Ni5Ge3 crystallizes in the monoclinic C2 space group. There are five inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 12-coordinate geometry to one Ni(1), one Ni(3), two equivalent Ni(4), two equivalent Ni(5), one Ge(1), one Ge(3), two equivalent Ge(2), and two equivalent Ge(4) atoms. In the second Ni site, Ni(2) is bonded in a 12-coordinate geometry to one Ni(2), one Ni(3), two equivalent Ni(4), two equivalent Ni(5), one Ge(1), one Ge(3), two equivalent Ge(2), and two equivalent Ge(4) atoms. In the third Ni site, Ni(3) is bonded to one Ni(1), one Ni(2), two equivalent Ni(4), two equivalent Ni(5), one Ge(1), one Ge(3), two equivalent Ge(2), and two equivalent Ge(4) atoms to form a mixture of distorted edge and corner-sharing NiNi6Ge6 cuboctahedra. In the fourth Ni site, Ni(4) is bonded in a 11-coordinate geometry to two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), one Ge(1), one Ge(2), one Ge(3), and two equivalent Ge(4) atoms. In the fifth Ni site, Ni(5) is bonded in a 11-coordinate geometry to two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), one Ge(1), one Ge(3), one Ge(4), and two equivalent Ge(2) atoms. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 10-coordinate geometry to two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), two equivalent Ni(4), and two equivalent Ni(5) atoms. In the second Ge site, Ge(2) is bonded in a 7-coordinate geometry to one Ni(4), two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), and two equivalent Ni(5) atoms. In the third Ge site, Ge(3) is bonded in a 10-coordinate geometry to two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), two equivalent Ni(4), and two equivalent Ni(5) atoms. In the fourth Ge site, Ge(4) is bonded in a 9-coordinate geometry to one Ni(5), two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), and two equivalent Ni(4) atoms.
Ni5Ge3 crystallizes in the monoclinic C2 space group. There are five inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 12-coordinate geometry to one Ni(1), one Ni(3), two equivalent Ni(4), two equivalent Ni(5), one Ge(1), one Ge(3), two equivalent Ge(2), and two equivalent Ge(4) atoms. The Ni(1)-Ni(1) bond length is 2.53 Å. The Ni(1)-Ni(3) bond length is 2.54 Å. There is one shorter (2.55 Å) and one longer (2.64 Å) Ni(1)-Ni(4) bond length. There is one shorter (2.60 Å) and one longer (2.66 Å) Ni(1)-Ni(5) bond length. The Ni(1)-Ge(1) bond length is 2.45 Å. The Ni(1)-Ge(3) bond length is 2.84 Å. There is one shorter (2.42 Å) and one longer (2.92 Å) Ni(1)-Ge(2) bond length. There is one shorter (2.42 Å) and one longer (2.52 Å) Ni(1)-Ge(4) bond length. In the second Ni site, Ni(2) is bonded in a 12-coordinate geometry to one Ni(2), one Ni(3), two equivalent Ni(4), two equivalent Ni(5), one Ge(1), one Ge(3), two equivalent Ge(2), and two equivalent Ge(4) atoms. The Ni(2)-Ni(2) bond length is 2.56 Å. The Ni(2)-Ni(3) bond length is 2.54 Å. There is one shorter (2.60 Å) and one longer (2.65 Å) Ni(2)-Ni(4) bond length. There is one shorter (2.58 Å) and one longer (2.69 Å) Ni(2)-Ni(5) bond length. The Ni(2)-Ge(1) bond length is 2.75 Å. The Ni(2)-Ge(3) bond length is 2.42 Å. There is one shorter (2.40 Å) and one longer (2.50 Å) Ni(2)-Ge(2) bond length. There is one shorter (2.45 Å) and one longer (2.83 Å) Ni(2)-Ge(4) bond length. In the third Ni site, Ni(3) is bonded to one Ni(1), one Ni(2), two equivalent Ni(4), two equivalent Ni(5), one Ge(1), one Ge(3), two equivalent Ge(2), and two equivalent Ge(4) atoms to form a mixture of distorted edge and corner-sharing NiNi6Ge6 cuboctahedra. There is one shorter (2.54 Å) and one longer (2.56 Å) Ni(3)-Ni(4) bond length. Both Ni(3)-Ni(5) bond lengths are 2.58 Å. The Ni(3)-Ge(1) bond length is 2.46 Å. The Ni(3)-Ge(3) bond length is 2.55 Å. There is one shorter (2.47 Å) and one longer (2.85 Å) Ni(3)-Ge(2) bond length. There is one shorter (2.46 Å) and one longer (2.72 Å) Ni(3)-Ge(4) bond length. In the fourth Ni site, Ni(4) is bonded in a 11-coordinate geometry to two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), one Ge(1), one Ge(2), one Ge(3), and two equivalent Ge(4) atoms. The Ni(4)-Ge(1) bond length is 2.62 Å. The Ni(4)-Ge(2) bond length is 2.47 Å. The Ni(4)-Ge(3) bond length is 2.35 Å. There is one shorter (2.35 Å) and one longer (2.37 Å) Ni(4)-Ge(4) bond length. In the fifth Ni site, Ni(5) is bonded in a 11-coordinate geometry to two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), one Ge(1), one Ge(3), one Ge(4), and two equivalent Ge(2) atoms. The Ni(5)-Ge(1) bond length is 2.36 Å. The Ni(5)-Ge(3) bond length is 2.55 Å. The Ni(5)-Ge(4) bond length is 2.49 Å. There is one shorter (2.34 Å) and one longer (2.36 Å) Ni(5)-Ge(2) bond length. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 10-coordinate geometry to two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), two equivalent Ni(4), and two equivalent Ni(5) atoms. In the second Ge site, Ge(2) is bonded in a 7-coordinate geometry to one Ni(4), two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), and two equivalent Ni(5) atoms. In the third Ge site, Ge(3) is bonded in a 10-coordinate geometry to two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), two equivalent Ni(4), and two equivalent Ni(5) atoms. In the fourth Ge site, Ge(4) is bonded in a 9-coordinate geometry to one Ni(5), two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), and two equivalent Ni(4) atoms.