Cu2As(HO3)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(10), one O(3), one O(5), one O(8), and one O(9) atom to form CuO5 square pyramids that share  a cornercorner with one Cu(4)O5 square pyramid,  a cornercorner with one As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra,  an edgeedge with one Cu(2)O6 octahedra, and  an edgeedge with one Cu(3)O6 octahedra. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(10), and two equivalent O(3) atoms to form distorted CuO6 octahedra that share corners with two equivalent Cu(4)O5 square pyramids, corners with four equivalent As(1)O4 tetrahedra, and edges with two equivalent Cu(1)O5 square pyramids. In the third Cu site, Cu(3) is bonded to two equivalent O(6), two equivalent O(8), and two equivalent O(9) atoms to form distorted CuO6 octahedra that share corners with four equivalent As(2)O4 tetrahedra and edges with two equivalent Cu(1)O5 square pyramids. In the fourth Cu site, Cu(4) is bonded to one O(1), one O(11), one O(5), and two equivalent O(4) atoms to form distorted CuO5 square pyramids that share  a cornercorner with one Cu(2)O6 octahedra,  a cornercorner with one Cu(1)O5 square pyramid,  a cornercorner with one As(2)O4 tetrahedra, corners with three equivalent As(1)O4 tetrahedra, and  an edgeedge with one Cu(4)O5 square pyramid. The corner-sharing octahedral tilt angles are 69°. In the fifth Cu site, Cu(5) is bonded in a 4-coordinate geometry to one O(11), one O(12), and two equivalent O(7) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form AsO4 tetrahedra that share corners with two equivalent Cu(2)O6 octahedra,  a cornercorner with one Cu(1)O5 square pyramid, and corners with three equivalent Cu(4)O5 square pyramids. The corner-sharing octahedral tilt angles range from 53-65°. In the second As site, As(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form AsO4 tetrahedra that share corners with two equivalent Cu(3)O6 octahedra,  a cornercorner with one Cu(4)O5 square pyramid, and corners with two equivalent Cu(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 49-66°. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(9) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(10) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(11) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(12) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Cu(2), one Cu(4), and one As(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one As(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Cu(1), one Cu(2), and one As(1) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to two equivalent Cu(4) and one As(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(4), and one As(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Cu(3) and one As(2) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to two equivalent Cu(5) and one As(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(3), and one As(2) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Cu(1), one Cu(3), and one H(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Cu(1), one Cu(2), and one H(2) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one Cu(4), one Cu(5), and one H(3) atom. In the twelfth O site, O(12) is bonded in a water-like geometry to one Cu(5) and one H(4) atom.
Cu2As(HO3)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(10), one O(3), one O(5), one O(8), and one O(9) atom to form CuO5 square pyramids that share  a cornercorner with one Cu(4)O5 square pyramid,  a cornercorner with one As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra,  an edgeedge with one Cu(2)O6 octahedra, and  an edgeedge with one Cu(3)O6 octahedra. The Cu(1)-O(10) bond length is 1.88 Å. The Cu(1)-O(3) bond length is 1.90 Å. The Cu(1)-O(5) bond length is 2.37 Å. The Cu(1)-O(8) bond length is 1.91 Å. The Cu(1)-O(9) bond length is 1.90 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(10), and two equivalent O(3) atoms to form distorted CuO6 octahedra that share corners with two equivalent Cu(4)O5 square pyramids, corners with four equivalent As(1)O4 tetrahedra, and edges with two equivalent Cu(1)O5 square pyramids. Both Cu(2)-O(1) bond lengths are 2.51 Å. Both Cu(2)-O(10) bond lengths are 1.92 Å. Both Cu(2)-O(3) bond lengths are 2.00 Å. In the third Cu site, Cu(3) is bonded to two equivalent O(6), two equivalent O(8), and two equivalent O(9) atoms to form distorted CuO6 octahedra that share corners with four equivalent As(2)O4 tetrahedra and edges with two equivalent Cu(1)O5 square pyramids. Both Cu(3)-O(6) bond lengths are 2.45 Å. Both Cu(3)-O(8) bond lengths are 2.04 Å. Both Cu(3)-O(9) bond lengths are 1.92 Å. In the fourth Cu site, Cu(4) is bonded to one O(1), one O(11), one O(5), and two equivalent O(4) atoms to form distorted CuO5 square pyramids that share  a cornercorner with one Cu(2)O6 octahedra,  a cornercorner with one Cu(1)O5 square pyramid,  a cornercorner with one As(2)O4 tetrahedra, corners with three equivalent As(1)O4 tetrahedra, and  an edgeedge with one Cu(4)O5 square pyramid. The corner-sharing octahedral tilt angles are 69°. The Cu(4)-O(1) bond length is 2.37 Å. The Cu(4)-O(11) bond length is 1.91 Å. The Cu(4)-O(5) bond length is 1.91 Å. There is one shorter (1.99 Å) and one longer (2.00 Å) Cu(4)-O(4) bond length. In the fifth Cu site, Cu(5) is bonded in a 4-coordinate geometry to one O(11), one O(12), and two equivalent O(7) atoms. The Cu(5)-O(11) bond length is 1.86 Å. The Cu(5)-O(12) bond length is 1.81 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) Cu(5)-O(7) bond length. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form AsO4 tetrahedra that share corners with two equivalent Cu(2)O6 octahedra,  a cornercorner with one Cu(1)O5 square pyramid, and corners with three equivalent Cu(4)O5 square pyramids. The corner-sharing octahedral tilt angles range from 53-65°. The As(1)-O(1) bond length is 1.70 Å. The As(1)-O(2) bond length is 1.67 Å. The As(1)-O(3) bond length is 1.78 Å. The As(1)-O(4) bond length is 1.82 Å. In the second As site, As(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form AsO4 tetrahedra that share corners with two equivalent Cu(3)O6 octahedra,  a cornercorner with one Cu(4)O5 square pyramid, and corners with two equivalent Cu(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 49-66°. The As(2)-O(5) bond length is 1.74 Å. The As(2)-O(6) bond length is 1.67 Å. The As(2)-O(7) bond length is 1.78 Å. The As(2)-O(8) bond length is 1.77 Å. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(9) atom. The H(1)-O(9) bond length is 0.99 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(10) atom. The H(2)-O(10) bond length is 1.00 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(11) atom. The H(3)-O(11) bond length is 1.00 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(12) atom. The H(4)-O(12) bond length is 0.99 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Cu(2), one Cu(4), and one As(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one As(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Cu(1), one Cu(2), and one As(1) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to two equivalent Cu(4) and one As(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(4), and one As(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Cu(3) and one As(2) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to two equivalent Cu(5) and one As(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(3), and one As(2) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Cu(1), one Cu(3), and one H(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Cu(1), one Cu(2), and one H(2) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one Cu(4), one Cu(5), and one H(3) atom. In the twelfth O site, O(12) is bonded in a water-like geometry to one Cu(5) and one H(4) atom.