Ca3GeO4F crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one O(1), two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms. Ge(1) is bonded in a tetrahedral geometry to one O(1), one O(3), and two equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), two equivalent Ca(2), and one Ge(1) atom to form OCa3Ge tetrahedra that share corners with six equivalent F(1)Ca6 octahedra, corners with three equivalent O(3)Ca4Ge trigonal pyramids, and  an edgeedge with one O(3)Ca4Ge trigonal pyramid. The corner-sharing octahedral tilt angles range from 12-54°. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), two equivalent Ca(2), and one Ge(1) atom. In the third O site, O(3) is bonded to two equivalent Ca(1), two equivalent Ca(2), and one Ge(1) atom to form distorted OCa4Ge trigonal pyramids that share corners with two equivalent F(1)Ca6 octahedra, corners with three equivalent O(1)Ca3Ge tetrahedra, corners with two equivalent O(3)Ca4Ge trigonal pyramids,  an edgeedge with one O(1)Ca3Ge tetrahedra, and faces with two equivalent F(1)Ca6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. F(1) is bonded to two equivalent Ca(1) and four equivalent Ca(2) atoms to form distorted FCa6 octahedra that share corners with six equivalent O(1)Ca3Ge tetrahedra, corners with two equivalent O(3)Ca4Ge trigonal pyramids, faces with two equivalent F(1)Ca6 octahedra, and faces with two equivalent O(3)Ca4Ge trigonal pyramids.
Ca3GeO4F crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one O(1), two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms. The Ca(1)-O(1) bond length is 2.35 Å. Both Ca(1)-O(2) bond lengths are 2.38 Å. There is one shorter (2.38 Å) and one longer (3.06 Å) Ca(1)-O(3) bond length. There is one shorter (2.40 Å) and one longer (2.72 Å) Ca(1)-F(1) bond length. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms. The Ca(2)-O(1) bond length is 2.36 Å. The Ca(2)-O(3) bond length is 2.35 Å. There is one shorter (2.35 Å) and one longer (2.39 Å) Ca(2)-O(2) bond length. There is one shorter (2.48 Å) and one longer (2.56 Å) Ca(2)-F(1) bond length. Ge(1) is bonded in a tetrahedral geometry to one O(1), one O(3), and two equivalent O(2) atoms. The Ge(1)-O(1) bond length is 1.91 Å. The Ge(1)-O(3) bond length is 1.94 Å. Both Ge(1)-O(2) bond lengths are 1.91 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), two equivalent Ca(2), and one Ge(1) atom to form OCa3Ge tetrahedra that share corners with six equivalent F(1)Ca6 octahedra, corners with three equivalent O(3)Ca4Ge trigonal pyramids, and  an edgeedge with one O(3)Ca4Ge trigonal pyramid. The corner-sharing octahedral tilt angles range from 12-54°. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), two equivalent Ca(2), and one Ge(1) atom. In the third O site, O(3) is bonded to two equivalent Ca(1), two equivalent Ca(2), and one Ge(1) atom to form distorted OCa4Ge trigonal pyramids that share corners with two equivalent F(1)Ca6 octahedra, corners with three equivalent O(1)Ca3Ge tetrahedra, corners with two equivalent O(3)Ca4Ge trigonal pyramids,  an edgeedge with one O(1)Ca3Ge tetrahedra, and faces with two equivalent F(1)Ca6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. F(1) is bonded to two equivalent Ca(1) and four equivalent Ca(2) atoms to form distorted FCa6 octahedra that share corners with six equivalent O(1)Ca3Ge tetrahedra, corners with two equivalent O(3)Ca4Ge trigonal pyramids, faces with two equivalent F(1)Ca6 octahedra, and faces with two equivalent O(3)Ca4Ge trigonal pyramids.