catena-Poly[[[diaqua­manganese(II)]-μ3-pyridine-2,3-dicarboxyl­ato-κ4 N,O 2:O 3:O 3′] dihydrate]

Zhong-Xiang Du; Jun-Xia Li

doi:10.1107/S1600536808029413

. 2008 Sep 20;64(Pt 10):m1295–m1296. doi: 10.1107/S1600536808029413

catena-Poly[[[diaquamanganese(II)]-μ₃-pyridine-2,3-dicarboxylato-κ⁴ N,O ²:O ³:O ^3′] dihydrate]

Zhong-Xiang Du ^a,^*, Jun-Xia Li ^a

PMCID: PMC2959413 PMID: 21201037

Abstract

In the title coordination polymer, {[Mn(C₇H₃NO₄)(H₂O)₂]·2H₂O}_n, the Mn^II ion is coordinated in a distorted octahedral environment by the O atoms of two water molecules, one N and one O atoms of the chelating pyridine-2,3-dicarboxylate (PDC) dianion, and two axial bridging carboxylate O atoms from two adjacent PDC ligands. The fully deprotonated PDC anion acts a μ₃-bridging ligand, establishing a chain structure along the a axis. These polymeric chains are connected into a three-dimensional framework via several intermolecular O—H⋯O hydrogen bonds.

Related literature

For related literature, see: Aghabozorg et al. (2007 ▶); Baruah et al. (2007 ▶); Drew et al. (1971 ▶); Ghoer & Youssef (1993 ▶); Kang et al. (2006 ▶); Li et al. (2006 ▶); Manteghi et al. (2007 ▶); Patrick et al. (2003 ▶); Sun et al. (2006 ▶); Takusagawa & Koetzle (1978 ▶); Turner & Batten (2007 ▶); Zhang & You (2003 ▶); Zhang et al. (2003 ▶).

Experimental

Crystal data

[Mn(C₇H₃NO₄)(H₂O)₂]·2H₂O
M _r = 292.11
Monoclinic,
a = 6.5719 (8) Å
b = 7.6703 (9) Å
c = 20.566 (3) Å
β = 93.3540 (10)°
V = 1034.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.31 mm⁻¹
T = 291 (2) K
0.38 × 0.15 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.639, T _max = 0.865
6428 measured reflections
1921 independent reflections
1774 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.095
S = 1.07
1921 reflections
154 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004 ▶); 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/S1600536808029413/sg2261sup1.cif

e-64-m1295-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808029413/sg2261Isup2.hkl

e-64-m1295-Isup2.hkl^{(94.6KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Mn1—O3	2.098 (3)
Mn1—O4	2.139 (3)
Mn1—O8ⁱ	2.144 (2)
Mn1—O5	2.160 (3)
Mn1—O6ⁱⁱ	2.242 (3)
Mn1—N1ⁱ	2.263 (3)

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O3—Mn1—O4	96.07 (11)
O3—Mn1—O8ⁱ	168.80 (10)
O3—Mn1—O5	87.98 (10)
O4—Mn1—O5	87.54 (10)
O8ⁱ—Mn1—O5	95.89 (9)
O3—Mn1—O6ⁱⁱ	84.63 (10)
O5—Mn1—O6ⁱⁱ	164.11 (10)
O4—Mn1—N1ⁱ	166.71 (11)

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

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯O8	0.84	1.95	2.793 (4)	177
O1—H2W⋯O2ⁱⁱⁱ	0.84	2.09	2.845 (4)	149
O2—H4W⋯O6^iv	0.84	2.07	2.884 (4)	165
O2—H4W⋯O4^v	0.84	2.56	3.043 (4)	118
O2—H3W⋯O4^vi	0.85	1.94	2.788 (4)	180
O3—H5W⋯O7^iv	0.84	1.85	2.691 (4)	175
O3—H6W⋯O1^iv	0.85	1.92	2.730 (4)	159
O4—H8W⋯O1ⁱ	0.85	2.61	3.457 (4)	180
O4—H7W⋯O1^vii	0.84	1.86	2.691 (4)	168
O4—H8W⋯O2^vii	0.85	2.37	2.788 (4)	111

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 20471026) and the Natural Science Foundation of Henan Province (grant No. 0311021200).

supplementary crystallographic information

Comment

Pyridine-2,3-dicarboxylic acid (H₂PDC), being a potential multidentate bridging ligand, has aroused considerable interests in recent decades and a number of metal complexes have been reported. In these complexes, pyridine-2,3-dicarboxylic acid is partly or fully deprotonated and shows diverse coordination modes, such as non-coordinate (Takusagawa & Koetzle, 1978; Manteghi et al., 2007), monodentate (Drew et al., 1971; Ghoer & Youssef, 1993; Patrick et al., 2003; Baruah et al., 2007), µ₂-bridging (Zhang et al., 2003; Aghabozorg et al., 2007; Sun et al., 2006; Turner & Batten, 2007; Kang et al., 2006), µ₃-bridging (Zhang & You, 2003; Li et al., 2006). Here we describe another new compound in which the PDC is µ₃-bridging, (I),(Fig. 1).

Complex (I) is composed of {[Mn(C₇H₃NO₄)(H₂O)₂].2H₂O}_n units, in which the Mn^II ion is six-coordinated in a distorted octahedral geometry (Table 1) formed by two coordinated water molecules, one N and one O atoms of a PDC dianion and two different carboxylate O atoms in the axial position from another two adjacent PDC ligands. The deprotonated PDC are µ₃-bridging ligands and they join the neighbouring Mn^II ions to form this one-dimensional linear chain structure along a axis. This kind of µ₃-bridging mode is different from that have been published (Zhang & You, 2003; Li et al., 2006) as in this paper one bridging carboxylate O atom only links one metal ions, while in the latter one bridging carboxylate O atom simultaneously links two metal ions,respectively.

The carboxylate O atoms of PDC dianion and coordinate and non coordinated water molecules are all involved in rich O—H···O intermolecular hydrogen bonds (Table 2) and they connect polymetric chains into a three-dimensional framework (Fig. 2).

Experimental

The ligand H₂PDC (1 mmol, 0.17 g) and NaOH (2 mmol, 0.08 g) were dissolved in water and methanol mixed solvent (20 ml, v/v 1:1). To this solution, Mn(CH₃COO)₂.4H₂O (1 mmol, 0.25 g) was added and the resulting mixture was stirred and refluxed at 343 K for 5 h, then cooled to room temperature. After filtration and evaporation in air for a week, pink block-shaped crystals were obtained in a yield of 37%. Analysis, found (%): C, 28.70; H, 3.80; N, 4.71. C₇H₁₁Mn N O₈ requires (%): C,28.75; H,3.76; N,4.79. (CCDC number 668395)