CaReN3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(3) and four equivalent N(2) atoms to form CaN6 octahedra that share corners with six equivalent Re(1)N4 tetrahedra, edges with two equivalent Ca(1)N6 octahedra, and edges with three equivalent Ca(2)N6 pentagonal pyramids. In the second Ca site, Ca(2) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms to form distorted CaN6 pentagonal pyramids that share corners with four equivalent Re(1)N4 tetrahedra, edges with three equivalent Ca(1)N6 octahedra, and edges with two equivalent Re(1)N4 tetrahedra. Re(1) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form ReN4 tetrahedra that share corners with three equivalent Ca(1)N6 octahedra, corners with two equivalent Ca(2)N6 pentagonal pyramids, corners with two equivalent Re(1)N4 tetrahedra, and  an edgeedge with one Ca(2)N6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 34-66°. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted T-shaped geometry to one Ca(2) and two equivalent Re(1) atoms. In the second N site, N(2) is bonded to one Ca(2), two equivalent Ca(1), and one Re(1) atom to form a mixture of distorted corner and edge-sharing NCa3Re tetrahedra. In the third N site, N(3) is bonded in a distorted T-shaped geometry to one Ca(1), one Ca(2), and one Re(1) atom.
CaReN3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(3) and four equivalent N(2) atoms to form CaN6 octahedra that share corners with six equivalent Re(1)N4 tetrahedra, edges with two equivalent Ca(1)N6 octahedra, and edges with three equivalent Ca(2)N6 pentagonal pyramids. Both Ca(1)-N(3) bond lengths are 2.38 Å. There are two shorter (2.44 Å) and two longer (2.48 Å) Ca(1)-N(2) bond lengths. In the second Ca site, Ca(2) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms to form distorted CaN6 pentagonal pyramids that share corners with four equivalent Re(1)N4 tetrahedra, edges with three equivalent Ca(1)N6 octahedra, and edges with two equivalent Re(1)N4 tetrahedra. Both Ca(2)-N(1) bond lengths are 2.61 Å. Both Ca(2)-N(2) bond lengths are 2.46 Å. Both Ca(2)-N(3) bond lengths are 2.54 Å. Re(1) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form ReN4 tetrahedra that share corners with three equivalent Ca(1)N6 octahedra, corners with two equivalent Ca(2)N6 pentagonal pyramids, corners with two equivalent Re(1)N4 tetrahedra, and  an edgeedge with one Ca(2)N6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 34-66°. The Re(1)-N(2) bond length is 1.77 Å. The Re(1)-N(3) bond length is 1.74 Å. There is one shorter (1.88 Å) and one longer (1.90 Å) Re(1)-N(1) bond length. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted T-shaped geometry to one Ca(2) and two equivalent Re(1) atoms. In the second N site, N(2) is bonded to one Ca(2), two equivalent Ca(1), and one Re(1) atom to form a mixture of distorted corner and edge-sharing NCa3Re tetrahedra. In the third N site, N(3) is bonded in a distorted T-shaped geometry to one Ca(1), one Ca(2), and one Re(1) atom.