Ba(BF4)(PF6) crystallizes in the hexagonal P-62m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to three equivalent F(2) and six equivalent F(4) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to three equivalent F(5) and six equivalent F(3) atoms. B(1) is bonded in a tetrahedral geometry to two equivalent F(4) and two equivalent F(5) atoms. P(1) is bonded in an octahedral geometry to one F(1), one F(2), and four equivalent F(3) atoms. There are five inequivalent F sites. In the first F site, F(5) is bonded in a distorted single-bond geometry to one Ba(2) and one B(1) atom. In the second F site, F(1) is bonded in a single-bond geometry to one P(1) atom. In the third F site, F(2) is bonded in a single-bond geometry to one Ba(1) and one P(1) atom. In the fourth F site, F(3) is bonded in a distorted single-bond geometry to one Ba(2) and one P(1) atom. In the fifth F site, F(4) is bonded in a distorted single-bond geometry to one Ba(1) and one B(1) atom.
Ba(BF4)(PF6) crystallizes in the hexagonal P-62m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to three equivalent F(2) and six equivalent F(4) atoms. All Ba(1)-F(2) bond lengths are 3.00 Å. All Ba(1)-F(4) bond lengths are 2.69 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to three equivalent F(5) and six equivalent F(3) atoms. All Ba(2)-F(5) bond lengths are 2.64 Å. All Ba(2)-F(3) bond lengths are 2.81 Å. B(1) is bonded in a tetrahedral geometry to two equivalent F(4) and two equivalent F(5) atoms. Both B(1)-F(4) bond lengths are 1.41 Å. Both B(1)-F(5) bond lengths are 1.42 Å. P(1) is bonded in an octahedral geometry to one F(1), one F(2), and four equivalent F(3) atoms. The P(1)-F(1) bond length is 1.61 Å. The P(1)-F(2) bond length is 1.63 Å. All P(1)-F(3) bond lengths are 1.65 Å. There are five inequivalent F sites. In the first F site, F(5) is bonded in a distorted single-bond geometry to one Ba(2) and one B(1) atom. In the second F site, F(1) is bonded in a single-bond geometry to one P(1) atom. In the third F site, F(2) is bonded in a single-bond geometry to one Ba(1) and one P(1) atom. In the fourth F site, F(3) is bonded in a distorted single-bond geometry to one Ba(2) and one P(1) atom. In the fifth F site, F(4) is bonded in a distorted single-bond geometry to one Ba(1) and one B(1) atom.