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Synthesis and Characterization of the Tetraphosphonic Acid Ester (Et 2 O 3 PCH 2 ) 4 C 6 H 2 and the Open‐Framework Cadmium Tetraphosphonate, Cd 2 [(HO 3 PCH 2 ) 4 C 6 H 2 ]
Author(s) -
Stock Norbert,
Guillou Nathalie,
Senker Jürgen,
Férey Gérard,
Bein Thomas
Publication year - 2005
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200400455
Subject(s) - triclinic crystal system , crystal structure , octahedron , chemistry , crystallography , hydrolysis , stereochemistry , hydrothermal synthesis , x ray crystallography , hydrothermal circulation , physics , diffraction , biochemistry , optics , seismology , geology
Following the strategy of using polyfunctional phosphonic acids for the synthesis of open‐framework metal phosphonates, the ethyl ester of a tetraphosphonic acid, i. e. (Et 2 O 3 PCH 2 ) 4 C 6 H 2 ( 1 ) was synthesized and used in the hydrothermal synthesis of the new cadmium tetraphosphonate, Cd 2 [(HO 3 PCH 2 ) 4 C 6 H 2 ] ( 2 ). The structure of 1 was solved from single crystal data ( 1 : triclinic, P 1¯, a = 12.3846(2), b = 12.6166(3), c = 12.9915(3) Å, α = 86.380(1), β = 63.372(1), γ = 89.589(1)°, V = 1810.51(7) Å 3 , Z = 2, R1 = 0.077, wR2 = 0.177). The in situ hydrolysis of the ethyl ester and the reaction with the Cd 2+ ions leads to the well‐crystallized microcrystalline product 2 . Its structure was solved and refined using X‐ray powder diffraction data ( 2 : triclinic, P 1¯, with a = 11.0435(5), b = 7.5809(3), c = 5.4250(2) Å, α = 98.354(2), β = 101.951(2), γ = 95.885(3)°, V = 435.48(9) Å 3 , Z = 1, R w p = 0.096, R p = 0.072, R B = 0.081, R F = 0.069). Whereas the structure of 1 is a molecular structure, the structure of Cd 2 [(HO 3 PCH 2 ) 4 C 6 H 2 ] ( 2 ) is built up from edge sharing CdO 6 octahedra forming dimeric [Cd 2 O 10 ] polyhedra. In the second coordination sphere of each of the Cd II ions six HO 3 PCH 2 R units are observed. The [Cd 2 O 10 ] polyhedra are connected to six other [Cd 2 O 10 ] polyhedra by ten hydrogenphosphonic acid units. Thus inorganic sheets are formed that are connected to a three‐dimensional framework with small channels, through the phenyl rings. Thermogravimetric as well as IR‐, 113 Cd‐MAS‐NMR and 31 P‐MAS‐NMR data are also presented.