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The cyclo-tetra-phosphate Cd(2)P(4)O(12), a member of the isotypic series M(2)P(4)O(12) (M = Mg, Mn, Fe, Co, Ni, Cu).

ABSTRACT: The title compound, Cd(2)P(4)O(12), dicadmium cyclo-tetra-phosphate, crystallizes isotypically with the members of the series M(II) (2)P(4)O(12), where M = Mg, Mn, Fe, Co, Ni or Cu. Two CdO(6) octa-hedra, one with 2 and one with symmetry, share corners with the centrosymmetric P(4)O(12) (4-) ring anion that is built up from four corner-sharing PO(4) tetra-hedra. The isolated ring anions are arranged in layers parallel to (10) with the CdO(6) octa-hedra situated between these layers. The main difference between the individual M(II) (2)P(4)O(12) structures pertains to the different sizes of the MO(6) octa-hedra whereas the geometric parameters of all cyclo-P(4)O(12) (4-) anions are very similar.

SUBMITTER: Weil M

PROVIDER: S-EPMC3009007 | biostudies-other | 2010

REPOSITORIES: biostudies-other

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The cyclo-tetra-phosphate Cd(2)P(4)O(12), a member of the isotypic series M(2)P(4)O(12) (M = Mg, Mn, Fe, Co, Ni, Cu).

Weil Matthias M

Acta crystallographica. Section E, Structure reports online 20101013 Pt 11

The title compound, Cd(2)P(4)O(12), dicadmium cyclo-tetra-phosphate, crystallizes isotypically with the members of the series M(II) (2)P(4)O(12), where M = Mg, Mn, Fe, Co, Ni or Cu. Two CdO(6) octa-hedra, one with 2 and one with symmetry, share corners with the centrosymmetric P(4)O(12) (4-) ring anion that is built up from four corner-sharing PO(4) tetra-hedra. The isolated ring anions are arranged in layers parallel to (10) with the CdO(6) octa-hedra situated between these layers. The main dif ...[more]

PMID: 21588790

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Project description:A series of five-coordinate thiolate-ligated complexes [M(II)(tren)N4S(Me2)]+ (M = Mn, Fe, Co, Ni, Cu, Zn; tren = tris(2-aminoethyl)amine) are reported, and their structural, electronic, and magnetic properties are compared. Isolation of dimeric [Ni(II)(SN4(tren)-RS(dang))]2 ("dang"= dangling, uncoordinated thiolate supported by H bonds), using the less bulky [(tren)N4S](1-) ligand, pointed to the need for gem-dimethyls adjacent to the sulfur to sterically prevent dimerization. All of the gem-dimethyl derivatized complexes are monomeric and, with the exception of [Ni(II)(S(Me2)N4(tren)]+, are isostructural and adopt a tetragonally distorted trigonal bipyramidal geometry favored by ligand constraints. The nickel complex uniquely adopts an approximately ideal square pyramidal geometry and resembles the active site of Ni-superoxide dismutase (Ni-SOD). Even in coordinating solvents such as MeCN, only five-coordinate structures are observed. The MII-S thiolate bonds systematically decrease in length across the series (Mn-S > Fe-S > Co-S > Ni-S approximately Cu-S < Zn-S) with exceptions occurring upon the occupation of sigma* orbitals. The copper complex, [Cu(II)(S(Me2)N4(tren)]+, represents a rare example of a stable CuII-thiolate, and models the perturbed "green" copper site of nitrite reductase. In contrast to the intensely colored, low-spin Fe(III)-thiolates, the M(II)-thiolates described herein are colorless to moderately colored and high-spin (in cases where more than one spin-state is possible), reflecting the poorer energy match between the metal d- and sulfur orbitals upon reduction of the metal ion. As the d-orbitals drop in energy proceeding across the across the series M(2+) (M= Mn, Fe, Co, Ni, Cu), the sulfur-to-metal charge-transfer transition moves into the visible region, and the redox potentials cathodically shift. The reduced M(+1) oxidation state is only accessible with copper, and the more oxidized M(+4) oxidation state is only accessible for manganese.

Dataset Information

The cyclo-tetra-phosphate Cd(2)P(4)O(12), a member of the isotypic series M(2)P(4)O(12) (M = Mg, Mn, Fe, Co, Ni, Cu).

Publications

The cyclo-tetra-phosphate Cd(2)P(4)O(12), a member of the isotypic series M(2)P(4)O(12) (M = Mg, Mn, Fe, Co, Ni, Cu).

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