Poly[triaqua-μ4-pyridine-3,5-dicarboxyl­ato-barium(II)]

Hossein Aghabozorg; Andya Nemati; Zohreh Derikvand; Mohammad Ghadermazi; Shirin Daneshvar

doi:10.1107/S1600536808001323

. 2008 Jan 23;64(Pt 2):m375. doi: 10.1107/S1600536808001323

Poly[triaqua-μ₄-pyridine-3,5-dicarboxylato-barium(II)]

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

PMCID: PMC2960421 PMID: 21201330

Abstract

The reaction of the proton-transfer compound (pdaH₂)(py-3,5-dc)·H₂O (pda = propane-1,3-diamine and py-3,5-dcH₂ = pyridine-3,5-dicarboxylic acid) with Ba(NO₃)₂ leads to the formation of the title polymeric compound, [Ba(C₇H₃NO₄)(H₂O)₃]_n. The Ba^II atom is nine-coordinated by six carboxylate O atoms from the (py-3,5-dc)²⁻ ligands, and three O atoms from the coordinated water molecules. The coordination polyhedron around the Ba^II atom is best described as tricapped trigonal-prismatic. In the crystal structure, intermolecular interactions, such as X—H⋯O hydrogen bonds (X = O and C) and π–π stacking [centroid–centroid distances between pyridine rings of 3.6191 (13) and 3.6192 (13) Å] play an important role in stabilizing the supramolecular structure.

Related literature

For related literature, see: Aghabozorg et al. (2006 ▶, 2007 ▶, 2008 ▶); Dorazco-Gonzalez et al. (2006 ▶); Starosta et al. (2002a ▶,b ▶).

Experimental

Crystal data

[Ba(C₇H₃NO₄)(H₂O)₃]
M _r = 356.49
Monoclinic,
a = 7.5922 (4) Å
b = 18.5576 (10) Å
c = 7.1832 (4) Å
β = 90.499 (5)°
V = 1012.02 (9) Å³
Z = 4
Mo Kα radiation
μ = 3.95 mm⁻¹
T = 100 (2) K
0.25 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (APEX2; Bruker, 2005 ▶) T _min = 0.386, T _max = 0.455
10713 measured reflections
2664 independent reflections
2575 reflections with I > 2/s(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.019
wR(F ²) = 0.048
S = 1.00
2664 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 1.18 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808001323/su2029sup1.cif

e-64-0m375-sup1.cif^{(20.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001323/su2029Isup2.hkl

e-64-0m375-Isup2.hkl^{(130.8KB, 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
O1W—H1WA⋯O1ⁱ	0.84	2.13	2.924 (2)	158
O1W—H1WB⋯O1ⁱⁱ	0.84	1.89	2.730 (2)	176
O2W—H2WA⋯O2ⁱⁱⁱ	0.81	1.96	2.761 (2)	172
O2W—H2WB⋯N1^iv	0.83	2.06	2.873 (3)	165
O3W—H3WA⋯N1^v	0.85	2.48	3.284 (3)	159
O3W—H3WB⋯O1W^vi	0.85	2.02	2.851 (3)	165
C3—H3⋯O2W^vii	0.93	2.47	3.362 (3)	161

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

supplementary crystallographic information

Comment

Recent interest of our researching group has focused on the synthesis and characterization of novel metal complexes of proton transfer compounds obtained using dipicolinic acid (Aghabozorg et al., 2007). A convenient path to obtain polymeric structures is to use a multifunctional ligand to link metal ions to form an infinite arrangement (Starosta et al., 2002a,b); Dorazco-Gonzalez et al., 2006). The reaction of the proton transfer compound (pdaH₂)(py-3,5-dc).H₂O [pda = propane-1,3-diamine and py-3,5-dcH₂ = pyridine-3,5-dicarboxylic acid (Aghabozorg et al., 2006)] with Ba(NO₃)₂, in aqueous solution with a 1:2 molar ratio, lead to the formation of the title polymeric compound, (I).

The monomeric units in the polymer (I) consist of one Ba^II atom, one (py-3,5-dc)^2- dianion and three aqua (H₂O) ligands. The Ba^II atom is nine-coordinate with six carboxylate oxygen atoms from the bridging (py-3,5-dc)^2- ligands and three oxygen atoms from the coordinated water molecules (Figs. 1 and 2). The summation of bond angles O2W—Ba1—O3ⁱⁱ, O3ⁱⁱ —Ba1—O1 and O2W—Ba1—O1 is 360.94° hence, the Ba1 atom is located in the center of the plane (O1,O2,O3Wⁱⁱ). Atoms O2, O3W and O3ⁱ form a triangle, and atoms O1W, O4ⁱⁱ, O4ⁱⁱⁱ form another triangle. So a prism, consisting of six O-atoms and three caps (O2W, O3ⁱⁱⁱ and O1) on the faces around the Ba(II) atom is formed. The coordination polyhedron around the Ba^II atom is hence, best described as a tricapped trigonal prism (Fig. 3).

In the molecular structure of (I) atoms O1 and O2, from one of the carboxylate groups, have only one Ba—O bond, while atoms O3 and O4 from three neighboring carboxylate groups have two Ba—O bonds. The bond distances between barium and the oxygen atoms are in the range 2.7399 (18)–2.8669 (16) Å.

In the crystal structure of (I) there are several O—H···O hydrogen bonds [in the range 2.730 (2)–2.924 (2) Å], and the pyridine N-atoms have N—H···O hydrogen bonds with neighboring coordinated water molecules [in the range 2.873 (3)–3.284 (3) Å]. C—H···O hydrogen bonds [with D···A distance 3.362 (3) Å], are also present (Table 1). There are π-π stacking interactions between symmetry related pyridine (N1/C1—C5) rings with centroid···centroid distances of 3.6191 (13) and 3.6192 (13) Å (symmetry codes: (i) = x, -y + 3/2, z + 1/2 and x; (ii) = -y + 3/2, z - 1/2, respectively] (Fig.4).

All of these intermolecular interactions play an important role in forming the three dimensional polymeric system and stabilizing the structure.

Experimental

The proton transfer compound (pdaH₂)(py-3,5-dc), was prepared by the reaction of pyridine-3,5-dicarboxylic acid [py-3,5-dcH₂], with propane-1,3-diamine [pda], (Aghabozorg et al., 2006). Compound (I) was prepared by the reaction between Ba(NO₃)₂ (292.5 mg, 0.5 mmol in water 25 ml) and the proton transfer compound (pdaH₂)(py-3,5-dc) (241 mg, 1.0 mmol in water 25 ml), in a 1:2 molar ratio. Crystals were obtained by slow evaporation of the solvent at room temperature.