LiBaCoF6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form distorted LiF5 trigonal bipyramids that share corners with three equivalent Co(1)F6 octahedra and  an edgeedge with one Co(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-55°. Ba(1) is bonded in a 10-coordinate geometry to one F(5), one F(6), two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. Co(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form CoF6 octahedra that share corners with three equivalent Li(1)F5 trigonal bipyramids and  an edgeedge with one Li(1)F5 trigonal bipyramid. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Ba(1), and one Co(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Ba(1), and one Co(1) atom. In the third F site, F(3) is bonded in a distorted water-like geometry to one Li(1), two equivalent Ba(1), and one Co(1) atom. In the fourth F site, F(4) is bonded to one Li(1), two equivalent Ba(1), and one Co(1) atom to form distorted corner-sharing FBa2LiCo tetrahedra. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to one Ba(1) and one Co(1) atom. In the sixth F site, F(6) is bonded in a distorted bent 150 degrees geometry to one Li(1), one Ba(1), and one Co(1) atom.
LiBaCoF6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form distorted LiF5 trigonal bipyramids that share corners with three equivalent Co(1)F6 octahedra and  an edgeedge with one Co(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-55°. The Li(1)-F(1) bond length is 1.94 Å. The Li(1)-F(2) bond length is 2.23 Å. The Li(1)-F(3) bond length is 1.96 Å. The Li(1)-F(4) bond length is 2.01 Å. The Li(1)-F(6) bond length is 1.94 Å. Ba(1) is bonded in a 10-coordinate geometry to one F(5), one F(6), two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. The Ba(1)-F(5) bond length is 2.76 Å. The Ba(1)-F(6) bond length is 2.96 Å. There is one shorter (2.72 Å) and one longer (2.87 Å) Ba(1)-F(1) bond length. There is one shorter (2.66 Å) and one longer (3.01 Å) Ba(1)-F(2) bond length. There is one shorter (2.94 Å) and one longer (2.98 Å) Ba(1)-F(3) bond length. Both Ba(1)-F(4) bond lengths are 2.79 Å. Co(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form CoF6 octahedra that share corners with three equivalent Li(1)F5 trigonal bipyramids and  an edgeedge with one Li(1)F5 trigonal bipyramid. The Co(1)-F(1) bond length is 1.98 Å. The Co(1)-F(2) bond length is 1.96 Å. The Co(1)-F(3) bond length is 1.98 Å. The Co(1)-F(4) bond length is 2.01 Å. The Co(1)-F(5) bond length is 1.87 Å. The Co(1)-F(6) bond length is 1.86 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Ba(1), and one Co(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Ba(1), and one Co(1) atom. In the third F site, F(3) is bonded in a distorted water-like geometry to one Li(1), two equivalent Ba(1), and one Co(1) atom. In the fourth F site, F(4) is bonded to one Li(1), two equivalent Ba(1), and one Co(1) atom to form distorted corner-sharing FBa2LiCo tetrahedra. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to one Ba(1) and one Co(1) atom. In the sixth F site, F(6) is bonded in a distorted bent 150 degrees geometry to one Li(1), one Ba(1), and one Co(1) atom.