 (12)	0.0642 (5)
S1	0.90233 (7)	0.20284 (5)	0.92615 (3)	0.04789 (14)
S11	0.43232 (7)	0.16631 (5)	0.78372 (3)	0.04908 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0405 (7)	0.0356 (6)	0.0286 (5)	−0.0036 (5)	−0.0012 (5)	−0.0032 (5)
C2	0.0340 (6)	0.0364 (6)	0.0257 (5)	0.0005 (5)	0.0004 (4)	−0.0029 (4)
C3	0.0481 (8)	0.0358 (7)	0.0358 (6)	0.0008 (6)	−0.0001 (6)	−0.0007 (5)
C4	0.0724 (12)	0.0460 (9)	0.0427 (8)	0.0019 (8)	0.0056 (8)	0.0102 (7)
C5	0.0638 (11)	0.0713 (12)	0.0299 (7)	0.0139 (9)	0.0000 (7)	0.0074 (7)
C6	0.0421 (7)	0.0435 (7)	0.0316 (6)	−0.0039 (6)	0.0007 (5)	−0.0066 (5)
C11	0.0440 (7)	0.0352 (7)	0.0356 (6)	0.0024 (6)	0.0029 (5)	0.0006 (5)
N1	0.0781 (10)	0.0370 (7)	0.0323 (6)	0.0049 (7)	0.0022 (6)	0.0002 (5)
N2	0.0484 (7)	0.0609 (9)	0.0286 (5)	0.0024 (6)	−0.0043 (5)	−0.0102 (5)
N11	0.0865 (12)	0.0625 (10)	0.0419 (7)	0.0034 (9)	−0.0070 (7)	−0.0116 (7)
S1	0.0704 (3)	0.0440 (2)	0.02793 (18)	0.01027 (18)	−0.00476 (16)	−0.00570 (13)
S11	0.0598 (3)	0.0521 (3)	0.0344 (2)	−0.00810 (19)	−0.00268 (16)	−0.00319 (15)

Geometric parameters (Å, º)

C1—N1	1.3154 (19)	C5—N2	1.337 (3)
C1—C2	1.4879 (18)	C5—H5	0.93
C1—S1	1.6677 (14)	C6—N2	1.3334 (19)
C2—C3	1.387 (2)	C6—H6	0.93
C2—C6	1.3879 (19)	C11—N11	1.155 (2)
C3—C4	1.388 (2)	C11—S11	1.6303 (16)
C3—H3	0.93	N1—H1A	0.86
C4—C5	1.367 (3)	N1—H1B	0.86
C4—H4	0.93	N2—H2	0.86
N1—C1—C2	116.23 (12)	N2—C5—H5	120.1
N1—C1—S1	123.75 (11)	C4—C5—H5	120.1
C2—C1—S1	120.02 (11)	N2—C6—C2	119.97 (15)
C3—C2—C6	118.52 (13)	N2—C6—H6	120
C3—C2—C1	120.76 (12)	C2—C6—H6	120
C6—C2—C1	120.71 (13)	N11—C11—S11	179.35 (17)
C2—C3—C4	119.60 (15)	C1—N1—H1A	120
C2—C3—H3	120.2	C1—N1—H1B	120
C4—C3—H3	120.2	H1A—N1—H1B	120
C5—C4—C3	119.51 (17)	C6—N2—C5	122.51 (14)
C5—C4—H4	120.2	C6—N2—H2	118.7
C3—C4—H4	120.2	C5—N2—H2	118.7
N2—C5—C4	119.88 (15)
N1—C1—C2—C3	−142.88 (16)	C2—C3—C4—C5	1.4 (3)
S1—C1—C2—C3	37.84 (19)	C3—C4—C5—N2	−1.1 (3)
N1—C1—C2—C6	38.3 (2)	C3—C2—C6—N2	0.1 (2)
S1—C1—C2—C6	−140.98 (13)	C1—C2—C6—N2	178.93 (13)
C6—C2—C3—C4	−0.9 (2)	C2—C6—N2—C5	0.2 (2)
C1—C2—C3—C4	−179.75 (15)	C4—C5—N2—C6	0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S11^i	0.86	2.54	3.3450 (15)	156
N1—H1B···S1^ii	0.86	2.55	3.3975 (14)	171
N2—H2···N11^iii	0.86	1.88	2.709 (2)	162

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