4,4′-Bipyridine–2-(carb­oxy­methyl­sulfan­yl)pyridine-3-carb­oxy­lic acid (1/1)

Xian-Rong Jiang; Xiao-Juan Wang; Yun-Long Feng

doi:10.1107/S1600536810048385

. 2010 Nov 27;66(Pt 12):o3308. doi: 10.1107/S1600536810048385

4,4′-Bipyridine–2-(carboxymethylsulfanyl)pyridine-3-carboxylic acid (1/1)

Xian-Rong Jiang ^a, Xiao-Juan Wang ^a, Yun-Long Feng ^a,^*

PMCID: PMC3011421 PMID: 21589586

Abstract

In the title co-crystal, C₁₀H₈N₂·C₈H₇NO₄S, the formate group is coplanar with the pyridyl ring of the acid [dihedral angle = 6.2 (7)°], while the carboxymethylsulfanyl group makes a C—S—C—C torsion angle of 70.2 (1)° with the pyridine ring. The dihedral angle between the pyridyl rings of the 4,4′-bipyridine molecule is 27.4 (1)°. The acid and the 4,4′-bipyridine molecules are involved in hydrogen bonding via carboxylic O and pyridyl N atoms. The structure is further consolidated by intermolecular C—H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

For related structures, see: Wang & Feng (2010 ▶); Zhu et al. (2002 ▶); Smith & Sagatys (2003 ▶).

Experimental

Crystal data

C₁₀H₈N₂·C₈H₇NO₄S
M _r = 369.40
Monoclinic,
a = 9.3684 (3) Å
b = 10.3044 (3) Å
c = 18.2264 (5) Å
β = 106.494 (2)°
V = 1687.09 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 296 K
0.41 × 0.25 × 0.10 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.935, T _max = 0.978
24834 measured reflections
3927 independent reflections
3106 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.144
S = 1.08
3927 reflections
241 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810048385/pv2357sup1.cif

e-66-o3308-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048385/pv2357Isup2.hkl

e-66-o3308-Isup2.hkl^{(192.5KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯N2ⁱ	0.86 (2)	1.79 (2)	2.6564 (18)	178 (2)
O3—H3B⋯N3ⁱⁱ	0.86 (2)	1.82 (2)	2.6618 (18)	167 (2)
C4—H4A⋯O4ⁱⁱⁱ	0.93	2.55	3.213 (2)	128
C15—H15A⋯O2ⁱⁱ	0.93	2.39	3.0664 (19)	130
C18—H18A⋯o2ⁱⁱ	0.93	2.70	3.232 (2)	117

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

supplementary crystallographic information

Comment

The crystal structures of a number of mercaptonicotinic derivatives have been reported, such as 2-(carboxymethylsulfanyl)pyridine-3-carboxylic acid monohydrate (Wang et al., 2010), bis(3-carboxypyrid-2-yl)disulfide monohydrate (Zhu et al., 2002) and ammonium 2-mercaptopyridine-3-carboxylate monohydrate (Smith et al., 2003). In an attempt to synthesize a cobalt complex with 2-(carboxymethylsulfanyl)pyridine-3-carboxylic acid and 4,4'-bipyridine, we obtained the title compound, (I), unexpectedly. In this article, we report the crystal structure of (I).

The title compound is composed of 2-(carboxymethylsulfanyl)pyridine-3-carboxylic acid (C₈H₇NO₄S) and 4,4'-bipyridine (C₁₀H₈N₂) (Fig. 1). In the acid moiety, the formate group is coplanar with the pyridyl ring, while the carboxymethylsulfanyl group is almost vartical to the plane formed by the pyridine ring atoms with torsion angle, C1—S1—C7—C8, 70.2 (1)°. The dihedral angle between the pyridyl rings of the 4,4'-bipyridine molecule is 27.4 (1)°. The acid and the 4,4'-bipyridine molecules are involved in hydrogen bonding via carboxylic O and pyridyl N atoms. The structure is further consolidated by intermolecular hydrogen bonds of type C—H···O (Fig. 2 and Tab. 1).

Experimental

2-(Carboxymethylsulfanyl)pyridine-3-carboxylic acid was prepared according to the literature method (Wang et al., 2010). A mixture of CoCl₂.6H₂O (0.2379 g, 1.0 mmol), 4,4'-bipyridine (0.0468 g, 0.3 mmol) and 2-(carboxymethylsulfanyl)pyridine-3-carboxylic acid (0.2134 g, 1.0 mmol) was dissolved in 10.0 ml of distilled water and 3.0 ml ethanol at 328 K. The resulting solution was stirred and refluxed under basic condition for 2 h, the mixture was cooled to room temperature and filtered. Single crystals suitable for X-ray diffraction were obtained from the mother liquor by slow evaporation at room temperature for several days.