4-Amino­benzoic acid–4,4′-(propane-1,3-diyl)dipyridine (1/1)

Fwu Ming Shen; Shie Fu Lush

doi:10.1107/S1600536810039528

. 2010 Oct 9;66(Pt 11):o2748. doi: 10.1107/S1600536810039528

4-Aminobenzoic acid–4,4′-(propane-1,3-diyl)dipyridine (1/1)

Fwu Ming Shen ^a, Shie Fu Lush ^b,^*

PMCID: PMC3009261 PMID: 21588953

Abstract

In the crystal structure of the title compound, C₁₃H₁₄N₂·C₇H₇NO₂, the 4,4′-trimethylene-dipyridine (TMDP) molecule displays an approximately planar structure, the maximum atomic deviation excluding H atoms being 0.118 (2) Å and the dihedral angle between the pyridine rings 4.59 (10)°. The TMDP and 4-aminobenzoic acid (ABA) molecules are linked by O—H⋯N and N—H⋯N hydrogen bonding, while ABA molecules are linked by O—H⋯O hydrogen bonding. C—H⋯π interactions are also observed between the methylene groups of TMDP molecules and the benzene rings of ABA molecules.

Related literature

For general background to 4-aminobenzoic acid as a ligand, see: Smith et al. (2005 ▶). For related structures, see: Lynch & McClenaghan (2001 ▶); Smith et al. (1997 ▶, 2000 ▶).

Experimental

Crystal data

C₁₃H₁₄N₂·C₇H₇NO₂
M _r = 335.40
Monoclinic,
a = 7.6417 (6) Å
b = 11.1708 (9) Å
c = 20.8775 (18) Å
β = 99.436 (2)°
V = 1758.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 297 K
0.60 × 0.20 × 0.17 mm

Data collection

Bruker SMART 1000 CCD diffractometer
9816 measured reflections
3470 independent reflections
2055 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.131
S = 1.02
3470 reflections
238 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810039528/xu5045sup1.cif

e-66-o2748-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039528/xu5045Isup2.hkl

e-66-o2748-Isup2.hkl^{(166.7KB, hkl)}

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

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

Cg3 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N2	0.82 (2)	1.81 (2)	2.632 (2)	179 (3)
N1—H1A⋯N3ⁱ	0.86 (2)	2.19 (2)	3.045 (3)	172 (2)
N1—H1B⋯O1ⁱⁱ	0.86 (1)	2.30 (1)	3.151 (3)	170 (1)
C13—H13A⋯Cg3ⁱⁱⁱ	0.97	2.87	3.6606 (17)	139
C14—H14A⋯Cg3^iv	0.97	2.88	3.6902 (17)	142

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

Acknowledgments

This work was supported financially by Yuanpei University.

supplementary crystallographic information

Comment

4-Aminobenzoic acid is a useful ligand for structure extension through both the carboxylic acid and amine functional groups, forming linear hydrogen bonding associations (Smith et al., 2005). Other related reports with 4-aminobenzoic acid and Lewis base such as 4-(4-nitrobenzyl)pyridine (Smith, 1997), 4-aminobenzonitrile (smith et al., 2000) and 2-amino-4-(4-pyridyl)pyrimidine (Lynch & McClenaghan, 2001).

We present here the crystal structure analysis of the 1:1 4-aminobenzoic acid and 4,4'-trimethylene-dipyridine adduct (Fig 1). In the title compound, C₁₃H₁₄N₂.C₇H₇NO₂, comprises one 4-aminobenzoic acid molecule and one 4,4'-trimethylene-dipyridine molecule, with no proton transfer. The dihedral angle between pyridyl rings for the molecule is 4.59 (10) °.

4-Aminobenzoic acid molecules are linked by O—H···N hydrogen bonds to 4,4'-trimethylene-dipyridine, forming linear hydrogen bonding. The structure exhibits a hydrogen-bonding network involving NH···N(prridyl) [N···N 3.043 (3) Å], amine and carboxylic N—H··· O [N···O 3.152 (3) Å] (Table 1 and Fig. 2), respectively.

This layer is consolidated by C—H···π stackings, the distance between C13—H13Aⁱⁱⁱ···Cg3(C1—C6) and C14—H14A^iv···Cg3 are 2.87 and 2.88 Å [symmetry code: (iii) = X,1/2-Y,1/2+Z; (iV) = 1+X, 1/2-Y, 1/2+Z].

Experimental

The 4-aminobenzoic acid (137 mg, 1.0 mmol) and 4,4'-trimethylene-dipyridine (198 mg, 1.0 mmol) were dissolved in 20 ml methanol-water (1:1), the solution was refluxed for 30 min. The filtered solution was transferred to a 25 ml tube after one week at room temperature, and colorless transparent crystals formed (yield 50.22%).