Na5Cu3As4HO16 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(8), and two equivalent O(6) atoms. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(5), and two equivalent O(8) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(7) atom to form CuO5 square pyramids that share corners with two equivalent As(2)O4 tetrahedra and corners with three equivalent As(1)O4 tetrahedra. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(2) 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(3), one O(4), and one O(8) atom to form AsO4 tetrahedra that share corners with three equivalent Cu(1)O5 square pyramids. In the second As site, As(2) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form AsO4 tetrahedra that share corners with two equivalent Cu(1)O5 square pyramids. H(1) is bonded in a linear geometry to two equivalent O(8) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Cu(1), and one As(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Cu(2), and one As(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Cu(1), and one As(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one As(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Na(3), one Cu(1), and one As(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one As(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(2), and one As(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one As(1), and one H(1) atom.
Na5Cu3As4HO16 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(8), and two equivalent O(6) atoms. The Na(1)-O(2) bond length is 2.41 Å. The Na(1)-O(3) bond length is 2.45 Å. The Na(1)-O(8) bond length is 2.38 Å. There is one shorter (2.36 Å) and one longer (2.44 Å) Na(1)-O(6) bond length. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. The Na(2)-O(1) bond length is 2.37 Å. The Na(2)-O(2) bond length is 2.46 Å. The Na(2)-O(3) bond length is 2.48 Å. The Na(2)-O(4) bond length is 2.32 Å. The Na(2)-O(6) bond length is 2.46 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(5), and two equivalent O(8) atoms. Both Na(3)-O(1) bond lengths are 2.75 Å. Both Na(3)-O(5) bond lengths are 2.36 Å. Both Na(3)-O(8) bond lengths are 2.61 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(7) atom to form CuO5 square pyramids that share corners with two equivalent As(2)O4 tetrahedra and corners with three equivalent As(1)O4 tetrahedra. The Cu(1)-O(1) bond length is 1.97 Å. The Cu(1)-O(3) bond length is 1.97 Å. The Cu(1)-O(4) bond length is 2.25 Å. The Cu(1)-O(5) bond length is 1.95 Å. The Cu(1)-O(7) bond length is 2.06 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(2) and two equivalent O(7) atoms. Both Cu(2)-O(2) bond lengths are 1.95 Å. Both Cu(2)-O(7) bond lengths are 2.04 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form AsO4 tetrahedra that share corners with three equivalent Cu(1)O5 square pyramids. The As(1)-O(1) bond length is 1.74 Å. The As(1)-O(3) bond length is 1.75 Å. The As(1)-O(4) bond length is 1.68 Å. The As(1)-O(8) bond length is 1.75 Å. In the second As site, As(2) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form AsO4 tetrahedra that share corners with two equivalent Cu(1)O5 square pyramids. The As(2)-O(2) bond length is 1.74 Å. The As(2)-O(5) bond length is 1.71 Å. The As(2)-O(6) bond length is 1.71 Å. The As(2)-O(7) bond length is 1.78 Å. H(1) is bonded in a linear geometry to two equivalent O(8) atoms. Both H(1)-O(8) bond lengths are 1.21 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Cu(1), and one As(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Cu(2), and one As(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Cu(1), and one As(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one As(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Na(3), one Cu(1), and one As(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one As(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(2), and one As(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one As(1), and one H(1) atom.