Li2ZrF6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(5), one F(6), and two equivalent F(4) atoms to form distorted corner-sharing LiF5 trigonal bipyramids. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(5), one F(6), two equivalent F(2), and two equivalent F(3) atoms. Zr(1) is bonded in a 8-coordinate geometry to one F(2), one F(4), one F(5), one F(6), two equivalent F(1), and two equivalent F(3) atoms. There are six inequivalent F sites. In the first F site, F(6) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Zr(1) atom. In the second F site, F(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Zr(1) atoms. In the third F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Zr(1) atom. In the fourth F site, F(3) is bonded to two equivalent Li(2) and two equivalent Zr(1) atoms to form distorted edge-sharing FLi2Zr2 trigonal pyramids. In the fifth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(1) and one Zr(1) atom. In the sixth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Zr(1) atom.
Li2ZrF6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(5), one F(6), and two equivalent F(4) atoms to form distorted corner-sharing LiF5 trigonal bipyramids. The Li(1)-F(1) bond length is 1.98 Å. The Li(1)-F(5) bond length is 1.92 Å. The Li(1)-F(6) bond length is 2.06 Å. There is one shorter (1.90 Å) and one longer (1.99 Å) Li(1)-F(4) bond length. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(5), one F(6), two equivalent F(2), and two equivalent F(3) atoms. The Li(2)-F(5) bond length is 2.17 Å. The Li(2)-F(6) bond length is 1.93 Å. There is one shorter (1.88 Å) and one longer (1.96 Å) Li(2)-F(2) bond length. There is one shorter (1.97 Å) and one longer (2.38 Å) Li(2)-F(3) bond length. Zr(1) is bonded in a 8-coordinate geometry to one F(2), one F(4), one F(5), one F(6), two equivalent F(1), and two equivalent F(3) atoms. The Zr(1)-F(2) bond length is 2.06 Å. The Zr(1)-F(4) bond length is 2.07 Å. The Zr(1)-F(5) bond length is 2.03 Å. The Zr(1)-F(6) bond length is 2.03 Å. There is one shorter (2.14 Å) and one longer (2.23 Å) Zr(1)-F(1) bond length. There is one shorter (2.11 Å) and one longer (2.38 Å) Zr(1)-F(3) bond length. There are six inequivalent F sites. In the first F site, F(6) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Zr(1) atom. In the second F site, F(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Zr(1) atoms. In the third F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Zr(1) atom. In the fourth F site, F(3) is bonded to two equivalent Li(2) and two equivalent Zr(1) atoms to form distorted edge-sharing FLi2Zr2 trigonal pyramids. In the fifth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(1) and one Zr(1) atom. In the sixth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Zr(1) atom.