CuGeO3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. In the second Cu site, Cu(2) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Ge(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form corner-sharing GeO5 trigonal bipyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Cu(1), one Cu(2), and one Ge(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Cu(1) and two equivalent Ge(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Cu(2) and two equivalent Ge(1) atoms.
CuGeO3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Cu(1)-O(1) bond lengths are 1.90 Å. Both Cu(1)-O(2) bond lengths are 2.11 Å. In the second Cu site, Cu(2) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Cu(2)-O(1) bond lengths are 1.94 Å. Both Cu(2)-O(3) bond lengths are 2.01 Å. Ge(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form corner-sharing GeO5 trigonal bipyramids. The Ge(1)-O(1) bond length is 1.80 Å. There is one shorter (1.86 Å) and one longer (1.87 Å) Ge(1)-O(2) bond length. There is one shorter (1.90 Å) and one longer (1.93 Å) Ge(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Cu(1), one Cu(2), and one Ge(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Cu(1) and two equivalent Ge(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Cu(2) and two equivalent Ge(1) atoms.