4,4′-Bipyridinium bis(perchlorate)–4-aminobenzoic acid–4,4′-bipyridine–water (1/4/2/2)

Qun-Hui Meng; Lu Han; Jian-Dong Hou; Yi-Fan Luo; Rong-Hua Zeng

doi:10.1107/S1600536808042207

. 2008 Dec 17;65(Pt 1):o132–o133. doi: 10.1107/S1600536808042207

4,4′-Bipyridinium bis(perchlorate)–4-aminobenzoic acid–4,4′-bipyridine–water (1/4/2/2)

Qun-Hui Meng ^a, Lu Han ^a, Jian-Dong Hou ^a, Yi-Fan Luo ^a,^*, Rong-Hua Zeng ^a,^b

PMCID: PMC2968051 PMID: 21581593

Abstract

In the structure of the title compound, C₁₀H₁₀N₂ ²⁺·2ClO₄ ⁻·4C₇H₇NO₂·2C₁₀H₈N₂·2H₂O, the 4,4′-bipyridinium cation has a crystallographically imposed centre of symmetry. The cation is linked by N—H⋯N hydrogen bonds to adjacent 4,4′-bipyridine molecules, which in turn interact via O—H⋯N hydrogen bonds with 4-aminobenzoic acid molecules, forming chains running parallel to [30 Inline graphic ]. The chains are further connected into a three-dimensional network by N—H⋯O and O—H⋯O hydrogen-bonding interactions involving the perchlorate anion, the water molecules and the 4-aminobenzoic acid molecules. In addition, π–π stacking interactions with centroid–centroid distances ranging from 3.663 (6) to 3.695 (6) Å are present. The O atoms of the perchlorate anion are disordered over two sets of positions, with refined site occupancies of 0.724 (9) and 0.276 (9).

Related literature

For details of the hydrogen-bonding networks formed by 4-aminobenzoic acid and 4,4-bipyridine, see: Clemente & Marzotto (2004 ▶); Hu et al. (2003 ▶); Yang et al. (2004 ▶).

Experimental

Crystal data

C₁₀H₁₀N₂ ²⁺·2ClO₄ ⁻·4C₇H₇NO₂·2C₁₀H₈N₂·2H₂O
M _r = 1254.04
Triclinic,
a = 10.1007 (3) Å
b = 10.1105 (4) Å
c = 16.5830 (6) Å
α = 91.487 (2)°
β = 98.529 (3)°
γ = 118.500 (2)°
V = 1462.68 (10) Å³
Z = 1
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 296 (2) K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: none
18132 measured reflections
5242 independent reflections
3142 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.198
S = 1.04
5242 reflections
455 parameters
74 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042207/rz2274sup1.cif

e-65-0o132-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042207/rz2274Isup2.hkl

e-65-0o132-Isup2.hkl^{(256.7KB, 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—H1C⋯N2ⁱ	0.89 (4)	1.78 (4)	2.673 (4)	174 (5)
O3—H3C⋯O5ⁱⁱ	0.90 (5)	1.72 (4)	2.609 (4)	168 (5)
O5—H5B⋯O4ⁱⁱⁱ	0.86 (4)	1.93 (4)	2.775 (4)	171 (4)
O5—H5A⋯O2^iv	0.852 (11)	1.903 (13)	2.739 (4)	167 (3)
N5—H5C⋯N1	0.90 (5)	1.78 (5)	2.680 (4)	175 (5)
N3—H3A⋯O6	0.86	2.24	3.079 (6)	166
N3—H3A⋯O7′	0.86	2.31	3.113 (15)	156
N3—H3B⋯O6^v	0.86	2.25	3.085 (8)	166
N3—H3B⋯O6′^v	0.86	2.09	2.917 (18)	162
N4—H4A⋯O8^vi	0.86	2.22	3.028 (10)	157
N4—H4A⋯O8′^vi	0.86	2.55	3.351 (19)	156
N4—H4B⋯O8	0.86	2.57	3.174 (13)	129
N4—H4B⋯O8′	0.86	2.57	3.25 (2)	136

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

Acknowledgments

The authors acknowledge South China Normal University for supporting this work.

supplementary crystallographic information

Comment

Hydrogen-bonding interactions between ligands are specific and directional. In this sense, 4-aminobenzoic acid and 4,4-bipyridine are the excellent candidates for the construction of three-dimensional network motifs, as they form regular hydrogen bonds functioning as both hydrogen-bond donors and acceptors (Clemente & Marzotto, 2004; Hu et al., 2003; Yang et al., 2004). Recently, we obtained the title compound under hydrothermal conditions and report its crystal structure herein.

In the title compound (Fig. 1), all bond lengths and angles are unexceptional. The 4,4'-bipyridinium cation, which is located on a centre of symmetry, acts as a N—H hydrogen bond donor on both sides to unprotonated 4,4'-bipyridine molecules, which in turn act as O—H hydrogen bond acceptors from one of the two independent 4-aminobenzoic acid molecules. Two 4-aminobenzoic acid molecules, two 4,4'-bipyridine molecules and the cation are thus connected by hydrogen bonding interactions to form a linear centrosymmetric chain running parallel to the [3 0 2] direction. These chains are further connected by O—H···O and N—H···O hydrogen bonds (Table 1) via the interstitial solvate water molecules, the perchlorate anions and the other 4-aminobenzoic acid molecules, forming a three-dimensional network (Fig. 2). The crystal packing is stabilized by π-π stacking interactions involving both pyridine rings of the unprotonated 4,4'-bipyridine molecule, the N5/C25-C29 pyridine ring of the cation and the C12-C17 benzene ring of one 4-aminobenzoic acid molecule: Cg1···Cg2ⁱ = 3.695 (6) Å; Cg1···Cg3 = 3.663 (6) Å; Cg3···Cg4ⁱⁱ = 3.674 (7) Å [Cg1, Cg2, Cg3 and Cg4 are the centroids of the N1/C1–C5, N2/C6–C10, C12–CC17 and N5/C25–C29 rings, respectively. Symmetry codes: (i) = 1-x, 1-y, -z; (ii) = 1-x, y, z].

Experimental

4-Aminobenzoic acid (1 mmol, 0.137 g,), 4,4-bipyridine (1 mmol, 0.156 g,) and sodium perchlorate (1 mmol, 0.123 g,) were dissolved in hot water with stirring. Colourless single crystals were obtained at room temperature by slow evaporation of the solvent over a period of several days.