Ca5(RhN3)2 is Orthorhombic Perovskite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted pentagonal pyramidal geometry to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to one N(2), two equivalent N(1), and two equivalent N(3) atoms. Rh(1) is bonded in a 3-coordinate geometry to one N(1), one N(3), and two equivalent N(2) atoms. There are three inequivalent N sites. In the first N site, N(2) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(3), two equivalent Ca(2), and two equivalent Rh(1) atoms. In the second N site, N(3) is bonded to one Ca(1), two equivalent Ca(2), two equivalent Ca(3), and one Rh(1) atom to form a mixture of distorted edge, corner, and face-sharing NCa5Rh octahedra. The corner-sharing octahedral tilt angles range from 16-67°. In the third N site, N(1) is bonded to one Ca(1), two equivalent Ca(2), two equivalent Ca(3), and one Rh(1) atom to form a mixture of distorted edge and corner-sharing NCa5Rh octahedra. The corner-sharing octahedral tilt angles range from 16-67°.
Ca5(RhN3)2 is Orthorhombic Perovskite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted pentagonal pyramidal geometry to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms. Both Ca(1)-N(1) bond lengths are 2.40 Å. Both Ca(1)-N(2) bond lengths are 2.63 Å. Both Ca(1)-N(3) bond lengths are 2.61 Å. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms. There is one shorter (2.53 Å) and one longer (2.72 Å) Ca(2)-N(1) bond length. There is one shorter (2.79 Å) and one longer (3.09 Å) Ca(2)-N(2) bond length. There is one shorter (2.48 Å) and one longer (2.55 Å) Ca(2)-N(3) bond length. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to one N(2), two equivalent N(1), and two equivalent N(3) atoms. The Ca(3)-N(2) bond length is 2.47 Å. There is one shorter (2.47 Å) and one longer (2.51 Å) Ca(3)-N(1) bond length. There is one shorter (2.37 Å) and one longer (2.61 Å) Ca(3)-N(3) bond length. Rh(1) is bonded in a 3-coordinate geometry to one N(1), one N(3), and two equivalent N(2) atoms. The Rh(1)-N(1) bond length is 1.96 Å. The Rh(1)-N(3) bond length is 1.93 Å. There is one shorter (1.83 Å) and one longer (2.57 Å) Rh(1)-N(2) bond length. There are three inequivalent N sites. In the first N site, N(2) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(3), two equivalent Ca(2), and two equivalent Rh(1) atoms. In the second N site, N(3) is bonded to one Ca(1), two equivalent Ca(2), two equivalent Ca(3), and one Rh(1) atom to form a mixture of distorted edge, corner, and face-sharing NCa5Rh octahedra. The corner-sharing octahedral tilt angles range from 16-67°. In the third N site, N(1) is bonded to one Ca(1), two equivalent Ca(2), two equivalent Ca(3), and one Rh(1) atom to form a mixture of distorted edge and corner-sharing NCa5Rh octahedra. The corner-sharing octahedral tilt angles range from 16-67°.