Hf3P2 is Stibnite structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 5-coordinate geometry to two equivalent P(1) and three equivalent P(2) atoms. In the second Hf site, Hf(2) is bonded to two equivalent P(2) and three equivalent P(1) atoms to form edge-sharing HfP5 square pyramids. In the third Hf site, Hf(3) is bonded in a 5-coordinate geometry to two equivalent P(1) and three equivalent P(2) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent Hf(1), two equivalent Hf(3), and three equivalent Hf(2) atoms to form a mixture of distorted corner and edge-sharing PHf7 pentagonal bipyramids. In the second P site, P(2) is bonded in a 8-coordinate geometry to two equivalent Hf(2), three equivalent Hf(1), and three equivalent Hf(3) atoms.
Hf3P2 is Stibnite structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 5-coordinate geometry to two equivalent P(1) and three equivalent P(2) atoms. There is one shorter (2.62 Å) and one longer (2.74 Å) Hf(1)-P(1) bond length. There are two shorter (2.69 Å) and one longer (3.06 Å) Hf(1)-P(2) bond length. In the second Hf site, Hf(2) is bonded to two equivalent P(2) and three equivalent P(1) atoms to form edge-sharing HfP5 square pyramids. Both Hf(2)-P(2) bond lengths are 2.65 Å. There is one shorter (2.59 Å) and two longer (2.61 Å) Hf(2)-P(1) bond lengths. In the third Hf site, Hf(3) is bonded in a 5-coordinate geometry to two equivalent P(1) and three equivalent P(2) atoms. Both Hf(3)-P(1) bond lengths are 2.63 Å. There are two shorter (2.64 Å) and one longer (2.73 Å) Hf(3)-P(2) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent Hf(1), two equivalent Hf(3), and three equivalent Hf(2) atoms to form a mixture of distorted corner and edge-sharing PHf7 pentagonal bipyramids. In the second P site, P(2) is bonded in a 8-coordinate geometry to two equivalent Hf(2), three equivalent Hf(1), and three equivalent Hf(3) atoms.