Li19Cu4(HO2)8 crystallizes in the triclinic P1 space group. There are nineteen inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(2), and one O(5) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(12), one O(2), and one O(4) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(14), one O(15), one O(16), one O(6), one O(7), and one O(8) atom. In the fourth Li site, Li(4) is bonded to one O(16), one O(5), one O(6), and one O(7) atom to form distorted corner-sharing LiO4 tetrahedra. In the fifth Li site, Li(5) is bonded to one O(15), one O(5), one O(6), and one O(8) atom to form distorted corner-sharing LiO4 trigonal pyramids. In the sixth Li site, Li(6) is bonded to one O(1), one O(3), one O(4), and one O(9) atom to form distorted corner-sharing LiO4 trigonal pyramids. In the seventh Li site, Li(7) is bonded to one O(10), one O(2), one O(3), and one O(4) atom to form distorted corner-sharing LiO4 trigonal pyramids. In the eighth Li site, Li(8) is bonded in a 3-coordinate geometry to one O(10), one O(11), one O(3), and one O(9) atom. In the ninth Li site, Li(9) is bonded in a 3-coordinate geometry to one O(13), one O(5), and one O(7) atom. In the tenth Li site, Li(10) is bonded in a distorted rectangular see-saw-like geometry to one O(14), one O(4), one O(7), and one O(8) atom. In the eleventh Li site, Li(11) is bonded in a 6-coordinate geometry to one O(14), one O(15), one O(16), one O(6), one O(7), and one O(8) atom. In the twelfth Li site, Li(12) is bonded in a distorted square co-planar geometry to one O(10), one O(12), one O(4), and one O(9) atom. In the thirteenth Li site, Li(13) is bonded to one O(13), one O(14), one O(15), and one O(8) atom to form distorted corner-sharing LiO4 tetrahedra. In the fourteenth Li site, Li(14) is bonded in a distorted see-saw-like geometry to one O(13), one O(14), one O(16), and one O(7) atom. In the fifteenth Li site, Li(15) is bonded to one O(10), one O(11), one O(12), and one O(2) atom to form distorted corner-sharing LiO4 tetrahedra. In the sixteenth Li site, Li(16) is bonded to one O(1), one O(11), one O(12), and one O(9) atom to form distorted corner-sharing LiO4 tetrahedra. In the seventeenth Li site, Li(17) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(15), one O(16), and one O(6) atom. In the eighteenth Li site, Li(18) is bonded in a 3-coordinate geometry to one O(13), one O(15), and one O(5) atom. In the nineteenth Li site, Li(19) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(2), and one O(3) atom. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a linear geometry to one O(14) and one O(4) atom. In the second Cu site, Cu(2) is bonded in a linear geometry to one O(11) and one O(5) atom. In the third Cu site, Cu(3) is bonded in a linear geometry to one O(12) and one O(6) atom. In the fourth Cu site, Cu(4) is bonded in a linear geometry to one O(13) and one O(3) atom. There are eight inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(1) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(8) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(7) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(9) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(15) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one O(10) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(16) atom. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Li(1), one Li(16), one Li(19), one Li(2), one Li(6), and one H(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Li(1), one Li(15), one Li(19), one Li(2), one Li(7), and one H(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(19), one Li(6), one Li(7), one Li(8), and one Cu(4) atom. In the fourth O site, O(4) is bonded to one Li(10), one Li(12), one Li(2), one Li(6), one Li(7), and one Cu(1) atom to form corner-sharing OLi5Cu octahedra. The corner-sharing octahedral tilt angles range from 9-41°. In the fifth O site, O(5) is bonded to one Li(1), one Li(18), one Li(4), one Li(5), one Li(9), and one Cu(2) atom to form corner-sharing OLi5Cu octahedra. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Li(11), one Li(17), one Li(3), one Li(4), one Li(5), and one Cu(3) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Li(10), one Li(11), one Li(14), one Li(3), one Li(4), one Li(9), and one H(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Li(10), one Li(11), one Li(13), one Li(3), one Li(5), and one H(3) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Li(12), one Li(16), one Li(6), one Li(8), and one H(5) atom. In the tenth O site, O(10) is bonded in a 1-coordinate geometry to one Li(12), one Li(15), one Li(7), one Li(8), and one H(7) atom. In the eleventh O site, O(11) is bonded in a 6-coordinate geometry to one Li(1), one Li(15), one Li(16), one Li(19), one Li(8), and one Cu(2) atom. In the twelfth O site, O(12) is bonded to one Li(12), one Li(15), one Li(16), one Li(17), one Li(2), and one Cu(3) atom to form corner-sharing OLi5Cu octahedra. The corner-sharing octahedral tilt angles range from 24-31°. In the thirteenth O site, O(13) is bonded to one Li(13), one Li(14), one Li(18), one Li(9), and one Cu(4) atom to form corner-sharing OLi4Cu square pyramids. The corner-sharing octahedral tilt angles range from 27-34°. In the fourteenth O site, O(14) is bonded to one Li(10), one Li(11), one Li(13), one Li(14), one Li(3), and one Cu(1) atom to form distorted OLi5Cu octahedra that share corners with two equivalent O(4)Li5Cu octahedra and corners with two equivalent O(13)Li4Cu square pyramids. The corner-sharing octahedral tilt angles range from 9-41°. In the fifteenth O site, O(15) is bonded in a distorted single-bond geometry to one Li(11), one Li(13), one Li(17), one Li(18), one Li(3), one Li(5), and one H(6) atom. In the sixteenth O site, O(16) is bonded in a distorted single-bond geometry to one Li(11), one Li(14), one Li(17), one Li(3), one Li(4), and one H(8) atom.
Li19Cu4(HO2)8 crystallizes in the triclinic P1 space group. There are nineteen inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(2), and one O(5) atom. The Li(1)-O(1) bond length is 2.18 Å. The Li(1)-O(11) bond length is 1.91 Å. The Li(1)-O(2) bond length is 2.15 Å. The Li(1)-O(5) bond length is 2.12 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(12), one O(2), and one O(4) atom. The Li(2)-O(1) bond length is 2.15 Å. The Li(2)-O(12) bond length is 2.04 Å. The Li(2)-O(2) bond length is 2.32 Å. The Li(2)-O(4) bond length is 2.05 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(14), one O(15), one O(16), one O(6), one O(7), and one O(8) atom. The Li(3)-O(14) bond length is 2.03 Å. The Li(3)-O(15) bond length is 2.17 Å. The Li(3)-O(16) bond length is 2.33 Å. The Li(3)-O(6) bond length is 2.25 Å. The Li(3)-O(7) bond length is 2.43 Å. The Li(3)-O(8) bond length is 2.19 Å. In the fourth Li site, Li(4) is bonded to one O(16), one O(5), one O(6), and one O(7) atom to form distorted corner-sharing LiO4 tetrahedra. The Li(4)-O(16) bond length is 2.03 Å. The Li(4)-O(5) bond length is 1.95 Å. The Li(4)-O(6) bond length is 1.94 Å. The Li(4)-O(7) bond length is 2.04 Å. In the fifth Li site, Li(5) is bonded to one O(15), one O(5), one O(6), and one O(8) atom to form distorted corner-sharing LiO4 trigonal pyramids. The Li(5)-O(15) bond length is 2.09 Å. The Li(5)-O(5) bond length is 1.94 Å. The Li(5)-O(6) bond length is 1.93 Å. The Li(5)-O(8) bond length is 2.03 Å. In the sixth Li site, Li(6) is bonded to one O(1), one O(3), one O(4), and one O(9) atom to form distorted corner-sharing LiO4 trigonal pyramids. The Li(6)-O(1) bond length is 2.07 Å. The Li(6)-O(3) bond length is 1.95 Å. The Li(6)-O(4) bond length is 1.97 Å. The Li(6)-O(9) bond length is 2.00 Å. In the seventh Li site, Li(7) is bonded to one O(10), one O(2), one O(3), and one O(4) atom to form distorted corner-sharing LiO4 trigonal pyramids. The Li(7)-O(10) bond length is 2.01 Å. The Li(7)-O(2) bond length is 2.06 Å. The Li(7)-O(3) bond length is 1.96 Å. The Li(7)-O(4) bond length is 1.96 Å. In the eighth Li site, Li(8) is bonded in a 3-coordinate geometry to one O(10), one O(11), one O(3), and one O(9) atom. The Li(8)-O(10) bond length is 2.04 Å. The Li(8)-O(11) bond length is 2.08 Å. The Li(8)-O(3) bond length is 2.34 Å. The Li(8)-O(9) bond length is 2.06 Å. In the ninth Li site, Li(9) is bonded in a 3-coordinate geometry to one O(13), one O(5), and one O(7) atom. The Li(9)-O(13) bond length is 1.97 Å. The Li(9)-O(5) bond length is 2.05 Å. The Li(9)-O(7) bond length is 2.10 Å. In the tenth Li site, Li(10) is bonded in a distorted rectangular see-saw-like geometry to one O(14), one O(4), one O(7), and one O(8) atom. The Li(10)-O(14) bond length is 1.93 Å. The Li(10)-O(4) bond length is 2.17 Å. The Li(10)-O(7) bond length is 2.19 Å. The Li(10)-O(8) bond length is 2.17 Å. In the eleventh Li site, Li(11) is bonded in a 6-coordinate geometry to one O(14), one O(15), one O(16), one O(6), one O(7), and one O(8) atom. The Li(11)-O(14) bond length is 2.24 Å. The Li(11)-O(15) bond length is 2.39 Å. The Li(11)-O(16) bond length is 2.23 Å. The Li(11)-O(6) bond length is 2.04 Å. The Li(11)-O(7) bond length is 2.18 Å. The Li(11)-O(8) bond length is 2.25 Å. In the twelfth Li site, Li(12) is bonded in a distorted square co-planar geometry to one O(10), one O(12), one O(4), and one O(9) atom. The Li(12)-O(10) bond length is 2.07 Å. The Li(12)-O(12) bond length is 2.11 Å. The Li(12)-O(4) bond length is 2.03 Å. The Li(12)-O(9) bond length is 2.07 Å. In the thirteenth Li site, Li(13) is bonded to one O(13), one O(14), one O(15), and one O(8) atom to form distorted corner-sharing LiO4 tetrahedra. The Li(13)-O(13) bond length is 1.92 Å. The Li(13)-O(14) bond length is 1.96 Å. The Li(13)-O(15) bond length is 2.04 Å. The Li(13)-O(8) bond length is 2.05 Å. In the fourteenth Li site, Li(14) is bonded in a distorted see-saw-like geometry to one O(13), one O(14), one O(16), and one O(7) atom. The Li(14)-O(13) bond length is 1.91 Å. The Li(14)-O(14) bond length is 1.95 Å. The Li(14)-O(16) bond length is 2.01 Å. The Li(14)-O(7) bond length is 2.09 Å. In the fifteenth Li site, Li(15) is bonded to one O(10), one O(11), one O(12), and one O(2) atom to form distorted corner-sharing LiO4 tetrahedra. The Li(15)-O(10) bond length is 1.94 Å. The Li(15)-O(11) bond length is 1.97 Å. The Li(15)-O(12) bond length is 1.92 Å. The Li(15)-O(2) bond length is 2.01 Å. In the sixteenth Li site, Li(16) is bonded to one O(1), one O(11), one O(12), and one O(9) atom to form distorted corner-sharing LiO4 tetrahedra. The Li(16)-O(1) bond length is 2.01 Å. The Li(16)-O(11) bond length is 1.96 Å. The Li(16)-O(12) bond length is 1.92 Å. The Li(16)-O(9) bond length is 1.94 Å. In the seventeenth Li site, Li(17) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(15), one O(16), and one O(6) atom. The Li(17)-O(12) bond length is 2.06 Å. The Li(17)-O(15) bond length is 2.13 Å. The Li(17)-O(16) bond length is 2.10 Å. The Li(17)-O(6) bond length is 1.92 Å. In the eighteenth Li site, Li(18) is bonded in a 3-coordinate geometry to one O(13), one O(15), and one O(5) atom. The Li(18)-O(13) bond length is 1.91 Å. The Li(18)-O(15) bond length is 2.12 Å. The Li(18)-O(5) bond length is 1.93 Å. In the nineteenth Li site, Li(19) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(2), and one O(3) atom. The Li(19)-O(1) bond length is 2.11 Å. The Li(19)-O(11) bond length is 2.24 Å. The Li(19)-O(2) bond length is 2.09 Å. The Li(19)-O(3) bond length is 1.94 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a linear geometry to one O(14) and one O(4) atom. The Cu(1)-O(14) bond length is 1.79 Å. The Cu(1)-O(4) bond length is 1.80 Å. In the second Cu site, Cu(2) is bonded in a linear geometry to one O(11) and one O(5) atom. The Cu(2)-O(11) bond length is 1.79 Å. The Cu(2)-O(5) bond length is 1.82 Å. In the third Cu site, Cu(3) is bonded in a linear geometry to one O(12) and one O(6) atom. The Cu(3)-O(12) bond length is 1.81 Å. The Cu(3)-O(6) bond length is 1.79 Å. In the fourth Cu site, Cu(4) is bonded in a linear geometry to one O(13) and one O(3) atom. The Cu(4)-O(13) bond length is 1.78 Å. The Cu(4)-O(3) bond length is 1.76 Å. There are eight inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(2) atom. The H(1)-O(2) bond length is 0.98 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(1) atom. The H(2)-O(1) bond length is 0.98 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(8) atom. The H(3)-O(8) bond length is 0.98 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(7) atom. The H(4)-O(7) bond length is 0.98 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(9) atom. The H(5)-O(9) bond length is 0.97 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(15) atom. The H(6)-O(15) bond length is 0.98 Å. In the seventh H site, H(7) is bonded in a single-bond geometry to one O(10) atom. The H(7)-O(10) bond length is 0.97 Å. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(16) atom. The H(8)-O(16) bond length is 0.98 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Li(1), one Li(16), one Li(19), one Li(2), one Li(6), and one H(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Li(1), one Li(15), one Li(19), one Li(2), one Li(7), and one H(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(19), one Li(6), one Li(7), one Li(8), and one Cu(4) atom. In the fourth O site, O(4) is bonded to one Li(10), one Li(12), one Li(2), one Li(6), one Li(7), and one Cu(1) atom to form corner-sharing OLi5Cu octahedra. The corner-sharing octahedral tilt angles range from 9-41°. In the fifth O site, O(5) is bonded to one Li(1), one Li(18), one Li(4), one Li(5), one Li(9), and one Cu(2) atom to form corner-sharing OLi5Cu octahedra. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Li(11), one Li(17), one Li(3), one Li(4), one Li(5), and one Cu(3) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Li(10), one Li(11), one Li(14), one Li(3), one Li(4), one Li(9), and one H(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Li(10), one Li(11), one Li(13), one Li(3), one Li(5), and one H(3) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Li(12), one Li(16), one Li(6), one Li(8), and one H(5) atom. In the tenth O site, O(10) is bonded in a 1-coordinate geometry to one Li(12), one Li(15), one Li(7), one Li(8), and one H(7) atom. In the eleventh O site, O(11) is bonded in a 6-coordinate geometry to one Li(1), one Li(15), one Li(16), one Li(19), one Li(8), and one Cu(2) atom. In the twelfth O site, O(12) is bonded to one Li(12), one Li(15), one Li(16), one Li(17), one Li(2), and one Cu(3) atom to form corner-sharing OLi5Cu octahedra. The corner-sharing octahedral tilt angles range from 24-31°. In the thirteenth O site, O(13) is bonded to one Li(13), one Li(14), one Li(18), one Li(9), and one Cu(4) atom to form corner-sharing OLi4Cu square pyramids. The corner-sharing octahedral tilt angles range from 27-34°. In the fourteenth O site, O(14) is bonded to one Li(10), one Li(11), one Li(13), one Li(14), one Li(3), and one Cu(1) atom to form distorted OLi5Cu octahedra that share corners with two equivalent O(4)Li5Cu octahedra and corners with two equivalent O(13)Li4Cu square pyramids. The corner-sharing octahedral tilt angles range from 9-41°. In the fifteenth O site, O(15) is bonded in a distorted single-bond geometry to one Li(11), one Li(13), one Li(17), one Li(18), one Li(3), one Li(5), and one H(6) atom. In the sixteenth O site, O(16) is bonded in a distorted single-bond geometry to one Li(11), one Li(14), one Li(17), one Li(3), one Li(4), and one H(8) atom.