Mn4N2Se3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent Se(2) atoms. In the second Mn site, Mn(2) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent Se(1) atoms. In the third Mn site, Mn(3) is bonded to two equivalent N(1), one Se(1), and three equivalent Se(2) atoms to form a mixture of distorted corner and edge-sharing MnSe4N2 octahedra. The corner-sharing octahedral tilt angles range from 59-65°. N(1) is bonded to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form distorted NMn4 tetrahedra that share corners with four equivalent Se(1)Mn4 tetrahedra and edges with two equivalent N(1)Mn4 tetrahedra. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Mn(2) and two equivalent Mn(3) atoms to form SeMn4 tetrahedra that share corners with two equivalent Se(1)Mn4 tetrahedra and corners with eight equivalent N(1)Mn4 tetrahedra. In the second Se site, Se(2) is bonded in a 4-coordinate geometry to one Mn(1) and three equivalent Mn(3) atoms.
Mn4N2Se3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent Se(2) atoms. Both Mn(1)-N(1) bond lengths are 1.97 Å. Both Mn(1)-Se(2) bond lengths are 2.54 Å. In the second Mn site, Mn(2) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent Se(1) atoms. Both Mn(2)-N(1) bond lengths are 1.80 Å. There is one shorter (2.39 Å) and one longer (2.51 Å) Mn(2)-Se(1) bond length. In the third Mn site, Mn(3) is bonded to two equivalent N(1), one Se(1), and three equivalent Se(2) atoms to form a mixture of distorted corner and edge-sharing MnSe4N2 octahedra. The corner-sharing octahedral tilt angles range from 59-65°. There is one shorter (1.91 Å) and one longer (1.95 Å) Mn(3)-N(1) bond length. The Mn(3)-Se(1) bond length is 2.61 Å. There are a spread of Mn(3)-Se(2) bond distances ranging from 2.60-2.63 Å. N(1) is bonded to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form distorted NMn4 tetrahedra that share corners with four equivalent Se(1)Mn4 tetrahedra and edges with two equivalent N(1)Mn4 tetrahedra. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Mn(2) and two equivalent Mn(3) atoms to form SeMn4 tetrahedra that share corners with two equivalent Se(1)Mn4 tetrahedra and corners with eight equivalent N(1)Mn4 tetrahedra. In the second Se site, Se(2) is bonded in a 4-coordinate geometry to one Mn(1) and three equivalent Mn(3) atoms.