Ni5(Mo2As3)6 crystallizes in the monoclinic C2/m space group. There are six inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 7-coordinate geometry to one Ni(1), one As(5), one As(7), two equivalent As(1), and two equivalent As(4) atoms. In the second Mo site, Mo(2) is bonded in a 7-coordinate geometry to one Ni(1), one As(4), one As(8), two equivalent As(2), and two equivalent As(5) atoms. In the third Mo site, Mo(3) is bonded in a 7-coordinate geometry to one Ni(2), one As(9), two equivalent As(3), and three equivalent As(6) atoms. In the fourth Mo site, Mo(4) is bonded in a 6-coordinate geometry to one As(1), two equivalent As(4), and three equivalent As(7) atoms. In the fifth Mo site, Mo(5) is bonded in a 7-coordinate geometry to one Ni(3), one As(2), one As(8), two equivalent As(5), and two equivalent As(9) atoms. In the sixth Mo site, Mo(6) is bonded in a 7-coordinate geometry to one Ni(3), one As(3), one As(9), two equivalent As(6), and two equivalent As(8) atoms. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one Mo(1), one Mo(2), one As(4), one As(5), two equivalent As(1), and two equivalent As(2) atoms to form distorted edge-sharing NiMo2As6 octahedra. In the second Ni site, Ni(2) is bonded to two equivalent Mo(3), two equivalent As(6), and four equivalent As(3) atoms to form distorted edge-sharing NiMo2As6 octahedra. In the third Ni site, Ni(3) is bonded in a 8-coordinate geometry to one Mo(5), one Mo(6), one As(2), one As(3), two equivalent As(8), and two equivalent As(9) atoms. There are nine inequivalent As sites. In the first As site, As(1) is bonded in a 5-coordinate geometry to one Mo(4), two equivalent Mo(1), and two equivalent Ni(1) atoms. In the second As site, As(2) is bonded in a 6-coordinate geometry to one Mo(5), two equivalent Mo(2), one Ni(3), and two equivalent Ni(1) atoms. In the third As site, As(3) is bonded in a 6-coordinate geometry to one Mo(6), two equivalent Mo(3), one Ni(3), and two equivalent Ni(2) atoms. In the fourth As site, As(4) is bonded in a 6-coordinate geometry to one Mo(2), two equivalent Mo(1), two equivalent Mo(4), and one Ni(1) atom. In the fifth As site, As(5) is bonded in a 6-coordinate geometry to one Mo(1), two equivalent Mo(2), two equivalent Mo(5), and one Ni(1) atom. In the sixth As site, As(6) is bonded in a 6-coordinate geometry to two equivalent Mo(6), three equivalent Mo(3), and one Ni(2) atom. In the seventh As site, As(7) is bonded in a 5-coordinate geometry to one Mo(1), three equivalent Mo(4), and one As(7) atom. In the eighth As site, As(8) is bonded in a 6-coordinate geometry to one Mo(2), one Mo(5), two equivalent Mo(6), and two equivalent Ni(3) atoms. In the ninth As site, As(9) is bonded in a 6-coordinate geometry to one Mo(3), one Mo(6), two equivalent Mo(5), and two equivalent Ni(3) atoms.
Ni5(Mo2As3)6 crystallizes in the monoclinic C2/m space group. There are six inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 7-coordinate geometry to one Ni(1), one As(5), one As(7), two equivalent As(1), and two equivalent As(4) atoms. The Mo(1)-Ni(1) bond length is 2.85 Å. The Mo(1)-As(5) bond length is 2.55 Å. The Mo(1)-As(7) bond length is 2.64 Å. Both Mo(1)-As(1) bond lengths are 2.61 Å. Both Mo(1)-As(4) bond lengths are 2.59 Å. In the second Mo site, Mo(2) is bonded in a 7-coordinate geometry to one Ni(1), one As(4), one As(8), two equivalent As(2), and two equivalent As(5) atoms. The Mo(2)-Ni(1) bond length is 2.82 Å. The Mo(2)-As(4) bond length is 2.50 Å. The Mo(2)-As(8) bond length is 2.60 Å. Both Mo(2)-As(2) bond lengths are 2.62 Å. Both Mo(2)-As(5) bond lengths are 2.56 Å. In the third Mo site, Mo(3) is bonded in a 7-coordinate geometry to one Ni(2), one As(9), two equivalent As(3), and three equivalent As(6) atoms. The Mo(3)-Ni(2) bond length is 2.85 Å. The Mo(3)-As(9) bond length is 2.58 Å. Both Mo(3)-As(3) bond lengths are 2.61 Å. There is one shorter (2.52 Å) and two longer (2.57 Å) Mo(3)-As(6) bond lengths. In the fourth Mo site, Mo(4) is bonded in a 6-coordinate geometry to one As(1), two equivalent As(4), and three equivalent As(7) atoms. The Mo(4)-As(1) bond length is 2.66 Å. Both Mo(4)-As(4) bond lengths are 2.59 Å. There are two shorter (2.54 Å) and one longer (2.63 Å) Mo(4)-As(7) bond length. In the fifth Mo site, Mo(5) is bonded in a 7-coordinate geometry to one Ni(3), one As(2), one As(8), two equivalent As(5), and two equivalent As(9) atoms. The Mo(5)-Ni(3) bond length is 2.77 Å. The Mo(5)-As(2) bond length is 2.63 Å. The Mo(5)-As(8) bond length is 2.52 Å. Both Mo(5)-As(5) bond lengths are 2.61 Å. Both Mo(5)-As(9) bond lengths are 2.57 Å. In the sixth Mo site, Mo(6) is bonded in a 7-coordinate geometry to one Ni(3), one As(3), one As(9), two equivalent As(6), and two equivalent As(8) atoms. The Mo(6)-Ni(3) bond length is 2.77 Å. The Mo(6)-As(3) bond length is 2.63 Å. The Mo(6)-As(9) bond length is 2.53 Å. Both Mo(6)-As(6) bond lengths are 2.59 Å. Both Mo(6)-As(8) bond lengths are 2.57 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one Mo(1), one Mo(2), one As(4), one As(5), two equivalent As(1), and two equivalent As(2) atoms to form distorted edge-sharing NiMo2As6 octahedra. The Ni(1)-As(4) bond length is 2.45 Å. The Ni(1)-As(5) bond length is 2.40 Å. Both Ni(1)-As(1) bond lengths are 2.47 Å. Both Ni(1)-As(2) bond lengths are 2.46 Å. In the second Ni site, Ni(2) is bonded to two equivalent Mo(3), two equivalent As(6), and four equivalent As(3) atoms to form distorted edge-sharing NiMo2As6 octahedra. Both Ni(2)-As(6) bond lengths are 2.42 Å. All Ni(2)-As(3) bond lengths are 2.48 Å. In the third Ni site, Ni(3) is bonded in a 8-coordinate geometry to one Mo(5), one Mo(6), one As(2), one As(3), two equivalent As(8), and two equivalent As(9) atoms. The Ni(3)-As(2) bond length is 2.62 Å. The Ni(3)-As(3) bond length is 2.63 Å. Both Ni(3)-As(8) bond lengths are 2.34 Å. Both Ni(3)-As(9) bond lengths are 2.35 Å. There are nine inequivalent As sites. In the first As site, As(1) is bonded in a 5-coordinate geometry to one Mo(4), two equivalent Mo(1), and two equivalent Ni(1) atoms. In the second As site, As(2) is bonded in a 6-coordinate geometry to one Mo(5), two equivalent Mo(2), one Ni(3), and two equivalent Ni(1) atoms. In the third As site, As(3) is bonded in a 6-coordinate geometry to one Mo(6), two equivalent Mo(3), one Ni(3), and two equivalent Ni(2) atoms. In the fourth As site, As(4) is bonded in a 6-coordinate geometry to one Mo(2), two equivalent Mo(1), two equivalent Mo(4), and one Ni(1) atom. In the fifth As site, As(5) is bonded in a 6-coordinate geometry to one Mo(1), two equivalent Mo(2), two equivalent Mo(5), and one Ni(1) atom. In the sixth As site, As(6) is bonded in a 6-coordinate geometry to two equivalent Mo(6), three equivalent Mo(3), and one Ni(2) atom. In the seventh As site, As(7) is bonded in a 5-coordinate geometry to one Mo(1), three equivalent Mo(4), and one As(7) atom. The As(7)-As(7) bond length is 2.89 Å. In the eighth As site, As(8) is bonded in a 6-coordinate geometry to one Mo(2), one Mo(5), two equivalent Mo(6), and two equivalent Ni(3) atoms. In the ninth As site, As(9) is bonded in a 6-coordinate geometry to one Mo(3), one Mo(6), two equivalent Mo(5), and two equivalent Ni(3) atoms.