Sr4MnN4 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Sr sites. In the first Sr site, Sr(1) is bonded to one N(2), one N(4), and three equivalent N(1) atoms to form a mixture of distorted corner and edge-sharing SrN5 trigonal bipyramids. In the second Sr site, Sr(2) is bonded in a distorted see-saw-like geometry to one N(3), one N(4), and two equivalent N(2) atoms. In the third Sr site, Sr(3) is bonded in a distorted see-saw-like geometry to one N(2), one N(4), and two equivalent N(3) atoms. In the fourth Sr site, Sr(4) is bonded in a 6-coordinate geometry to one N(1), one N(2), two equivalent N(3), and two equivalent N(4) atoms. Mn(1) is bonded in a trigonal planar geometry to one N(1), one N(2), and one N(3) atom. There are four inequivalent N sites. In the first N site, N(4) is bonded to one Sr(1), one Sr(2), one Sr(3), and two equivalent Sr(4) atoms to form NSr5 trigonal bipyramids that share corners with two equivalent N(2)Sr5Mn octahedra,  a cornercorner with one N(1)Sr4Mn trigonal bipyramid, corners with two equivalent N(4)Sr5 trigonal bipyramids, edges with two equivalent N(2)Sr5Mn octahedra, and edges with two equivalent N(1)Sr4Mn trigonal bipyramids. The corner-sharing octahedral tilt angles range from 55-56°. In the second N site, N(1) is bonded to one Sr(4), three equivalent Sr(1), and one Mn(1) atom to form distorted NSr4Mn trigonal bipyramids that share corners with three equivalent N(2)Sr5Mn octahedra,  a cornercorner with one N(4)Sr5 trigonal bipyramid, corners with two equivalent N(1)Sr4Mn trigonal bipyramids,  an edgeedge with one N(2)Sr5Mn octahedra, edges with two equivalent N(1)Sr4Mn trigonal bipyramids, and edges with two equivalent N(4)Sr5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-80°. In the third N site, N(2) is bonded to one Sr(1), one Sr(3), one Sr(4), two equivalent Sr(2), and one Mn(1) atom to form distorted NSr5Mn octahedra that share corners with two equivalent N(2)Sr5Mn octahedra, corners with two equivalent N(4)Sr5 trigonal bipyramids, corners with three equivalent N(1)Sr4Mn trigonal bipyramids,  an edgeedge with one N(1)Sr4Mn trigonal bipyramid, and edges with two equivalent N(4)Sr5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 20°. In the fourth N site, N(3) is bonded in a distorted single-bond geometry to one Sr(2), two equivalent Sr(3), two equivalent Sr(4), and one Mn(1) atom.
Sr4MnN4 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Sr sites. In the first Sr site, Sr(1) is bonded to one N(2), one N(4), and three equivalent N(1) atoms to form a mixture of distorted corner and edge-sharing SrN5 trigonal bipyramids. The Sr(1)-N(2) bond length is 2.65 Å. The Sr(1)-N(4) bond length is 2.59 Å. There is one shorter (2.63 Å) and two longer (2.70 Å) Sr(1)-N(1) bond lengths. In the second Sr site, Sr(2) is bonded in a distorted see-saw-like geometry to one N(3), one N(4), and two equivalent N(2) atoms. The Sr(2)-N(3) bond length is 2.78 Å. The Sr(2)-N(4) bond length is 2.48 Å. Both Sr(2)-N(2) bond lengths are 2.67 Å. In the third Sr site, Sr(3) is bonded in a distorted see-saw-like geometry to one N(2), one N(4), and two equivalent N(3) atoms. The Sr(3)-N(2) bond length is 2.72 Å. The Sr(3)-N(4) bond length is 2.42 Å. Both Sr(3)-N(3) bond lengths are 2.73 Å. In the fourth Sr site, Sr(4) is bonded in a 6-coordinate geometry to one N(1), one N(2), two equivalent N(3), and two equivalent N(4) atoms. The Sr(4)-N(1) bond length is 2.62 Å. The Sr(4)-N(2) bond length is 2.70 Å. There is one shorter (2.95 Å) and one longer (3.21 Å) Sr(4)-N(3) bond length. Both Sr(4)-N(4) bond lengths are 2.65 Å. Mn(1) is bonded in a trigonal planar geometry to one N(1), one N(2), and one N(3) atom. The Mn(1)-N(1) bond length is 1.69 Å. The Mn(1)-N(2) bond length is 1.78 Å. The Mn(1)-N(3) bond length is 1.71 Å. There are four inequivalent N sites. In the first N site, N(4) is bonded to one Sr(1), one Sr(2), one Sr(3), and two equivalent Sr(4) atoms to form NSr5 trigonal bipyramids that share corners with two equivalent N(2)Sr5Mn octahedra,  a cornercorner with one N(1)Sr4Mn trigonal bipyramid, corners with two equivalent N(4)Sr5 trigonal bipyramids, edges with two equivalent N(2)Sr5Mn octahedra, and edges with two equivalent N(1)Sr4Mn trigonal bipyramids. The corner-sharing octahedral tilt angles range from 55-56°. In the second N site, N(1) is bonded to one Sr(4), three equivalent Sr(1), and one Mn(1) atom to form distorted NSr4Mn trigonal bipyramids that share corners with three equivalent N(2)Sr5Mn octahedra,  a cornercorner with one N(4)Sr5 trigonal bipyramid, corners with two equivalent N(1)Sr4Mn trigonal bipyramids,  an edgeedge with one N(2)Sr5Mn octahedra, edges with two equivalent N(1)Sr4Mn trigonal bipyramids, and edges with two equivalent N(4)Sr5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-80°. In the third N site, N(2) is bonded to one Sr(1), one Sr(3), one Sr(4), two equivalent Sr(2), and one Mn(1) atom to form distorted NSr5Mn octahedra that share corners with two equivalent N(2)Sr5Mn octahedra, corners with two equivalent N(4)Sr5 trigonal bipyramids, corners with three equivalent N(1)Sr4Mn trigonal bipyramids,  an edgeedge with one N(1)Sr4Mn trigonal bipyramid, and edges with two equivalent N(4)Sr5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 20°. In the fourth N site, N(3) is bonded in a distorted single-bond geometry to one Sr(2), two equivalent Sr(3), two equivalent Sr(4), and one Mn(1) atom.