Poly[piperazinediium [[aqua­bismuth­ate(III)]-di-μ-pyridine-2,6-dicarboxyl­ato-bis­muthate(III)-di-μ-pyridine-2,6-dicarboxyl­ato] monohydrate]

Hossein Aghabozorg; Andya Nemati; Zohreh Derikvand; Mohammad Ghadermazi

doi:10.1107/S160053680800161X

. 2008 Jan 23;64(Pt 2):m374. doi: 10.1107/S160053680800161X

Poly[piperazinediium [[aquabismuthate(III)]-di-μ-pyridine-2,6-dicarboxylato-bismuthate(III)-di-μ-pyridine-2,6-dicarboxylato] monohydrate]

Hossein Aghabozorg ^a,^*, Andya Nemati ^a, Zohreh Derikvand ^a, Mohammad Ghadermazi ^b

PMCID: PMC2960170 PMID: 21201329

Abstract

The title compound, {(C₄H₁₂N₂)[Bi₂(C₇H₃NO₄)₄(H₂O)]·H₂O}_n or {(pipzH₂)[Bi₂(pydc)₄(H₂O)]·H₂O}_n, where pydcH₂ is pyridine-2,6-dicarboxylic acid and pipz is piperazine, was obtained by reaction of Bi(NO₃)₃·5H₂O with (pipzH₂)(pydcH)₂·3H₂O in a 1:2 molar ratio in aqueous solution. There are two independent Bi^III atoms in the structure, one of which is eight-coordinate with a distorted bicapped trigonal-prismatic geometry, and another which is nine-coordinate with a distorted tricapped trigonal-prismatic geometry. The carboxylate groups of the (pydc)²⁻ ligands link dinuclear [Bi₂(C₇H₃NO₄)₄(H₂O)]²⁻ units into one-dimensional coordination polymers. The pipzH₂ ²⁺ cations (site symmetry Inline graphic ) and non-coordinated water molecules lie between these polymers, forming N—H⋯O and O—H⋯O hydrogen bonds to the O atoms of the carboxylate groups.

Related literature

For related literature, see: Aghabozorg, Attar Gharamaleki, Ghadermazi et al. (2007 ▶); Aghabozorg, Attar Gharamaleki, Ghasemikhah et al. (2007 ▶); Aghabozorg, Motyeian et al. (2007 ▶); Aghabozorg, Daneshvar et al. (2007 ▶); Sharif et al. (2007 ▶); Sheshmani et al. (2006 ▶).

Experimental

Crystal data

(C₄H₁₂N₂)[Bi₂(C₇H₃NO₄)₄(H₂O)]·H₂O
M _r = 1202.56
Triclinic,
a = 10.8111 (4) Å
b = 12.1660 (5) Å
c = 14.0402 (5) Å
α = 96.094 (1)°
β = 93.169 (1)°
γ = 113.848 (1)°
V = 1669.65 (11) Å³
Z = 2
Mo Kα radiation
μ = 10.62 mm⁻¹
T = 100 (2) K
0.15 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.204, T _max = 0.346
22723 measured reflections
8005 independent reflections
6952 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.048
S = 1.03
8005 reflections
523 parameters
H-atom parameters constrained
Δρ_max = 1.32 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: APEX2; 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 datablocks global, I. DOI: 10.1107/S160053680800161X/bi2264sup1.cif

e-64-0m374-sup1.cif^{(39.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800161X/bi2264Isup2.hkl

e-64-0m374-Isup2.hkl^{(391.6KB, 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
N5—H5N1⋯O2Wⁱ	0.90	2.00	2.761 (4)	141
N5—H5N2⋯O6	0.90	1.86	2.722 (4)	160
N6—H6N1⋯O16ⁱⁱ	0.90	1.78	2.676 (4)	176
N6—H6N2⋯O12	0.90	1.95	2.762 (4)	149
O1W—H1W1⋯O7	0.85	2.08	2.891 (3)	160
O1W—H1W2⋯O9ⁱⁱⁱ	0.85	2.53	3.337 (4)	158
O2W—H2W1⋯O14	0.85	2.04	2.887 (4)	176
O2W—H2W2⋯O5	0.85	2.35	3.162 (4)	159

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

supplementary crystallographic information

Comment

The preparation and characterization of self-assembling systems have been considered by chemists in recent years. A literature review shows that the (pydc)^2- ligand can form complexes with transition metals (Aghabozorg, Attar Gharamaleki, Ghadermazi et al., 2007; Aghabozorg, Attar Gharamaleki, Ghasemikhah et al., 2007; Aghabozorg, Motyeian et al., 2007; Aghabozorg, Daneshvar et al., 2007; Sharif et al., 2007). In this work, (pydc)^2- acts as tridentate ligand with one N atom of pyridine and two O atoms of carboxylates acting as donors and also has a bridging role between the binuclear units containing Bi1 and Bi2. The binuclear units consist of two Bi^III atoms, four (pydc)^2- ligands, and one coordinated water molecule, while one (pipzH₂)²⁺ cation and one uncoordinated water molecule are also present in the asymmetric unit (Fig. 1).

Two Bi1—O7—C14—O8—Bi2 bridging bonds between neighboring binuclear units link them together and form several rings with four Bi^III atoms, six O atoms and two C atoms (Fig. 2). Atom Bi1 is eight coordinated by two tridentate (pydc)^2- ligands, one O atom from the Bi1—O9—Bi2 bridge and one O atom from the neighbouring carboxylate group (Bi1—O14ⁱ = 2.971 (3) Å, symmetry code: (i) -x, 1 - y, 1 - z). Atom Bi2 is nine coordinated by two tridentate (pydc)^2- ligands, one O atom from the Bi1—O1—Bi2 bridge, one O atom from a coordinated water molecule (Bi2—O1W = 2.960 (3) Å) and one O atom from a neighbouring carboxylate group (Bi2—O8ⁱⁱ = 2.883 (2) Å, symmetry code: (ii) -x, 1 - y, -z). The sum of the van der Waals radii for Bi and O is 3.86 Å, which is significantly longer than the bond distances for Bi1—O14ⁱ and Bi2—O8ⁱⁱ. The coordination polyhedron around Bi1 is a distorted bicapped trigonal prism which is nearly eclipsed, in which O1, O7, O9 and O3, O5, O14 form two triangles and N1 and N2 form two caps of the prism. The sum of the bond angles N3—Bi2—O1W (113.37 (8)°), O1W—Bi2—N4 (125.24 (8)°) and N4—Bi2—N3 (121.00 (9)°) is equal to 359.61°, indicating that Bi2 is located in the center of the O1W/N3/N4 plane. Atoms O8, O11, O15 and O1, O9, O13 build two triangles. So, a prism consisting of six O atoms and three caps (N3, N4 and O1W) on its faces is formed around Bi2, that is the coordination polyhedron may be described as a distorted tricapped trigonal prism.

N—H···O hydrogen bonds are formed between (pipzH₂)²⁺ and the carboxylate groups (Table1) and also O—H···O hydrogen bonds are formed between uncoordinated water molecules and the carboxylate groups. In addition, C—H···O contacts with C···O distances ranging from 2.887 (4)Å to 3.656 (4) Å are observed between (pipzH₂)²⁺ cations and carboxylate groups. There are C29—H29B···Cg1 interactions (3.638 (5) Å; x, y + 1, z), where Cg1 is the centroid of the N4/C23—C27 ring and also C32—H32B···Cg2 interactions (3.656 (5) Å; x - 1,y, z), where Cg2 is the centroid of the N2/C9—C13 ring (Fig. 3).

Experimental

The proton transfer compound (pipzH₂)(pydcH)₂.3H₂O was prepared by reaction of pyridine-2,6-dicarboxylic acid (pydcH₂) with piperazine (pipz) (Sheshmani et al., 2006). A solution of Bi(NO₃)₃.5H₂O (242 mg, 0.5 mmol) in water (25 ml) was added to (pipzH₂)(pydcH)₂.3H₂O (253 mg, 1.0 mmol) in 25 ml water and colorless crystals were obtained by slow evaporation of the solvent at room temperature.