Ca2WAgO6 crystallizes in the triclinic P1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the second Ca site, Ca(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted CaO6 pentagonal pyramids that share corners with three equivalent Ag(1)O5 square pyramids, edges with three equivalent W(1)O6 octahedra, and  an edgeedge with one Ag(1)O5 square pyramid. W(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form WO6 octahedra that share corners with five equivalent Ag(1)O5 square pyramids and edges with three equivalent Ca(2)O6 pentagonal pyramids. Ag(1) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(6) atom to form distorted AgO5 square pyramids that share corners with five equivalent W(1)O6 octahedra, corners with three equivalent Ca(2)O6 pentagonal pyramids, and  an edgeedge with one Ca(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 34-45°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Ca(2), one W(1), and one Ag(1) atom to form a mixture of distorted edge and corner-sharing OCa2AgW trigonal pyramids. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Ca(1), one Ca(2), one W(1), and one Ag(1) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Ca(1), one Ca(2), one W(1), and one Ag(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one W(1) atom. In the fifth O site, O(5) is bonded to one Ca(1), one Ca(2), one W(1), and one Ag(1) atom to form a mixture of distorted edge and corner-sharing OCa2AgW trigonal pyramids. In the sixth O site, O(6) is bonded to one Ca(1), one Ca(2), one W(1), and one Ag(1) atom to form a mixture of distorted edge and corner-sharing OCa2AgW tetrahedra.
Ca2WAgO6 crystallizes in the triclinic P1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Ca(1)-O(1) bond length is 2.56 Å. The Ca(1)-O(2) bond length is 2.36 Å. The Ca(1)-O(3) bond length is 2.41 Å. The Ca(1)-O(4) bond length is 2.31 Å. The Ca(1)-O(5) bond length is 2.36 Å. The Ca(1)-O(6) bond length is 2.35 Å. In the second Ca site, Ca(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted CaO6 pentagonal pyramids that share corners with three equivalent Ag(1)O5 square pyramids, edges with three equivalent W(1)O6 octahedra, and  an edgeedge with one Ag(1)O5 square pyramid. The Ca(2)-O(1) bond length is 2.32 Å. The Ca(2)-O(2) bond length is 2.42 Å. The Ca(2)-O(3) bond length is 2.62 Å. The Ca(2)-O(4) bond length is 2.39 Å. The Ca(2)-O(5) bond length is 2.27 Å. The Ca(2)-O(6) bond length is 2.30 Å. W(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form WO6 octahedra that share corners with five equivalent Ag(1)O5 square pyramids and edges with three equivalent Ca(2)O6 pentagonal pyramids. The W(1)-O(1) bond length is 2.02 Å. The W(1)-O(2) bond length is 1.94 Å. The W(1)-O(3) bond length is 1.91 Å. The W(1)-O(4) bond length is 1.90 Å. The W(1)-O(5) bond length is 1.96 Å. The W(1)-O(6) bond length is 2.06 Å. Ag(1) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(6) atom to form distorted AgO5 square pyramids that share corners with five equivalent W(1)O6 octahedra, corners with three equivalent Ca(2)O6 pentagonal pyramids, and  an edgeedge with one Ca(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 34-45°. The Ag(1)-O(1) bond length is 2.18 Å. The Ag(1)-O(2) bond length is 2.37 Å. The Ag(1)-O(3) bond length is 2.39 Å. The Ag(1)-O(5) bond length is 2.47 Å. The Ag(1)-O(6) bond length is 2.17 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Ca(2), one W(1), and one Ag(1) atom to form a mixture of distorted edge and corner-sharing OCa2AgW trigonal pyramids. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Ca(1), one Ca(2), one W(1), and one Ag(1) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Ca(1), one Ca(2), one W(1), and one Ag(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one W(1) atom. In the fifth O site, O(5) is bonded to one Ca(1), one Ca(2), one W(1), and one Ag(1) atom to form a mixture of distorted edge and corner-sharing OCa2AgW trigonal pyramids. In the sixth O site, O(6) is bonded to one Ca(1), one Ca(2), one W(1), and one Ag(1) atom to form a mixture of distorted edge and corner-sharing OCa2AgW tetrahedra.