Zr2Ni3Si4 crystallizes in the orthorhombic Cmce space group. Zr(1) is bonded in a 9-coordinate geometry to three equivalent Ni(1), four equivalent Ni(2), four equivalent Si(1), and four equivalent Si(2) atoms. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to six equivalent Zr(1), two equivalent Si(2), and four equivalent Si(1) atoms to form a mixture of distorted edge and face-sharing NiZr6Si6 cuboctahedra. In the second Ni site, Ni(2) is bonded in a 11-coordinate geometry to four equivalent Zr(1), two equivalent Ni(2), one Si(1), and four equivalent Si(2) atoms. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 7-coordinate geometry to four equivalent Zr(1), one Ni(2), and two equivalent Ni(1) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to four equivalent Zr(1), one Ni(1), and four equivalent Ni(2) atoms.
Zr2Ni3Si4 crystallizes in the orthorhombic Cmce space group. Zr(1) is bonded in a 9-coordinate geometry to three equivalent Ni(1), four equivalent Ni(2), four equivalent Si(1), and four equivalent Si(2) atoms. There are two shorter (3.03 Å) and one longer (3.11 Å) Zr(1)-Ni(1) bond length. There are two shorter (2.84 Å) and two longer (3.20 Å) Zr(1)-Ni(2) bond lengths. There are two shorter (2.78 Å) and two longer (2.82 Å) Zr(1)-Si(1) bond lengths. There are a spread of Zr(1)-Si(2) bond distances ranging from 2.82-3.03 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to six equivalent Zr(1), two equivalent Si(2), and four equivalent Si(1) atoms to form a mixture of distorted edge and face-sharing NiZr6Si6 cuboctahedra. Both Ni(1)-Si(2) bond lengths are 2.50 Å. All Ni(1)-Si(1) bond lengths are 2.31 Å. In the second Ni site, Ni(2) is bonded in a 11-coordinate geometry to four equivalent Zr(1), two equivalent Ni(2), one Si(1), and four equivalent Si(2) atoms. Both Ni(2)-Ni(2) bond lengths are 2.59 Å. The Ni(2)-Si(1) bond length is 2.27 Å. There are two shorter (2.35 Å) and two longer (2.38 Å) Ni(2)-Si(2) bond lengths. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 7-coordinate geometry to four equivalent Zr(1), one Ni(2), and two equivalent Ni(1) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to four equivalent Zr(1), one Ni(1), and four equivalent Ni(2) atoms.