Zr24P8H crystallizes in the monoclinic P2 space group. There are twelve inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a distorted bent 150 degrees geometry to one P(3) and one P(4) atom. In the second Zr site, Zr(2) is bonded in a distorted bent 150 degrees geometry to one P(3) and one P(4) atom. In the third Zr site, Zr(3) is bonded in a 1-coordinate geometry to one P(1), one P(2), and one H(1) atom. In the fourth Zr site, Zr(4) is bonded in a distorted single-bond geometry to one P(1), one P(2), and one H(1) atom. In the fifth Zr site, Zr(5) is bonded in a distorted see-saw-like geometry to two equivalent P(1) and two equivalent P(4) atoms. In the sixth Zr site, Zr(6) is bonded in a distorted see-saw-like geometry to two equivalent P(2) and two equivalent P(3) atoms. In the seventh Zr site, Zr(7) is bonded in a distorted see-saw-like geometry to two equivalent P(2) and two equivalent P(3) atoms. In the eighth Zr site, Zr(8) is bonded in a distorted see-saw-like geometry to two equivalent P(1) and two equivalent P(4) atoms. In the ninth Zr site, Zr(9) is bonded in a 3-coordinate geometry to one P(1), one P(3), and one P(4) atom. In the tenth Zr site, Zr(10) is bonded in a 3-coordinate geometry to one P(2), one P(3), and one P(4) atom. In the eleventh Zr site, Zr(11) is bonded in a 3-coordinate geometry to one P(1), one P(2), and one P(3) atom. In the twelfth Zr site, Zr(12) is bonded in a 3-coordinate geometry to one P(1), one P(2), and one P(4) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one Zr(11), one Zr(12), one Zr(3), one Zr(4), one Zr(9), two equivalent Zr(5), and two equivalent Zr(8) atoms. In the second P site, P(2) is bonded in a 9-coordinate geometry to one Zr(10), one Zr(11), one Zr(12), one Zr(3), one Zr(4), two equivalent Zr(6), and two equivalent Zr(7) atoms. In the third P site, P(3) is bonded in a 9-coordinate geometry to one Zr(1), one Zr(10), one Zr(11), one Zr(2), one Zr(9), two equivalent Zr(6), and two equivalent Zr(7) atoms. In the fourth P site, P(4) is bonded in a 9-coordinate geometry to one Zr(1), one Zr(10), one Zr(12), one Zr(2), one Zr(9), two equivalent Zr(5), and two equivalent Zr(8) atoms. H(1) is bonded in a tetrahedral geometry to two equivalent Zr(3) and two equivalent Zr(4) atoms.
Zr24P8H crystallizes in the monoclinic P2 space group. There are twelve inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a distorted bent 150 degrees geometry to one P(3) and one P(4) atom. The Zr(1)-P(3) bond length is 2.74 Å. The Zr(1)-P(4) bond length is 2.78 Å. In the second Zr site, Zr(2) is bonded in a distorted bent 150 degrees geometry to one P(3) and one P(4) atom. The Zr(2)-P(3) bond length is 2.79 Å. The Zr(2)-P(4) bond length is 2.74 Å. In the third Zr site, Zr(3) is bonded in a 1-coordinate geometry to one P(1), one P(2), and one H(1) atom. The Zr(3)-P(1) bond length is 2.72 Å. The Zr(3)-P(2) bond length is 2.79 Å. The Zr(3)-H(1) bond length is 2.05 Å. In the fourth Zr site, Zr(4) is bonded in a distorted single-bond geometry to one P(1), one P(2), and one H(1) atom. The Zr(4)-P(1) bond length is 2.77 Å. The Zr(4)-P(2) bond length is 2.74 Å. The Zr(4)-H(1) bond length is 2.05 Å. In the fifth Zr site, Zr(5) is bonded in a distorted see-saw-like geometry to two equivalent P(1) and two equivalent P(4) atoms. There is one shorter (2.76 Å) and one longer (2.85 Å) Zr(5)-P(1) bond length. There is one shorter (2.76 Å) and one longer (2.77 Å) Zr(5)-P(4) bond length. In the sixth Zr site, Zr(6) is bonded in a distorted see-saw-like geometry to two equivalent P(2) and two equivalent P(3) atoms. There is one shorter (2.76 Å) and one longer (2.85 Å) Zr(6)-P(2) bond length. Both Zr(6)-P(3) bond lengths are 2.77 Å. In the seventh Zr site, Zr(7) is bonded in a distorted see-saw-like geometry to two equivalent P(2) and two equivalent P(3) atoms. There is one shorter (2.76 Å) and one longer (2.78 Å) Zr(7)-P(2) bond length. There is one shorter (2.77 Å) and one longer (2.85 Å) Zr(7)-P(3) bond length. In the eighth Zr site, Zr(8) is bonded in a distorted see-saw-like geometry to two equivalent P(1) and two equivalent P(4) atoms. There is one shorter (2.76 Å) and one longer (2.77 Å) Zr(8)-P(1) bond length. There is one shorter (2.76 Å) and one longer (2.85 Å) Zr(8)-P(4) bond length. In the ninth Zr site, Zr(9) is bonded in a 3-coordinate geometry to one P(1), one P(3), and one P(4) atom. The Zr(9)-P(1) bond length is 2.88 Å. The Zr(9)-P(3) bond length is 2.70 Å. The Zr(9)-P(4) bond length is 2.82 Å. In the tenth Zr site, Zr(10) is bonded in a 3-coordinate geometry to one P(2), one P(3), and one P(4) atom. The Zr(10)-P(2) bond length is 2.88 Å. The Zr(10)-P(3) bond length is 2.82 Å. The Zr(10)-P(4) bond length is 2.69 Å. In the eleventh Zr site, Zr(11) is bonded in a 3-coordinate geometry to one P(1), one P(2), and one P(3) atom. The Zr(11)-P(1) bond length is 2.70 Å. The Zr(11)-P(2) bond length is 2.82 Å. The Zr(11)-P(3) bond length is 2.86 Å. In the twelfth Zr site, Zr(12) is bonded in a 3-coordinate geometry to one P(1), one P(2), and one P(4) atom. The Zr(12)-P(1) bond length is 2.84 Å. The Zr(12)-P(2) bond length is 2.70 Å. The Zr(12)-P(4) bond length is 2.86 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one Zr(11), one Zr(12), one Zr(3), one Zr(4), one Zr(9), two equivalent Zr(5), and two equivalent Zr(8) atoms. In the second P site, P(2) is bonded in a 9-coordinate geometry to one Zr(10), one Zr(11), one Zr(12), one Zr(3), one Zr(4), two equivalent Zr(6), and two equivalent Zr(7) atoms. In the third P site, P(3) is bonded in a 9-coordinate geometry to one Zr(1), one Zr(10), one Zr(11), one Zr(2), one Zr(9), two equivalent Zr(6), and two equivalent Zr(7) atoms. In the fourth P site, P(4) is bonded in a 9-coordinate geometry to one Zr(1), one Zr(10), one Zr(12), one Zr(2), one Zr(9), two equivalent Zr(5), and two equivalent Zr(8) atoms. H(1) is bonded in a tetrahedral geometry to two equivalent Zr(3) and two equivalent Zr(4) atoms.