Ca3(MnN2)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 to two equivalent N(2) and four equivalent N(1) atoms to form distorted CaN6 octahedra that share corners with six equivalent Mn(2)N4 trigonal pyramids, edges with two equivalent Ca(2)N6 octahedra, and edges with three equivalent Mn(1)N4 tetrahedra. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form MnN4 tetrahedra that share edges with three equivalent Ca(2)N6 octahedra and edges with two equivalent Mn(2)N4 trigonal pyramids. In the second Mn site, Mn(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted MnN4 trigonal pyramids that share corners with six equivalent Ca(2)N6 octahedra and edges with two equivalent Mn(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-81°. 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 Mn(1), and one Mn(2) atom. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ca(2), three equivalent Ca(1), one Mn(1), and one Mn(2) atom.
Ca3(MnN2)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 2.39 Å. There are a spread of Ca(1)-N(2) bond distances ranging from 2.41-2.53 Å. In the second Ca site, Ca(2) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form distorted CaN6 octahedra that share corners with six equivalent Mn(2)N4 trigonal pyramids, edges with two equivalent Ca(2)N6 octahedra, and edges with three equivalent Mn(1)N4 tetrahedra. Both Ca(2)-N(2) bond lengths are 2.72 Å. There are two shorter (2.52 Å) and two longer (2.53 Å) Ca(2)-N(1) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form MnN4 tetrahedra that share edges with three equivalent Ca(2)N6 octahedra and edges with two equivalent Mn(2)N4 trigonal pyramids. Both Mn(1)-N(1) bond lengths are 1.84 Å. Both Mn(1)-N(2) bond lengths are 1.86 Å. In the second Mn site, Mn(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted MnN4 trigonal pyramids that share corners with six equivalent Ca(2)N6 octahedra and edges with two equivalent Mn(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-81°. Both Mn(2)-N(1) bond lengths are 2.00 Å. Both Mn(2)-N(2) bond lengths are 1.95 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 Mn(1), and one Mn(2) atom. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ca(2), three equivalent Ca(1), one Mn(1), and one Mn(2) atom.