Hydrothermal synthesis and structural characterization of the (C(n)H(2n+6)N(2)[Mn(3)(HPO(3))4] (n = 3-8) new layered inorganic-organic hybrid manganese(II) phosphites. Crystal structure and spectroscopic and magnetic properties of (C(3)H(12)N(2)[Mn(3)(HPO(3))4]

Inorg Chem. 2001 Jul 2;40(14):3476-83. doi: 10.1021/ic010166g.

Abstract

The (C(n)H(2n+6)N(2))[Mn(3)(HPO(3))(4)] (n = 3-8) compounds have been prepared by hydrothermal synthesis and characterized by X-ray diffraction data and spectroscopic techniques. The crystal structure of (C(3)H(12)N(2))[Mn(3)(HPO(3))(4)] has been solved from single-crystal X-ray diffraction. The unit-cell parameters are a = 9.502(1), b = 5.472(1), c = 14.523(4) A, beta = 95.01(3) degrees, monoclinic, C2/m, with Z = 2. The compound shows a layered structure stacked along the c-axis with the alkyldiammonium cations placed in the interlayer space. The sheets are formed by Mn(3)O(12) trimer units extended in the ab-plane and connected by (HPO(3))(2-) anions. The study of the (C(n)H(2n+6)N(2))[Mn(3)(HPO(3))(4)] (n = 4-8) phases by X-ray powder diffraction indicates an isotype relation with the propanediammonium compound. The Dq and Racah parameters calculated for (C(3)H(12)N(2))[Mn(3)(HPO(3))(4)] are Dq = 880, B = 660 and C = 3610 cm(-1). The ESR spectra show isotropic signals with a g-value of 2.008. Magnetic measurements indicate the presence of antiferromagnetic interactions inside the [Mn(3)(HPO(3))(4)](2-) sheets. The J/K value has been estimated to be -15 K by considering that the system behaves like an isolated trimer at high temperatures.