Synthesis, Structure Determination, and Magnetic Properties of [Cr3(dpa)4Cl2][CuCl2], a Compound Comprising a Trinuclear Chain Cation

Abstract

The new compound [Cr3(dpa)4Cl2][CuCl2] (1) (dpa = di-2,2'-pyridylamido) was synthesized by reacting Cr2(dpa)4 and anhydrous CuCl2 in dry tetrahydrofuran. Partial oxidation of Cr2(dpa)4 by Cu(II) forms Cr3+ ions, which coordinate to the free N donor atoms of the dpa ligands, and led to the formation of a trinuclear chain cation [Cr3(dpa)4Cl2]+. Recrystallization from CH2Cl2/ethyl ether yielded dark-brown, block-shaped crystals suitable for X-ray structure determination (Pccn (no. 56), a=1246:8(5), b=1487:3(3), c=2184:8(1) pm, V =4051.6(8) ·106 pm3, Z =4). The crystal structure is composed of discrete [Cr3(dpa)4Cl2]+ cations and [CuCl2]- anions. The Cr3 chain comprises quadruply-bonded diamagnetic (Cr2)4+ dimers and a pseudo-octahedrally coordinated, paramagnetic Cr3+ ion, manifesting itself in the effective magnetic moment μeff of 3:54μB (d3, S = 3=2) and the almost ideal Curie-paramagnetic behavior observed between 2 and 300 K with a Weiss constant θ = -0:25(4)K and χ0 = 4:9(7)×10-4 emu mol-1