Ca3(BiN2)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(2) and four equivalent N(1) atoms to form a mixture of edge and corner-sharing CaN5 square pyramids. In the second Ca site, Ca(2) is bonded in a 2-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Bi(1) is bonded in a 3-coordinate geometry to one N(1) and two equivalent N(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ca(2), four equivalent Ca(1), and one Bi(1) atom to form a mixture of distorted edge, face, and corner-sharing NCa5Bi octahedra. The corner-sharing octahedral tilt angles are 10°. In the second N site, N(2) is bonded in a distorted see-saw-like geometry to one Ca(1), one Ca(2), and two equivalent Bi(1) atoms.
Ca3(BiN2)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(2) and four equivalent N(1) atoms to form a mixture of edge and corner-sharing CaN5 square pyramids. The Ca(1)-N(2) bond length is 2.40 Å. There are a spread of Ca(1)-N(1) bond distances ranging from 2.40-2.73 Å. In the second Ca site, Ca(2) is bonded in a 2-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Ca(2)-N(1) bond lengths are 2.91 Å. Both Ca(2)-N(2) bond lengths are 2.31 Å. Bi(1) is bonded in a 3-coordinate geometry to one N(1) and two equivalent N(2) atoms. The Bi(1)-N(1) bond length is 2.21 Å. Both Bi(1)-N(2) bond lengths are 2.26 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ca(2), four equivalent Ca(1), and one Bi(1) atom to form a mixture of distorted edge, face, and corner-sharing NCa5Bi octahedra. The corner-sharing octahedral tilt angles are 10°. In the second N site, N(2) is bonded in a distorted see-saw-like geometry to one Ca(1), one Ca(2), and two equivalent Bi(1) atoms.