catena-Poly[[aqua­sodium(I)]-μ-[2,2′-(disulfanedi­yl)bis­(pyridine N-oxide)]-μ-(pyridine-2-thiol­ato 1-oxide)]

B Ravindran Durai Nayagam; Samuel Robinson Jebas; J Jebaraj Devadasan; R Murugesan; Dieter Schollmeyer

doi:10.1107/S1600536810000073

. 2010 Jan 13;66(Pt 2):m142–m143. doi: 10.1107/S1600536810000073

catena-Poly[[aquasodium(I)]-μ-[2,2′-(disulfanediyl)bis(pyridine N-oxide)]-μ-(pyridine-2-thiolato 1-oxide)]

B Ravindran Durai Nayagam ^a,^*, Samuel Robinson Jebas ^b, J Jebaraj Devadasan ^c, R Murugesan ^d, Dieter Schollmeyer ^e

PMCID: PMC2979839 PMID: 21579623

Abstract

There are two monomeric units in the asymmetric unit of the polymeric title compound, [Na(C₅H₄NOS)(C₁₀H₈N₂O₂S₂)(H₂O)]_n. The Na^I ions are six coordinated by four O atoms, one S atom and one water molecule, forming a slightly distorted octahedral geometry. An intramolecular O—H⋯O hydrogen bond stabilizes the conformation of the molecule. The crystal packing is consolidated by intermolecular O—H⋯O, O—H⋯N and O—H⋯S hydrogen bonds, π–π interactions [with centroid–centroid distances of 3.587 (2) Å] together with weak C—H⋯π interactions. The molecules are linked into polymeric chains along the b-axis direction.

Related literature

For the biological activity of N-oxides and their derivatives, see: Lobana & Bhatia (1989 ▶); Symons et al. (1985 ▶). For their involvement in DNA strand scission under physiological conditions, see: Katsuyuki et al. (1991 ▶); Bovin et al. (1992 ▶). Pyridine N-oxides bearing a sulfur group in position two display significant antimicrobial activity, see: Leonard et al. (1955 ▶). For related structures, see: Jebas et al. (2005 ▶); Ravindran et al. (2008 ▶).

Experimental

Crystal data

[Na(C₅H₄NOS)(C₁₀H₈N₂O₂S₂)(H₂O)]
M _r = 838.92
Orthorhombic,
a = 24.829 (2) Å
b = 7.3290 (7) Å
c = 19.1378 (17) Å
V = 3482.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 173 K
0.54 × 0.19 × 0.14 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T _min = 0.782, T _max = 0.936
38861 measured reflections
8403 independent reflections
6205 reflections with I > 2σ(I)
R _int = 0.077

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.074
S = 0.93
8403 reflections
469 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ▶), 4068 Friedel pairs
Flack parameter: 0.47 (6)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: SHELXTL (Sheldrick, 2008b ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810000073/bt5158sup1.cif

e-66-0m142-sup1.cif^{(36.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000073/bt5158Isup2.hkl

e-66-0m142-Isup2.hkl^{(411.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the N34/C33–C35 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O49—H49A⋯O16ⁱ	0.90	1.91	2.784 (3)	165
O49—H49A⋯N11ⁱ	0.90	2.67	3.417 (3)	141
O49—H49B⋯S32ⁱⁱ	0.89	2.37	3.198 (2)	154
O50—H50A⋯O39ⁱⁱⁱ	0.92	1.88	2.798 (3)	177
O50—H50A⋯N34ⁱⁱⁱ	0.92	2.62	3.455 (3)	151
O50—H50B⋯S24	0.86	2.33	3.193 (2)	174
C29—H29⋯Cg1^iv	0.95	2.89	3.618 (4)	134

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

N-oxides and their derivatives show a broad spectrum of biological activity such as antifungal, antimicrobial and antibacterial activities (Lobana & Bhatia, 1989; Symons et al., 1985). These compounds are also found to be involved in DNA strand scission under physiological conditions (Katsuyuki et al., 1991; Bovin et al., 1992). Pyridine N-oxides bearing a sulfur group in position two display significant antimicrobial activity (Leonard et al., 1955). In view of the importance of N-oxides, we have previously reported the crystal structures of N-oxide derivatives (Jebas et al., 2005; Ravindran et al., 2008). As an extension of our work on N-oxide derivatives, we report here the crystal structure of the title compound (I).

In the asymmetric unit of (I)(Fig 1), the Na^I ion is six coordinated by four oxygen atoms, two from 1-oxypyridine-2-thiolato and two from 2,2-thiobis(pyridine N-oxide) ligands, and one sulfur atom from 1-oxypyridine-2-thiolato ligand. The pyridyl rings are essentially planar with the maximum deviation from planarity of -0.034 (5) Å for atom C10. The N–O bond lengths are in good agreement with the mean value of 1.304 (15) Å reported in the literature for pyridine N-oxides.

Intramolecular O—H···O hydrogen bonding influence the conformation of the molecule. The crystal packing (Fig 2) is consolidated by intermolecular O—H···O, O—H···N and O—H···S hydrogen bonding together with intramolecular S···O= 2.587 (3) to 3.069 (3) Å; N···S=2.686 (4) to 2.700 (5) Å; S···Na=3.807 (2) Å, intermolecular S···Oⁱ=3.065 (3) Å, O···Oⁱ=2.784 (3), O···Oⁱⁱ=2.798 (3) Å, intramolecular S···O =2.587 (3)to 3.069 (3) Å; O···O = 2.784 (3) to 2.798 (3) Å; S···Na=3.807 (2) Å and N···S=2.686 (4) to 2.700 (5) Å short contacts [symmetry code: (i) 1/2+X,1-Y,Z (ii) -1/2+X, 1-Y, Z]. π—π interactions with cg1-cg4ⁱⁱⁱ=3.587 (2)Å (Where Cg1 is N1/C2—C6; Cg2 is N25/C26—C30) [symmetry code: (iii) X, -1+Y, Z] together with weak C—H··· π interactions. The molecules are linked into polymeric chains along the b-direction.

Experimental

A mixture of Sodium salt of 1-hydroxypyidine-2-thione (0.298 2mmol), ethanol (10 ml)and sodium ethoxide (10ml) was heated at 333 K with stirring for 30 min. After two days again Sodium salt of 1-hydroxypyidine-2-thione(0.149,1mmol)was added. The solution was again heated at 333 K with stirring for 30 min. The mixture was then kept aside for slow evaporation. After a week colourless crystals were formed.