Mn5(GeN3)2 crystallizes in the monoclinic C2/c 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 edge-sharing MnN4 tetrahedra. In the second Mn site, Mn(2) is bonded in a 4-coordinate geometry to one N(2), one N(3), and two equivalent N(1) atoms. In the third Mn site, Mn(3) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Ge(1) is bonded in a 3-coordinate geometry to one N(2) and two equivalent N(3) atoms. There are three inequivalent N sites. In the first N site, N(2) is bonded to one Mn(2), one Mn(3), two equivalent Mn(1), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing NMn4Ge trigonal bipyramids. In the second N site, N(3) is bonded in a T-shaped geometry to one Mn(2) and two equivalent Ge(1) atoms. In the third N site, N(1) is bonded in a 5-coordinate geometry to one Mn(3), two equivalent Mn(1), and two equivalent Mn(2) atoms.
Mn5(GeN3)2 crystallizes in the monoclinic C2/c 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 edge-sharing MnN4 tetrahedra. There is one shorter (1.81 Å) and one longer (1.90 Å) Mn(1)-N(1) bond length. There is one shorter (1.90 Å) and one longer (1.93 Å) Mn(1)-N(2) bond length. In the second Mn site, Mn(2) is bonded in a 4-coordinate geometry to one N(2), one N(3), and two equivalent N(1) atoms. The Mn(2)-N(2) bond length is 2.03 Å. The Mn(2)-N(3) bond length is 1.94 Å. There is one shorter (1.87 Å) and one longer (2.16 Å) Mn(2)-N(1) bond length. In the third Mn site, Mn(3) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Mn(3)-N(1) bond lengths are 2.02 Å. Both Mn(3)-N(2) bond lengths are 1.92 Å. Ge(1) is bonded in a 3-coordinate geometry to one N(2) and two equivalent N(3) atoms. The Ge(1)-N(2) bond length is 2.09 Å. There is one shorter (1.93 Å) and one longer (1.98 Å) Ge(1)-N(3) bond length. There are three inequivalent N sites. In the first N site, N(2) is bonded to one Mn(2), one Mn(3), two equivalent Mn(1), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing NMn4Ge trigonal bipyramids. In the second N site, N(3) is bonded in a T-shaped geometry to one Mn(2) and two equivalent Ge(1) atoms. In the third N site, N(1) is bonded in a 5-coordinate geometry to one Mn(3), two equivalent Mn(1), and two equivalent Mn(2) atoms.