Cs2NaTiF6 is (Cubic) Perovskite-derived structured and crystallizes in the trigonal P-3m1 space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to three equivalent F(2) and nine equivalent F(1) atoms to form CsF12 cuboctahedra that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with six equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Na(1)F6 octahedra,  a faceface with one Cs(3)F12 cuboctahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Na(2)F6 octahedra, and faces with four equivalent Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles are 1°. In the second Cs site, Cs(2) is bonded to three equivalent F(1), three equivalent F(3), and six equivalent F(2) atoms to form CsF12 cuboctahedra that share corners with three equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Cs(3)F12 cuboctahedra, corners with six equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with three equivalent Cs(3)F12 cuboctahedra,  a faceface with one Na(2)F6 octahedra,  a faceface with one Ti(2)F6 octahedra, faces with three equivalent Na(1)F6 octahedra, and faces with three equivalent Ti(1)F6 octahedra. In the third Cs site, Cs(3) is bonded to three equivalent F(2) and nine equivalent F(3) atoms to form distorted CsF12 cuboctahedra that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with six equivalent Cs(3)F12 cuboctahedra, corners with three equivalent Ti(1)F6 octahedra,  a faceface with one Cs(1)F12 cuboctahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Cs(3)F12 cuboctahedra, faces with three equivalent Ti(2)F6 octahedra, and faces with four equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles are 11°. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form distorted NaF6 octahedra that share corners with three equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Ti(2)F6 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(3)F12 cuboctahedra, and  a faceface with one Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the second Na site, Na(2) is bonded to six equivalent F(1) atoms to form NaF6 octahedra that share corners with six equivalent Ti(1)F6 octahedra, faces with two equivalent Cs(2)F12 cuboctahedra, and faces with six equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 1°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form TiF6 octahedra that share corners with three equivalent Cs(3)F12 cuboctahedra, corners with three equivalent Na(2)F6 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra, and  a faceface with one Na(1)F6 octahedra. The corner-sharing octahedral tilt angles are 1°. In the second Ti site, Ti(2) is bonded to six equivalent F(3) atoms to form TiF6 octahedra that share corners with six equivalent Na(1)F6 octahedra, faces with two equivalent Cs(2)F12 cuboctahedra, and faces with six equivalent Cs(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 5°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Cs(2), three equivalent Cs(1), one Na(2), and one Ti(1) atom. In the second F site, F(2) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), one Na(1), and one Ti(1) atom. In the third F site, F(3) is bonded in a distorted linear geometry to one Cs(2), three equivalent Cs(3), one Na(1), and one Ti(2) atom.
Cs2NaTiF6 is (Cubic) Perovskite-derived structured and crystallizes in the trigonal P-3m1 space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to three equivalent F(2) and nine equivalent F(1) atoms to form CsF12 cuboctahedra that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with six equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Na(1)F6 octahedra,  a faceface with one Cs(3)F12 cuboctahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Na(2)F6 octahedra, and faces with four equivalent Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles are 1°. All Cs(1)-F(2) bond lengths are 3.12 Å. There are three shorter (3.19 Å) and six longer (3.21 Å) Cs(1)-F(1) bond lengths. In the second Cs site, Cs(2) is bonded to three equivalent F(1), three equivalent F(3), and six equivalent F(2) atoms to form CsF12 cuboctahedra that share corners with three equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Cs(3)F12 cuboctahedra, corners with six equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with three equivalent Cs(3)F12 cuboctahedra,  a faceface with one Na(2)F6 octahedra,  a faceface with one Ti(2)F6 octahedra, faces with three equivalent Na(1)F6 octahedra, and faces with three equivalent Ti(1)F6 octahedra. All Cs(2)-F(1) bond lengths are 3.16 Å. All Cs(2)-F(3) bond lengths are 3.20 Å. All Cs(2)-F(2) bond lengths are 3.22 Å. In the third Cs site, Cs(3) is bonded to three equivalent F(2) and nine equivalent F(3) atoms to form distorted CsF12 cuboctahedra that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with six equivalent Cs(3)F12 cuboctahedra, corners with three equivalent Ti(1)F6 octahedra,  a faceface with one Cs(1)F12 cuboctahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Cs(3)F12 cuboctahedra, faces with three equivalent Ti(2)F6 octahedra, and faces with four equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles are 11°. All Cs(3)-F(2) bond lengths are 3.17 Å. There are six shorter (3.25 Å) and three longer (3.39 Å) Cs(3)-F(3) bond lengths. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form distorted NaF6 octahedra that share corners with three equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Ti(2)F6 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(3)F12 cuboctahedra, and  a faceface with one Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles are 5°. All Na(1)-F(2) bond lengths are 2.41 Å. All Na(1)-F(3) bond lengths are 2.30 Å. In the second Na site, Na(2) is bonded to six equivalent F(1) atoms to form NaF6 octahedra that share corners with six equivalent Ti(1)F6 octahedra, faces with two equivalent Cs(2)F12 cuboctahedra, and faces with six equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 1°. All Na(2)-F(1) bond lengths are 2.43 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form TiF6 octahedra that share corners with three equivalent Cs(3)F12 cuboctahedra, corners with three equivalent Na(2)F6 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra, and  a faceface with one Na(1)F6 octahedra. The corner-sharing octahedral tilt angles are 1°. All Ti(1)-F(1) bond lengths are 2.00 Å. All Ti(1)-F(2) bond lengths are 2.01 Å. In the second Ti site, Ti(2) is bonded to six equivalent F(3) atoms to form TiF6 octahedra that share corners with six equivalent Na(1)F6 octahedra, faces with two equivalent Cs(2)F12 cuboctahedra, and faces with six equivalent Cs(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 5°. All Ti(2)-F(3) bond lengths are 2.01 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Cs(2), three equivalent Cs(1), one Na(2), and one Ti(1) atom. In the second F site, F(2) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), one Na(1), and one Ti(1) atom. In the third F site, F(3) is bonded in a distorted linear geometry to one Cs(2), three equivalent Cs(3), one Na(1), and one Ti(2) atom.