Mn4GeN4 crystallizes in the orthorhombic Pnna space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form a mixture of distorted edge and corner-sharing MnN4 tetrahedra. In the second Mn site, Mn(2) is bonded in a bent 120 degrees geometry to two equivalent N(1) atoms. In the third Mn site, Mn(3) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form a mixture of distorted edge and corner-sharing MnN4 trigonal pyramids. Ge(1) is bonded in a 2-coordinate geometry to two equivalent N(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded in a rectangular see-saw-like geometry to one Mn(2), one Mn(3), and two equivalent Mn(1) atoms. In the second N site, N(2) is bonded in a distorted rectangular see-saw-like geometry to one Mn(3), two equivalent Mn(1), and one Ge(1) atom.
Mn4GeN4 crystallizes in the orthorhombic Pnna space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form a mixture of distorted edge and corner-sharing MnN4 tetrahedra. Both Mn(1)-N(1) bond lengths are 1.90 Å. There is one shorter (1.92 Å) and one longer (1.93 Å) Mn(1)-N(2) bond length. In the second Mn site, Mn(2) is bonded in a bent 120 degrees geometry to two equivalent N(1) atoms. Both Mn(2)-N(1) bond lengths are 1.76 Å. In the third Mn site, Mn(3) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form a mixture of distorted edge and corner-sharing MnN4 trigonal pyramids. Both Mn(3)-N(1) bond lengths are 1.91 Å. Both Mn(3)-N(2) bond lengths are 1.84 Å. Ge(1) is bonded in a 2-coordinate geometry to two equivalent N(2) atoms. Both Ge(1)-N(2) bond lengths are 2.08 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a rectangular see-saw-like geometry to one Mn(2), one Mn(3), and two equivalent Mn(1) atoms. In the second N site, N(2) is bonded in a distorted rectangular see-saw-like geometry to one Mn(3), two equivalent Mn(1), and one Ge(1) atom.