ZnP2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one P(2), one P(4), and two equivalent P(3) atoms to form ZnP4 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(2)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with two equivalent P(4)Zn2P2 tetrahedra. In the second Zn site, Zn(2) is bonded to one P(2), one P(4), and two equivalent P(1) atoms to form ZnP4 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(2)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with two equivalent P(4)Zn2P2 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to two equivalent Zn(2), one P(2), and one P(4) atom to form distorted PZn2P2 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(2)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with two equivalent P(4)Zn2P2 tetrahedra. In the second P site, P(2) is bonded to one Zn(1), one Zn(2), one P(1), and one P(3) atom to form distorted PZn2P2 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with four equivalent P(4)Zn2P2 tetrahedra. In the third P site, P(3) is bonded to two equivalent Zn(1), one P(2), and one P(4) atom to form distorted PZn2P2 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(2)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with two equivalent P(4)Zn2P2 tetrahedra. In the fourth P site, P(4) is bonded to one Zn(1), one Zn(2), one P(1), and one P(3) atom to form distorted PZn2P2 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with four equivalent P(2)Zn2P2 tetrahedra.
ZnP2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one P(2), one P(4), and two equivalent P(3) atoms to form ZnP4 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(2)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with two equivalent P(4)Zn2P2 tetrahedra. The Zn(1)-P(2) bond length is 2.41 Å. The Zn(1)-P(4) bond length is 2.42 Å. There is one shorter (2.35 Å) and one longer (2.41 Å) Zn(1)-P(3) bond length. In the second Zn site, Zn(2) is bonded to one P(2), one P(4), and two equivalent P(1) atoms to form ZnP4 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(2)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with two equivalent P(4)Zn2P2 tetrahedra. The Zn(2)-P(2) bond length is 2.35 Å. The Zn(2)-P(4) bond length is 2.38 Å. Both Zn(2)-P(1) bond lengths are 2.33 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to two equivalent Zn(2), one P(2), and one P(4) atom to form distorted PZn2P2 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(2)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with two equivalent P(4)Zn2P2 tetrahedra. The P(1)-P(2) bond length is 2.18 Å. The P(1)-P(4) bond length is 2.19 Å. In the second P site, P(2) is bonded to one Zn(1), one Zn(2), one P(1), and one P(3) atom to form distorted PZn2P2 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with four equivalent P(4)Zn2P2 tetrahedra. The P(2)-P(3) bond length is 2.21 Å. In the third P site, P(3) is bonded to two equivalent Zn(1), one P(2), and one P(4) atom to form distorted PZn2P2 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(2)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with two equivalent P(4)Zn2P2 tetrahedra. The P(3)-P(4) bond length is 2.21 Å. In the fourth P site, P(4) is bonded to one Zn(1), one Zn(2), one P(1), and one P(3) atom to form distorted PZn2P2 tetrahedra that share corners with two equivalent Zn(1)P4 tetrahedra, corners with two equivalent Zn(2)P4 tetrahedra, corners with two equivalent P(1)Zn2P2 tetrahedra, corners with two equivalent P(3)Zn2P2 tetrahedra, and corners with four equivalent P(2)Zn2P2 tetrahedra.