Co4GeN4 crystallizes in the orthorhombic Pnna space group. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded in a distorted see-saw-like geometry to one N(2) and three equivalent N(1) atoms. In the second Co site, Co(2) is bonded to four equivalent N(2) atoms to form distorted edge-sharing CoN4 trigonal pyramids. In the third Co site, Co(3) is bonded in a distorted linear geometry to two equivalent N(1) atoms. Ge(1) is bonded in a distorted L-shaped geometry to two equivalent N(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Co(3) and three equivalent Co(1) atoms to form distorted NCo4 trigonal pyramids that share corners with three equivalent N(2)Co3Ge trigonal pyramids, corners with three equivalent N(1)Co4 trigonal pyramids, and edges with two equivalent N(1)Co4 trigonal pyramids. In the second N site, N(2) is bonded to one Co(1), two equivalent Co(2), and one Ge(1) atom to form distorted NCo3Ge trigonal pyramids that share corners with three equivalent N(2)Co3Ge trigonal pyramids, corners with three equivalent N(1)Co4 trigonal pyramids, and edges with two equivalent N(2)Co3Ge trigonal pyramids.
Co4GeN4 crystallizes in the orthorhombic Pnna space group. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded in a distorted see-saw-like geometry to one N(2) and three equivalent N(1) atoms. The Co(1)-N(2) bond length is 1.83 Å. There are a spread of Co(1)-N(1) bond distances ranging from 1.86-1.94 Å. In the second Co site, Co(2) is bonded to four equivalent N(2) atoms to form distorted edge-sharing CoN4 trigonal pyramids. There are two shorter (1.87 Å) and two longer (1.93 Å) Co(2)-N(2) bond lengths. In the third Co site, Co(3) is bonded in a distorted linear geometry to two equivalent N(1) atoms. Both Co(3)-N(1) bond lengths are 1.79 Å. Ge(1) is bonded in a distorted L-shaped geometry to two equivalent N(2) atoms. Both Ge(1)-N(2) bond lengths are 1.94 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Co(3) and three equivalent Co(1) atoms to form distorted NCo4 trigonal pyramids that share corners with three equivalent N(2)Co3Ge trigonal pyramids, corners with three equivalent N(1)Co4 trigonal pyramids, and edges with two equivalent N(1)Co4 trigonal pyramids. In the second N site, N(2) is bonded to one Co(1), two equivalent Co(2), and one Ge(1) atom to form distorted NCo3Ge trigonal pyramids that share corners with three equivalent N(2)Co3Ge trigonal pyramids, corners with three equivalent N(1)Co4 trigonal pyramids, and edges with two equivalent N(2)Co3Ge trigonal pyramids.