3-Amino­benzoic acid–4,4′-bipyridine (2/3)

Pornsuda Lhengwan; Supakit Achiwawanich; Tanwawan Duangthongyou

doi:10.1107/S1600536812033181

. 2012 Jul 28;68(Pt 8):o2569. doi: 10.1107/S1600536812033181

3-Aminobenzoic acid–4,4′-bipyridine (2/3)

Pornsuda Lhengwan ^a, Supakit Achiwawanich ^a, Tanwawan Duangthongyou ^a,^*

PMCID: PMC3415010 PMID: 22904997

Abstract

The asymmetric unit of the title compound, 3C₁₀H₈N₂·2C₇H₇NO₂, consists of three molecules of 4,4′-bipyridine (bpy) and two molecules of 3-aminobenzoic acid (bza). Two molecules of bza and two molecules of bpy are connected via O—H⋯N, N—H⋯N and N—H⋯O hydrogen bonds, forming forming infinite double-stranded zigzag chains along the c axis. The third molecule of bpy is linked to the chain by weak C—H⋯O interactions. Adjacent chains are linked via π–π interactions [centroid–centroid distances = 3.759 (3)–3.928 (3) Å] involving the pyridine rings of bpy molecules, resulting in a sheet-like structure parallel to (100). These sheets are stacked via C—H⋯π interactions, resulting finally in the formation of a three-dimensional supramolecular structure.

Related literature

For related structures, see: Karpova et al. (2004 ▶); Koteswara Rao et al. (2012 ▶); Yao et al. (2008 ▶); Zhao et al. (2007 ▶). graphic file with name e-68-o2569-scheme1.jpg

Experimental

Crystal data

3C₁₀H₈N₂·2C₇H₇NO₂
M _r = 742.82
Triclinic,
a = 9.371 (3) Å
b = 11.991 (4) Å
c = 17.653 (6) Å
α = 94.910 (11)°
β = 90.224 (10)°
γ = 102.128 (11)°
V = 1931.6 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.62 × 0.34 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
14412 measured reflections
6518 independent reflections
3893 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.071
wR(F ²) = 0.252
S = 1.07
6518 reflections
513 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2011 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536812033181/qm2077sup1.cif

e-68-o2569-sup1.cif^{(29.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033181/qm2077Isup2.hkl

e-68-o2569-Isup2.hkl^{(319KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812033181/qm2077Isup3.cml

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

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

Cg7 and Cg8 are the centroids of the C31–C36 and C38–C43 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H′⋯N4	0.98 (4)	1.67 (4)	2.647 (4)	171 (3)
O4—H′′⋯N5	1.03 (5)	1.60 (5)	2.627 (4)	175 (4)
N7—H7A⋯N3ⁱ	0.86	2.16	3.007 (4)	169 (4)
N7—H7B⋯O3	0.86	2.23	3.038 (4)	156
N8—H8A⋯N6ⁱⁱ	0.86	2.16	3.006 (4)	169 (4)
N8—H8B⋯O1	0.86	2.21	3.019 (4)	158
C36—H36A⋯O3	0.93	2.52	3.300 (4)	141
C43—H43A⋯O1	0.93	2.53	3.304 (4)	141
C7—H7C⋯Cg7ⁱⁱⁱ	0.93	2.87	3.751 (4)	157
C17—H17A⋯Cg8^iv	0.93	2.72	3.562 (4)	151
C19—H19A⋯Cg8^v	0.93	2.78	3.643 (4)	154
C22—H22A⋯Cg7^vi	0.93	2.72	3.567 (4)	151

Open in a new tab

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

Acknowledgments

The authors thank Kasetsart University Research and Development Institute and the Department of Chemistry, Faculty of Science, Kasetsart University, for research funds.

supplementary crystallographic information

Comment

The title compound was obtained as a side-product in the synthesis of metal-organic framework materials which similar to previeously observed organic compounds (Karpova et al. (2004); Koteswara Rao et al. (2012); Yao et al. (2008); Zhao et al. (2007). The asymmetric unit is composed of crystallographically independent of 4,4'-bipyridine (bpy) and 3-aminobenzoic acid (bza) in the stoichiometric ratio of 3:2 (Fig. 1). Three strong intermolecular hydrogen bonds are formed between bpy molecules and bza molecules via (1) amino and carboxylic acid groups of bza molecules (N—H···O), (2) amino groups of bza molecules and an N atom of bpy (N—H···N) and (3) a carboxylic group and an N atom of bpy (O—H···N), resulting in infinite double zigzag chain along c-axis (Table 1, Fig. 2) . The infinite chain is further stabilized by weak C—H···N interactions (distance 2.75 Å) with the third bpy molecule. In the chain the bpy and bza molecules are arranged in a nonplanar structure. Moreover the pyridine rings of bpy molecules exhibit a nonplanar configuration with dihedral angles in the range 28.9–32.66°. In addition, each of the infinite zigzag chains is linked to adjacent chains through π -π interactions between the pyridine rings of bpy molecules(distance 3.85 Å) forming a two-dimensional sheet sructure (Fig. 2). The two-dimensional– sheets are further connected through C—H···π interactions (distance 2.74 Å), resulting in a three-dimensional supramolecular structure (Fig. 3)

Experimental

A solution of Mn(OAc)₂.4H₂O (1 mmol), 2-aminoterephthalic acid (1 mmol) and 4,4'-bipyridine(1 mmol) in 15 ml of H₂O:DMF (1:1) was transferred into a Teflon lined aotoclave and heat at 170° for 15 h. Then, solution was slowly cooled to room temperature. Yellow crystral was obtained as a minor product from fragmentation of 2-aminoterephthalic acid to 3-aminobenzoic acid during reaction.