Nb3Cl7 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a 4-coordinate geometry to one Cl(4), two equivalent Cl(2), and two equivalent Cl(5) atoms. In the second Nb site, Nb(2) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), and one Cl(5) atom to form distorted corner-sharing NbCl5 square pyramids. There are five inequivalent Cl sites. In the first Cl site, Cl(3) is bonded in a distorted L-shaped geometry to two equivalent Nb(2) atoms. In the second Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Nb(1) and two equivalent Nb(2) atoms. In the third Cl site, Cl(5) is bonded in a 2-coordinate geometry to one Nb(1) and one Nb(2) atom. In the fourth Cl site, Cl(1) is bonded in a distorted bent 150 degrees geometry to two equivalent Nb(2) atoms. In the fifth Cl site, Cl(2) is bonded in a 2-coordinate geometry to one Nb(1) and one Nb(2) atom.
Nb3Cl7 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a 4-coordinate geometry to one Cl(4), two equivalent Cl(2), and two equivalent Cl(5) atoms. The Nb(1)-Cl(4) bond length is 3.12 Å. Both Nb(1)-Cl(2) bond lengths are 2.45 Å. Both Nb(1)-Cl(5) bond lengths are 2.45 Å. In the second Nb site, Nb(2) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), and one Cl(5) atom to form distorted corner-sharing NbCl5 square pyramids. The Nb(2)-Cl(1) bond length is 2.67 Å. The Nb(2)-Cl(2) bond length is 2.48 Å. The Nb(2)-Cl(3) bond length is 2.45 Å. The Nb(2)-Cl(4) bond length is 2.52 Å. The Nb(2)-Cl(5) bond length is 2.47 Å. There are five inequivalent Cl sites. In the first Cl site, Cl(3) is bonded in a distorted L-shaped geometry to two equivalent Nb(2) atoms. In the second Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Nb(1) and two equivalent Nb(2) atoms. In the third Cl site, Cl(5) is bonded in a 2-coordinate geometry to one Nb(1) and one Nb(2) atom. In the fourth Cl site, Cl(1) is bonded in a distorted bent 150 degrees geometry to two equivalent Nb(2) atoms. In the fifth Cl site, Cl(2) is bonded in a 2-coordinate geometry to one Nb(1) and one Nb(2) atom.