Bis(μ-4-nitro­phthalato)bis­[diaqua­(1,10-phenanthroline)manganese(II)]

Bi-Yi Xu; Ting Xie; Sheng-Jun Lu; Bin Xue; Wei Li

doi:10.1107/S1600536809024064

. 2009 Jul 1;65(Pt 8):m856–m857. doi: 10.1107/S1600536809024064

Bis(μ-4-nitrophthalato)bis[diaqua(1,10-phenanthroline)manganese(II)]

Bi-Yi Xu ^a, Ting Xie ^b, Sheng-Jun Lu ^b, Bin Xue ^b, Wei Li ^b,^*

PMCID: PMC2977488 PMID: 21583325

Abstract

In the title compound, [Mn₂(C₈H₃NO₆)₂(C₁₂H₈N₂)₂(H₂O)₄], the Mn^II atom in the centrosymmetric binuclear unit has a distorted octahedral geometry and is coordinated by a chelating 1,10-phenanthroline ligand, two monodentate carboxylate anions from two 4-nitrophthalates and two coordinated water molecules. The two Mn^II ions in the molecule are bridged by two 4-nitrophthalate anions, both in a bis-monodentate mode, which finally leads to the formation of the binuclear unit. Intramolecular O—H⋯O hydrogen bonds between the coordinated and uncoordinated O atoms of one monodentate carboxylate group and the corresponding coordinated water molecules result in an eight-membered and two six-membered rings. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link the dinuclear molecules into supramolecular chains propagating parallel to [100].

Related literature

For general background to self-assembly coordination complexes with metal ions and 4-nitrophthalic acid, see: Guo & Guo (2007 ▶); Qi et al. (2008 ▶).

Experimental

Crystal data

[Mn₂(C₈H₃NO₆)₂(C₁₂H₈N₂)₂(H₂O)₄]
M _r = 960.58
Orthorhombic,
a = 7.1601 (9) Å
b = 20.039 (3) Å
c = 26.592 (3) Å
V = 3815.5 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 293 K
0.30 × 0.15 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.890, T _max = 0.928
27311 measured reflections
3416 independent reflections
2608 reflections with I > 2σ(I)
R _int = 0.075

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.107
S = 1.05
3416 reflections
305 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXL97 (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024064/at2807sup1.cif

e-65-0m856-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024064/at2807Isup2.hkl

e-65-0m856-Isup2.hkl^{(167.6KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn1—O3ⁱ	2.1212 (19)
Mn1—O1	2.1524 (18)
Mn1—O1W	2.1969 (19)
Mn1—O2W	2.2413 (19)
Mn1—N2	2.284 (2)
Mn1—N3	2.287 (2)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2W—H2A⋯O2	0.845 (10)	2.25 (3)	2.935 (3)	139 (3)
O2W—H2B⋯O4ⁱⁱ	0.845 (10)	2.012 (13)	2.844 (3)	167 (4)
O1W—H1A⋯O1ⁱ	0.845 (10)	1.896 (12)	2.732 (2)	170 (4)
O1W—H1B⋯O4ⁱⁱ	0.845 (10)	2.07 (2)	2.827 (3)	149 (3)

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

Acknowledgments

This work was supported by the Science and Technology Foundation of Guizhou Province (No. [2008]2216).

supplementary crystallographic information

Comment

The self-assembly of complexes from phthalic acid ligand and transition metal ions has attracted considerable attention in recent years because these complexes have various intriguing topological structures and potential applications in material chemistry. However, only a few metal-nitrophthalate complexes have been reported to date in contrast with the abundance of metal-phthalate complexes (Guo et al., 2007; Qi et al., 2008). In order to enrich the metal-nitrophthalate complexes, we utilized the 4-nitrophthalic acid to assemble with manganese ions in the presence of ancillary 1,10-phenanthroline ligand and obtained the title binuclear Mn^II complex [Mn(1,10-phenanthroline)(C₈H₃NO₆)(H₂O)₂]₂.

As depicted in Fig. 1, the title complex exhibits a binuclear structure and in the dimer each Mn^II ion has a distorted octahedral geometry and was coordinated by a chelating 1,10-phenanthroline, two monodentate carboxylates from two 4-nitrophthalates and two coordinated water molecules. And it is noteworthy that the two Mn^II ions in the complex are bridged by two 4-nitrophthalates both in a bis-monodentate mode to lead to the formation of a dinuclear unit because of the presence of an inversion center in the crystal structure. Intramolecular O—H···O hydrogen bonds between the coordinated and uncoordinated oxygen atoms of one monodentate carboxylate in a 4-nitrophthalate and corresponding coordinated water molecules result in an eight-membered and two six-membered rings (Table 2). Furthermore, the intermolecular O—H···O hydrogen bonds between two water molecules and another monodentate carboxylate in the same 4-nitrophthalate link the dinuclear molecules into a one-dimensional supramolecular chain, as shown in Fig. 2.

Experimental

Mn(CH₃COO)₂.4H₂O (0.50 mmol, 0.122 g), 4-nitrophthalic acid (0.50 mmol, 0.103 g), 1,10-phenanthroline (0.50 mmol, 0.099 g) and NaOH (1.0 mmol, 0.040 g) were well mixed in 8 ml distilled water, and the solution was stirred for 15 min and then transferred into a 23 ml Teflon-lined bomb at 398 K for 3 days and slowly cooled to room temperature. Light yellow sheet crystals which were suitable for X-ray analysis were obtained.