Y3Sn4BiO14 crystallizes in the trigonal R-3m space group. Y(1) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(2), and four equivalent O(3) atoms. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to six equivalent O(3) atoms to form corner-sharing SnO6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the second Sn site, Sn(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form corner-sharing SnO6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. Bi(1) is bonded in a body-centered cubic geometry to two equivalent O(1) and six equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Y(1) and one Bi(1) atom to form OY3Bi tetrahedra that share corners with four equivalent O(1)Y3Bi tetrahedra, corners with six equivalent O(3)Y2Sn2 tetrahedra, corners with six equivalent O(2)YSn2Bi tetrahedra, edges with three equivalent O(3)Y2Sn2 tetrahedra, and edges with three equivalent O(2)YSn2Bi tetrahedra. In the second O site, O(2) is bonded to one Y(1), two equivalent Sn(2), and one Bi(1) atom to form distorted OYSn2Bi tetrahedra that share corners with two equivalent O(1)Y3Bi tetrahedra, corners with four equivalent O(3)Y2Sn2 tetrahedra, corners with eight equivalent O(2)YSn2Bi tetrahedra,  an edgeedge with one O(1)Y3Bi tetrahedra, edges with two equivalent O(3)Y2Sn2 tetrahedra, and edges with two equivalent O(2)YSn2Bi tetrahedra. In the third O site, O(3) is bonded to two equivalent Y(1), one Sn(1), and one Sn(2) atom to form distorted OY2Sn2 tetrahedra that share corners with two equivalent O(1)Y3Bi tetrahedra, corners with four equivalent O(2)YSn2Bi tetrahedra, corners with eight equivalent O(3)Y2Sn2 tetrahedra,  an edgeedge with one O(1)Y3Bi tetrahedra, edges with two equivalent O(3)Y2Sn2 tetrahedra, and edges with two equivalent O(2)YSn2Bi tetrahedra.
Y3Sn4BiO14 crystallizes in the trigonal R-3m space group. Y(1) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(2), and four equivalent O(3) atoms. Both Y(1)-O(1) bond lengths are 2.27 Å. Both Y(1)-O(2) bond lengths are 2.51 Å. All Y(1)-O(3) bond lengths are 2.54 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to six equivalent O(3) atoms to form corner-sharing SnO6 octahedra. The corner-sharing octahedral tilt angles are 53°. All Sn(1)-O(3) bond lengths are 2.09 Å. In the second Sn site, Sn(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form corner-sharing SnO6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. Both Sn(2)-O(3) bond lengths are 2.08 Å. All Sn(2)-O(2) bond lengths are 2.08 Å. Bi(1) is bonded in a body-centered cubic geometry to two equivalent O(1) and six equivalent O(2) atoms. Both Bi(1)-O(1) bond lengths are 2.36 Å. All Bi(1)-O(2) bond lengths are 2.57 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Y(1) and one Bi(1) atom to form OY3Bi tetrahedra that share corners with four equivalent O(1)Y3Bi tetrahedra, corners with six equivalent O(3)Y2Sn2 tetrahedra, corners with six equivalent O(2)YSn2Bi tetrahedra, edges with three equivalent O(3)Y2Sn2 tetrahedra, and edges with three equivalent O(2)YSn2Bi tetrahedra. In the second O site, O(2) is bonded to one Y(1), two equivalent Sn(2), and one Bi(1) atom to form distorted OYSn2Bi tetrahedra that share corners with two equivalent O(1)Y3Bi tetrahedra, corners with four equivalent O(3)Y2Sn2 tetrahedra, corners with eight equivalent O(2)YSn2Bi tetrahedra,  an edgeedge with one O(1)Y3Bi tetrahedra, edges with two equivalent O(3)Y2Sn2 tetrahedra, and edges with two equivalent O(2)YSn2Bi tetrahedra. In the third O site, O(3) is bonded to two equivalent Y(1), one Sn(1), and one Sn(2) atom to form distorted OY2Sn2 tetrahedra that share corners with two equivalent O(1)Y3Bi tetrahedra, corners with four equivalent O(2)YSn2Bi tetrahedra, corners with eight equivalent O(3)Y2Sn2 tetrahedra,  an edgeedge with one O(1)Y3Bi tetrahedra, edges with two equivalent O(3)Y2Sn2 tetrahedra, and edges with two equivalent O(2)YSn2Bi tetrahedra.