CaWAsO5 crystallizes in the triclinic P1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(11), one O(15), one O(2), one O(6), and one O(7) atom to form distorted CaO5 trigonal bipyramids that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one W(3)O6 octahedra, and  a cornercorner with one W(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-61°. In the second Ca site, Ca(2) is bonded to one O(1), one O(12), one O(16), one O(5), and one O(8) atom to form distorted CaO5 trigonal bipyramids that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one W(3)O6 octahedra, and  a cornercorner with one W(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-60°. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to one O(13), one O(4), one O(5), one O(8), and one O(9) atom. In the fourth Ca site, Ca(4) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(3), one O(6), and one O(7) atom. There are four inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(11), one O(14), one O(17), one O(20), and one O(4) atom to form WO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ca(2)O5 trigonal bipyramid, and edges with two equivalent W(4)O6 octahedra. In the second W site, W(2) is bonded to one O(12), one O(13), one O(18), one O(19), one O(2), and one O(3) atom to form WO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ca(2)O5 trigonal bipyramid, and edges with two equivalent W(3)O6 octahedra. In the third W site, W(3) is bonded to one O(16), one O(18), one O(19), one O(2), one O(3), and one O(9) atom to form WO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ca(2)O5 trigonal bipyramid, and edges with two equivalent W(2)O6 octahedra. In the fourth W site, W(4) is bonded to one O(1), one O(10), one O(15), one O(17), one O(20), and one O(4) atom to form WO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ca(2)O5 trigonal bipyramid, and edges with two equivalent W(1)O6 octahedra. There are four inequivalent As sites. In the first As site, As(1) is bonded in a distorted trigonal non-coplanar geometry to one O(13), one O(5), and one O(9) atom. In the second As site, As(2) is bonded in a distorted trigonal non-coplanar geometry to one O(10), one O(14), and one O(6) atom. In the third As site, As(3) is bonded in a distorted trigonal non-coplanar geometry to one O(11), one O(15), and one O(7) atom. In the fourth As site, As(4) is bonded in a distorted trigonal non-coplanar geometry to one O(12), one O(16), and one O(8) atom. There are twenty inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(2), one W(1), and one W(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Ca(1), one W(2), and one W(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Ca(4), one W(2), and one W(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ca(3), one W(1), and one W(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(2), one Ca(3), and one As(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Ca(4), and one As(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Ca(4), and one As(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Ca(2), one Ca(3), and one As(4) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Ca(3), one W(3), and one As(1) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Ca(4), one W(4), and one As(2) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Ca(1), one W(1), and one As(3) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one Ca(2), one W(2), and one As(4) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Ca(3), one W(2), and one As(1) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Ca(4), one W(1), and one As(2) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Ca(1), one W(4), and one As(3) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Ca(2), one W(3), and one As(4) atom. In the seventeenth O site, O(17) is bonded in a water-like geometry to one W(1) and one W(4) atom. In the eighteenth O site, O(18) is bonded in a water-like geometry to one W(2) and one W(3) atom. In the nineteenth O site, O(19) is bonded in a distorted L-shaped geometry to one W(2) and one W(3) atom. In the twentieth O site, O(20) is bonded in a distorted L-shaped geometry to one W(1) and one W(4) atom.
CaWAsO5 crystallizes in the triclinic P1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(11), one O(15), one O(2), one O(6), and one O(7) atom to form distorted CaO5 trigonal bipyramids that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one W(3)O6 octahedra, and  a cornercorner with one W(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-61°. The Ca(1)-O(11) bond length is 2.58 Å. The Ca(1)-O(15) bond length is 2.45 Å. The Ca(1)-O(2) bond length is 2.48 Å. The Ca(1)-O(6) bond length is 2.24 Å. The Ca(1)-O(7) bond length is 2.39 Å. In the second Ca site, Ca(2) is bonded to one O(1), one O(12), one O(16), one O(5), and one O(8) atom to form distorted CaO5 trigonal bipyramids that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one W(3)O6 octahedra, and  a cornercorner with one W(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-60°. The Ca(2)-O(1) bond length is 2.48 Å. The Ca(2)-O(12) bond length is 2.58 Å. The Ca(2)-O(16) bond length is 2.45 Å. The Ca(2)-O(5) bond length is 2.24 Å. The Ca(2)-O(8) bond length is 2.39 Å. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to one O(13), one O(4), one O(5), one O(8), and one O(9) atom. The Ca(3)-O(13) bond length is 2.41 Å. The Ca(3)-O(4) bond length is 2.40 Å. The Ca(3)-O(5) bond length is 2.46 Å. The Ca(3)-O(8) bond length is 2.29 Å. The Ca(3)-O(9) bond length is 2.54 Å. In the fourth Ca site, Ca(4) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(3), one O(6), and one O(7) atom. The Ca(4)-O(10) bond length is 2.54 Å. The Ca(4)-O(14) bond length is 2.41 Å. The Ca(4)-O(3) bond length is 2.40 Å. The Ca(4)-O(6) bond length is 2.46 Å. The Ca(4)-O(7) bond length is 2.29 Å. There are four inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(11), one O(14), one O(17), one O(20), and one O(4) atom to form WO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ca(2)O5 trigonal bipyramid, and edges with two equivalent W(4)O6 octahedra. The W(1)-O(1) bond length is 2.09 Å. The W(1)-O(11) bond length is 2.01 Å. The W(1)-O(14) bond length is 2.01 Å. The W(1)-O(17) bond length is 2.04 Å. The W(1)-O(20) bond length is 1.99 Å. The W(1)-O(4) bond length is 2.00 Å. In the second W site, W(2) is bonded to one O(12), one O(13), one O(18), one O(19), one O(2), and one O(3) atom to form WO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ca(2)O5 trigonal bipyramid, and edges with two equivalent W(3)O6 octahedra. The W(2)-O(12) bond length is 2.01 Å. The W(2)-O(13) bond length is 2.00 Å. The W(2)-O(18) bond length is 2.04 Å. The W(2)-O(19) bond length is 1.99 Å. The W(2)-O(2) bond length is 2.09 Å. The W(2)-O(3) bond length is 2.00 Å. In the third W site, W(3) is bonded to one O(16), one O(18), one O(19), one O(2), one O(3), and one O(9) atom to form WO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ca(2)O5 trigonal bipyramid, and edges with two equivalent W(2)O6 octahedra. The W(3)-O(16) bond length is 2.01 Å. The W(3)-O(18) bond length is 1.99 Å. The W(3)-O(19) bond length is 2.05 Å. The W(3)-O(2) bond length is 2.00 Å. The W(3)-O(3) bond length is 2.09 Å. The W(3)-O(9) bond length is 2.01 Å. In the fourth W site, W(4) is bonded to one O(1), one O(10), one O(15), one O(17), one O(20), and one O(4) atom to form WO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ca(2)O5 trigonal bipyramid, and edges with two equivalent W(1)O6 octahedra. The W(4)-O(1) bond length is 2.00 Å. The W(4)-O(10) bond length is 2.01 Å. The W(4)-O(15) bond length is 2.01 Å. The W(4)-O(17) bond length is 1.99 Å. The W(4)-O(20) bond length is 2.05 Å. The W(4)-O(4) bond length is 2.09 Å. There are four inequivalent As sites. In the first As site, As(1) is bonded in a distorted trigonal non-coplanar geometry to one O(13), one O(5), and one O(9) atom. The As(1)-O(13) bond length is 1.84 Å. The As(1)-O(5) bond length is 1.76 Å. The As(1)-O(9) bond length is 1.90 Å. In the second As site, As(2) is bonded in a distorted trigonal non-coplanar geometry to one O(10), one O(14), and one O(6) atom. The As(2)-O(10) bond length is 1.90 Å. The As(2)-O(14) bond length is 1.84 Å. The As(2)-O(6) bond length is 1.76 Å. In the third As site, As(3) is bonded in a distorted trigonal non-coplanar geometry to one O(11), one O(15), and one O(7) atom. The As(3)-O(11) bond length is 1.91 Å. The As(3)-O(15) bond length is 1.86 Å. The As(3)-O(7) bond length is 1.76 Å. In the fourth As site, As(4) is bonded in a distorted trigonal non-coplanar geometry to one O(12), one O(16), and one O(8) atom. The As(4)-O(12) bond length is 1.91 Å. The As(4)-O(16) bond length is 1.86 Å. The As(4)-O(8) bond length is 1.76 Å. There are twenty inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(2), one W(1), and one W(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Ca(1), one W(2), and one W(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Ca(4), one W(2), and one W(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ca(3), one W(1), and one W(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(2), one Ca(3), and one As(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Ca(4), and one As(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Ca(4), and one As(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Ca(2), one Ca(3), and one As(4) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Ca(3), one W(3), and one As(1) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Ca(4), one W(4), and one As(2) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Ca(1), one W(1), and one As(3) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one Ca(2), one W(2), and one As(4) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Ca(3), one W(2), and one As(1) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Ca(4), one W(1), and one As(2) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Ca(1), one W(4), and one As(3) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Ca(2), one W(3), and one As(4) atom. In the seventeenth O site, O(17) is bonded in a water-like geometry to one W(1) and one W(4) atom. In the eighteenth O site, O(18) is bonded in a water-like geometry to one W(2) and one W(3) atom. In the nineteenth O site, O(19) is bonded in a distorted L-shaped geometry to one W(2) and one W(3) atom. In the twentieth O site, O(20) is bonded in a distorted L-shaped geometry to one W(1) and one W(4) atom.