Bis(2,3-diamino­pyridinium) bis­(μ-pyridine-2,6-dicarboxyl­ato)-κ4 O 2,N,O 6:O 6;κ4 O 2:O 2,N,O 6-bis­[aqua­(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)bis­muthate(III)] tetra­hydrate

Hossein Aghabozorg; Shokoofeh Kazemi; Ali Akbar Agah; Masoud Mirzaei; Behrouz Notash

doi:10.1107/S1600536811005629

. 2011 Feb 23;67(Pt 3):m360–m361. doi: 10.1107/S1600536811005629

Bis(2,3-diaminopyridinium) bis(μ-pyridine-2,6-dicarboxylato)-κ⁴ O ²,N,O ⁶:O ⁶;κ⁴ O ²:O ²,N,O ⁶-bis[aqua(pyridine-2,6-dicarboxylato-κ³ O ²,N,O ⁶)bismuthate(III)] tetrahydrate

Hossein Aghabozorg ^a,^*, Shokoofeh Kazemi ^a, Ali Akbar Agah ^b, Masoud Mirzaei ^c, Behrouz Notash ^d

PMCID: PMC3052092 PMID: 21522286

Abstract

In the centrosymmetric dinuclear complex anion of the title compound, (C₅H₈N₃)₂[Bi₂(C₇H₃NO₄)₄(H₂O)₂]·4H₂O, the Bi^III atom is eight-coordinated in an N₂O₆ environment and has a distorted bicapped trigonal–prismatic coordination environment. Extensive intermolecular O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds lead to the stability of the crystal structure. Interactions between one C—H group of the 2,3-diaminopyridinium [(2,3-dapyH)⁺] cation and the aromatic ring of the pyridine-2,6-dicarboxylate (pydc) ligand (C—H⋯centroid distance = 2.78 Å) and π–π interactions between the (2,3-dapyH)⁺ cations and between the (2,3-dapyH)⁺ cation and the pydc ligand [centroid–centroid distances = 3.489 (5) and 3.694 (5) Å] are observed.

Related literature

For related structures, see: Aghabozorg et al. (2008 ▶, 2010 ▶); Sheshmani et al. (2005 ▶).

Experimental

Crystal data

(C₅H₈N₃)₂[Bi₂(C₇H₃NO₄)₄(H₂O)₂]·4H₂O
M _r = 1406.76
Triclinic,
a = 9.3462 (19) Å
b = 10.726 (2) Å
c = 11.098 (2) Å
α = 95.13 (3)°
β = 91.38 (3)°
γ = 90.47 (3)°
V = 1107.7 (4) Å³
Z = 1
Mo Kα radiation
μ = 8.03 mm⁻¹
T = 298 K
0.33 × 0.27 × 0.23 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005 ▶) T _min = 0.083, T _max = 0.156
12406 measured reflections
5940 independent reflections
5539 reflections with I > 2σ(I)
R _int = 0.113

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.154
S = 1.05
5940 reflections
347 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.98 e Å⁻³
Δρ_min = −2.93 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005629/hy2406sup1.cif

e-67-0m360-sup1.cif^{(25.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005629/hy2406Isup2.hkl

e-67-0m360-Isup2.hkl^{(290.8KB, 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
N3—H3A⋯O11ⁱ	0.87 (14)	2.02 (14)	2.797 (10)	148 (12)
N4—H4A⋯O2ⁱⁱ	0.86	2.11	2.924 (9)	158
N4—H4B⋯O6ⁱ	0.86	1.97	2.830 (10)	178
N5—H5A⋯O3ⁱⁱⁱ	0.86	2.53	3.216 (10)	138
N5—H5B⋯O6ⁱ	0.86	2.11	2.972 (10)	176
O9—H9A⋯O8^iv	0.81 (7)	2.07 (12)	2.746 (10)	141 (15)
O9—H9B⋯O11^v	0.84 (8)	1.99 (10)	2.771 (11)	155 (15)
O10—H10A⋯O5	0.94 (8)	1.96 (8)	2.862 (9)	160 (11)
O10—H10B⋯O7^vi	0.80 (8)	2.21 (8)	2.972 (10)	160 (13)
O11—H11A⋯O4ⁱⁱⁱ	0.89 (8)	2.01 (13)	2.717 (11)	136 (14)
O11—H11B⋯O10^vii	0.92 (9)	1.96 (9)	2.836 (12)	158 (13)
C11—H11⋯O8^viii	0.93	2.26	3.050 (10)	142

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

Acknowledgments

We are grateful to the Islamic Azad University, North Tehran Branch, for financial support.

supplementary crystallographic information

Comment

Pyridine-2,6-dicarboxylic acid (pydcH₂) can form various complexes containing transition and main metals (Aghabozorg et al., 2008). There are complexes in which pydc acts as a bridging ligand between two metal atoms (Aghabozorg et al., 2010; Sheshmani et al., 2005).

Herein, we report the crystal structure of the title compund as another example of bismuth(III) coordination compound, which bears heterocyclic 2,3-diaminopyridine (2,3-dapy) and pydcH₂ ligands. The molecular structure of the title compound is shown in Fig. 1. The centrosymmetric binuclear unit consists of two Bi^III atoms, four (pydc)^2- ligands, two coordinated water molecules. Two pydc ligands act as tridentate ligands with an N atom of the pyridine ring and two O atoms of the dicarboxylate groups acting as donors. One of the dicarboxylate O atoms for the other two pydc ligands plays a bridging role between two Bi atoms. The structure also contains two (2,3-dapyH)⁺ cations and four uncoordinated water molecules. The Bi^III atom is eight-coordinated in an N₂O₆ environment and has a distorted bicapped trigonal-prismatic geometry, as it is shown in Fig. 2. There are extensive intermolecular O—H···O, N—H···O and weak C—H···O hydrogen bonds, which cause the stability of the crystal structure (Fig. 3, Table 1). There are also π–π interactions between the (2,3-dapyH)⁺ rings and between the (2,3-dapyH)⁺ and pydc rings (Fig. 4), with centroid–centroid distances of 3.489 (5) and 3.694 (5) Å, respectively. Furthermore, there is C—H···π interacton between C—H group of the (2,3-dapyH)⁺ cation and pydc ligand, with an C—H···centroid distance of 2.78 Å (Fig. 5).

Experimental

An aqueous solution of Bi(NO₃)₃ (1 mmol), pydcH₂ (3 mmol) and 2,3-dapy (1 mmol) was refluxed for about 30 min in a 1:3:1 molar ratio. Brown crystals of the title compound were obtained from the solution by slow evaporation of the solvent within two weeks at room temperature.