Dipyridinium 2,2′-dithio­dinicotinate

Yehye, W.A.; Ariffin, A.; Rahman, N.A.; Ng, S.W.

doi:10.1107/S1600536809013543

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1068

doi:10.1107/S1600536809013543

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Dipyridinium 2,2′-dithiodinicotinate

Wagee A. Yehye,^a Azhar Ariffin,^a Noorsaadah Abdul Rahman ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 7 April 2009; accepted 10 April 2009; online 18 April 2009)

The dianion of the title salt, 2C₅H₆N⁺·C₁₂H₆N₂O₄S₂²⁻, lies on a special position of 2 site symmetry that relates one thionicotinate part to the other, and the dihedral angle between the niotinate planes is 89.2 (2)°. The pyridinium cations are hydrogen bonded to the carboxylate group by way of N—H⋯O links.

Related literature

The structure is a non-merohedral twin; for the program to model twinned crystal structures, see: Spek (2003 ). For 1,1′-dithio-2,2′-dinicotinic acid, see: Zhu et al. (2002 ). For the methyl, ethyl and n-butyl esters, see: Cindrić et al. (2001 ); Toma et al. (2004 ).

Experimental

Crystal data

2C₅H₆N⁺·C₁₂H₆N₂O₄S₂²⁻
M_r = 466.52
Monoclinic, C 2/c
a = 7.9621 (3) Å
b = 12.3354 (4) Å
c = 21.5057 (8) Å
β = 95.917 (2)°
V = 2100.9 (1) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 123 K
0.28 × 0.16 × 0.08 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.923, T_max = 0.977
6726 measured reflections
1855 independent reflections
1496 reflections with I > 2σ(I)
R_int = 0.101

Refinement

R[F² > 2σ(F²)] = 0.092
wR(F²) = 0.269
S = 1.59
1855 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.88	1.71	2.586 (7)	174

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013543/si2170sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013543/si2170Isup2.hkl

checkCIF report

Related literature top

The structure is a non-merohedral twin; for the program to de-twin twinned crystal structures, see: Spek (2003). For 1,1'-dithio-2,2'-dinicotinic acid, see: Zhu et al. (2002). For the methyl, ethyl and n-butyl esters, see: Cindrić et al. (2001); Toma et al. (2004).

Experimental top

The title compound was isolated as one of the by-products when 2-(3,5-di-tert-butyl-4-hydroxybenzylsulfanyl)nicotinic acid (0.37 g, 1 mmol) and thiocarbohydrazide (0.10 g, 1 mmol) were reacted in pyridine (10 ml) for 3 h. The product from a cool mixture was collected and recrystallized from pyridine

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of 2(C₅H₆N) (C₁₂H₆N₂O₄S₂) at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Dipyridinium 2,2'-dithiodinicotinate top

Crystal data top

2C₅H₆N⁺·C₁₂H₆N₂O₄S₂²⁻	F(000) = 968
M_r = 466.52	D_x = 1.475 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1585 reflections
a = 7.9621 (3) Å	θ = 3.1–24.0°
b = 12.3354 (4) Å	µ = 0.29 mm⁻¹
c = 21.5057 (8) Å	T = 123 K
β = 95.917 (2)°	Chip, light yellow
V = 2100.9 (1) Å³	0.28 × 0.16 × 0.08 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1855 independent reflections
Radiation source: fine-focus sealed tube	1496 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.101
ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.923, T_max = 0.977	k = −14→14
6726 measured reflections	l = −25→25

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)] = 0.092	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.269	H-atom parameters constrained
S = 1.59	w = 1/[σ²(F_o²) + (0.1P)² + 5P] where P = (F_o² + 2F_c²)/3
1855 reflections	(Δ/σ)_max = 0.001
146 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

2C₅H₆N⁺·C₁₂H₆N₂O₄S₂²⁻	V = 2100.9 (1) Å³
M_r = 466.52	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 7.9621 (3) Å	µ = 0.29 mm⁻¹
b = 12.3354 (4) Å	T = 123 K
c = 21.5057 (8) Å	0.28 × 0.16 × 0.08 mm
β = 95.917 (2)°

Data collection top

Bruker SMART APEX diffractometer	1855 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1496 reflections with I > 2σ(I)
T_min = 0.923, T_max = 0.977	R_int = 0.101
6726 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.092	0 restraints
wR(F²) = 0.269	H-atom parameters constrained
S = 1.59	Δρ_max = 0.47 e Å⁻³
1855 reflections	Δρ_min = −0.57 e Å⁻³
146 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.5434 (2)	0.61088 (12)	0.29627 (7)	0.0213 (5)
O1	0.6450 (6)	0.6042 (4)	0.4204 (2)	0.0317 (12)
O2	0.5265 (6)	0.6888 (4)	0.4968 (2)	0.0336 (12)
N1	0.3073 (7)	0.7643 (4)	0.2874 (2)	0.0249 (12)
N2	0.7396 (7)	0.5816 (4)	0.5721 (3)	0.0278 (13)
H2	0.6690	0.6218	0.5478	0.033*
C1	0.2040 (9)	0.8378 (5)	0.3103 (3)	0.0299 (16)
H1	0.1300	0.8778	0.2814	0.036*
C2	0.1994 (8)	0.8583 (5)	0.3731 (3)	0.0271 (15)
H2A	0.1240	0.9102	0.3873	0.033*
C3	0.3092 (8)	0.8001 (5)	0.4142 (3)	0.0249 (14)
H3	0.3091	0.8116	0.4579	0.030*
C4	0.4190 (8)	0.7255 (5)	0.3929 (3)	0.0204 (13)
C5	0.4125 (8)	0.7097 (5)	0.3280 (3)	0.0191 (13)
C6	0.5418 (8)	0.6678 (5)	0.4383 (3)	0.0227 (14)
C7	0.7634 (9)	0.5987 (6)	0.6336 (3)	0.0311 (16)
H7	0.7030	0.6557	0.6510	0.037*
C8	0.8721 (9)	0.5368 (6)	0.6728 (3)	0.0342 (17)
H8	0.8862	0.5512	0.7164	0.041*
C9	0.9605 (9)	0.4535 (6)	0.6481 (3)	0.0325 (16)
H9	1.0335	0.4081	0.6744	0.039*
C10	0.9398 (10)	0.4379 (6)	0.5841 (3)	0.0329 (16)
H10	1.0030	0.3842	0.5651	0.039*
C11	0.8259 (9)	0.5018 (5)	0.5485 (3)	0.0280 (15)
H11	0.8078	0.4883	0.5049	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0232 (9)	0.0189 (8)	0.0212 (8)	0.0044 (6)	−0.0002 (6)	0.0000 (6)
O1	0.035 (3)	0.036 (3)	0.023 (2)	0.016 (2)	−0.003 (2)	−0.0003 (19)
O2	0.038 (3)	0.040 (3)	0.022 (2)	0.017 (2)	−0.002 (2)	0.000 (2)
N1	0.023 (3)	0.021 (3)	0.029 (3)	0.010 (2)	−0.003 (2)	0.000 (2)
N2	0.025 (3)	0.029 (3)	0.029 (3)	0.001 (2)	−0.003 (2)	0.000 (2)
C1	0.029 (4)	0.020 (3)	0.039 (4)	0.004 (3)	−0.003 (3)	0.001 (3)
C2	0.023 (3)	0.018 (3)	0.040 (4)	0.000 (3)	0.004 (3)	−0.003 (3)
C3	0.027 (3)	0.023 (3)	0.027 (3)	0.004 (3)	0.009 (3)	−0.001 (3)
C4	0.019 (3)	0.016 (3)	0.025 (3)	−0.003 (2)	−0.003 (3)	0.002 (2)
C5	0.020 (3)	0.018 (3)	0.019 (3)	0.000 (2)	0.003 (2)	0.003 (2)
C6	0.024 (3)	0.017 (3)	0.026 (3)	−0.001 (3)	−0.001 (3)	−0.001 (2)
C7	0.027 (4)	0.037 (4)	0.028 (4)	−0.002 (3)	−0.003 (3)	−0.006 (3)
C8	0.024 (4)	0.053 (5)	0.024 (3)	0.001 (3)	−0.005 (3)	−0.001 (3)
C9	0.021 (3)	0.037 (4)	0.038 (4)	−0.003 (3)	−0.005 (3)	0.004 (3)
C10	0.034 (4)	0.025 (3)	0.039 (4)	0.002 (3)	−0.002 (3)	−0.001 (3)
C11	0.028 (4)	0.029 (3)	0.027 (3)	0.002 (3)	0.002 (3)	−0.002 (3)

Geometric parameters (Å, º) top

S1—C5	1.785 (6)	C3—C4	1.380 (9)
S1—S1ⁱ	2.038 (3)	C3—H3	0.9500
O1—C6	1.226 (8)	C4—C5	1.405 (9)
O2—C6	1.302 (8)	C4—C6	1.490 (8)
N1—C5	1.329 (8)	C7—C8	1.375 (10)
N1—C1	1.350 (8)	C7—H7	0.9500
N2—C11	1.330 (9)	C8—C9	1.383 (10)
N2—C7	1.333 (8)	C8—H8	0.9500
N2—H2	0.8800	C9—C10	1.384 (10)
C1—C2	1.376 (9)	C9—H9	0.9500
C1—H1	0.9500	C10—C11	1.372 (10)
C2—C3	1.380 (9)	C10—H10	0.9500
C2—H2A	0.9500	C11—H11	0.9500

C5—S1—S1ⁱ	102.7 (2)	C4—C5—S1	120.8 (5)
C5—N1—C1	117.8 (6)	O1—C6—O2	124.2 (6)
C11—N2—C7	117.9 (6)	O1—C6—C4	121.1 (6)
C11—N2—H2	121.0	O2—C6—C4	114.7 (5)
C7—N2—H2	121.0	N2—C7—C8	122.4 (7)
N1—C1—C2	124.0 (6)	N2—C7—H7	118.8
N1—C1—H1	118.0	C8—C7—H7	118.8
C2—C1—H1	118.0	C7—C8—C9	119.4 (7)
C1—C2—C3	117.0 (6)	C7—C8—H8	120.3
C1—C2—H2A	121.5	C9—C8—H8	120.3
C3—C2—H2A	121.5	C8—C9—C10	118.2 (6)
C4—C3—C2	121.0 (6)	C8—C9—H9	120.9
C4—C3—H3	119.5	C10—C9—H9	120.9
C2—C3—H3	119.5	C11—C10—C9	118.6 (7)
C3—C4—C5	117.6 (6)	C11—C10—H10	120.7
C3—C4—C6	119.8 (6)	C9—C10—H10	120.7
C5—C4—C6	122.6 (6)	N2—C11—C10	123.4 (6)
N1—C5—C4	122.5 (6)	N2—C11—H11	118.3
N1—C5—S1	116.7 (5)	C10—C11—H11	118.3

C5—N1—C1—C2	−1.0 (10)	S1ⁱ—S1—C5—C4	172.6 (5)
N1—C1—C2—C3	0.6 (10)	C3—C4—C6—O1	−177.2 (6)
C1—C2—C3—C4	0.5 (9)	C5—C4—C6—O1	0.9 (9)
C2—C3—C4—C5	−1.2 (9)	C3—C4—C6—O2	4.3 (8)
C2—C3—C4—C6	177.1 (6)	C5—C4—C6—O2	−177.5 (6)
C1—N1—C5—C4	0.2 (9)	C11—N2—C7—C8	−0.4 (10)
C1—N1—C5—S1	178.5 (5)	N2—C7—C8—C9	−0.1 (11)
C3—C4—C5—N1	0.9 (9)	C7—C8—C9—C10	2.1 (11)
C6—C4—C5—N1	−177.3 (5)	C8—C9—C10—C11	−3.5 (10)
C3—C4—C5—S1	−177.4 (5)	C7—N2—C11—C10	−1.2 (10)
C6—C4—C5—S1	4.4 (8)	C9—C10—C11—N2	3.2 (11)
S1ⁱ—S1—C5—N1	−5.7 (5)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.88	1.71	2.586 (7)	174

Experimental details

Crystal data
Chemical formula	2C₅H₆N⁺·C₁₂H₆N₂O₄S₂²⁻
M_r	466.52
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	123
a, b, c (Å)	7.9621 (3), 12.3354 (4), 21.5057 (8)
β (°)	95.917 (2)
V (Å³)	2100.9 (1)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.28 × 0.16 × 0.08

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.923, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	6726, 1855, 1496
R_int	0.101
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.092, 0.269, 1.59
No. of reflections	1855
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.57

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.88	1.71	2.586 (7)	174

Acknowledgements

We thank the University of Malaya for supporting this study.

References

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