Ca5(GeN3)2 crystallizes in the monoclinic C2/c space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(2), two equivalent N(1), and two equivalent N(3) atoms to form distorted CaN5 square pyramids that share corners with three equivalent Ge(1)N4 tetrahedra, corners with six equivalent Ca(2)N5 trigonal bipyramids, edges with two equivalent Ca(1)N5 square pyramids, edges with two equivalent Ge(1)N4 tetrahedra, and  an edgeedge with one Ca(2)N5 trigonal bipyramid. In the second Ca site, Ca(2) is bonded to one N(3), two equivalent N(1), and two equivalent N(2) atoms to form distorted CaN5 trigonal bipyramids that share corners with six equivalent Ca(1)N5 square pyramids, corners with two equivalent Ge(1)N4 tetrahedra, corners with two equivalent Ca(2)N5 trigonal bipyramids,  an edgeedge with one Ca(1)N5 square pyramid, edges with two equivalent Ge(1)N4 tetrahedra, and  an edgeedge with one Ca(2)N5 trigonal bipyramid. In the third Ca site, Ca(3) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Ge(1) is bonded to one N(1), one N(2), and two equivalent N(3) atoms to form GeN4 tetrahedra that share corners with three equivalent Ca(1)N5 square pyramids, corners with two equivalent Ca(2)N5 trigonal bipyramids, edges with two equivalent Ca(1)N5 square pyramids,  an edgeedge with one Ge(1)N4 tetrahedra, and edges with two equivalent Ca(2)N5 trigonal bipyramids. There are three inequivalent N sites. In the first N site, N(2) is bonded to one Ca(1), one Ca(3), two equivalent Ca(2), and one Ge(1) atom to form distorted NCa4Ge trigonal bipyramids that share corners with five equivalent N(1)Ca5Ge octahedra, corners with three equivalent N(2)Ca4Ge trigonal bipyramids, and edges with two equivalent N(1)Ca5Ge octahedra. The corner-sharing octahedral tilt angles range from 11-76°. In the second N site, N(3) is bonded in a 5-coordinate geometry to one Ca(2), two equivalent Ca(1), and two equivalent Ge(1) atoms. In the third N site, N(1) is bonded to one Ca(3), two equivalent Ca(1), two equivalent Ca(2), and one Ge(1) atom to form distorted NCa5Ge octahedra that share corners with five equivalent N(2)Ca4Ge trigonal bipyramids,  an edgeedge with one N(1)Ca5Ge octahedra, edges with two equivalent N(2)Ca4Ge trigonal bipyramids, and  a faceface with one N(1)Ca5Ge octahedra.
Ca5(GeN3)2 crystallizes in the monoclinic C2/c space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(2), two equivalent N(1), and two equivalent N(3) atoms to form distorted CaN5 square pyramids that share corners with three equivalent Ge(1)N4 tetrahedra, corners with six equivalent Ca(2)N5 trigonal bipyramids, edges with two equivalent Ca(1)N5 square pyramids, edges with two equivalent Ge(1)N4 tetrahedra, and  an edgeedge with one Ca(2)N5 trigonal bipyramid. The Ca(1)-N(2) bond length is 2.61 Å. There is one shorter (2.51 Å) and one longer (2.55 Å) Ca(1)-N(1) bond length. There is one shorter (2.62 Å) and one longer (2.66 Å) Ca(1)-N(3) bond length. In the second Ca site, Ca(2) is bonded to one N(3), two equivalent N(1), and two equivalent N(2) atoms to form distorted CaN5 trigonal bipyramids that share corners with six equivalent Ca(1)N5 square pyramids, corners with two equivalent Ge(1)N4 tetrahedra, corners with two equivalent Ca(2)N5 trigonal bipyramids,  an edgeedge with one Ca(1)N5 square pyramid, edges with two equivalent Ge(1)N4 tetrahedra, and  an edgeedge with one Ca(2)N5 trigonal bipyramid. The Ca(2)-N(3) bond length is 2.52 Å. There is one shorter (2.32 Å) and one longer (2.56 Å) Ca(2)-N(1) bond length. There is one shorter (2.42 Å) and one longer (2.51 Å) Ca(2)-N(2) bond length. In the third Ca site, Ca(3) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Ca(3)-N(1) bond lengths are 2.56 Å. Both Ca(3)-N(2) bond lengths are 2.32 Å. Ge(1) is bonded to one N(1), one N(2), and two equivalent N(3) atoms to form GeN4 tetrahedra that share corners with three equivalent Ca(1)N5 square pyramids, corners with two equivalent Ca(2)N5 trigonal bipyramids, edges with two equivalent Ca(1)N5 square pyramids,  an edgeedge with one Ge(1)N4 tetrahedra, and edges with two equivalent Ca(2)N5 trigonal bipyramids. The Ge(1)-N(1) bond length is 1.84 Å. The Ge(1)-N(2) bond length is 1.87 Å. There is one shorter (1.93 Å) and one longer (1.99 Å) Ge(1)-N(3) bond length. There are three inequivalent N sites. In the first N site, N(2) is bonded to one Ca(1), one Ca(3), two equivalent Ca(2), and one Ge(1) atom to form distorted NCa4Ge trigonal bipyramids that share corners with five equivalent N(1)Ca5Ge octahedra, corners with three equivalent N(2)Ca4Ge trigonal bipyramids, and edges with two equivalent N(1)Ca5Ge octahedra. The corner-sharing octahedral tilt angles range from 11-76°. In the second N site, N(3) is bonded in a 5-coordinate geometry to one Ca(2), two equivalent Ca(1), and two equivalent Ge(1) atoms. In the third N site, N(1) is bonded to one Ca(3), two equivalent Ca(1), two equivalent Ca(2), and one Ge(1) atom to form distorted NCa5Ge octahedra that share corners with five equivalent N(2)Ca4Ge trigonal bipyramids,  an edgeedge with one N(1)Ca5Ge octahedra, edges with two equivalent N(2)Ca4Ge trigonal bipyramids, and  a faceface with one N(1)Ca5Ge octahedra.