Ca3As2(W5O4)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 3-coordinate geometry to one O(1), one O(4), and one O(7) atom. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to one W(2), one O(1), one O(2), one O(3), one O(4), and one O(5) atom. In the third Ca site, Ca(3) is bonded in a 3-coordinate geometry to one As(1), one O(3), one O(5), and one O(6) atom. There are ten inequivalent W sites. In the first W site, W(1) is bonded in a single-bond geometry to one O(6) atom. In the second W site, W(2) is bonded in a 9-coordinate geometry to one Ca(2), one W(5), one W(6), two equivalent W(4), two equivalent W(7), and two equivalent W(9) atoms. In the third W site, W(3) is bonded in a distorted L-shaped geometry to one O(1) and one O(2) atom. In the fourth W site, W(4) is bonded in a single-bond geometry to two equivalent W(2), two equivalent W(7), and one O(1) atom. In the fifth W site, W(5) is bonded in a 2-coordinate geometry to one W(2), one W(7), one As(1), and two equivalent O(8) atoms. In the sixth W site, W(6) is bonded in a distorted single-bond geometry to one W(2), one W(7), two equivalent As(1), and one O(8) atom. In the seventh W site, W(7) is bonded in a 9-coordinate geometry to one W(5), one W(6), one W(8), two equivalent W(2), two equivalent W(4), and two equivalent W(9) atoms. In the eighth W site, W(8) is bonded in a distorted L-shaped geometry to one W(7), one As(1), one O(7), and one O(8) atom. In the ninth W site, W(9) is bonded in a single-bond geometry to two equivalent W(2), two equivalent W(7), and one O(1) atom. In the tenth W site, W(10) is bonded in a 3-coordinate geometry to one O(5), one O(6), and one O(7) atom. There are two inequivalent As sites. In the first As site, As(1) is bonded to one Ca(3), one W(5), one W(8), and two equivalent W(6) atoms to form distorted edge-sharing AsCaW4 square pyramids. In the second As site, As(2) is bonded in a tetrahedral geometry to one O(2), one O(3), one O(4), and one O(5) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted square pyramidal geometry to one Ca(1), one Ca(2), one W(3), one W(4), and one W(9) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Ca(2), one W(3), and one As(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(2), one Ca(3), and one As(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Ca(1), one Ca(2), and one As(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(3), one W(10), and one As(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Ca(3), one W(1), and one W(10) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Ca(1), one W(10), and one W(8) atom. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to one W(6), one W(8), and two equivalent W(5) atoms.
Ca3As2(W5O4)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 3-coordinate geometry to one O(1), one O(4), and one O(7) atom. The Ca(1)-O(1) bond length is 2.52 Å. The Ca(1)-O(4) bond length is 2.26 Å. The Ca(1)-O(7) bond length is 2.28 Å. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to one W(2), one O(1), one O(2), one O(3), one O(4), and one O(5) atom. The Ca(2)-W(2) bond length is 3.91 Å. The Ca(2)-O(1) bond length is 2.81 Å. The Ca(2)-O(2) bond length is 2.30 Å. The Ca(2)-O(3) bond length is 2.76 Å. The Ca(2)-O(4) bond length is 2.25 Å. The Ca(2)-O(5) bond length is 2.66 Å. In the third Ca site, Ca(3) is bonded in a 3-coordinate geometry to one As(1), one O(3), one O(5), and one O(6) atom. The Ca(3)-As(1) bond length is 3.04 Å. The Ca(3)-O(3) bond length is 2.26 Å. The Ca(3)-O(5) bond length is 2.53 Å. The Ca(3)-O(6) bond length is 2.12 Å. There are ten inequivalent W sites. In the first W site, W(1) is bonded in a single-bond geometry to one O(6) atom. The W(1)-O(6) bond length is 1.98 Å. In the second W site, W(2) is bonded in a 9-coordinate geometry to one Ca(2), one W(5), one W(6), two equivalent W(4), two equivalent W(7), and two equivalent W(9) atoms. The W(2)-W(5) bond length is 2.80 Å. The W(2)-W(6) bond length is 2.91 Å. There is one shorter (2.75 Å) and one longer (2.79 Å) W(2)-W(4) bond length. There is one shorter (3.13 Å) and one longer (3.15 Å) W(2)-W(7) bond length. There is one shorter (2.88 Å) and one longer (3.10 Å) W(2)-W(9) bond length. In the third W site, W(3) is bonded in a distorted L-shaped geometry to one O(1) and one O(2) atom. The W(3)-O(1) bond length is 2.16 Å. The W(3)-O(2) bond length is 2.29 Å. In the fourth W site, W(4) is bonded in a single-bond geometry to two equivalent W(2), two equivalent W(7), and one O(1) atom. Both W(4)-W(7) bond lengths are 2.81 Å. The W(4)-O(1) bond length is 2.14 Å. In the fifth W site, W(5) is bonded in a 2-coordinate geometry to one W(2), one W(7), one As(1), and two equivalent O(8) atoms. The W(5)-W(7) bond length is 3.05 Å. The W(5)-As(1) bond length is 2.71 Å. There is one shorter (2.12 Å) and one longer (2.27 Å) W(5)-O(8) bond length. In the sixth W site, W(6) is bonded in a distorted single-bond geometry to one W(2), one W(7), two equivalent As(1), and one O(8) atom. The W(6)-W(7) bond length is 2.93 Å. There is one shorter (2.65 Å) and one longer (2.72 Å) W(6)-As(1) bond length. The W(6)-O(8) bond length is 2.18 Å. In the seventh W site, W(7) is bonded in a 9-coordinate geometry to one W(5), one W(6), one W(8), two equivalent W(2), two equivalent W(4), and two equivalent W(9) atoms. The W(7)-W(8) bond length is 2.74 Å. There is one shorter (2.87 Å) and one longer (2.90 Å) W(7)-W(9) bond length. In the eighth W site, W(8) is bonded in a distorted L-shaped geometry to one W(7), one As(1), one O(7), and one O(8) atom. The W(8)-As(1) bond length is 2.58 Å. The W(8)-O(7) bond length is 1.97 Å. The W(8)-O(8) bond length is 2.16 Å. In the ninth W site, W(9) is bonded in a single-bond geometry to two equivalent W(2), two equivalent W(7), and one O(1) atom. The W(9)-O(1) bond length is 2.27 Å. In the tenth W site, W(10) is bonded in a 3-coordinate geometry to one O(5), one O(6), and one O(7) atom. The W(10)-O(5) bond length is 2.49 Å. The W(10)-O(6) bond length is 2.14 Å. The W(10)-O(7) bond length is 2.12 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded to one Ca(3), one W(5), one W(8), and two equivalent W(6) atoms to form distorted edge-sharing AsCaW4 square pyramids. In the second As site, As(2) is bonded in a tetrahedral geometry to one O(2), one O(3), one O(4), and one O(5) atom. The As(2)-O(2) bond length is 1.76 Å. The As(2)-O(3) bond length is 1.71 Å. The As(2)-O(4) bond length is 1.72 Å. The As(2)-O(5) bond length is 1.75 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted square pyramidal geometry to one Ca(1), one Ca(2), one W(3), one W(4), and one W(9) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Ca(2), one W(3), and one As(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(2), one Ca(3), and one As(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Ca(1), one Ca(2), and one As(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(3), one W(10), and one As(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Ca(3), one W(1), and one W(10) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Ca(1), one W(10), and one W(8) atom. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to one W(6), one W(8), and two equivalent W(5) atoms.