Ba2TiOF6 crystallizes in the monoclinic Cc space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one F(3), one F(5), two equivalent F(1), two equivalent F(2), two equivalent F(4), and two equivalent F(6) atoms. In the second Ba site, Ba(2) is bonded in a 11-coordinate geometry to two equivalent O(1), one F(2), one F(3), one F(4), two equivalent F(1), two equivalent F(5), and two equivalent F(6) atoms. Ti(1) is bonded to two equivalent O(1), one F(2), one F(3), one F(4), and one F(5) atom to form corner-sharing TiO2F4 octahedra. The corner-sharing octahedral tilt angles are 36°. O(1) is bonded in a 2-coordinate geometry to two equivalent Ba(2) and two equivalent Ti(1) atoms. There are six inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Ba(1) and two equivalent Ba(2) atoms to form a mixture of edge, corner, and face-sharing FBa4 trigonal pyramids. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(1), and one Ti(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one Ti(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(1), and one Ti(1) atom. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(2), and one Ti(1) atom. In the sixth F site, F(6) is bonded to two equivalent Ba(1) and two equivalent Ba(2) atoms to form a mixture of edge, corner, and face-sharing FBa4 tetrahedra.
Ba2TiOF6 crystallizes in the monoclinic Cc space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one F(3), one F(5), two equivalent F(1), two equivalent F(2), two equivalent F(4), and two equivalent F(6) atoms. The Ba(1)-F(3) bond length is 2.81 Å. The Ba(1)-F(5) bond length is 2.89 Å. There is one shorter (2.77 Å) and one longer (2.81 Å) Ba(1)-F(1) bond length. There is one shorter (2.75 Å) and one longer (3.07 Å) Ba(1)-F(2) bond length. There is one shorter (2.84 Å) and one longer (2.85 Å) Ba(1)-F(4) bond length. There is one shorter (2.69 Å) and one longer (2.73 Å) Ba(1)-F(6) bond length. In the second Ba site, Ba(2) is bonded in a 11-coordinate geometry to two equivalent O(1), one F(2), one F(3), one F(4), two equivalent F(1), two equivalent F(5), and two equivalent F(6) atoms. There is one shorter (2.96 Å) and one longer (3.29 Å) Ba(2)-O(1) bond length. The Ba(2)-F(2) bond length is 2.92 Å. The Ba(2)-F(3) bond length is 2.88 Å. The Ba(2)-F(4) bond length is 2.93 Å. There is one shorter (2.65 Å) and one longer (2.77 Å) Ba(2)-F(1) bond length. There is one shorter (2.95 Å) and one longer (3.09 Å) Ba(2)-F(5) bond length. There is one shorter (2.63 Å) and one longer (2.85 Å) Ba(2)-F(6) bond length. Ti(1) is bonded to two equivalent O(1), one F(2), one F(3), one F(4), and one F(5) atom to form corner-sharing TiO2F4 octahedra. The corner-sharing octahedral tilt angles are 36°. There is one shorter (1.74 Å) and one longer (2.11 Å) Ti(1)-O(1) bond length. The Ti(1)-F(2) bond length is 1.96 Å. The Ti(1)-F(3) bond length is 1.92 Å. The Ti(1)-F(4) bond length is 1.99 Å. The Ti(1)-F(5) bond length is 1.93 Å. O(1) is bonded in a 2-coordinate geometry to two equivalent Ba(2) and two equivalent Ti(1) atoms. There are six inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Ba(1) and two equivalent Ba(2) atoms to form a mixture of edge, corner, and face-sharing FBa4 trigonal pyramids. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(1), and one Ti(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one Ti(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(1), and one Ti(1) atom. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(2), and one Ti(1) atom. In the sixth F site, F(6) is bonded to two equivalent Ba(1) and two equivalent Ba(2) atoms to form a mixture of edge, corner, and face-sharing FBa4 tetrahedra.