Crystal structure of 3-carbamo­thio­yl­pyridinium thio­cyanate

Bouchareb, H.; Boudraa, M.; Bouacida, S.; Merazig, H.; Chtoun, E.H.

doi:10.1107/S2056989014026437

organic compounds

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ISSN: 2056-9890

Volume 71| Part 1| January 2015| Pages o30-o31

https://doi.org/10.1107/S2056989014026437

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Crystal structure of 3-carbamothioylpyridinium thiocyanate

Hasna Bouchareb,^a Mhamed Boudraa,^a Sofiane Bouacida,^a,^b ^* Hocine Merazig ^a and El Hossain Chtoun ^c

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Université Constantine 1, 25000 , Algeria, ^bDépartement Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Oum El Bouaghi, Algeria, and ^cUniversité Abdelmalek Essaadi, Faculté des Sciences, BP 2121 M'Hannech II, 93002 Tétouan, Morroco
^*Correspondence e-mail: bouacida_sofiane@yahoo.fr

Edited by O. Büyükgüngör, Ondokuz Mayıs University, Turkey (Received 29 November 2014; accepted 1 December 2014; online 1 January 2015)

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).

Keywords: crystal structure; 3-carbamothioylpyridinium cation; thiocyanate anion; N—H⋯S hydrogen bonding.

CCDC reference: 1037011

1. 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 ).

2. Experimental

2.1. Crystal data

C₆H₇N₂S⁺·CNS⁻
M_r = 197.28
Monoclinic, P 2₁ /n
a = 7.2495 (2) Å
b = 9.3759 (3) Å
c = 13.5949 (3) Å
β = 94.454 (1)°
V = 921.26 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 295 K
0.2 × 0.16 × 0.1 mm

2.2. Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.679, T_max = 0.746
12686 measured reflections
3313 independent reflections
2563 reflections with I > 2σ(I)
R_int = 0.023

2.3. Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.140
S = 1.04
3313 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S11ⁱ	0.86	2.54	3.3450 (15)	156
N1—H1B⋯S1ⁱⁱ	0.86	2.55	3.3975 (14)	171
N2—H2⋯N11ⁱⁱⁱ	0.86	1.88	2.709 (2)	162
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+2, -y, -z+2; (iii) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; 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).

Supporting information

CCDC reference: 1037011

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989014026437/bq2397sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989014026437/bq2397Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989014026437/bq2397Isup3.cml

checkCIF report

Comment top

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 top

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).

Experimental top

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.

Structure description top

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).

Computing details top

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 top

	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 top

Crystal data top

C₆H₇N₂S⁺·CNS⁻	F(000) = 408
M_r = 197.28	D_x = 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) Å³	Prism, colorless
Z = 4	0.2 × 0.16 × 0.1 mm

Data collection top

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

Refinement top

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0808P)² + 0.1946P] where P = (F_o² + 2F_c²)/3
3313 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₆H₇N₂S⁺·CNS⁻	V = 921.26 (4) Å³
M_r = 197.28	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.2495 (2) Å	µ = 0.52 mm⁻¹
b = 9.3759 (3) Å	T = 295 K
c = 13.5949 (3) Å	0.2 × 0.16 × 0.1 mm
β = 94.454 (1)°

Data collection top

Bruker APEXII diffractometer	3313 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	2563 reflections with I > 2σ(I)
T_min = 0.679, T_max = 0.746	R_int = 0.023
12686 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.04	Δρ_max = 0.58 e Å⁻³
3313 reflections	Δρ_min = −0.26 e Å⁻³
109 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S11ⁱ	0.86	2.54	3.3450 (15)	156
N1—H1B···S1ⁱⁱ	0.86	2.55	3.3975 (14)	171
N2—H2···N11ⁱⁱⁱ	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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S11ⁱ	0.8600	2.5400	3.3450 (15)	156.00
N1—H1B···S1ⁱⁱ	0.8600	2.5500	3.3975 (14)	171.00
N2—H2···N11ⁱⁱⁱ	0.8600	1.8800	2.709 (2)	162.00

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

Acknowledgements

Thanks are due to MESRS and ATRST (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique et l'Agence Thématique de Recherche en Sciences et Technologie – Algérie) via the PNR programme for financial support.

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