CaW3P4O14 crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CaO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent W(1)O5 square pyramids. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(2), one O(3), one O(5), and two equivalent O(7) atoms to form distorted WO5 square pyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Ca(1)O6 octahedra, and  an edgeedge with one W(1)O5 square pyramid. In the second W site, W(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(6) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra, corners with three equivalent W(1)O5 square pyramids, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-64°. In the second P site, P(2) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra, corners with two equivalent W(1)O5 square pyramids, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a distorted single-bond geometry to one W(1) and one P(1) atom. In the second O site, O(6) is bonded in a distorted bent 150 degrees geometry to one W(2) and one P(2) atom. In the third O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent W(1) and one P(2) atom. In the fourth O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(1), one W(2), and one P(2) atom. In the fifth O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one W(1), and one P(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Ca(1), one W(1), and one P(1) atom. In the seventh O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.
CaW3P4O14 crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CaO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent W(1)O5 square pyramids. Both Ca(1)-O(1) bond lengths are 2.72 Å. Both Ca(1)-O(2) bond lengths are 2.47 Å. Both Ca(1)-O(3) bond lengths are 2.34 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(2), one O(3), one O(5), and two equivalent O(7) atoms to form distorted WO5 square pyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Ca(1)O6 octahedra, and  an edgeedge with one W(1)O5 square pyramid. The W(1)-O(2) bond length is 2.22 Å. The W(1)-O(3) bond length is 2.24 Å. The W(1)-O(5) bond length is 2.36 Å. There is one shorter (2.24 Å) and one longer (2.25 Å) W(1)-O(7) bond length. In the second W site, W(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(6) atoms. Both W(2)-O(1) bond lengths are 2.25 Å. Both W(2)-O(6) bond lengths are 2.20 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra, corners with three equivalent W(1)O5 square pyramids, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-64°. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.62 Å. The P(1)-O(5) bond length is 1.50 Å. In the second P site, P(2) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra, corners with two equivalent W(1)O5 square pyramids, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.62 Å. The P(2)-O(6) bond length is 1.51 Å. The P(2)-O(7) bond length is 1.57 Å. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a distorted single-bond geometry to one W(1) and one P(1) atom. In the second O site, O(6) is bonded in a distorted bent 150 degrees geometry to one W(2) and one P(2) atom. In the third O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent W(1) and one P(2) atom. In the fourth O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(1), one W(2), and one P(2) atom. In the fifth O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one W(1), and one P(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Ca(1), one W(1), and one P(1) atom. In the seventh O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.