CaAl3PSO14 crystallizes in the trigonal R3m space group. Ca(1) is bonded to three equivalent O(1), three equivalent O(2), three equivalent O(5), and three equivalent O(6) atoms to form CaO12 cuboctahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent S(1)O4 tetrahedra, and faces with six equivalent Al(1)O6 octahedra. Al(1) is bonded to one O(1), one O(2), two equivalent O(5), and two equivalent O(6) atoms to form AlO6 octahedra that share corners with four equivalent Al(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one S(1)O4 tetrahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 38-42°. P(1) is bonded to one O(3) and three equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Ca(1)O12 cuboctahedra and corners with three equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. S(1) is bonded to one O(4) and three equivalent O(2) atoms to form SO4 tetrahedra that share corners with three equivalent Ca(1)O12 cuboctahedra and corners with three equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Ca(1), one Al(1), and one P(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Ca(1), one Al(1), and one S(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to one P(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one S(1) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Ca(1) and two equivalent Al(1) atoms. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and two equivalent Al(1) atoms.
CaAl3PSO14 crystallizes in the trigonal R3m space group. Ca(1) is bonded to three equivalent O(1), three equivalent O(2), three equivalent O(5), and three equivalent O(6) atoms to form CaO12 cuboctahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent S(1)O4 tetrahedra, and faces with six equivalent Al(1)O6 octahedra. All Ca(1)-O(1) bond lengths are 2.70 Å. All Ca(1)-O(2) bond lengths are 2.75 Å. All Ca(1)-O(5) bond lengths are 2.62 Å. All Ca(1)-O(6) bond lengths are 2.64 Å. Al(1) is bonded to one O(1), one O(2), two equivalent O(5), and two equivalent O(6) atoms to form AlO6 octahedra that share corners with four equivalent Al(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one S(1)O4 tetrahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 38-42°. The Al(1)-O(1) bond length is 1.96 Å. The Al(1)-O(2) bond length is 2.03 Å. Both Al(1)-O(5) bond lengths are 1.85 Å. Both Al(1)-O(6) bond lengths are 1.85 Å. P(1) is bonded to one O(3) and three equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Ca(1)O12 cuboctahedra and corners with three equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. The P(1)-O(3) bond length is 1.54 Å. All P(1)-O(1) bond lengths are 1.55 Å. S(1) is bonded to one O(4) and three equivalent O(2) atoms to form SO4 tetrahedra that share corners with three equivalent Ca(1)O12 cuboctahedra and corners with three equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. The S(1)-O(4) bond length is 1.44 Å. All S(1)-O(2) bond lengths are 1.51 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Ca(1), one Al(1), and one P(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Ca(1), one Al(1), and one S(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to one P(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one S(1) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Ca(1) and two equivalent Al(1) atoms. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and two equivalent Al(1) atoms.