Li3CuPO5 is Stannite-like structured and crystallizes in the orthorhombic Pna2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(2), one O(5), and two equivalent O(3) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Cu(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and corners with four equivalent P(1)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Cu(1)O4 tetrahedra. Cu(1) is bonded to one O(4), one O(5), and two equivalent O(1) atoms to form CuO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with four equivalent Li(3)O4 tetrahedra. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), and two equivalent Cu(1) atoms to form OLi2Cu2 tetrahedra that share  a cornercorner with one O(3)Li3P tetrahedra, corners with two equivalent O(1)Li2Cu2 tetrahedra, corners with two equivalent O(2)Li3P tetrahedra, corners with three equivalent O(5)Li2CuP tetrahedra, and corners with four equivalent O(4)Li2CuP trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and one P(1) atom to form OLi3P tetrahedra that share corners with two equivalent O(1)Li2Cu2 tetrahedra, corners with three equivalent O(5)Li2CuP tetrahedra, corners with four equivalent O(3)Li3P tetrahedra, and corners with three equivalent O(4)Li2CuP trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), and one P(1) atom to form distorted OLi3P tetrahedra that share  a cornercorner with one O(1)Li2Cu2 tetrahedra, corners with two equivalent O(3)Li3P tetrahedra, corners with four equivalent O(5)Li2CuP tetrahedra, corners with four equivalent O(2)Li3P tetrahedra, and  a cornercorner with one O(4)Li2CuP trigonal pyramid. In the fourth O site, O(4) is bonded to two equivalent Li(3), one Cu(1), and one P(1) atom to form distorted OLi2CuP trigonal pyramids that share  a cornercorner with one O(3)Li3P tetrahedra, corners with two equivalent O(5)Li2CuP tetrahedra, corners with three equivalent O(2)Li3P tetrahedra, corners with four equivalent O(1)Li2Cu2 tetrahedra, and corners with two equivalent O(4)Li2CuP trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Cu(1), and one P(1) atom to form distorted OLi2CuP tetrahedra that share corners with three equivalent O(1)Li2Cu2 tetrahedra, corners with three equivalent O(2)Li3P tetrahedra, corners with four equivalent O(3)Li3P tetrahedra, and corners with two equivalent O(4)Li2CuP trigonal pyramids.
Li3CuPO5 is Stannite-like structured and crystallizes in the orthorhombic Pna2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. The Li(1)-O(1) bond length is 1.91 Å. The Li(1)-O(2) bond length is 2.04 Å. The Li(1)-O(3) bond length is 2.04 Å. The Li(1)-O(5) bond length is 2.00 Å. In the second Li site, Li(2) is bonded to one O(2), one O(5), and two equivalent O(3) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Cu(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and corners with four equivalent P(1)O4 tetrahedra. The Li(2)-O(2) bond length is 1.99 Å. The Li(2)-O(5) bond length is 2.00 Å. There is one shorter (2.02 Å) and one longer (2.03 Å) Li(2)-O(3) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Cu(1)O4 tetrahedra. The Li(3)-O(1) bond length is 1.96 Å. The Li(3)-O(2) bond length is 2.06 Å. There is one shorter (2.05 Å) and one longer (2.07 Å) Li(3)-O(4) bond length. Cu(1) is bonded to one O(4), one O(5), and two equivalent O(1) atoms to form CuO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with four equivalent Li(3)O4 tetrahedra. The Cu(1)-O(4) bond length is 2.14 Å. The Cu(1)-O(5) bond length is 2.15 Å. There is one shorter (1.84 Å) and one longer (1.86 Å) Cu(1)-O(1) bond length. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.57 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), and two equivalent Cu(1) atoms to form OLi2Cu2 tetrahedra that share  a cornercorner with one O(3)Li3P tetrahedra, corners with two equivalent O(1)Li2Cu2 tetrahedra, corners with two equivalent O(2)Li3P tetrahedra, corners with three equivalent O(5)Li2CuP tetrahedra, and corners with four equivalent O(4)Li2CuP trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and one P(1) atom to form OLi3P tetrahedra that share corners with two equivalent O(1)Li2Cu2 tetrahedra, corners with three equivalent O(5)Li2CuP tetrahedra, corners with four equivalent O(3)Li3P tetrahedra, and corners with three equivalent O(4)Li2CuP trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), and one P(1) atom to form distorted OLi3P tetrahedra that share  a cornercorner with one O(1)Li2Cu2 tetrahedra, corners with two equivalent O(3)Li3P tetrahedra, corners with four equivalent O(5)Li2CuP tetrahedra, corners with four equivalent O(2)Li3P tetrahedra, and  a cornercorner with one O(4)Li2CuP trigonal pyramid. In the fourth O site, O(4) is bonded to two equivalent Li(3), one Cu(1), and one P(1) atom to form distorted OLi2CuP trigonal pyramids that share  a cornercorner with one O(3)Li3P tetrahedra, corners with two equivalent O(5)Li2CuP tetrahedra, corners with three equivalent O(2)Li3P tetrahedra, corners with four equivalent O(1)Li2Cu2 tetrahedra, and corners with two equivalent O(4)Li2CuP trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Cu(1), and one P(1) atom to form distorted OLi2CuP tetrahedra that share corners with three equivalent O(1)Li2Cu2 tetrahedra, corners with three equivalent O(2)Li3P tetrahedra, corners with four equivalent O(3)Li3P tetrahedra, and corners with two equivalent O(4)Li2CuP trigonal pyramids.