The structural chemistry of calcium nitrides is represented by just two different intermediate phases: cubic Ca(3)N(2) (referred to as alpha-Ca(3)N(2), Mn(2)O(3) type structure) and Ca(2)N (CdCl(2) type structure). Other binary phases ("gamma-Ca(3)N(2)", "Ca(11)N(8)") have been proven to represent cyanamide nitrides, Ca(4)N(2)[CN(2)] and Ca(11)N(6)[CN(2)](2), respectively. The metastable nitride beta-Ca(3)N(2) is prepared either by reaction of freshly distilled calcium metal with nitrogen at 700 K, or by reaction of Ca(2)N with N(2) at 500 K. beta-Ca(3)N(2) transforms monotropically (T(trans) approximately 810 K) to cubic alpha-Ca(3)N(2). The crystal structure of beta-Ca(3)N(2) (rhombohedral R3c, no. 167, a=619.884(3) pm, c=1662.958(10) pm) is an isotype of the corundum structure (alpha-Al(2)O(3)) and comprises a network of NCa(6/4) octahedra that share common faces and edges. Magnetic susceptibility and electrical resistivity measurements confirm that beta-Ca(3)N(2) is a diamagnetic semiconductor.