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ISSN: 2056-9890

3-Carbamo­thioylpyridinium iodide

aMaterials Chemistry Laboratory, Department of Chemistry, Government College University, Lahore 54000, Pakistan, bDepartment of Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey, cDepartment of Chemistry, Quaid-i-azam University, Islamabad, Pakistan, and dDepartment of Chemistry, University of Engineering and Technology, Lahore 54890, Pakistan
*Correspondence e-mail: akkurt@erciyes.edu.tr, saeed_a786@hotmail.com

(Received 4 September 2009; accepted 4 September 2009; online 9 September 2009)

In the crystal of the title salt, C6H7N2S+·I, inversion-related cations form an R22(8) dimer linked by a pair of N—H⋯S hydrogen bonds. Pairs of iodide anions are located between adjacent cation dimers and are linked to them by way of N—H⋯I hydrogen bonds. This results in zigzag chains propagating in [001] lying parallel to the bc plane.

Related literature

For graph-set theory, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C6H7N2S+·I

  • Mr = 266.11

  • Triclinic, [P \overline 1]

  • a = 4.4024 (3) Å

  • b = 8.1943 (5) Å

  • c = 12.6815 (8) Å

  • α = 102.485 (2)°

  • β = 96.496 (2)°

  • γ = 102.288 (2)°

  • V = 430.31 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 3.89 mm−1

  • T = 296 K

  • 0.17 × 0.15 × 0.14 mm

Data collection
  • Bruker Kappa APEXII CCD diffractometer

  • Absorption correction: none

  • 8839 measured reflections

  • 2087 independent reflections

  • 1890 reflections with I > 2σ(I)

  • Rint = 0.020

Refinement
  • R[F2 > 2σ(F2)] = 0.019

  • wR(F2) = 0.047

  • S = 1.04

  • 2087 reflections

  • 91 parameters

  • H-atom parameters constrained

  • Δρmax = 0.65 e Å−3

  • Δρmin = −0.43 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—HN1⋯I1i 0.86 2.62 3.444 (2) 161
N2—H2A⋯I1ii 0.86 3.04 3.747 (3) 140
N2—H2B⋯S1iii 0.86 2.58 3.420 (3) 164
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x+1, y, z; (iii) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999[Altomare, A., Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Rizzi, R. (1999). J. Appl. Cryst. 32, 339-340.]); 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, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

In the present study we attempted to prepare a palladium(II) iodide complex with thionicotinamide, but it is surprising to note that the resulting compound is a simple salt of pyridine. Here we report the crystal structure of the salt (I).

In the title compund (I), (Fig. 1), the bond lengths and angles are entirely as expected. In the crystal structure of (I), two crystallographically independent cations form a dimer through N—H···S hydrogen bonds. The two iodide anions are located between two adjacent dimers and forms N—H···I hydrogen bonds with two iodide anions from each dimer. Thus, the molecules linked in the form of zigzag in the layers parallel to the bc plane along the b axis (Fig. 2 and Fig. 3, Table 1).

Related literature top

For graph-set theory, see: Bernstein et al. (1995).

Experimental top

The title compound was prepared by adding 2 equivalents of thionicotinamide in 15 ml methanol to a solution of K2[PdCl4] (0.326 g) in 15 ml of water followed by addition of 2 equivalents of potassium iodide in water after half an hour stirring. The dark brown solution was the stirred for one hour. The resulting solution was filtrated and filtrate was kept at room temperature for crystallization. The brown product obtained from water-methanol mixture wasre-dissolved in methanol, which on slow evaporation yielded light brown crystals of (I).

Refinement top

All H atoms were located geometrically and treated as riding with C—H = 0.93 Å and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(C, N).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with displacement ellipsoids for the non-H atoms drawn at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram for (I) viewed down the a axis, showing the R22(8) dimer motif further linked by N—H···I hydrogen bonds between the adjacent dimers thorough the iodide anions to form an infinite chain in the [010] direction. Hydrogen atoms not involved in the showed interactions have been omitted for clarity.
[Figure 3] Fig. 3. A view of the packing and hydrogen bonding of (I). Hydrogen atoms not involved in the showed interactions have been omitted for clarity.
3-Carbamothioylpyridinium iodide top
Crystal data top
C6H7N2S+·IZ = 2
Mr = 266.11F(000) = 252
Triclinic, P1Dx = 2.054 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.4024 (3) ÅCell parameters from 6584 reflections
b = 8.1943 (5) Åθ = 2.6–28.3°
c = 12.6815 (8) ŵ = 3.89 mm1
α = 102.485 (2)°T = 296 K
β = 96.496 (2)°Irregular chunk, light brown
γ = 102.288 (2)°0.17 × 0.15 × 0.14 mm
V = 430.31 (5) Å3
Data collection top
Bruker Kappa APEXII CCD
diffractometer
1890 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.020
Graphite monochromatorθmax = 28.3°, θmin = 2.6°
phi and ω scansh = 55
8839 measured reflectionsk = 910
2087 independent reflectionsl = 1616
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)] = 0.019Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.047H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0227P)2 + 0.219P]
where P = (Fo2 + 2Fc2)/3
2087 reflections(Δ/σ)max = 0.001
91 parametersΔρmax = 0.65 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
C6H7N2S+·Iγ = 102.288 (2)°
Mr = 266.11V = 430.31 (5) Å3
Triclinic, P1Z = 2
a = 4.4024 (3) ÅMo Kα radiation
b = 8.1943 (5) ŵ = 3.89 mm1
c = 12.6815 (8) ÅT = 296 K
α = 102.485 (2)°0.17 × 0.15 × 0.14 mm
β = 96.496 (2)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer
1890 reflections with I > 2σ(I)
8839 measured reflectionsRint = 0.020
2087 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.047H-atom parameters constrained
S = 1.04Δρmax = 0.65 e Å3
2087 reflectionsΔρmin = 0.43 e Å3
91 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
S10.1191 (2)0.24949 (10)0.01595 (5)0.0620 (3)
N10.3984 (5)0.2110 (3)0.37108 (16)0.0423 (6)
N20.2489 (8)0.5132 (3)0.1550 (2)0.0708 (12)
C10.3138 (6)0.3026 (3)0.30244 (18)0.0377 (7)
C20.5245 (6)0.0778 (3)0.3413 (2)0.0449 (8)
C30.5737 (7)0.0300 (3)0.2358 (2)0.0479 (8)
C40.4852 (6)0.1197 (3)0.1621 (2)0.0438 (8)
C50.3541 (5)0.2583 (3)0.19426 (17)0.0345 (6)
C60.2468 (6)0.3524 (3)0.11482 (19)0.0395 (7)
I10.08685 (4)0.70787 (2)0.39126 (1)0.0426 (1)
H10.228400.395500.327300.0450*
HN10.369800.239700.437900.0510*
H20.578900.017700.392000.0540*
H2A0.310100.559200.223900.0850*
H2B0.189100.573400.112600.0850*
H30.665300.061500.214100.0570*
H40.514000.086800.089800.0530*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.1014 (6)0.0573 (4)0.0263 (3)0.0304 (4)0.0032 (3)0.0045 (3)
N10.0534 (12)0.0464 (12)0.0256 (9)0.0090 (10)0.0078 (9)0.0083 (9)
N20.131 (3)0.0457 (14)0.0331 (12)0.0312 (15)0.0095 (14)0.0070 (10)
C10.0430 (12)0.0388 (12)0.0296 (11)0.0094 (10)0.0060 (9)0.0055 (9)
C20.0541 (15)0.0409 (13)0.0377 (13)0.0076 (11)0.0003 (11)0.0132 (11)
C30.0572 (15)0.0428 (14)0.0441 (14)0.0204 (12)0.0045 (12)0.0057 (11)
C40.0539 (14)0.0471 (14)0.0291 (11)0.0151 (12)0.0083 (10)0.0033 (10)
C50.0377 (11)0.0371 (11)0.0261 (10)0.0063 (9)0.0030 (8)0.0063 (9)
C60.0470 (13)0.0426 (13)0.0283 (11)0.0095 (11)0.0046 (9)0.0098 (9)
I10.0421 (1)0.0492 (1)0.0351 (1)0.0154 (1)0.0065 (1)0.0034 (1)
Geometric parameters (Å, º) top
S1—C61.661 (2)C2—C31.366 (4)
N1—C11.337 (3)C3—C41.379 (4)
N1—C21.330 (3)C4—C51.386 (3)
N2—C61.304 (4)C5—C61.489 (3)
N1—HN10.8600C1—H10.9300
N2—H2B0.8600C2—H20.9300
N2—H2A0.8600C3—H30.9300
C1—C51.383 (3)C4—H40.9300
I1···C1i3.639 (3)C1···C3i3.433 (4)
I1···C2ii3.818 (3)C2···I1x3.818 (3)
I1···N23.694 (3)C2···I1iv3.793 (3)
I1···N1iii3.444 (2)C3···C1ix3.433 (4)
I1···C2iv3.794 (3)C4···S1vii3.564 (3)
I1···H13.1600C1···H2A2.5200
I1···H2v3.1900H1···H2A2.0800
I1···H2Ai3.0400H1···I13.1600
I1···H2A3.1100H1···N22.5800
I1···H2iv3.3800HN1···I1iii2.6200
I1···HN1iii2.6200H2···I1xi3.1900
S1···N2vi3.420 (3)H2···I1iv3.3800
S1···C4vii3.564 (3)H2A···H12.0800
S1···H3viii3.0100H2A···I13.1100
S1···H2Bvi2.5800H2A···I1ix3.0400
S1···H42.8000H2A···C12.5200
N1···I1iii3.444 (2)H2B···S1vi2.5800
N2···S1vi3.420 (3)H3···S1viii3.0100
N2···I13.694 (3)H4···S12.8000
N2···H12.5800H4···H4viii2.3800
C1···I1ix3.639 (3)
C1—N1—C2123.4 (2)C4—C5—C6121.6 (2)
C1—N1—HN1118.00S1—C6—C5119.92 (18)
C2—N1—HN1118.00N2—C6—C5116.3 (2)
C6—N2—H2A120.00S1—C6—N2123.7 (2)
H2A—N2—H2B120.00N1—C1—H1120.00
C6—N2—H2B120.00C5—C1—H1120.00
N1—C1—C5119.6 (2)N1—C2—H2120.00
N1—C2—C3119.5 (2)C3—C2—H2120.00
C2—C3—C4118.9 (2)C2—C3—H3121.00
C3—C4—C5121.0 (2)C4—C3—H3121.00
C1—C5—C4117.7 (2)C3—C4—H4120.00
C1—C5—C6120.6 (2)C5—C4—H4119.00
C2—N1—C1—C50.7 (4)C3—C4—C5—C10.4 (4)
C1—N1—C2—C30.3 (4)C3—C4—C5—C6177.8 (2)
N1—C1—C5—C40.6 (4)C1—C5—C6—S1147.9 (2)
N1—C1—C5—C6176.8 (2)C1—C5—C6—N229.5 (4)
N1—C2—C3—C41.2 (4)C4—C5—C6—S129.4 (3)
C2—C3—C4—C51.3 (4)C4—C5—C6—N2153.1 (3)
Symmetry codes: (i) x1, y, z; (ii) x, y+1, z; (iii) x, y+1, z+1; (iv) x+1, y+1, z+1; (v) x1, y+1, z; (vi) x, y+1, z; (vii) x, y, z; (viii) x+1, y, z; (ix) x+1, y, z; (x) x, y1, z; (xi) x+1, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—HN1···I1iii0.862.623.444 (2)161
N2—H2A···I1ix0.863.043.747 (3)140
N2—H2B···S1vi0.862.583.420 (3)164
Symmetry codes: (iii) x, y+1, z+1; (vi) x, y+1, z; (ix) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC6H7N2S+·I
Mr266.11
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)4.4024 (3), 8.1943 (5), 12.6815 (8)
α, β, γ (°)102.485 (2), 96.496 (2), 102.288 (2)
V3)430.31 (5)
Z2
Radiation typeMo Kα
µ (mm1)3.89
Crystal size (mm)0.17 × 0.15 × 0.14
Data collection
DiffractometerBruker Kappa APEXII CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8839, 2087, 1890
Rint0.020
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.047, 1.04
No. of reflections2087
No. of parameters91
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.65, 0.43

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—HN1···I1i0.862.623.444 (2)161
N2—H2A···I1ii0.863.043.747 (3)140
N2—H2B···S1iii0.862.583.420 (3)164
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z; (iii) x, y+1, z.
 

References

First citationAltomare, A., Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Rizzi, R. (1999). J. Appl. Cryst. 32, 339–340.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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