Mn5FeN4 is Ilmenite-like structured and crystallizes in the orthorhombic Pmmn space group. There are two 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 N(2) atoms. In the second Mn site, Mn(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form MnN4 tetrahedra that share corners with four equivalent Fe(1)N4 tetrahedra. Fe(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted FeN4 tetrahedra that share corners with four equivalent Mn(2)N4 tetrahedra. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Mn(2), four equivalent Mn(1), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing NMn5Fe pentagonal pyramids. The corner-sharing octahedral tilt angles range from 42-70°. In the second N site, N(2) is bonded to one Mn(2), four equivalent Mn(1), and one Fe(1) atom to form a mixture of corner and edge-sharing NMn5Fe octahedra. The corner-sharing octahedral tilt angles range from 56-69°.
Mn5FeN4 is Ilmenite-like structured and crystallizes in the orthorhombic Pmmn space group. There are two 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 N(2) atoms. There is one shorter (1.94 Å) and one longer (2.24 Å) Mn(1)-N(1) bond length. There is one shorter (1.97 Å) and one longer (1.98 Å) Mn(1)-N(2) bond length. In the second Mn site, Mn(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form MnN4 tetrahedra that share corners with four equivalent Fe(1)N4 tetrahedra. Both Mn(2)-N(1) bond lengths are 1.89 Å. Both Mn(2)-N(2) bond lengths are 2.00 Å. Fe(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted FeN4 tetrahedra that share corners with four equivalent Mn(2)N4 tetrahedra. Both Fe(1)-N(1) bond lengths are 1.94 Å. Both Fe(1)-N(2) bond lengths are 1.90 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Mn(2), four equivalent Mn(1), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing NMn5Fe pentagonal pyramids. The corner-sharing octahedral tilt angles range from 42-70°. In the second N site, N(2) is bonded to one Mn(2), four equivalent Mn(1), and one Fe(1) atom to form a mixture of corner and edge-sharing NMn5Fe octahedra. The corner-sharing octahedral tilt angles range from 56-69°.