NaCu(O3I)3 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent O(8) atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedral tilt angles are 65°. In the second Cu site, Cu(2) is bonded to two equivalent O(7), two equivalent O(8), and two equivalent O(9) atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedral tilt angles are 65°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one I(1), and one I(3) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Na(1) and one I(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one I(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one I(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(1), and one I(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Cu(1), and one I(2) atom. In the seventh O site, O(7) is bonded in a trigonal non-coplanar geometry to one Na(1), one Cu(2), and one I(2) atom. In the eighth O site, O(8) is bonded to one Na(1), one Cu(1), one Cu(2), and one I(3) atom to form distorted corner-sharing ONaCu2I trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Cu(2) and one I(1) atom. There are three inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one O(1), one O(3), one O(5), and one O(9) atom. In the second I site, I(2) is bonded in a 3-coordinate geometry to one O(2), one O(6), and one O(7) atom. In the third I site, I(3) is bonded in a trigonal non-coplanar geometry to one O(1), one O(4), and one O(8) atom.
NaCu(O3I)3 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The Na(1)-O(1) bond length is 2.56 Å. The Na(1)-O(2) bond length is 2.46 Å. The Na(1)-O(4) bond length is 2.52 Å. The Na(1)-O(5) bond length is 2.49 Å. The Na(1)-O(6) bond length is 2.89 Å. The Na(1)-O(7) bond length is 2.64 Å. The Na(1)-O(8) bond length is 2.61 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent O(8) atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedral tilt angles are 65°. Both Cu(1)-O(5) bond lengths are 1.94 Å. Both Cu(1)-O(6) bond lengths are 2.05 Å. Both Cu(1)-O(8) bond lengths are 2.49 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(7), two equivalent O(8), and two equivalent O(9) atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedral tilt angles are 65°. Both Cu(2)-O(7) bond lengths are 1.96 Å. Both Cu(2)-O(8) bond lengths are 2.45 Å. Both Cu(2)-O(9) bond lengths are 2.00 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one I(1), and one I(3) atom. The O(1)-I(1) bond length is 2.62 Å. The O(1)-I(3) bond length is 1.85 Å. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Na(1) and one I(2) atom. The O(2)-I(2) bond length is 1.83 Å. In the third O site, O(3) is bonded in a distorted single-bond geometry to one I(1) atom. The O(3)-I(1) bond length is 1.81 Å. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one I(3) atom. The O(4)-I(3) bond length is 1.83 Å. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(1), and one I(1) atom. The O(5)-I(1) bond length is 1.86 Å. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Cu(1), and one I(2) atom. The O(6)-I(2) bond length is 1.87 Å. In the seventh O site, O(7) is bonded in a trigonal non-coplanar geometry to one Na(1), one Cu(2), and one I(2) atom. The O(7)-I(2) bond length is 1.87 Å. In the eighth O site, O(8) is bonded to one Na(1), one Cu(1), one Cu(2), and one I(3) atom to form distorted corner-sharing ONaCu2I trigonal pyramids. The O(8)-I(3) bond length is 1.84 Å. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Cu(2) and one I(1) atom. The O(9)-I(1) bond length is 1.87 Å. There are three inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one O(1), one O(3), one O(5), and one O(9) atom. In the second I site, I(2) is bonded in a 3-coordinate geometry to one O(2), one O(6), and one O(7) atom. In the third I site, I(3) is bonded in a trigonal non-coplanar geometry to one O(1), one O(4), and one O(8) atom.