GeSe2 crystallizes in the orthorhombic Fdd2 space group. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to two equivalent Se(1) and two equivalent Se(2) atoms to form corner-sharing GeSe4 tetrahedra. In the second Ge site, Ge(2) is bonded to one Se(1), one Se(2), and two equivalent Se(3) atoms to form corner-sharing GeSe4 tetrahedra. There are three inequivalent Se sites. In the first Se site, Se(3) is bonded in a water-like geometry to two equivalent Ge(2) atoms. In the second Se site, Se(1) is bonded in a water-like geometry to one Ge(1) and one Ge(2) atom. In the third Se site, Se(2) is bonded in a water-like geometry to one Ge(1) and one Ge(2) atom.
GeSe2 crystallizes in the orthorhombic Fdd2 space group. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to two equivalent Se(1) and two equivalent Se(2) atoms to form corner-sharing GeSe4 tetrahedra. Both Ge(1)-Se(1) bond lengths are 2.41 Å. Both Ge(1)-Se(2) bond lengths are 2.41 Å. In the second Ge site, Ge(2) is bonded to one Se(1), one Se(2), and two equivalent Se(3) atoms to form corner-sharing GeSe4 tetrahedra. The Ge(2)-Se(1) bond length is 2.40 Å. The Ge(2)-Se(2) bond length is 2.39 Å. There is one shorter (2.40 Å) and one longer (2.41 Å) Ge(2)-Se(3) bond length. There are three inequivalent Se sites. In the first Se site, Se(3) is bonded in a water-like geometry to two equivalent Ge(2) atoms. In the second Se site, Se(1) is bonded in a water-like geometry to one Ge(1) and one Ge(2) atom. In the third Se site, Se(2) is bonded in a water-like geometry to one Ge(1) and one Ge(2) atom.