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Acta Cryst. (2009). E65, o1068    [ doi:10.1107/S1600536809013543 ]

Dipyridinium 2,2'-dithiodinicotinate

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

Abstract top

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 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

Refinement top

The specimen used in the diffraction measurements is a multiply-twinned crystal; twinning was evident when examined by the RLATT routine of the data collection software, with a major of about 60%. The diffraction images were integrated on the major component.

The structure initially refined to an R> index of 13%. The structure is a non-merohedral twin, as suggested by PLATON (Spek, 2003). The intensities were de-twinned by the TwinRotMat routine.

The carbon- and nitrogen-bound H-atoms were placed in calculated positions (C—H 0.95 Å, N–H 0.88 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 times U(C,N).

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
[Figure 1] 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
Mr = 466.52Dx = 1.475 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1585 reflections
a = 7.9621 (3) Åθ = 3.1–24.0°
b = 12.3354 (4) ŵ = 0.29 mm−1
c = 21.5057 (8) ÅT = 123 K
β = 95.917 (2)°Chip, light yellow
V = 2100.9 (1) Å30.28 × 0.16 × 0.08 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		1855 independent reflections
Radiation source: fine-focus sealed tube1496 reflections with I > 2σ(I)
graphiteRint = 0.101
ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.923, Tmax = 0.977k = −14→14
6726 measured reflectionsl = −25→25
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)] = 0.092Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.269H-atom parameters constrained
S = 1.59 w = 1/[σ2(Fo2) + (0.1P)2 + 5P]
where P = (Fo2 + 2Fc2)/3
1855 reflections(Δ/σ)max = 0.001
146 parametersΔρmax = 0.47 e Å−3
0 restraintsΔρmin = −0.57 e Å−3
Crystal data top
2C5H6N+·C12H6N2O4S22−V = 2100.9 (1) Å3
Mr = 466.52Z = 4
Monoclinic, C2/cMo Kα radiation
a = 7.9621 (3) ŵ = 0.29 mm−1
b = 12.3354 (4) ÅT = 123 K
c = 21.5057 (8) Å0.28 × 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)
Tmin = 0.923, Tmax = 0.977Rint = 0.101
6726 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.092H-atom parameters constrained
wR(F2) = 0.269Δρmax = 0.47 e Å−3
S = 1.59Δρmin = −0.57 e Å−3
1855 reflectionsAbsolute structure: ?
146 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.5434 (2)0.61088 (12)0.29627 (7)0.0213 (5)
O10.6450 (6)0.6042 (4)0.4204 (2)0.0317 (12)
O20.5265 (6)0.6888 (4)0.4968 (2)0.0336 (12)
N10.3073 (7)0.7643 (4)0.2874 (2)0.0249 (12)
N20.7396 (7)0.5816 (4)0.5721 (3)0.0278 (13)
H20.66900.62180.54780.033*
C10.2040 (9)0.8378 (5)0.3103 (3)0.0299 (16)
H10.13000.87780.28140.036*
C20.1994 (8)0.8583 (5)0.3731 (3)0.0271 (15)
H2A0.12400.91020.38730.033*
C30.3092 (8)0.8001 (5)0.4142 (3)0.0249 (14)
H30.30910.81160.45790.030*
C40.4190 (8)0.7255 (5)0.3929 (3)0.0204 (13)
C50.4125 (8)0.7097 (5)0.3280 (3)0.0191 (13)
C60.5418 (8)0.6678 (5)0.4383 (3)0.0227 (14)
C70.7634 (9)0.5987 (6)0.6336 (3)0.0311 (16)
H70.70300.65570.65100.037*
C80.8721 (9)0.5368 (6)0.6728 (3)0.0342 (17)
H80.88620.55120.71640.041*
C90.9605 (9)0.4535 (6)0.6481 (3)0.0325 (16)
H91.03350.40810.67440.039*
C100.9398 (10)0.4379 (6)0.5841 (3)0.0329 (16)
H101.00300.38420.56510.039*
C110.8259 (9)0.5018 (5)0.5485 (3)0.0280 (15)
H110.80780.48830.50490.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0232 (9)0.0189 (8)0.0212 (8)0.0044 (6)−0.0002 (6)0.0000 (6)
O10.035 (3)0.036 (3)0.023 (2)0.016 (2)−0.003 (2)−0.0003 (19)
O20.038 (3)0.040 (3)0.022 (2)0.017 (2)−0.002 (2)0.000 (2)
N10.023 (3)0.021 (3)0.029 (3)0.010 (2)−0.003 (2)0.000 (2)
N20.025 (3)0.029 (3)0.029 (3)0.001 (2)−0.003 (2)0.000 (2)
C10.029 (4)0.020 (3)0.039 (4)0.004 (3)−0.003 (3)0.001 (3)
C20.023 (3)0.018 (3)0.040 (4)0.000 (3)0.004 (3)−0.003 (3)
C30.027 (3)0.023 (3)0.027 (3)0.004 (3)0.009 (3)−0.001 (3)
C40.019 (3)0.016 (3)0.025 (3)−0.003 (2)−0.003 (3)0.002 (2)
C50.020 (3)0.018 (3)0.019 (3)0.000 (2)0.003 (2)0.003 (2)
C60.024 (3)0.017 (3)0.026 (3)−0.001 (3)−0.001 (3)−0.001 (2)
C70.027 (4)0.037 (4)0.028 (4)−0.002 (3)−0.003 (3)−0.006 (3)
C80.024 (4)0.053 (5)0.024 (3)0.001 (3)−0.005 (3)−0.001 (3)
C90.021 (3)0.037 (4)0.038 (4)−0.003 (3)−0.005 (3)0.004 (3)
C100.034 (4)0.025 (3)0.039 (4)0.002 (3)−0.002 (3)−0.001 (3)
C110.028 (4)0.029 (3)0.027 (3)0.002 (3)0.002 (3)−0.002 (3)
Geometric parameters (Å, °) top
S1—C51.785 (6)C3—C41.380 (9)
S1—S1i2.038 (3)C3—H30.9500
O1—C61.226 (8)C4—C51.405 (9)
O2—C61.302 (8)C4—C61.490 (8)
N1—C51.329 (8)C7—C81.375 (10)
N1—C11.350 (8)C7—H70.9500
N2—C111.330 (9)C8—C91.383 (10)
N2—C71.333 (8)C8—H80.9500
N2—H20.8800C9—C101.384 (10)
C1—C21.376 (9)C9—H90.9500
C1—H10.9500C10—C111.372 (10)
C2—C31.380 (9)C10—H100.9500
C2—H2A0.9500C11—H110.9500
C5—S1—S1i102.7 (2)C4—C5—S1120.8 (5)
C5—N1—C1117.8 (6)O1—C6—O2124.2 (6)
C11—N2—C7117.9 (6)O1—C6—C4121.1 (6)
C11—N2—H2121.0O2—C6—C4114.7 (5)
C7—N2—H2121.0N2—C7—C8122.4 (7)
N1—C1—C2124.0 (6)N2—C7—H7118.8
N1—C1—H1118.0C8—C7—H7118.8
C2—C1—H1118.0C7—C8—C9119.4 (7)
C1—C2—C3117.0 (6)C7—C8—H8120.3
C1—C2—H2A121.5C9—C8—H8120.3
C3—C2—H2A121.5C8—C9—C10118.2 (6)
C4—C3—C2121.0 (6)C8—C9—H9120.9
C4—C3—H3119.5C10—C9—H9120.9
C2—C3—H3119.5C11—C10—C9118.6 (7)
C3—C4—C5117.6 (6)C11—C10—H10120.7
C3—C4—C6119.8 (6)C9—C10—H10120.7
C5—C4—C6122.6 (6)N2—C11—C10123.4 (6)
N1—C5—C4122.5 (6)N2—C11—H11118.3
N1—C5—S1116.7 (5)C10—C11—H11118.3
C5—N1—C1—C2−1.0 (10)S1i—S1—C5—C4172.6 (5)
N1—C1—C2—C30.6 (10)C3—C4—C6—O1−177.2 (6)
C1—C2—C3—C40.5 (9)C5—C4—C6—O10.9 (9)
C2—C3—C4—C5−1.2 (9)C3—C4—C6—O24.3 (8)
C2—C3—C4—C6177.1 (6)C5—C4—C6—O2−177.5 (6)
C1—N1—C5—C40.2 (9)C11—N2—C7—C8−0.4 (10)
C1—N1—C5—S1178.5 (5)N2—C7—C8—C9−0.1 (11)
C3—C4—C5—N10.9 (9)C7—C8—C9—C102.1 (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—S14.4 (8)C9—C10—C11—N23.2 (11)
S1i—S1—C5—N1−5.7 (5)
Symmetry codes: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O20.881.712.586 (7)174
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O20.881.712.586 (7)174
Acknowledgements top

We thank the University of Malaya for supporting this study.

references
References top

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