Ca3(ReN2)2 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 4-coordinate geometry to one N(1) and three equivalent N(2) atoms. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent N(2) and four equivalent N(1) atoms. There are two inequivalent Re sites. In the first Re site, Re(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form edge-sharing ReN4 tetrahedra. In the second Re site, Re(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing ReN4 trigonal pyramids. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to one Ca(1), two equivalent Ca(2), one Re(1), and one Re(2) atom. In the second N site, N(2) is bonded to one Ca(2), three equivalent Ca(1), one Re(1), and one Re(2) atom to form a mixture of distorted corner, edge, and face-sharing NCa4Re2 octahedra. The corner-sharing octahedral tilt angles range from 42-65°.
Ca3(ReN2)2 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 4-coordinate geometry to one N(1) and three equivalent N(2) atoms. The Ca(1)-N(1) bond length is 2.38 Å. There are a spread of Ca(1)-N(2) bond distances ranging from 2.39-2.58 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent N(2) and four equivalent N(1) atoms. Both Ca(2)-N(2) bond lengths are 2.83 Å. There are two shorter (2.58 Å) and two longer (2.71 Å) Ca(2)-N(1) bond lengths. There are two inequivalent Re sites. In the first Re site, Re(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form edge-sharing ReN4 tetrahedra. Both Re(1)-N(1) bond lengths are 1.96 Å. Both Re(1)-N(2) bond lengths are 1.97 Å. In the second Re site, Re(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing ReN4 trigonal pyramids. Both Re(2)-N(1) bond lengths are 2.16 Å. Both Re(2)-N(2) bond lengths are 2.05 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to one Ca(1), two equivalent Ca(2), one Re(1), and one Re(2) atom. In the second N site, N(2) is bonded to one Ca(2), three equivalent Ca(1), one Re(1), and one Re(2) atom to form a mixture of distorted corner, edge, and face-sharing NCa4Re2 octahedra. The corner-sharing octahedral tilt angles range from 42-65°.