Na2Cu3H8(CO2)8 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(5), two equivalent O(6), 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(2), one O(3), one O(4), and one O(8) atom to form corner-sharing CuO5 square pyramids. The corner-sharing octahedral tilt angles are 68°. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form distorted corner-sharing CuO6 octahedra. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one H(1), one O(1), and one O(2) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one H(2), one O(3), and one O(4) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one H(3), one O(5), and one O(6) atom. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one H(4), one O(7), and one O(8) atom. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(4) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Cu(1), one Cu(2), and one C(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(1), and one C(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(1), and one C(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(2), and one C(3) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to two equivalent Na(1) and one C(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Cu(2) and one C(4) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Cu(1), and one C(4) atom.
Na2Cu3H8(CO2)8 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(5), two equivalent O(6), and two equivalent O(8) atoms. The Na(1)-O(2) bond length is 2.41 Å. The Na(1)-O(3) bond length is 2.44 Å. The Na(1)-O(5) bond length is 2.46 Å. There is one shorter (2.33 Å) and one longer (2.80 Å) Na(1)-O(6) bond length. There is one shorter (2.52 Å) and one longer (2.69 Å) Na(1)-O(8) bond length. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(8) atom to form corner-sharing CuO5 square pyramids. The corner-sharing octahedral tilt angles are 68°. The Cu(1)-O(1) bond length is 1.99 Å. The Cu(1)-O(2) bond length is 2.02 Å. The Cu(1)-O(3) bond length is 2.02 Å. The Cu(1)-O(4) bond length is 2.00 Å. The Cu(1)-O(8) bond length is 2.20 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form distorted corner-sharing CuO6 octahedra. Both Cu(2)-O(1) bond lengths are 2.60 Å. Both Cu(2)-O(5) bond lengths are 1.96 Å. Both Cu(2)-O(7) bond lengths are 2.00 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one H(1), one O(1), and one O(2) atom. The C(1)-H(1) bond length is 1.11 Å. The C(1)-O(1) bond length is 1.27 Å. The C(1)-O(2) bond length is 1.27 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one H(2), one O(3), and one O(4) atom. The C(2)-H(2) bond length is 1.11 Å. The C(2)-O(3) bond length is 1.27 Å. The C(2)-O(4) bond length is 1.26 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one H(3), one O(5), and one O(6) atom. The C(3)-H(3) bond length is 1.11 Å. The C(3)-O(5) bond length is 1.29 Å. The C(3)-O(6) bond length is 1.25 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one H(4), one O(7), and one O(8) atom. The C(4)-H(4) bond length is 1.11 Å. The C(4)-O(7) bond length is 1.27 Å. The C(4)-O(8) bond length is 1.26 Å. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(4) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Cu(1), one Cu(2), and one C(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(1), and one C(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(1), and one C(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(2), and one C(3) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to two equivalent Na(1) and one C(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Cu(2) and one C(4) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Cu(1), and one C(4) atom.