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Synthesis and Structural Characterization of a Metal Cluster and a Coordination Polymer Based on the [Mn(6)(mu(4)-O)(2)] Unit.

Moushi EE, Tasiopoulos AJ, Manos MJ - Bioinorg Chem Appl (2010)

Bottom Line: A new 1-D coordination polymer {[Mn(6)O(2)(O(2)CMe)(10)(H(2)O)(4)].2.5H(2)O}(infinity) (1.2.5H(2)O)(infinity) and the cluster [Mn(6)O(2)(O(2)(O(2)CPh)(10) (py)(2)(MeCN)(H(2)O)].2MeCN (2.2MeCN) are reported.Both compounds were synthesized by room temperature reactions of [Mn(3)(mu(3)-O)(O(2)CR)(6)(L)(2)(L')] (R = Me, L = L' = py, (1.2.5H(2)O)(infinity); R = Ph, L = py, L' = H(2)O, 2.2MeCN) in the presence of 3-hydroxymethylpyridine (3hmpH) in acetonitrile.The structures of these complexes are based on hexanuclear mixed-valent manganese carboxylate clusters containing the [Mn(4) (II)Mn(2) (III)(mu(4)-O)(2)](10+) structural core. (1.2.5H(2)O)(infinity) consists of zigzag chain polymers constructed from [Mn(6)O(2)(O(2)CMe)(10)(H(2)O)(4)] repeating units linked through acetate ligands, whereas 2.2MeCN comprises a discrete Mn(6)-benzoate cluster.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus.

ABSTRACT
A new 1-D coordination polymer {[Mn(6)O(2)(O(2)CMe)(10)(H(2)O)(4)].2.5H(2)O}(infinity) (1.2.5H(2)O)(infinity) and the cluster [Mn(6)O(2)(O(2)(O(2)CPh)(10) (py)(2)(MeCN)(H(2)O)].2MeCN (2.2MeCN) are reported. Both compounds were synthesized by room temperature reactions of [Mn(3)(mu(3)-O)(O(2)CR)(6)(L)(2)(L')] (R = Me, L = L' = py, (1.2.5H(2)O)(infinity); R = Ph, L = py, L' = H(2)O, 2.2MeCN) in the presence of 3-hydroxymethylpyridine (3hmpH) in acetonitrile. The structures of these complexes are based on hexanuclear mixed-valent manganese carboxylate clusters containing the [Mn(4) (II)Mn(2) (III)(mu(4)-O)(2)](10+) structural core. (1.2.5H(2)O)(infinity) consists of zigzag chain polymers constructed from [Mn(6)O(2)(O(2)CMe)(10)(H(2)O)(4)] repeating units linked through acetate ligands, whereas 2.2MeCN comprises a discrete Mn(6)-benzoate cluster.

No MeSH data available.


A partially labeled plot of the repeating unit of (1)∞. The yellow lines emphasize the [Mn4IIMn2III(μ4-O)2]10+ core. Color code: MnII, green; MnIII, dark green; O, red; C, grey. H atoms are omitted for clarity.
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fig1: A partially labeled plot of the repeating unit of (1)∞. The yellow lines emphasize the [Mn4IIMn2III(μ4-O)2]10+ core. Color code: MnII, green; MnIII, dark green; O, red; C, grey. H atoms are omitted for clarity.

Mentions: Compound (1·2.5H2O)∞ crystallizes in the orthorhombic space group Pbca. Its repeating unit comprises the hexanuclear cluster [Mn6O2(O2CMe)10(H2O)4] (Figure 1) and totally 2.5H2O molecules of crystallization. Charge considerations, bond valence sum calculations (Table 4) and inspection of metric parameters indicate that the cluster is mixed-valent containing four MnII and two MnIII ions. The [Mn4IIMn2III(μ4-O)2]10+ core of 1 has appeared several times in the literature as will be discussed in detail below and can be described as consisting of two edge-sharing (μ4-O)Mn4 tetrahedra. Such units are defined as anti-T1 tetrahedra (T1 is a structural unit having a cation at the center and four anions at the apices of the tetrahedron) [26]. The common edge of the two anti-T1 tetrahedra is formed by the two MnIII ions, whereas the four MnII ions occupy the corners of the [Mn4IIMn2III(μ4-O)2]10+ core. The peripheral ligation of the Mn atoms is completed by 4 terminal H2O molecules (ligated to the four MnII atoms) and 10 acetate ligands.


Synthesis and Structural Characterization of a Metal Cluster and a Coordination Polymer Based on the [Mn(6)(mu(4)-O)(2)] Unit.

Moushi EE, Tasiopoulos AJ, Manos MJ - Bioinorg Chem Appl (2010)

A partially labeled plot of the repeating unit of (1)∞. The yellow lines emphasize the [Mn4IIMn2III(μ4-O)2]10+ core. Color code: MnII, green; MnIII, dark green; O, red; C, grey. H atoms are omitted for clarity.
© Copyright Policy - open-access
Related In: Results  -  Collection

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fig1: A partially labeled plot of the repeating unit of (1)∞. The yellow lines emphasize the [Mn4IIMn2III(μ4-O)2]10+ core. Color code: MnII, green; MnIII, dark green; O, red; C, grey. H atoms are omitted for clarity.
Mentions: Compound (1·2.5H2O)∞ crystallizes in the orthorhombic space group Pbca. Its repeating unit comprises the hexanuclear cluster [Mn6O2(O2CMe)10(H2O)4] (Figure 1) and totally 2.5H2O molecules of crystallization. Charge considerations, bond valence sum calculations (Table 4) and inspection of metric parameters indicate that the cluster is mixed-valent containing four MnII and two MnIII ions. The [Mn4IIMn2III(μ4-O)2]10+ core of 1 has appeared several times in the literature as will be discussed in detail below and can be described as consisting of two edge-sharing (μ4-O)Mn4 tetrahedra. Such units are defined as anti-T1 tetrahedra (T1 is a structural unit having a cation at the center and four anions at the apices of the tetrahedron) [26]. The common edge of the two anti-T1 tetrahedra is formed by the two MnIII ions, whereas the four MnII ions occupy the corners of the [Mn4IIMn2III(μ4-O)2]10+ core. The peripheral ligation of the Mn atoms is completed by 4 terminal H2O molecules (ligated to the four MnII atoms) and 10 acetate ligands.

Bottom Line: A new 1-D coordination polymer {[Mn(6)O(2)(O(2)CMe)(10)(H(2)O)(4)].2.5H(2)O}(infinity) (1.2.5H(2)O)(infinity) and the cluster [Mn(6)O(2)(O(2)(O(2)CPh)(10) (py)(2)(MeCN)(H(2)O)].2MeCN (2.2MeCN) are reported.Both compounds were synthesized by room temperature reactions of [Mn(3)(mu(3)-O)(O(2)CR)(6)(L)(2)(L')] (R = Me, L = L' = py, (1.2.5H(2)O)(infinity); R = Ph, L = py, L' = H(2)O, 2.2MeCN) in the presence of 3-hydroxymethylpyridine (3hmpH) in acetonitrile.The structures of these complexes are based on hexanuclear mixed-valent manganese carboxylate clusters containing the [Mn(4) (II)Mn(2) (III)(mu(4)-O)(2)](10+) structural core. (1.2.5H(2)O)(infinity) consists of zigzag chain polymers constructed from [Mn(6)O(2)(O(2)CMe)(10)(H(2)O)(4)] repeating units linked through acetate ligands, whereas 2.2MeCN comprises a discrete Mn(6)-benzoate cluster.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus.

ABSTRACT
A new 1-D coordination polymer {[Mn(6)O(2)(O(2)CMe)(10)(H(2)O)(4)].2.5H(2)O}(infinity) (1.2.5H(2)O)(infinity) and the cluster [Mn(6)O(2)(O(2)(O(2)CPh)(10) (py)(2)(MeCN)(H(2)O)].2MeCN (2.2MeCN) are reported. Both compounds were synthesized by room temperature reactions of [Mn(3)(mu(3)-O)(O(2)CR)(6)(L)(2)(L')] (R = Me, L = L' = py, (1.2.5H(2)O)(infinity); R = Ph, L = py, L' = H(2)O, 2.2MeCN) in the presence of 3-hydroxymethylpyridine (3hmpH) in acetonitrile. The structures of these complexes are based on hexanuclear mixed-valent manganese carboxylate clusters containing the [Mn(4) (II)Mn(2) (III)(mu(4)-O)(2)](10+) structural core. (1.2.5H(2)O)(infinity) consists of zigzag chain polymers constructed from [Mn(6)O(2)(O(2)CMe)(10)(H(2)O)(4)] repeating units linked through acetate ligands, whereas 2.2MeCN comprises a discrete Mn(6)-benzoate cluster.

No MeSH data available.