Novel structural arrangement for divalent metal phosphonates: synthesis of tert-butylphosphonates and structure of Co[(CH3)3CPO3]·H2O

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Abstract
The synthesis and characterization of new divalent metal tert-butylphosphonates are described: MII[(CH3)3CPO3]·xH2O [MII= Co, Mn (x= 1) MII= Zn (x= 2/3)] and Cu1.75O0.75[(CH3)3CPO3]·H2O. Co[(CH3)3CPO3]·H2O crystallizes in the monoclinic space group P21/c with a= 12.256(1)Å, b= 17.939(1)Å, c= 10.769(1)Å, β= 93.57(1)°, V = 2363.1 (4)Å3, Z= 12, with R= 0.064 and Rw= 0.075 for 1805 observed reflections, according to the criterion I > 3σ(I). The layer arrangement of this new phase is different from that observed in the case of the n-alkyl MII( RPO3)·H2O analogues owing to the steric effect of the bulky tert-butyl group. The structural relationship between the cobalt, manganese and zinc compounds is discussed. The observed magnetic moments are consistent with the presence of high-spin MnII or CoII and with the existence of both octahedral and tetrahedral environments about these metals.