ZrMnSi2 crystallizes in the orthorhombic Immm space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 8-coordinate geometry to one Si(3), one Si(4), two equivalent Si(1), two equivalent Si(2), and two equivalent Si(5) atoms. In the second Zr site, Zr(2) is bonded to one Si(3), two equivalent Si(2), two equivalent Si(4), and two equivalent Si(5) atoms to form a mixture of distorted edge and corner-sharing ZrSi7 pentagonal bipyramids. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to two equivalent Si(3), two equivalent Si(4), and two equivalent Si(5) atoms. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to two equivalent Si(1), two equivalent Si(2), and two equivalent Si(5) atoms. There are five inequivalent Si sites. In the first Si site, Si(5) is bonded in a 7-coordinate geometry to one Zr(2), two equivalent Zr(1), one Mn(2), two equivalent Mn(1), and one Si(5) atom. In the second Si site, Si(1) is bonded in a 2-coordinate geometry to four equivalent Zr(1) and two equivalent Mn(2) atoms. In the third Si site, Si(2) is bonded in a 10-coordinate geometry to two equivalent Zr(2), four equivalent Zr(1), two equivalent Mn(2), and two equivalent Si(2) atoms. In the fourth Si site, Si(3) is bonded in a 7-coordinate geometry to one Zr(2), two equivalent Zr(1), and four equivalent Mn(1) atoms. In the fifth Si site, Si(4) is bonded in a 8-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), and four equivalent Mn(1) atoms.
ZrMnSi2 crystallizes in the orthorhombic Immm space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 8-coordinate geometry to one Si(3), one Si(4), two equivalent Si(1), two equivalent Si(2), and two equivalent Si(5) atoms. The Zr(1)-Si(3) bond length is 2.76 Å. The Zr(1)-Si(4) bond length is 2.78 Å. Both Zr(1)-Si(1) bond lengths are 2.91 Å. Both Zr(1)-Si(2) bond lengths are 2.81 Å. Both Zr(1)-Si(5) bond lengths are 2.82 Å. In the second Zr site, Zr(2) is bonded to one Si(3), two equivalent Si(2), two equivalent Si(4), and two equivalent Si(5) atoms to form a mixture of distorted edge and corner-sharing ZrSi7 pentagonal bipyramids. The Zr(2)-Si(3) bond length is 2.72 Å. Both Zr(2)-Si(2) bond lengths are 2.78 Å. Both Zr(2)-Si(4) bond lengths are 2.86 Å. Both Zr(2)-Si(5) bond lengths are 2.77 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to two equivalent Si(3), two equivalent Si(4), and two equivalent Si(5) atoms. Both Mn(1)-Si(3) bond lengths are 2.50 Å. Both Mn(1)-Si(4) bond lengths are 2.45 Å. Both Mn(1)-Si(5) bond lengths are 2.48 Å. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to two equivalent Si(1), two equivalent Si(2), and two equivalent Si(5) atoms. Both Mn(2)-Si(1) bond lengths are 2.36 Å. Both Mn(2)-Si(2) bond lengths are 2.39 Å. Both Mn(2)-Si(5) bond lengths are 2.50 Å. There are five inequivalent Si sites. In the first Si site, Si(5) is bonded in a 7-coordinate geometry to one Zr(2), two equivalent Zr(1), one Mn(2), two equivalent Mn(1), and one Si(5) atom. The Si(5)-Si(5) bond length is 2.36 Å. In the second Si site, Si(1) is bonded in a 2-coordinate geometry to four equivalent Zr(1) and two equivalent Mn(2) atoms. In the third Si site, Si(2) is bonded in a 10-coordinate geometry to two equivalent Zr(2), four equivalent Zr(1), two equivalent Mn(2), and two equivalent Si(2) atoms. There is one shorter (2.53 Å) and one longer (2.63 Å) Si(2)-Si(2) bond length. In the fourth Si site, Si(3) is bonded in a 7-coordinate geometry to one Zr(2), two equivalent Zr(1), and four equivalent Mn(1) atoms. In the fifth Si site, Si(4) is bonded in a 8-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), and four equivalent Mn(1) atoms.