LiCu4(PO4)3 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(4), and two equivalent O(8) atoms. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(12), one O(2), one O(6), and two equivalent O(11) atoms to form CuO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Cu(1)O5 trigonal bipyramid, and  an edgeedge with one Cu(4)O5 trigonal bipyramid. In the second Cu site, Cu(2) is bonded to one O(3), one O(5), one O(7), and two equivalent O(1) atoms to form distorted CuO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Cu(4)O5 trigonal bipyramid,  an edgeedge with one Cu(2)O5 square pyramid, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. In the third Cu site, Cu(3) is bonded to one O(10), one O(5), one O(7), and two equivalent O(9) atoms to form distorted CuO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Cu(2)O5 square pyramid, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. In the fourth Cu site, Cu(4) is bonded to one O(12), one O(3), one O(4), one O(6), and one O(8) atom to form CuO5 trigonal bipyramids that share  a cornercorner with one Cu(2)O5 square pyramid,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O5 square pyramid,  a cornercorner with one Cu(3)O5 trigonal bipyramid, corners with two equivalent Cu(1)O5 trigonal bipyramids, and corners with two equivalent Cu(4)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(10), one O(3), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cu(2)O5 square pyramids,  a cornercorner with one Cu(1)O5 trigonal bipyramid, corners with two equivalent Cu(3)O5 trigonal bipyramids, and corners with two equivalent Cu(4)O5 trigonal bipyramids. In the third P site, P(3) is bonded to one O(1), one O(11), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cu(2)O5 square pyramids,  a cornercorner with one Cu(4)O5 trigonal bipyramid, corners with two equivalent Cu(1)O5 trigonal bipyramids, and corners with two equivalent Cu(3)O5 trigonal bipyramids. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Cu(2) and one P(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Cu(2), one Cu(4), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Cu(4), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Cu(2), one Cu(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(4), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(3), and one P(2) atom. In the eighth O site, O(8) is bonded to two equivalent Li(1), one Cu(4), and one P(3) atom to form distorted edge-sharing OLi2CuP tetrahedra. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to two equivalent Cu(3) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Cu(3) and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to two equivalent Cu(1) and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(4), and one P(1) atom.
LiCu4(PO4)3 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(4), and two equivalent O(8) atoms. The Li(1)-O(2) bond length is 2.40 Å. The Li(1)-O(4) bond length is 2.55 Å. There is one shorter (2.30 Å) and one longer (2.49 Å) Li(1)-O(8) bond length. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(12), one O(2), one O(6), and two equivalent O(11) atoms to form CuO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Cu(1)O5 trigonal bipyramid, and  an edgeedge with one Cu(4)O5 trigonal bipyramid. The Cu(1)-O(12) bond length is 1.96 Å. The Cu(1)-O(2) bond length is 2.02 Å. The Cu(1)-O(6) bond length is 2.24 Å. There is one shorter (1.94 Å) and one longer (2.10 Å) Cu(1)-O(11) bond length. In the second Cu site, Cu(2) is bonded to one O(3), one O(5), one O(7), and two equivalent O(1) atoms to form distorted CuO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Cu(4)O5 trigonal bipyramid,  an edgeedge with one Cu(2)O5 square pyramid, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. The Cu(2)-O(3) bond length is 1.95 Å. The Cu(2)-O(5) bond length is 1.96 Å. The Cu(2)-O(7) bond length is 2.00 Å. There is one shorter (1.94 Å) and one longer (2.36 Å) Cu(2)-O(1) bond length. In the third Cu site, Cu(3) is bonded to one O(10), one O(5), one O(7), and two equivalent O(9) atoms to form distorted CuO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Cu(2)O5 square pyramid, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. The Cu(3)-O(10) bond length is 1.90 Å. The Cu(3)-O(5) bond length is 2.00 Å. The Cu(3)-O(7) bond length is 2.02 Å. There is one shorter (1.94 Å) and one longer (2.40 Å) Cu(3)-O(9) bond length. In the fourth Cu site, Cu(4) is bonded to one O(12), one O(3), one O(4), one O(6), and one O(8) atom to form CuO5 trigonal bipyramids that share  a cornercorner with one Cu(2)O5 square pyramid,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. The Cu(4)-O(12) bond length is 2.16 Å. The Cu(4)-O(3) bond length is 2.02 Å. The Cu(4)-O(4) bond length is 1.93 Å. The Cu(4)-O(6) bond length is 1.95 Å. The Cu(4)-O(8) bond length is 2.16 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O5 square pyramid,  a cornercorner with one Cu(3)O5 trigonal bipyramid, corners with two equivalent Cu(1)O5 trigonal bipyramids, and corners with two equivalent Cu(4)O5 trigonal bipyramids. The P(1)-O(12) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(10), one O(3), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cu(2)O5 square pyramids,  a cornercorner with one Cu(1)O5 trigonal bipyramid, corners with two equivalent Cu(3)O5 trigonal bipyramids, and corners with two equivalent Cu(4)O5 trigonal bipyramids. The P(2)-O(10) bond length is 1.50 Å. The P(2)-O(3) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(1), one O(11), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cu(2)O5 square pyramids,  a cornercorner with one Cu(4)O5 trigonal bipyramid, corners with two equivalent Cu(1)O5 trigonal bipyramids, and corners with two equivalent Cu(3)O5 trigonal bipyramids. The P(3)-O(1) bond length is 1.54 Å. The P(3)-O(11) bond length is 1.57 Å. The P(3)-O(8) bond length is 1.54 Å. The P(3)-O(9) bond length is 1.57 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Cu(2) and one P(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Cu(2), one Cu(4), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Cu(4), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Cu(2), one Cu(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(4), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(3), and one P(2) atom. In the eighth O site, O(8) is bonded to two equivalent Li(1), one Cu(4), and one P(3) atom to form distorted edge-sharing OLi2CuP tetrahedra. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to two equivalent Cu(3) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Cu(3) and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to two equivalent Cu(1) and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(4), and one P(1) atom.