Ba4P3HF24 crystallizes in the triclinic P-1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 4-coordinate geometry to one F(1), one F(3), and two equivalent F(2) atoms. In the second Ba site, Ba(2) is bonded in a 11-coordinate geometry to one F(1), one F(10), one F(11), one F(2), one F(5), one F(7), one F(8), two equivalent F(12), and two equivalent F(3) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded in an octahedral geometry to one F(4), one F(5), one F(6), one F(7), one F(8), and one F(9) atom. In the second P site, P(2) is bonded in an octahedral geometry to two equivalent F(10), two equivalent F(11), and two equivalent F(12) atoms. H(1) is bonded in a linear geometry to two equivalent F(1) atoms. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one H(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Ba(2) and two equivalent Ba(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Ba(1) and two equivalent Ba(2) atoms. In the fourth F site, F(4) is bonded in a single-bond geometry to one P(1) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one Ba(2) and one P(1) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one P(1) atom. In the seventh F site, F(7) is bonded in a single-bond geometry to one Ba(2) and one P(1) atom. In the eighth F site, F(8) is bonded in a distorted single-bond geometry to one Ba(2) and one P(1) atom. In the ninth F site, F(9) is bonded in a single-bond geometry to one P(1) atom. In the tenth F site, F(10) is bonded in a single-bond geometry to one Ba(2) and one P(2) atom. In the eleventh F site, F(11) is bonded in a single-bond geometry to one Ba(2) and one P(2) atom. In the twelfth F site, F(12) is bonded in a single-bond geometry to two equivalent Ba(2) and one P(2) atom.
Ba4P3HF24 crystallizes in the triclinic P-1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 4-coordinate geometry to one F(1), one F(3), and two equivalent F(2) atoms. The Ba(1)-F(1) bond length is 2.68 Å. The Ba(1)-F(3) bond length is 2.59 Å. There is one shorter (2.56 Å) and one longer (2.57 Å) Ba(1)-F(2) bond length. In the second Ba site, Ba(2) is bonded in a 11-coordinate geometry to one F(1), one F(10), one F(11), one F(2), one F(5), one F(7), one F(8), two equivalent F(12), and two equivalent F(3) atoms. The Ba(2)-F(1) bond length is 2.67 Å. The Ba(2)-F(10) bond length is 3.34 Å. The Ba(2)-F(11) bond length is 3.24 Å. The Ba(2)-F(2) bond length is 2.63 Å. The Ba(2)-F(5) bond length is 3.05 Å. The Ba(2)-F(7) bond length is 3.07 Å. The Ba(2)-F(8) bond length is 2.84 Å. There is one shorter (3.08 Å) and one longer (3.35 Å) Ba(2)-F(12) bond length. There is one shorter (2.55 Å) and one longer (2.58 Å) Ba(2)-F(3) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded in an octahedral geometry to one F(4), one F(5), one F(6), one F(7), one F(8), and one F(9) atom. The P(1)-F(4) bond length is 1.63 Å. The P(1)-F(5) bond length is 1.62 Å. The P(1)-F(6) bond length is 1.65 Å. The P(1)-F(7) bond length is 1.65 Å. The P(1)-F(8) bond length is 1.63 Å. The P(1)-F(9) bond length is 1.65 Å. In the second P site, P(2) is bonded in an octahedral geometry to two equivalent F(10), two equivalent F(11), and two equivalent F(12) atoms. Both P(2)-F(10) bond lengths are 1.64 Å. Both P(2)-F(11) bond lengths are 1.64 Å. Both P(2)-F(12) bond lengths are 1.64 Å. H(1) is bonded in a linear geometry to two equivalent F(1) atoms. Both H(1)-F(1) bond lengths are 1.16 Å. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one H(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Ba(2) and two equivalent Ba(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Ba(1) and two equivalent Ba(2) atoms. In the fourth F site, F(4) is bonded in a single-bond geometry to one P(1) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one Ba(2) and one P(1) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one P(1) atom. In the seventh F site, F(7) is bonded in a single-bond geometry to one Ba(2) and one P(1) atom. In the eighth F site, F(8) is bonded in a distorted single-bond geometry to one Ba(2) and one P(1) atom. In the ninth F site, F(9) is bonded in a single-bond geometry to one P(1) atom. In the tenth F site, F(10) is bonded in a single-bond geometry to one Ba(2) and one P(2) atom. In the eleventh F site, F(11) is bonded in a single-bond geometry to one Ba(2) and one P(2) atom. In the twelfth F site, F(12) is bonded in a single-bond geometry to two equivalent Ba(2) and one P(2) atom.