3-Carbamothioylpyridinium iodide

Sharif, S.; Akkurt, M.; Khan, I.U.; Nadeem, S.; Tirmizi, S.A.; Ahmad, S.

doi:10.1107/S1600536809035892

organic compounds

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Volume 65| Part 10| October 2009| Page o2423

doi:10.1107/S1600536809035892

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3-Carbamothioylpyridinium iodide

Shahzad Sharif,^a Mehmet Akkurt,^b ^* Islam Ullah Khan,^a Shafqat Nadeem,^c Syed Ahmed Tirmizi ^c and Saeed Ahmad ^d ^*

^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 ).

Experimental

Crystal data

C₆H₇N₂S⁺·I⁻
M_r = 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)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.047
S = 1.04
2087 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035892/hb5088sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035892/hb5088Isup2.hkl

checkCIF report

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).

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

	Fig. 1. The molecular structure of (I) with displacement ellipsoids for the non-H atoms drawn at the 50% probability level.
	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.
	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⁺·I⁻	Z = 2
M_r = 266.11	F(000) = 252
Triclinic, P1	D_x = 2.054 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.4024 (3) Å	Cell parameters from 6584 reflections
b = 8.1943 (5) Å	θ = 2.6–28.3°
c = 12.6815 (8) Å	µ = 3.89 mm⁻¹
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 tube	R_int = 0.020
Graphite monochromator	θ_max = 28.3°, θ_min = 2.6°
phi and ω scans	h = −5→5
8839 measured reflections	k = −9→10
2087 independent reflections	l = −16→16

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.047	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0227P)² + 0.219P] where P = (F_o² + 2F_c²)/3
2087 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₆H₇N₂S⁺·I⁻	γ = 102.288 (2)°
M_r = 266.11	V = 430.31 (5) Å³
Triclinic, P1	Z = 2
a = 4.4024 (3) Å	Mo Kα radiation
b = 8.1943 (5) Å	µ = 3.89 mm⁻¹
c = 12.6815 (8) Å	T = 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 reflections	R_int = 0.020
2087 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.047	H-atom parameters constrained
S = 1.04	Δρ_max = 0.65 e Å⁻³
2087 reflections	Δρ_min = −0.43 e Å⁻³
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

	x	y	z	U_iso*/U_eq
S1	0.1191 (2)	0.24949 (10)	−0.01595 (5)	0.0620 (3)
N1	0.3984 (5)	0.2110 (3)	0.37108 (16)	0.0423 (6)
N2	0.2489 (8)	0.5132 (3)	0.1550 (2)	0.0708 (12)
C1	0.3138 (6)	0.3026 (3)	0.30244 (18)	0.0377 (7)
C2	0.5245 (6)	0.0778 (3)	0.3413 (2)	0.0449 (8)
C3	0.5737 (7)	0.0300 (3)	0.2358 (2)	0.0479 (8)
C4	0.4852 (6)	0.1197 (3)	0.1621 (2)	0.0438 (8)
C5	0.3541 (5)	0.2583 (3)	0.19426 (17)	0.0345 (6)
C6	0.2468 (6)	0.3524 (3)	0.11482 (19)	0.0395 (7)
I1	−0.08685 (4)	0.70787 (2)	0.39126 (1)	0.0426 (1)
H1	0.22840	0.39550	0.32730	0.0450*
HN1	0.36980	0.23970	0.43790	0.0510*
H2	0.57890	0.01770	0.39200	0.0540*
H2A	0.31010	0.55920	0.22390	0.0850*
H2B	0.18910	0.57340	0.11260	0.0850*
H3	0.66530	−0.06150	0.21410	0.0570*
H4	0.51400	0.08680	0.08980	0.0530*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.1014 (6)	0.0573 (4)	0.0263 (3)	0.0304 (4)	−0.0032 (3)	0.0045 (3)
N1	0.0534 (12)	0.0464 (12)	0.0256 (9)	0.0090 (10)	0.0078 (9)	0.0083 (9)
N2	0.131 (3)	0.0457 (14)	0.0331 (12)	0.0312 (15)	−0.0095 (14)	0.0070 (10)
C1	0.0430 (12)	0.0388 (12)	0.0296 (11)	0.0094 (10)	0.0060 (9)	0.0055 (9)
C2	0.0541 (15)	0.0409 (13)	0.0377 (13)	0.0076 (11)	0.0003 (11)	0.0132 (11)
C3	0.0572 (15)	0.0428 (14)	0.0441 (14)	0.0204 (12)	0.0045 (12)	0.0057 (11)
C4	0.0539 (14)	0.0471 (14)	0.0291 (11)	0.0151 (12)	0.0083 (10)	0.0033 (10)
C5	0.0377 (11)	0.0371 (11)	0.0261 (10)	0.0063 (9)	0.0030 (8)	0.0063 (9)
C6	0.0470 (13)	0.0426 (13)	0.0283 (11)	0.0095 (11)	0.0046 (9)	0.0098 (9)
I1	0.0421 (1)	0.0492 (1)	0.0351 (1)	0.0154 (1)	0.0065 (1)	0.0034 (1)

Geometric parameters (Å, º) top

S1—C6	1.661 (2)	C2—C3	1.366 (4)
N1—C1	1.337 (3)	C3—C4	1.379 (4)
N1—C2	1.330 (3)	C4—C5	1.386 (3)
N2—C6	1.304 (4)	C5—C6	1.489 (3)
N1—HN1	0.8600	C1—H1	0.9300
N2—H2B	0.8600	C2—H2	0.9300
N2—H2A	0.8600	C3—H3	0.9300
C1—C5	1.383 (3)	C4—H4	0.9300

I1···C1ⁱ	3.639 (3)	C1···C3ⁱ	3.433 (4)
I1···C2ⁱⁱ	3.818 (3)	C2···I1^x	3.818 (3)
I1···N2	3.694 (3)	C2···I1^iv	3.793 (3)
I1···N1ⁱⁱⁱ	3.444 (2)	C3···C1^ix	3.433 (4)
I1···C2^iv	3.794 (3)	C4···S1^vii	3.564 (3)
I1···H1	3.1600	C1···H2A	2.5200
I1···H2^v	3.1900	H1···H2A	2.0800
I1···H2Aⁱ	3.0400	H1···I1	3.1600
I1···H2A	3.1100	H1···N2	2.5800
I1···H2^iv	3.3800	HN1···I1ⁱⁱⁱ	2.6200
I1···HN1ⁱⁱⁱ	2.6200	H2···I1^xi	3.1900
S1···N2^vi	3.420 (3)	H2···I1^iv	3.3800
S1···C4^vii	3.564 (3)	H2A···H1	2.0800
S1···H3^viii	3.0100	H2A···I1	3.1100
S1···H2B^vi	2.5800	H2A···I1^ix	3.0400
S1···H4	2.8000	H2A···C1	2.5200
N1···I1ⁱⁱⁱ	3.444 (2)	H2B···S1^vi	2.5800
N2···S1^vi	3.420 (3)	H3···S1^viii	3.0100
N2···I1	3.694 (3)	H4···S1	2.8000
N2···H1	2.5800	H4···H4^viii	2.3800
C1···I1^ix	3.639 (3)

C1—N1—C2	123.4 (2)	C4—C5—C6	121.6 (2)
C1—N1—HN1	118.00	S1—C6—C5	119.92 (18)
C2—N1—HN1	118.00	N2—C6—C5	116.3 (2)
C6—N2—H2A	120.00	S1—C6—N2	123.7 (2)
H2A—N2—H2B	120.00	N1—C1—H1	120.00
C6—N2—H2B	120.00	C5—C1—H1	120.00
N1—C1—C5	119.6 (2)	N1—C2—H2	120.00
N1—C2—C3	119.5 (2)	C3—C2—H2	120.00
C2—C3—C4	118.9 (2)	C2—C3—H3	121.00
C3—C4—C5	121.0 (2)	C4—C3—H3	121.00
C1—C5—C4	117.7 (2)	C3—C4—H4	120.00
C1—C5—C6	120.6 (2)	C5—C4—H4	119.00

C2—N1—C1—C5	0.7 (4)	C3—C4—C5—C1	−0.4 (4)
C1—N1—C2—C3	0.3 (4)	C3—C4—C5—C6	−177.8 (2)
N1—C1—C5—C4	−0.6 (4)	C1—C5—C6—S1	−147.9 (2)
N1—C1—C5—C6	176.8 (2)	C1—C5—C6—N2	29.5 (4)
N1—C2—C3—C4	−1.2 (4)	C4—C5—C6—S1	29.4 (3)
C2—C3—C4—C5	1.3 (4)	C4—C5—C6—N2	−153.1 (3)

Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) x−1, y+1, z; (vi) −x, −y+1, −z; (vii) −x, −y, −z; (viii) −x+1, −y, −z; (ix) x+1, y, z; (x) x, y−1, z; (xi) x+1, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—HN1···I1ⁱⁱⁱ	0.86	2.62	3.444 (2)	161
N2—H2A···I1^ix	0.86	3.04	3.747 (3)	140
N2—H2B···S1^vi	0.86	2.58	3.420 (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 formula	C₆H₇N₂S⁺·I⁻
M_r	266.11
Crystal system, space group	Triclinic, 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)
V (Å³)	430.31 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.89
Crystal size (mm)	0.17 × 0.15 × 0.14

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8839, 2087, 1890
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.047, 1.04
No. of reflections	2087
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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.

References

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. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bernstein, 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
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2423

doi:10.1107/S1600536809035892

Open

access