Cd4B3BiO10 crystallizes in the monoclinic Cm space group. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one O(2), one O(6), two equivalent O(3), and two equivalent O(4) atoms to form CdO6 octahedra that share  a cornercorner with one Cd(1)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, and edges with two equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-73°. In the second Cd site, Cd(2) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(5) and two equivalent O(4) atoms. Bi(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form BiO6 octahedra that share corners with four equivalent Cd(1)O6 octahedra and edges with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-69°. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Cd(2), one B(1), and one Bi(1) atom to form distorted OCd2BiB tetrahedra that share corners with two equivalent O(6)Cd2Bi2 tetrahedra, corners with two equivalent O(4)Cd3B tetrahedra, and corners with three equivalent O(1)Cd2BiB tetrahedra. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Cd(1), two equivalent Cd(2), and one B(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Cd(2), two equivalent Cd(1), and one B(1) atom. In the fourth O site, O(4) is bonded to one Cd(2), two equivalent Cd(1), and one B(2) atom to form distorted OCd3B tetrahedra that share corners with two equivalent O(6)Cd2Bi2 tetrahedra, corners with two equivalent O(1)Cd2BiB tetrahedra, and corners with three equivalent O(4)Cd3B tetrahedra. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one B(2) and two equivalent Bi(1) atoms. In the sixth O site, O(6) is bonded to two equivalent Cd(1) and two equivalent Bi(1) atoms to form OCd2Bi2 tetrahedra that share corners with two equivalent O(6)Cd2Bi2 tetrahedra, corners with four equivalent O(1)Cd2BiB tetrahedra, and corners with four equivalent O(4)Cd3B tetrahedra.
Cd4B3BiO10 crystallizes in the monoclinic Cm space group. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one O(2), one O(6), two equivalent O(3), and two equivalent O(4) atoms to form CdO6 octahedra that share  a cornercorner with one Cd(1)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, and edges with two equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-73°. The Cd(1)-O(2) bond length is 2.30 Å. The Cd(1)-O(6) bond length is 2.30 Å. There is one shorter (2.34 Å) and one longer (2.37 Å) Cd(1)-O(3) bond length. There is one shorter (2.36 Å) and one longer (2.39 Å) Cd(1)-O(4) bond length. In the second Cd site, Cd(2) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms. The Cd(2)-O(3) bond length is 2.48 Å. The Cd(2)-O(4) bond length is 2.29 Å. There is one shorter (2.32 Å) and one longer (2.37 Å) Cd(2)-O(1) bond length. There is one shorter (2.37 Å) and one longer (2.64 Å) Cd(2)-O(2) bond length. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The B(1)-O(1) bond length is 1.41 Å. The B(1)-O(2) bond length is 1.38 Å. The B(1)-O(3) bond length is 1.38 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(5) and two equivalent O(4) atoms. The B(2)-O(5) bond length is 1.39 Å. Both B(2)-O(4) bond lengths are 1.39 Å. Bi(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form BiO6 octahedra that share corners with four equivalent Cd(1)O6 octahedra and edges with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-69°. Both Bi(1)-O(1) bond lengths are 2.47 Å. There is one shorter (2.40 Å) and one longer (2.49 Å) Bi(1)-O(5) bond length. There is one shorter (2.31 Å) and one longer (2.32 Å) Bi(1)-O(6) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Cd(2), one B(1), and one Bi(1) atom to form distorted OCd2BiB tetrahedra that share corners with two equivalent O(6)Cd2Bi2 tetrahedra, corners with two equivalent O(4)Cd3B tetrahedra, and corners with three equivalent O(1)Cd2BiB tetrahedra. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Cd(1), two equivalent Cd(2), and one B(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Cd(2), two equivalent Cd(1), and one B(1) atom. In the fourth O site, O(4) is bonded to one Cd(2), two equivalent Cd(1), and one B(2) atom to form distorted OCd3B tetrahedra that share corners with two equivalent O(6)Cd2Bi2 tetrahedra, corners with two equivalent O(1)Cd2BiB tetrahedra, and corners with three equivalent O(4)Cd3B tetrahedra. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one B(2) and two equivalent Bi(1) atoms. In the sixth O site, O(6) is bonded to two equivalent Cd(1) and two equivalent Bi(1) atoms to form OCd2Bi2 tetrahedra that share corners with two equivalent O(6)Cd2Bi2 tetrahedra, corners with four equivalent O(1)Cd2BiB tetrahedra, and corners with four equivalent O(4)Cd3B tetrahedra.