4,4′-Bipyridine–4-(p-toluene­sulfonamido)­benzoic acid (1/2)

Miao-Ling Huang

doi:10.1107/S1600536811034544

. 2011 Aug 27;67(Pt 9):o2495. doi: 10.1107/S1600536811034544

4,4′-Bipyridine–4-(p-toluenesulfonamido)benzoic acid (1/2)

Miao-Ling Huang ^a,^*

PMCID: PMC3200677 PMID: 22059045

Abstract

In the title compound, C₁₄H₁₃NO₄S·0.5C₁₀H₈N₂, the two benzene rings are nearly perpendicular to each other [dihedral angle = 83.21 (10)°]. The bipyridine molecule is centrosymmetric, the mid-point of the C—C bond linking the pyridine rings being located on an inversion center. Intermolecular N—H⋯O and O—H⋯N hydrogen bonds and weak intermolecular C—H⋯O hydrogen bonds are present in the crystal structure.

Related literature

For the background to the compound, see: Antolini et al. (1984 ▶); Menabue & Saladini (1988 ▶).

Experimental

Crystal data

C₁₄H₁₃NO₄S·0.5C₁₀H₈N₂
M _r = 369.41
Monoclinic,
a = 5.8732 (7) Å
b = 8.124 (1) Å
c = 36.806 (5) Å
β = 94.137 (2)°
V = 1751.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.39 × 0.24 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.922, T _max = 0.957
7704 measured reflections
3234 independent reflections
2255 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.107
S = 0.99
3234 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811034544/xu5301sup1.cif

e-67-o2495-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034544/xu5301Isup2.hkl

e-67-o2495-Isup2.hkl^{(158.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811034544/xu5301Isup3.cml

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
N1—H1⋯O1ⁱ	0.86	2.03	2.861 (2)	162
O2—H2A⋯N2ⁱⁱ	0.82	1.87	2.691 (2)	175
C2—H2⋯O4ⁱⁱ	0.93	2.51	3.413 (2)	163

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

Acknowledgments

This work was supported by the Master Construction Project of Quanzhou Normal University, China.

supplementary crystallographic information

Comment

N-Protected amino acids possess R-CONH-R' group analogous to the structure of O-terminal of peptide and proteins (Menabue & Saladini, 1988, Antolini et al., 1984). The substitution of an Ar—SO₂-group on amine makes the 4-aminobenzeoic acid increase the coordination donors to three types-O, N donors from carboxyl, sulfoxyl and amine respectively, which may result in different coordination mode. In this paper, we attempt synthesizing the N-p-tolysulfonyl-4-amionbenzoic acid adduct of Erbium and 4,4'-bipyridine, but the result to get the title compound.

The title compound contains of one N-p-tolysulfonyl-4-amionbenzoic acid molecule and one 4,4'-bipyridine in the asymmetric unit (Fig.1). The molecule has a C4—N1—S1—C8 of 74.247 (2) °, and the dihedral angle between the benzene rings is 83.213 (6) °. There exit intermolecular hydrogen bonds between carboxylate group oxygen atoms, secondary amine nitrogen atoms and pyridine ring nitrogen atoms of N—H···O and O—H···N. Then, an extended one-dimensional chain structure along b axis is formed (Fig.2). It is interesting that the hydrogen bonds play an important role in forming the one-dimensional structure and stabilize the superamolecular structure(Fig.3).

Experimental

A mixture of N-p-tolysulfonylchloride (1 mmol) and 4-amionbenzoic acid (1 mmol) in water (20 mL) was stirred at room temperature for 10 h. Then HCl (12 mol/L) was slowly added to the resulting solution. The mixture was stirred for 5 min and filtrated. The precipitate was washed by distilled water, and dried to constant heavy [product 1].

To a solution of the product 1 (1 mmol) in water-DMF 1:1 (10 mL), an aqueous solution (5 ml) of Er(NO₃)₃.6H₂O (0.5 mmol) and a solution of 4,4'-bipyridine (0.25 mmol) in ethanol (95%, 5 ml) was added. After refluxing for 12 h at 343 K, the mixture was filtered off while hot. The block colourless single crystals suitable for X-ray analysis were obtained by slow evaporation of the filtrate at room temperature after one week.