organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Crystal structure of 3-carbamo­thio­yl­pyridinium thio­cyanate

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).

1. Related literature

For isomeric thio­nicotinamide structures, see: Downie et al. (1972[Downie, T. C., Harrison, W., Raper, E. S. & Hepworth, M. A. (1972). Acta Cryst. B28, 283-290.]); Form et al. (1973[Form, G. R., Raper, E. S. & Downie, T. C. (1973). Acta Cryst. B29, 776-782.]); Colleter & Gadret (1967[Colleter, J. C. & Gadret, M. (1967). Bull. Soc. Chim. Fr. pp. 3463-3469.]). For a related structure, see: Sharif et al. (2009[Sharif, S., Akkurt, M., Khan, I. U., Nadeem, S., Tirmizi, S. A. & Ahmad, S. (2009). Acta Cryst. E65, o2423.]). For the structural inter­est of thio­nicotinamides, see: Fonari et al. (2007[Fonari, M. S., Ganin, E. V., Tang, S. W., Wang, W. J. & Simonov, Y. A. (2007). J. Mol. Struct. 826, 89-95.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C6H7N2S+·CNS

  • Mr = 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[Sheldrick, G. M. (2002). SADABS. University of Göttingen, Germany.]) Tmin = 0.679, Tmax = 0.746

  • 12686 measured reflections

  • 3313 independent reflections

  • 2563 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.58 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2011). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2011[Bruker (2011). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005[Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and DIAMOND (Brandenburg & Berndt, 2001[Brandenburg, K. & Berndt, M. (2001). DIAMOND. Crystal Impact, Bonn, Germany.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).

Supporting information


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.

Refinement top

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 Uiso = 1.2Ueq(C or N).

Structure description 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).

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
[Figure 1] 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.
[Figure 2] 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+·CNSF(000) = 408
Mr = 197.28Dx = 1.422 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 7.2495 (2) ÅCell parameters from 5267 reflections
b = 9.3759 (3) Åθ = 2.6–32.1°
c = 13.5949 (3) ŵ = 0.52 mm1
β = 94.454 (1)°T = 295 K
V = 921.26 (4) Å3Prism, colorless
Z = 40.2 × 0.16 × 0.1 mm
Data collection top
Bruker APEXII
diffractometer
3313 independent reflections
Radiation source: sealed tube2563 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
φ and ω scansθmax = 32.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 1010
Tmin = 0.679, Tmax = 0.746k = 1414
12686 measured reflectionsl = 2020
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0808P)2 + 0.1946P]
where P = (Fo2 + 2Fc2)/3
3313 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C6H7N2S+·CNSV = 921.26 (4) Å3
Mr = 197.28Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.2495 (2) ŵ = 0.52 mm1
b = 9.3759 (3) ÅT = 295 K
c = 13.5949 (3) Å0.2 × 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)
Tmin = 0.679, Tmax = 0.746Rint = 0.023
12686 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.140H-atom parameters constrained
S = 1.04Δρmax = 0.58 e Å3
3313 reflectionsΔρmin = 0.26 e Å3
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
xyzUiso*/Ueq
C10.9430 (2)0.08889 (15)0.83615 (10)0.0351 (3)
C20.91545 (18)0.13467 (15)0.73124 (9)0.0322 (3)
C30.9619 (2)0.27153 (17)0.70337 (11)0.0401 (3)
H31.01140.3360.75030.048*
C40.9342 (3)0.3117 (2)0.60509 (13)0.0536 (4)
H40.96750.40250.58540.064*
C50.8576 (3)0.2168 (2)0.53738 (12)0.0552 (5)
H50.83650.24340.47160.066*
C60.8395 (2)0.04215 (18)0.65938 (10)0.0392 (3)
H60.80720.05010.67640.047*
C110.3607 (2)0.10281 (16)0.67580 (11)0.0383 (3)
N10.9976 (2)0.04356 (15)0.85163 (10)0.0492 (3)
H1A1.01530.09830.80250.059*
H1B1.01560.07540.91090.059*
N20.81305 (19)0.08559 (17)0.56595 (9)0.0464 (3)
H20.76550.0270.52240.056*
N110.3114 (3)0.0569 (2)0.59942 (12)0.0642 (5)
S10.90233 (7)0.20284 (5)0.92615 (3)0.04789 (14)
S110.43232 (7)0.16631 (5)0.78372 (3)0.04908 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0405 (7)0.0356 (6)0.0286 (5)0.0036 (5)0.0012 (5)0.0032 (5)
C20.0340 (6)0.0364 (6)0.0257 (5)0.0005 (5)0.0004 (4)0.0029 (4)
C30.0481 (8)0.0358 (7)0.0358 (6)0.0008 (6)0.0001 (6)0.0007 (5)
C40.0724 (12)0.0460 (9)0.0427 (8)0.0019 (8)0.0056 (8)0.0102 (7)
C50.0638 (11)0.0713 (12)0.0299 (7)0.0139 (9)0.0000 (7)0.0074 (7)
C60.0421 (7)0.0435 (7)0.0316 (6)0.0039 (6)0.0007 (5)0.0066 (5)
C110.0440 (7)0.0352 (7)0.0356 (6)0.0024 (6)0.0029 (5)0.0006 (5)
N10.0781 (10)0.0370 (7)0.0323 (6)0.0049 (7)0.0022 (6)0.0002 (5)
N20.0484 (7)0.0609 (9)0.0286 (5)0.0024 (6)0.0043 (5)0.0102 (5)
N110.0865 (12)0.0625 (10)0.0419 (7)0.0034 (9)0.0070 (7)0.0116 (7)
S10.0704 (3)0.0440 (2)0.02793 (18)0.01027 (18)0.00476 (16)0.00570 (13)
S110.0598 (3)0.0521 (3)0.0344 (2)0.00810 (19)0.00268 (16)0.00319 (15)
Geometric parameters (Å, º) top
C1—N11.3154 (19)C5—N21.337 (3)
C1—C21.4879 (18)C5—H50.93
C1—S11.6677 (14)C6—N21.3334 (19)
C2—C31.387 (2)C6—H60.93
C2—C61.3879 (19)C11—N111.155 (2)
C3—C41.388 (2)C11—S111.6303 (16)
C3—H30.93N1—H1A0.86
C4—C51.367 (3)N1—H1B0.86
C4—H40.93N2—H20.86
N1—C1—C2116.23 (12)N2—C5—H5120.1
N1—C1—S1123.75 (11)C4—C5—H5120.1
C2—C1—S1120.02 (11)N2—C6—C2119.97 (15)
C3—C2—C6118.52 (13)N2—C6—H6120
C3—C2—C1120.76 (12)C2—C6—H6120
C6—C2—C1120.71 (13)N11—C11—S11179.35 (17)
C2—C3—C4119.60 (15)C1—N1—H1A120
C2—C3—H3120.2C1—N1—H1B120
C4—C3—H3120.2H1A—N1—H1B120
C5—C4—C3119.51 (17)C6—N2—C5122.51 (14)
C5—C4—H4120.2C6—N2—H2118.7
C3—C4—H4120.2C5—N2—H2118.7
N2—C5—C4119.88 (15)
N1—C1—C2—C3142.88 (16)C2—C3—C4—C51.4 (3)
S1—C1—C2—C337.84 (19)C3—C4—C5—N21.1 (3)
N1—C1—C2—C638.3 (2)C3—C2—C6—N20.1 (2)
S1—C1—C2—C6140.98 (13)C1—C2—C6—N2178.93 (13)
C6—C2—C3—C40.9 (2)C2—C6—N2—C50.2 (2)
C1—C2—C3—C4179.75 (15)C4—C5—N2—C60.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···S11i0.862.543.3450 (15)156
N1—H1B···S1ii0.862.553.3975 (14)171
N2—H2···N11iii0.861.882.709 (2)162
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (ii) x+2, y, z+2; (iii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···S11i0.86002.54003.3450 (15)156.00
N1—H1B···S1ii0.86002.55003.3975 (14)171.00
N2—H2···N11iii0.86001.88002.709 (2)162.00
Symmetry codes: (i) x+3/2, y1/2, 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.

References

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