Ca4RhN4 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(3) and three equivalent N(2) atoms to form distorted CaN5 trigonal bipyramids that share corners with two equivalent N(2)Ca5N octahedra and edges with four equivalent Ca(1)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 107°. In the second Ca site, Ca(2) is bonded in a distorted water-like geometry to one N(1) and one N(3) atom. In the third Ca site, Ca(3) is bonded in a 7-coordinate geometry to three equivalent Rh(1), one N(2), one N(3), and two equivalent N(1) atoms. In the fourth Ca site, Ca(4) is bonded in a 5-coordinate geometry to one N(2), two equivalent N(1), and two equivalent N(4) atoms. Rh(1) is bonded in a distorted single-bond geometry to three equivalent Ca(3) and one N(4) atom. There are four inequivalent N sites. In the first N site, N(4) is bonded in a 4-coordinate geometry to two equivalent Ca(4), one Rh(1), and one N(1) atom. In the second N site, N(1) is bonded in a 4-coordinate geometry to one Ca(2), two equivalent Ca(3), two equivalent Ca(4), and one N(4) atom. In the third N site, N(2) is bonded to one Ca(3), one Ca(4), three equivalent Ca(1), and one N(3) atom to form distorted NCa5N octahedra that share corners with two equivalent N(2)Ca5N octahedra, corners with two equivalent Ca(1)N5 trigonal bipyramids, and edges with two equivalent N(2)Ca5N octahedra. The corner-sharing octahedral tilt angles are 35°. In the fourth N site, N(3) is bonded in a 5-coordinate geometry to one Ca(2), one Ca(3), two equivalent Ca(1), and one N(2) atom.
Ca4RhN4 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(3) and three equivalent N(2) atoms to form distorted CaN5 trigonal bipyramids that share corners with two equivalent N(2)Ca5N octahedra and edges with four equivalent Ca(1)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 107°. Both Ca(1)-N(3) bond lengths are 2.39 Å. There are two shorter (2.39 Å) and one longer (2.47 Å) Ca(1)-N(2) bond length. In the second Ca site, Ca(2) is bonded in a distorted water-like geometry to one N(1) and one N(3) atom. The Ca(2)-N(1) bond length is 2.40 Å. The Ca(2)-N(3) bond length is 2.27 Å. In the third Ca site, Ca(3) is bonded in a 7-coordinate geometry to three equivalent Rh(1), one N(2), one N(3), and two equivalent N(1) atoms. There is one shorter (2.96 Å) and two longer (3.06 Å) Ca(3)-Rh(1) bond lengths. The Ca(3)-N(2) bond length is 2.37 Å. The Ca(3)-N(3) bond length is 2.59 Å. Both Ca(3)-N(1) bond lengths are 3.15 Å. In the fourth Ca site, Ca(4) is bonded in a 5-coordinate geometry to one N(2), two equivalent N(1), and two equivalent N(4) atoms. The Ca(4)-N(2) bond length is 2.18 Å. Both Ca(4)-N(1) bond lengths are 2.52 Å. Both Ca(4)-N(4) bond lengths are 2.55 Å. Rh(1) is bonded in a distorted single-bond geometry to three equivalent Ca(3) and one N(4) atom. The Rh(1)-N(4) bond length is 1.91 Å. There are four inequivalent N sites. In the first N site, N(4) is bonded in a 4-coordinate geometry to two equivalent Ca(4), one Rh(1), and one N(1) atom. The N(4)-N(1) bond length is 1.27 Å. In the second N site, N(1) is bonded in a 4-coordinate geometry to one Ca(2), two equivalent Ca(3), two equivalent Ca(4), and one N(4) atom. In the third N site, N(2) is bonded to one Ca(3), one Ca(4), three equivalent Ca(1), and one N(3) atom to form distorted NCa5N octahedra that share corners with two equivalent N(2)Ca5N octahedra, corners with two equivalent Ca(1)N5 trigonal bipyramids, and edges with two equivalent N(2)Ca5N octahedra. The corner-sharing octahedral tilt angles are 35°. The N(2)-N(3) bond length is 1.41 Å. In the fourth N site, N(3) is bonded in a 5-coordinate geometry to one Ca(2), one Ca(3), two equivalent Ca(1), and one N(2) atom.