Na2Cu4H5(SO5)4 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a distorted body-centered cubic geometry to two equivalent O(10), two equivalent O(7), two equivalent O(8), and two equivalent O(9) 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(5), one O(6), one O(8), and one O(9) atom to form distorted CuO6 octahedra that share corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra, and edges with two equivalent Cu(2)O6 octahedra. In the second Cu site, Cu(2) is bonded to one O(10), one O(2), one O(3), one O(5), one O(6), and one O(9) atom to form CuO6 octahedra that share corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra, and edges with two equivalent Cu(1)O6 octahedra. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(5) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) atom. In the third H site, H(3) is bonded in a linear geometry to two equivalent O(6) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(10), one O(3), one O(4), and one O(8) atom to form SO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra and corners with two equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. In the second S site, S(2) is bonded to one O(1), one O(2), one O(7), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra and corners with two equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-51°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Cu(1), and one S(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(2), and one S(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Cu(1), one Cu(2), and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Cu(1), one Cu(2), and one H(1) atom. In the sixth O site, O(6) is bonded to one Cu(1), one Cu(2), one H(2), and one H(3) atom to form distorted corner-sharing OCu2H2 tetrahedra. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Na(2) and one S(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one S(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(2), one Cu(1), one Cu(2), and one S(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Na(2), one Cu(2), and one S(1) atom.
Na2Cu4H5(SO5)4 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Both Na(1)-O(1) bond lengths are 2.80 Å. Both Na(1)-O(2) bond lengths are 2.61 Å. Both Na(1)-O(3) bond lengths are 2.50 Å. Both Na(1)-O(4) bond lengths are 2.70 Å. In the second Na site, Na(2) is bonded in a distorted body-centered cubic geometry to two equivalent O(10), two equivalent O(7), two equivalent O(8), and two equivalent O(9) atoms. Both Na(2)-O(10) bond lengths are 2.60 Å. Both Na(2)-O(7) bond lengths are 2.70 Å. Both Na(2)-O(8) bond lengths are 2.78 Å. Both Na(2)-O(9) bond lengths are 2.51 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(5), one O(6), one O(8), and one O(9) atom to form distorted CuO6 octahedra that share corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra, and edges with two equivalent Cu(2)O6 octahedra. The Cu(1)-O(1) bond length is 1.98 Å. The Cu(1)-O(3) bond length is 2.50 Å. The Cu(1)-O(5) bond length is 1.87 Å. The Cu(1)-O(6) bond length is 1.97 Å. The Cu(1)-O(8) bond length is 1.95 Å. The Cu(1)-O(9) bond length is 2.54 Å. In the second Cu site, Cu(2) is bonded to one O(10), one O(2), one O(3), one O(5), one O(6), and one O(9) atom to form CuO6 octahedra that share corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra, and edges with two equivalent Cu(1)O6 octahedra. The Cu(2)-O(10) bond length is 1.99 Å. The Cu(2)-O(2) bond length is 2.00 Å. The Cu(2)-O(3) bond length is 2.45 Å. The Cu(2)-O(5) bond length is 1.91 Å. The Cu(2)-O(6) bond length is 2.02 Å. The Cu(2)-O(9) bond length is 2.43 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(5) atom. The H(1)-O(5) bond length is 0.99 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) atom. The H(2)-O(6) bond length is 1.00 Å. In the third H site, H(3) is bonded in a linear geometry to two equivalent O(6) atoms. Both H(3)-O(6) bond lengths are 1.22 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(10), one O(3), one O(4), and one O(8) atom to form SO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra and corners with two equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. The S(1)-O(10) bond length is 1.51 Å. The S(1)-O(3) bond length is 1.49 Å. The S(1)-O(4) bond length is 1.46 Å. The S(1)-O(8) bond length is 1.53 Å. In the second S site, S(2) is bonded to one O(1), one O(2), one O(7), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra and corners with two equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-51°. The S(2)-O(1) bond length is 1.52 Å. The S(2)-O(2) bond length is 1.51 Å. The S(2)-O(7) bond length is 1.46 Å. The S(2)-O(9) bond length is 1.49 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Cu(1), and one S(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(2), and one S(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Cu(1), one Cu(2), and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Cu(1), one Cu(2), and one H(1) atom. In the sixth O site, O(6) is bonded to one Cu(1), one Cu(2), one H(2), and one H(3) atom to form distorted corner-sharing OCu2H2 tetrahedra. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Na(2) and one S(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one S(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(2), one Cu(1), one Cu(2), and one S(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Na(2), one Cu(2), and one S(1) atom.