PMo12 crystallizes in the trigonal R3 space group. There are eight inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 12-coordinate geometry to one Mo(2), one Mo(4), one Mo(7), two equivalent Mo(1), two equivalent Mo(3), two equivalent Mo(6), two equivalent Mo(8), and one P(2) atom. In the second Mo site, Mo(2) is bonded in a 11-coordinate geometry to one Mo(1), one Mo(7), one Mo(8), two equivalent Mo(3), two equivalent Mo(4), two equivalent Mo(5), and two equivalent Mo(6) atoms. In the third Mo site, Mo(3) is bonded in a 11-coordinate geometry to one Mo(4), one Mo(5), one Mo(6), two equivalent Mo(1), two equivalent Mo(2), two equivalent Mo(7), and two equivalent Mo(8) atoms. In the fourth Mo site, Mo(4) is bonded in a 1-coordinate geometry to one Mo(1), one Mo(3), one Mo(6), two equivalent Mo(2), two equivalent Mo(7), and one P(1) atom. In the fifth Mo site, Mo(5) is bonded in a 1-coordinate geometry to one Mo(3), one Mo(6), one Mo(8), two equivalent Mo(2), two equivalent Mo(7), and one P(1) atom. In the sixth Mo site, Mo(6) is bonded to one Mo(3), one Mo(4), one Mo(5), two equivalent Mo(1), two equivalent Mo(2), two equivalent Mo(7), two equivalent Mo(8), and one P(2) atom to form distorted MoMo11P cuboctahedra that share corners with two equivalent Mo(6)Mo11P cuboctahedra, corners with three equivalent Mo(7)Mo11P cuboctahedra, corners with two equivalent P(1)Mo6 octahedra, edges with two equivalent Mo(7)Mo11P cuboctahedra, edges with four equivalent Mo(6)Mo11P cuboctahedra, and faces with two equivalent Mo(7)Mo11P cuboctahedra. The corner-sharing octahedral tilt angles range from 50-58°. In the seventh Mo site, Mo(7) is bonded to one Mo(1), one Mo(2), one Mo(8), two equivalent Mo(3), two equivalent Mo(4), two equivalent Mo(5), two equivalent Mo(6), and one P(2) atom to form distorted MoMo11P cuboctahedra that share corners with two equivalent Mo(7)Mo11P cuboctahedra, corners with three equivalent Mo(6)Mo11P cuboctahedra,  a cornercorner with one P(1)Mo6 octahedra, edges with two equivalent Mo(6)Mo11P cuboctahedra, edges with four equivalent Mo(7)Mo11P cuboctahedra, faces with two equivalent Mo(6)Mo11P cuboctahedra, and  a faceface with one P(1)Mo6 octahedra. The corner-sharing octahedral tilt angles are 52°. In the eighth Mo site, Mo(8) is bonded in a 11-coordinate geometry to one Mo(2), one Mo(5), one Mo(7), two equivalent Mo(1), two equivalent Mo(3), two equivalent Mo(6), and two equivalent Mo(8) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to three equivalent Mo(4) and three equivalent Mo(5) atoms to form PMo6 octahedra that share corners with three equivalent Mo(7)Mo11P cuboctahedra, corners with six equivalent Mo(6)Mo11P cuboctahedra, and faces with three equivalent Mo(7)Mo11P cuboctahedra. In the second P site, P(2) is bonded in a distorted q6 geometry to three equivalent Mo(1), three equivalent Mo(6), and three equivalent Mo(7) atoms.
PMo12 crystallizes in the trigonal R3 space group. There are eight inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 12-coordinate geometry to one Mo(2), one Mo(4), one Mo(7), two equivalent Mo(1), two equivalent Mo(3), two equivalent Mo(6), two equivalent Mo(8), and one P(2) atom. The Mo(1)-Mo(2) bond length is 2.69 Å. The Mo(1)-Mo(4) bond length is 2.68 Å. The Mo(1)-Mo(7) bond length is 3.10 Å. Both Mo(1)-Mo(1) bond lengths are 2.83 Å. There is one shorter (2.79 Å) and one longer (3.19 Å) Mo(1)-Mo(3) bond length. There is one shorter (2.86 Å) and one longer (2.90 Å) Mo(1)-Mo(6) bond length. There is one shorter (2.64 Å) and one longer (2.82 Å) Mo(1)-Mo(8) bond length. The Mo(1)-P(2) bond length is 2.65 Å. In the second Mo site, Mo(2) is bonded in a 11-coordinate geometry to one Mo(1), one Mo(7), one Mo(8), two equivalent Mo(3), two equivalent Mo(4), two equivalent Mo(5), and two equivalent Mo(6) atoms. The Mo(2)-Mo(7) bond length is 3.14 Å. The Mo(2)-Mo(8) bond length is 2.81 Å. There is one shorter (2.58 Å) and one longer (2.82 Å) Mo(2)-Mo(3) bond length. There is one shorter (2.85 Å) and one longer (2.97 Å) Mo(2)-Mo(4) bond length. There is one shorter (2.67 Å) and one longer (3.02 Å) Mo(2)-Mo(5) bond length. There is one shorter (2.77 Å) and one longer (3.11 Å) Mo(2)-Mo(6) bond length. In the third Mo site, Mo(3) is bonded in a 11-coordinate geometry to one Mo(4), one Mo(5), one Mo(6), two equivalent Mo(1), two equivalent Mo(2), two equivalent Mo(7), and two equivalent Mo(8) atoms. The Mo(3)-Mo(4) bond length is 2.52 Å. The Mo(3)-Mo(5) bond length is 2.64 Å. The Mo(3)-Mo(6) bond length is 3.00 Å. There is one shorter (2.88 Å) and one longer (2.97 Å) Mo(3)-Mo(7) bond length. There is one shorter (2.76 Å) and one longer (3.07 Å) Mo(3)-Mo(8) bond length. In the fourth Mo site, Mo(4) is bonded in a 1-coordinate geometry to one Mo(1), one Mo(3), one Mo(6), two equivalent Mo(2), two equivalent Mo(7), and one P(1) atom. The Mo(4)-Mo(6) bond length is 2.68 Å. There is one shorter (2.75 Å) and one longer (2.91 Å) Mo(4)-Mo(7) bond length. The Mo(4)-P(1) bond length is 2.37 Å. In the fifth Mo site, Mo(5) is bonded in a 1-coordinate geometry to one Mo(3), one Mo(6), one Mo(8), two equivalent Mo(2), two equivalent Mo(7), and one P(1) atom. The Mo(5)-Mo(6) bond length is 2.71 Å. The Mo(5)-Mo(8) bond length is 2.72 Å. There is one shorter (2.86 Å) and one longer (2.98 Å) Mo(5)-Mo(7) bond length. The Mo(5)-P(1) bond length is 2.35 Å. In the sixth Mo site, Mo(6) is bonded to one Mo(3), one Mo(4), one Mo(5), two equivalent Mo(1), two equivalent Mo(2), two equivalent Mo(7), two equivalent Mo(8), and one P(2) atom to form distorted MoMo11P cuboctahedra that share corners with two equivalent Mo(6)Mo11P cuboctahedra, corners with three equivalent Mo(7)Mo11P cuboctahedra, corners with two equivalent P(1)Mo6 octahedra, edges with two equivalent Mo(7)Mo11P cuboctahedra, edges with four equivalent Mo(6)Mo11P cuboctahedra, and faces with two equivalent Mo(7)Mo11P cuboctahedra. The corner-sharing octahedral tilt angles range from 50-58°. There is one shorter (2.60 Å) and one longer (2.72 Å) Mo(6)-Mo(7) bond length. There is one shorter (2.82 Å) and one longer (3.01 Å) Mo(6)-Mo(8) bond length. The Mo(6)-P(2) bond length is 2.71 Å. In the seventh Mo site, Mo(7) is bonded to one Mo(1), one Mo(2), one Mo(8), two equivalent Mo(3), two equivalent Mo(4), two equivalent Mo(5), two equivalent Mo(6), and one P(2) atom to form distorted MoMo11P cuboctahedra that share corners with two equivalent Mo(7)Mo11P cuboctahedra, corners with three equivalent Mo(6)Mo11P cuboctahedra,  a cornercorner with one P(1)Mo6 octahedra, edges with two equivalent Mo(6)Mo11P cuboctahedra, edges with four equivalent Mo(7)Mo11P cuboctahedra, faces with two equivalent Mo(6)Mo11P cuboctahedra, and  a faceface with one P(1)Mo6 octahedra. The corner-sharing octahedral tilt angles are 52°. The Mo(7)-Mo(8) bond length is 2.87 Å. The Mo(7)-P(2) bond length is 2.71 Å. In the eighth Mo site, Mo(8) is bonded in a 11-coordinate geometry to one Mo(2), one Mo(5), one Mo(7), two equivalent Mo(1), two equivalent Mo(3), two equivalent Mo(6), and two equivalent Mo(8) atoms. Both Mo(8)-Mo(8) bond lengths are 2.77 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to three equivalent Mo(4) and three equivalent Mo(5) atoms to form PMo6 octahedra that share corners with three equivalent Mo(7)Mo11P cuboctahedra, corners with six equivalent Mo(6)Mo11P cuboctahedra, and faces with three equivalent Mo(7)Mo11P cuboctahedra. In the second P site, P(2) is bonded in a distorted q6 geometry to three equivalent Mo(1), three equivalent Mo(6), and three equivalent Mo(7) atoms.