Li4Cu4OCl10 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one Cl(2), one Cl(3), one Cl(4), and two equivalent Cl(1) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one Cl(1), one Cl(2), one Cl(4), and two equivalent Cl(3) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one Cl(2), one Cl(3), and one Cl(6) atom. In the second Cu site, Cu(2) is bonded in a 5-coordinate geometry to one O(1), one Cl(1), one Cl(2), one Cl(4), and one Cl(5) atom. O(1) is bonded to two equivalent Cu(1) and two equivalent Cu(2) atoms to form OCu4 tetrahedra that share corners with two equivalent Cl(1)Li3Cu trigonal pyramids and corners with two equivalent Cl(3)Li3Cu trigonal pyramids. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Li(2), two equivalent Li(1), and one Cu(2) atom to form distorted ClLi3Cu trigonal pyramids that share  a cornercorner with one O(1)Cu4 tetrahedra, corners with two equivalent Cl(1)Li3Cu trigonal pyramids, corners with two equivalent Cl(3)Li3Cu trigonal pyramids, and  an edgeedge with one Cl(3)Li3Cu trigonal pyramid. In the second Cl site, Cl(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Cu(1), and one Cu(2) atom. In the third Cl site, Cl(3) is bonded to one Li(1), two equivalent Li(2), and one Cu(1) atom to form distorted ClLi3Cu trigonal pyramids that share  a cornercorner with one O(1)Cu4 tetrahedra, corners with two equivalent Cl(1)Li3Cu trigonal pyramids, corners with two equivalent Cl(3)Li3Cu trigonal pyramids, and  an edgeedge with one Cl(1)Li3Cu trigonal pyramid. In the fourth Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one Cu(2) atom. In the fifth Cl site, Cl(5) is bonded in a 2-coordinate geometry to two equivalent Cu(2) atoms. In the sixth Cl site, Cl(6) is bonded in an L-shaped geometry to two equivalent Cu(1) atoms.
Li4Cu4OCl10 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one Cl(2), one Cl(3), one Cl(4), and two equivalent Cl(1) atoms. The Li(1)-Cl(2) bond length is 2.41 Å. The Li(1)-Cl(3) bond length is 2.79 Å. The Li(1)-Cl(4) bond length is 2.64 Å. There is one shorter (2.53 Å) and one longer (2.66 Å) Li(1)-Cl(1) bond length. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one Cl(1), one Cl(2), one Cl(4), and two equivalent Cl(3) atoms. The Li(2)-Cl(1) bond length is 2.79 Å. The Li(2)-Cl(2) bond length is 3.03 Å. The Li(2)-Cl(4) bond length is 2.49 Å. There is one shorter (2.61 Å) and one longer (2.77 Å) Li(2)-Cl(3) bond length. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one Cl(2), one Cl(3), and one Cl(6) atom. The Cu(1)-O(1) bond length is 2.00 Å. The Cu(1)-Cl(2) bond length is 2.23 Å. The Cu(1)-Cl(3) bond length is 2.25 Å. The Cu(1)-Cl(6) bond length is 2.26 Å. In the second Cu site, Cu(2) is bonded in a 5-coordinate geometry to one O(1), one Cl(1), one Cl(2), one Cl(4), and one Cl(5) atom. The Cu(2)-O(1) bond length is 1.91 Å. The Cu(2)-Cl(1) bond length is 2.27 Å. The Cu(2)-Cl(2) bond length is 2.78 Å. The Cu(2)-Cl(4) bond length is 2.32 Å. The Cu(2)-Cl(5) bond length is 2.39 Å. O(1) is bonded to two equivalent Cu(1) and two equivalent Cu(2) atoms to form OCu4 tetrahedra that share corners with two equivalent Cl(1)Li3Cu trigonal pyramids and corners with two equivalent Cl(3)Li3Cu trigonal pyramids. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Li(2), two equivalent Li(1), and one Cu(2) atom to form distorted ClLi3Cu trigonal pyramids that share  a cornercorner with one O(1)Cu4 tetrahedra, corners with two equivalent Cl(1)Li3Cu trigonal pyramids, corners with two equivalent Cl(3)Li3Cu trigonal pyramids, and  an edgeedge with one Cl(3)Li3Cu trigonal pyramid. In the second Cl site, Cl(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Cu(1), and one Cu(2) atom. In the third Cl site, Cl(3) is bonded to one Li(1), two equivalent Li(2), and one Cu(1) atom to form distorted ClLi3Cu trigonal pyramids that share  a cornercorner with one O(1)Cu4 tetrahedra, corners with two equivalent Cl(1)Li3Cu trigonal pyramids, corners with two equivalent Cl(3)Li3Cu trigonal pyramids, and  an edgeedge with one Cl(1)Li3Cu trigonal pyramid. In the fourth Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one Cu(2) atom. In the fifth Cl site, Cl(5) is bonded in a 2-coordinate geometry to two equivalent Cu(2) atoms. In the sixth Cl site, Cl(6) is bonded in an L-shaped geometry to two equivalent Cu(1) atoms.