Ni3Si2 is beta Plutonium-derived structured and crystallizes in the orthorhombic Cmcm space group. There are six inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Ni(2), four equivalent Ni(6), two equivalent Si(2), and four equivalent Si(4) atoms to form face-sharing NiSi6Ni6 cuboctahedra. In the second Ni site, Ni(2) is bonded in a 13-coordinate geometry to one Ni(1), one Ni(2), one Ni(3), two equivalent Ni(5), two equivalent Ni(6), one Si(1), one Si(2), two equivalent Si(3), and two equivalent Si(4) atoms. In the third Ni site, Ni(3) is bonded in a 10-coordinate geometry to two equivalent Ni(2), two equivalent Ni(4), one Si(1), one Si(2), and four equivalent Si(3) atoms. In the fourth Ni site, Ni(4) is bonded in a 10-coordinate geometry to one Ni(3), one Ni(5), two equivalent Ni(6), one Si(1), one Si(4), and four equivalent Si(3) atoms. In the fifth Ni site, Ni(5) is bonded in a 3-coordinate geometry to one Ni(4), two equivalent Ni(2), four equivalent Ni(6), one Si(4), and four equivalent Si(3) atoms. In the sixth Ni site, Ni(6) is bonded in a 12-coordinate geometry to one Ni(1), one Ni(2), one Ni(4), two equivalent Ni(5), two equivalent Ni(6), one Si(2), two equivalent Si(3), and two equivalent Si(4) atoms. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded in a 5-coordinate geometry to one Ni(3), two equivalent Ni(2), and two equivalent Ni(4) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to one Ni(3), two equivalent Ni(1), two equivalent Ni(2), and four equivalent Ni(6) atoms. In the third Si site, Si(3) is bonded in a 8-coordinate geometry to one Ni(2), one Ni(3), two equivalent Ni(4), two equivalent Ni(5), and two equivalent Ni(6) atoms. In the fourth Si site, Si(4) is bonded in a 8-coordinate geometry to one Ni(4), one Ni(5), two equivalent Ni(1), two equivalent Ni(2), and four equivalent Ni(6) atoms.
Ni3Si2 is beta Plutonium-derived structured and crystallizes in the orthorhombic Cmcm space group. There are six inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Ni(2), four equivalent Ni(6), two equivalent Si(2), and four equivalent Si(4) atoms to form face-sharing NiSi6Ni6 cuboctahedra. Both Ni(1)-Ni(2) bond lengths are 2.55 Å. All Ni(1)-Ni(6) bond lengths are 2.48 Å. Both Ni(1)-Si(2) bond lengths are 2.39 Å. All Ni(1)-Si(4) bond lengths are 2.32 Å. In the second Ni site, Ni(2) is bonded in a 13-coordinate geometry to one Ni(1), one Ni(2), one Ni(3), two equivalent Ni(5), two equivalent Ni(6), one Si(1), one Si(2), two equivalent Si(3), and two equivalent Si(4) atoms. The Ni(2)-Ni(2) bond length is 2.59 Å. The Ni(2)-Ni(3) bond length is 2.66 Å. Both Ni(2)-Ni(5) bond lengths are 2.71 Å. Both Ni(2)-Ni(6) bond lengths are 2.57 Å. The Ni(2)-Si(1) bond length is 2.26 Å. The Ni(2)-Si(2) bond length is 2.30 Å. Both Ni(2)-Si(3) bond lengths are 2.28 Å. Both Ni(2)-Si(4) bond lengths are 2.71 Å. In the third Ni site, Ni(3) is bonded in a 10-coordinate geometry to two equivalent Ni(2), two equivalent Ni(4), one Si(1), one Si(2), and four equivalent Si(3) atoms. Both Ni(3)-Ni(4) bond lengths are 2.55 Å. The Ni(3)-Si(1) bond length is 2.24 Å. The Ni(3)-Si(2) bond length is 2.43 Å. All Ni(3)-Si(3) bond lengths are 2.37 Å. In the fourth Ni site, Ni(4) is bonded in a 10-coordinate geometry to one Ni(3), one Ni(5), two equivalent Ni(6), one Si(1), one Si(4), and four equivalent Si(3) atoms. The Ni(4)-Ni(5) bond length is 2.68 Å. Both Ni(4)-Ni(6) bond lengths are 2.52 Å. The Ni(4)-Si(1) bond length is 2.39 Å. The Ni(4)-Si(4) bond length is 2.51 Å. There are two shorter (2.28 Å) and two longer (2.63 Å) Ni(4)-Si(3) bond lengths. In the fifth Ni site, Ni(5) is bonded in a 3-coordinate geometry to one Ni(4), two equivalent Ni(2), four equivalent Ni(6), one Si(4), and four equivalent Si(3) atoms. There are two shorter (2.51 Å) and two longer (2.55 Å) Ni(5)-Ni(6) bond lengths. The Ni(5)-Si(4) bond length is 2.24 Å. There are two shorter (2.31 Å) and two longer (2.50 Å) Ni(5)-Si(3) bond lengths. In the sixth Ni site, Ni(6) is bonded in a 12-coordinate geometry to one Ni(1), one Ni(2), one Ni(4), two equivalent Ni(5), two equivalent Ni(6), one Si(2), two equivalent Si(3), and two equivalent Si(4) atoms. There is one shorter (2.61 Å) and one longer (2.67 Å) Ni(6)-Ni(6) bond length. The Ni(6)-Si(2) bond length is 2.49 Å. There is one shorter (2.28 Å) and one longer (2.40 Å) Ni(6)-Si(3) bond length. There is one shorter (2.32 Å) and one longer (2.38 Å) Ni(6)-Si(4) bond length. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded in a 5-coordinate geometry to one Ni(3), two equivalent Ni(2), and two equivalent Ni(4) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to one Ni(3), two equivalent Ni(1), two equivalent Ni(2), and four equivalent Ni(6) atoms. In the third Si site, Si(3) is bonded in a 8-coordinate geometry to one Ni(2), one Ni(3), two equivalent Ni(4), two equivalent Ni(5), and two equivalent Ni(6) atoms. In the fourth Si site, Si(4) is bonded in a 8-coordinate geometry to one Ni(4), one Ni(5), two equivalent Ni(1), two equivalent Ni(2), and four equivalent Ni(6) atoms.