Ca3MnN3 crystallizes in the orthorhombic Cmcm 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 distorted edge and corner-sharing CaN5 square pyramids. In the second Ca site, Ca(2) is bonded to two equivalent N(1) and three equivalent N(2) atoms to form a mixture of edge and corner-sharing CaN5 square pyramids. Mn(1) is bonded in a trigonal planar geometry to one N(2) and two equivalent N(1) 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 Mn(1) atom to form a mixture of distorted edge and corner-sharing NCa5Mn octahedra. The corner-sharing octahedral tilt angles range from 8-50°. In the second N site, N(2) is bonded to two equivalent Ca(1), three equivalent Ca(2), and one Mn(1) atom to form a mixture of edge and corner-sharing NCa5Mn octahedra. The corner-sharing octahedral tilt angles are 8°.
Ca3MnN3 crystallizes in the orthorhombic Cmcm 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 distorted edge and corner-sharing CaN5 square pyramids. The Ca(1)-N(2) bond length is 2.41 Å. There are a spread of Ca(1)-N(1) bond distances ranging from 2.48-2.75 Å. In the second Ca site, Ca(2) is bonded to two equivalent N(1) and three equivalent N(2) atoms to form a mixture of edge and corner-sharing CaN5 square pyramids. Both Ca(2)-N(1) bond lengths are 2.58 Å. There is one shorter (2.38 Å) and two longer (2.52 Å) Ca(2)-N(2) bond lengths. Mn(1) is bonded in a trigonal planar geometry to one N(2) and two equivalent N(1) atoms. The Mn(1)-N(2) bond length is 1.79 Å. Both Mn(1)-N(1) bond lengths are 1.78 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 Mn(1) atom to form a mixture of distorted edge and corner-sharing NCa5Mn octahedra. The corner-sharing octahedral tilt angles range from 8-50°. In the second N site, N(2) is bonded to two equivalent Ca(1), three equivalent Ca(2), and one Mn(1) atom to form a mixture of edge and corner-sharing NCa5Mn octahedra. The corner-sharing octahedral tilt angles are 8°.