2-[(2-Carboxy­phen­yl)disulfan­yl]benzoic acid–4,4′-bipyridyl N,N′-dioxide (1/2)

Rodolfo Moreno-Fuquen; Javier Ellena; Carlos A De Simone; Leandro Ribeiro; Regina Helena De Almeida Santos

doi:10.1107/S1600536810018775

. 2010 May 26;66(Pt 6):o1442. doi: 10.1107/S1600536810018775

2-[(2-Carboxyphenyl)disulfanyl]benzoic acid–4,4′-bipyridyl N,N′-dioxide (1/2)

Rodolfo Moreno-Fuquen ^a,^*, Javier Ellena ^b, Carlos A De Simone ^b, Leandro Ribeiro ^b, Regina Helena De Almeida Santos ^c

PMCID: PMC2979473 PMID: 21579515

Abstract

In the title 2:1 adduct, C₁₄H₁₀O₄S₂·0.5C₁₀H₈N₂O₂, which arose from an unexpected oxidation of a precursor, the dihedral angle between the aromatic rings in the disulfide is 82.51 (11)°. In the crystal, the molecules are linked by O—H⋯O, O—H⋯N and C—H⋯O interactions, generating sheets.

Related literature

For structural studies of 4,4′-bipyridyl N,N′-dioxide, see: Lou & Huang (2007 ▶); Reddy et al. (2006 ▶). For the disulfide bond in polypeptide chains, see: Gortner & Hoffman (1941 ▶). For a related structure, see: Moreno-Fuquen et al. (2003 ▶). For hydrogen bonding, see: Etter (1990 ▶); Nardelli (1995 ▶).

Experimental

Crystal data

C₁₄H₁₀O₄S₂·0.5C₁₀H₈N₂O₂
M _r = 400.45
Monoclinic,
a = 21.314 (2) Å
b = 10.5621 (8) Å
c = 16.005 (8) Å
β = 105.412 (8)°
V = 3473.5 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 291 K
0.22 × 0.18 × 0.12 mm

Data collection

Rigaku AFC-7S diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.951, T _max = 0.990
3066 measured reflections
2781 independent reflections
2658 reflections with I > 2σ(I)
R _int = 0.046
3 standard reflections every 120 min intensity decay: 0.9%

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.192
S = 1.11
2781 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993 ▶); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810018775/hg2676sup1.cif

e-66-o1442-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018775/hg2676Isup2.hkl

e-66-o1442-Isup2.hkl^{(136.6KB, 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
O5—H55⋯O1ⁱ	0.82	1.77	2.583 (3)	174
O3—H3⋯O1ⁱⁱ	0.82	1.86	2.672 (3)	170
O5—H55⋯N1ⁱ	0.82	2.50	3.255 (3)	154
C17—H17⋯O2ⁱⁱⁱ	0.93	2.59	3.359 (4)	140

Open in a new tab

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

Acknowledgments

RMF is grateful to the Spanish Research Council (CSIC) for the use of a free-of-charge licence to the Cambridge Structural Database (Allen, 2002 ▶). RMF also wishes to thank the Universidad del Valle, Colombia, and the Instituto de Física de São Carlos, Brasil, for partial financial support. LR acknowledges CNPq Brazil for a research fellowship.

supplementary crystallographic information

Comment

The title compound, C₁₄H₁₀O₄S₂, 0.5(C₁₀H₈N₂O₂), (I), belongs to a series of molecular systems based on 4,4'-bipyridyl N,N'-dioxide (DPNO) with diverse hydrogen-bond donors, that has been synthesized in our research group (Moreno-Fuquen et al., 2003). Several authors have reported the formation of co-crystals from DPNO moiety (Lou & Huang, 2007; Reddy et al., 2006), taking advantage of the strong acceptor character of the N-oxide group. Initially, it was unclear which intermolecular hydrogen bond is formed: S—H ··· O or O—H ··· O. The oxidation of sulfhydryl (S—H) group, of the 2-mercaptobenzoic acid (MBA), allows the formation of 2,2'-dicarboxyphenyldisulfide molecule (CPS), which enters in the reaction with DPNO to form the title co-crystal. The strong S—S disulfide bond formed in this structure, is important in linking polypeptide chains of proteins (Gortner & Hoffman, 1941). A perspective view of the molecule of the title compound, showing the atomic numbering scheme, is given in Fig. 1. The DPNO and CPS molecules are held together by an intermolecular hydrogen bonds between the O1 atom of the N-oxide group of DPNO and the O5 and O3 of the CPS molecule, with O···O distances of 2.583 (3) and 2.672 (3) Å respectively. The central S1—S2 bond length is 2.0397 (10) Å and the Car-S—S-Car torsion angle is -86.15 (14)%. There are no intramolecular O—H ··· S bonds in the structure. It is noted however, that carboxylic groups of the CPS molecule, exhibit different behaviors with respect to the presence of the neighboring sulfur atom. Indeed, while one of the O—H group of carboxylic group is oriented away from the S1 atom [torsion angle C13 C14 C19 O5, -12.7 (5)°], the second O—H group is oriented near to S2 atom [torsion angle C8 C7 C6 O3 163.8 (3)]. the DPNO molecule is almost coplanar with one of the planes of the CPS molecule showing a dihedral angle of 0.71 (7)°. With the other plane of CPS, the DPNO molecule forms a dihedral angle of 82.52 (11)°. The growth of the crystal system can be explained through a hydrogen bonding scheme (Table 1) (Nardelli, 1995). The title molecule is characterized by the formation of O—H···O and O—H···N hydrogen bonds and other weak C—H···O interactions. In a first substructure atom O5 in the molecule at (x+1/2,-y+1/2,+z-1/2) and atom O3 in the molecule at (-x,-y,-z+1) act simultaneously as hydrogen bond donors to O1 atom in the molecule at (x,y,z). In turn, the O5 atom is linked to the N1 atom at (x,y,z). The propagation of these interactions forms a large R⁷₆(57) ring (Etter, 1990) in the (1 0 -2) plane (Fig. 2). In a second substructure, atom C17 in the molecule at (x,y,z) acts as hydrogen bond donor to O2 atom in the molecule at -x+1/2,+y-1/2,-z+1/2. The propagation of this interaction forms C(11) continuous chains and running along [010] direction. All of these interactions define an infinite two-dimensional network for the structure (I) (Fig. 3).

Experimental

The sinthesis of the title compound (I) was carried out by slow evaporation of equimolar quantities of 2-mercaptobenzoic acid (0.537 g., 0.0035 mol) and 4,4'-bipyridyl N,N'-dioxide (0.655 g) in 50 ml of dry acetonitrile. Pale-yellow prisms of good quality, suitable for X-ray analysis were obtained. The initial reagents were purchased from Aldrich Chemical Co. and were used as received.