Ca4MnN4 crystallizes in the triclinic P-1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(1), one N(3), one N(4), and two equivalent N(2) atoms to form distorted CaN5 trigonal bipyramids that share  a cornercorner with one Ca(3)N5 square pyramid, corners with three equivalent Mn(1)N4 tetrahedra, edges with two equivalent Ca(3)N5 square pyramids,  an edgeedge with one Mn(1)N4 tetrahedra, and  an edgeedge with one Ca(1)N5 trigonal bipyramid. In the second Ca site, Ca(2) is bonded in a rectangular see-saw-like geometry to two equivalent N(2) and two equivalent N(3) atoms. In the third Ca site, Ca(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted CaN5 square pyramids that share corners with three equivalent Mn(1)N4 tetrahedra,  a cornercorner with one Ca(1)N5 trigonal bipyramid, edges with two equivalent Ca(3)N5 square pyramids,  an edgeedge with one Mn(1)N4 tetrahedra, and edges with two equivalent Ca(1)N5 trigonal bipyramids. In the fourth Ca site, Ca(4) is bonded in a 6-coordinate geometry to one N(2), one N(3), two equivalent N(1), and two equivalent N(4) atoms. Mn(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form MnN4 tetrahedra that share corners with three equivalent Ca(3)N5 square pyramids, corners with three equivalent Ca(1)N5 trigonal bipyramids,  an edgeedge with one Ca(3)N5 square pyramid, and  an edgeedge with one Ca(1)N5 trigonal bipyramid. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one Mn(1) atom to form a mixture of edge and corner-sharing NCa5Mn octahedra. The corner-sharing octahedral tilt angles range from 14-17°. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ca(4), two equivalent Ca(1), two equivalent Ca(2), and one Mn(1) atom. In the third N site, N(3) is bonded to one Ca(1), one Ca(3), one Ca(4), two equivalent Ca(2), 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 14-17°. In the fourth N site, N(4) is bonded in a 6-coordinate geometry to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one Mn(1) atom.
Ca4MnN4 crystallizes in the triclinic P-1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(1), one N(3), one N(4), and two equivalent N(2) atoms to form distorted CaN5 trigonal bipyramids that share  a cornercorner with one Ca(3)N5 square pyramid, corners with three equivalent Mn(1)N4 tetrahedra, edges with two equivalent Ca(3)N5 square pyramids,  an edgeedge with one Mn(1)N4 tetrahedra, and  an edgeedge with one Ca(1)N5 trigonal bipyramid. The Ca(1)-N(1) bond length is 2.40 Å. The Ca(1)-N(3) bond length is 2.54 Å. The Ca(1)-N(4) bond length is 2.60 Å. There is one shorter (2.44 Å) and one longer (2.58 Å) Ca(1)-N(2) bond length. In the second Ca site, Ca(2) is bonded in a rectangular see-saw-like geometry to two equivalent N(2) and two equivalent N(3) atoms. There is one shorter (2.40 Å) and one longer (2.43 Å) Ca(2)-N(2) bond length. There is one shorter (2.39 Å) and one longer (2.49 Å) Ca(2)-N(3) bond length. In the third Ca site, Ca(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted CaN5 square pyramids that share corners with three equivalent Mn(1)N4 tetrahedra,  a cornercorner with one Ca(1)N5 trigonal bipyramid, edges with two equivalent Ca(3)N5 square pyramids,  an edgeedge with one Mn(1)N4 tetrahedra, and edges with two equivalent Ca(1)N5 trigonal bipyramids. The Ca(3)-N(3) bond length is 2.42 Å. There is one shorter (2.38 Å) and one longer (2.41 Å) Ca(3)-N(1) bond length. There is one shorter (2.53 Å) and one longer (2.57 Å) Ca(3)-N(4) bond length. In the fourth Ca site, Ca(4) is bonded in a 6-coordinate geometry to one N(2), one N(3), two equivalent N(1), and two equivalent N(4) atoms. The Ca(4)-N(2) bond length is 2.97 Å. The Ca(4)-N(3) bond length is 2.47 Å. There is one shorter (2.46 Å) and one longer (2.53 Å) Ca(4)-N(1) bond length. There is one shorter (2.52 Å) and one longer (2.68 Å) Ca(4)-N(4) bond length. Mn(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form MnN4 tetrahedra that share corners with three equivalent Ca(3)N5 square pyramids, corners with three equivalent Ca(1)N5 trigonal bipyramids,  an edgeedge with one Ca(3)N5 square pyramid, and  an edgeedge with one Ca(1)N5 trigonal bipyramid. The Mn(1)-N(1) bond length is 1.87 Å. The Mn(1)-N(2) bond length is 1.88 Å. The Mn(1)-N(3) bond length is 1.89 Å. The Mn(1)-N(4) bond length is 1.89 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one Mn(1) atom to form a mixture of edge and corner-sharing NCa5Mn octahedra. The corner-sharing octahedral tilt angles range from 14-17°. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ca(4), two equivalent Ca(1), two equivalent Ca(2), and one Mn(1) atom. In the third N site, N(3) is bonded to one Ca(1), one Ca(3), one Ca(4), two equivalent Ca(2), 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 14-17°. In the fourth N site, N(4) is bonded in a 6-coordinate geometry to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one Mn(1) atom.