Cs4GeO4 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms. In the second Cs site, Cs(2) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(4) atoms. In the third Cs site, Cs(3) is bonded in a 4-coordinate geometry to one O(1), one O(4), and two equivalent O(3) atoms. In the fourth Cs site, Cs(4) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), and two equivalent O(2) atoms. Ge(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Cs(3), one Cs(4), two equivalent Cs(1), and one Ge(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Cs(1), two equivalent Cs(2), two equivalent Cs(4), and one Ge(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Cs(4), two equivalent Cs(1), two equivalent Cs(3), and one Ge(1) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), two equivalent Cs(2), and one Ge(1) atom.
Cs4GeO4 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms. The Cs(1)-O(2) bond length is 3.23 Å. The Cs(1)-O(4) bond length is 3.35 Å. There is one shorter (3.20 Å) and one longer (3.26 Å) Cs(1)-O(1) bond length. There is one shorter (2.88 Å) and one longer (3.21 Å) Cs(1)-O(3) bond length. In the second Cs site, Cs(2) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(4) atoms. There is one shorter (2.90 Å) and one longer (2.92 Å) Cs(2)-O(2) bond length. There is one shorter (2.92 Å) and one longer (2.98 Å) Cs(2)-O(4) bond length. In the third Cs site, Cs(3) is bonded in a 4-coordinate geometry to one O(1), one O(4), and two equivalent O(3) atoms. The Cs(3)-O(1) bond length is 3.03 Å. The Cs(3)-O(4) bond length is 3.03 Å. There is one shorter (2.83 Å) and one longer (2.96 Å) Cs(3)-O(3) bond length. In the fourth Cs site, Cs(4) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), and two equivalent O(2) atoms. The Cs(4)-O(1) bond length is 3.19 Å. The Cs(4)-O(3) bond length is 3.11 Å. The Cs(4)-O(4) bond length is 3.38 Å. There is one shorter (2.97 Å) and one longer (3.06 Å) Cs(4)-O(2) bond length. Ge(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Ge(1)-O(1) bond length is 1.78 Å. The Ge(1)-O(2) bond length is 1.79 Å. The Ge(1)-O(3) bond length is 1.80 Å. The Ge(1)-O(4) bond length is 1.79 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Cs(3), one Cs(4), two equivalent Cs(1), and one Ge(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Cs(1), two equivalent Cs(2), two equivalent Cs(4), and one Ge(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Cs(4), two equivalent Cs(1), two equivalent Cs(3), and one Ge(1) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), two equivalent Cs(2), and one Ge(1) atom.