Ca3(InN2)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 two equivalent N(2) and three equivalent N(1) atoms to form distorted CaN5 trigonal bipyramids that share corners with five equivalent Ca(2)N6 octahedra, corners with six equivalent In(1)N4 tetrahedra, corners with two equivalent Ca(1)N5 trigonal bipyramids,  an edgeedge with one Ca(2)N6 octahedra, edges with two equivalent In(1)N4 tetrahedra, and edges with three equivalent Ca(1)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-59°. In the second Ca site, Ca(2) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form distorted CaN6 octahedra that share corners with four equivalent In(1)N4 tetrahedra, corners with ten equivalent Ca(1)N5 trigonal bipyramids, edges with two equivalent Ca(2)N6 octahedra, edges with four equivalent In(1)N4 tetrahedra, and edges with two equivalent Ca(1)N5 trigonal bipyramids. In(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted InN4 tetrahedra that share corners with two equivalent Ca(2)N6 octahedra, corners with two equivalent In(1)N4 tetrahedra, corners with six equivalent Ca(1)N5 trigonal bipyramids, edges with two equivalent Ca(2)N6 octahedra,  an edgeedge with one In(1)N4 tetrahedra, and edges with two equivalent Ca(1)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 29-68°. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Ca(2), three equivalent Ca(1), and two equivalent In(1) atoms. In the second N site, N(2) is bonded in a 6-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), and two equivalent In(1) atoms.
Ca3(InN2)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 two equivalent N(2) and three equivalent N(1) atoms to form distorted CaN5 trigonal bipyramids that share corners with five equivalent Ca(2)N6 octahedra, corners with six equivalent In(1)N4 tetrahedra, corners with two equivalent Ca(1)N5 trigonal bipyramids,  an edgeedge with one Ca(2)N6 octahedra, edges with two equivalent In(1)N4 tetrahedra, and edges with three equivalent Ca(1)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-59°. There is one shorter (2.42 Å) and one longer (2.72 Å) Ca(1)-N(2) bond length. There are a spread of Ca(1)-N(1) bond distances ranging from 2.45-2.74 Å. In the second Ca site, Ca(2) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form distorted CaN6 octahedra that share corners with four equivalent In(1)N4 tetrahedra, corners with ten equivalent Ca(1)N5 trigonal bipyramids, edges with two equivalent Ca(2)N6 octahedra, edges with four equivalent In(1)N4 tetrahedra, and edges with two equivalent Ca(1)N5 trigonal bipyramids. Both Ca(2)-N(1) bond lengths are 2.72 Å. There are two shorter (2.40 Å) and two longer (2.75 Å) Ca(2)-N(2) bond lengths. In(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted InN4 tetrahedra that share corners with two equivalent Ca(2)N6 octahedra, corners with two equivalent In(1)N4 tetrahedra, corners with six equivalent Ca(1)N5 trigonal bipyramids, edges with two equivalent Ca(2)N6 octahedra,  an edgeedge with one In(1)N4 tetrahedra, and edges with two equivalent Ca(1)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 29-68°. There is one shorter (2.24 Å) and one longer (2.28 Å) In(1)-N(1) bond length. There is one shorter (2.17 Å) and one longer (2.18 Å) In(1)-N(2) bond length. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Ca(2), three equivalent Ca(1), and two equivalent In(1) atoms. In the second N site, N(2) is bonded in a 6-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), and two equivalent In(1) atoms.