NaU2Cl6 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one Cl(1), one Cl(12), one Cl(4), one Cl(6), one Cl(7), and one Cl(9) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one Cl(10), one Cl(11), one Cl(2), one Cl(3), one Cl(5), and one Cl(8) atom. There are four inequivalent U sites. In the first U site, U(1) is bonded in a 9-coordinate geometry to one Cl(12), one Cl(3), one Cl(7), two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(4) atoms. In the second U site, U(2) is bonded in a 9-coordinate geometry to one Cl(11), one Cl(8), one Cl(9), two equivalent Cl(10), two equivalent Cl(5), and two equivalent Cl(6) atoms. In the third U site, U(3) is bonded in a 9-coordinate geometry to one Cl(2), one Cl(4), one Cl(5), two equivalent Cl(3), two equivalent Cl(7), and two equivalent Cl(8) atoms. In the fourth U site, U(4) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(10), one Cl(6), two equivalent Cl(11), two equivalent Cl(12), and two equivalent Cl(9) atoms. There are twelve inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Na(1), one U(4), and two equivalent U(1) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the second Cl site, Cl(2) is bonded to one Na(2), one U(3), and two equivalent U(1) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the third Cl site, Cl(3) is bonded to one Na(2), one U(1), and two equivalent U(3) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the fourth Cl site, Cl(4) is bonded to one Na(1), one U(3), and two equivalent U(1) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the fifth Cl site, Cl(5) is bonded to one Na(2), one U(3), and two equivalent U(2) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the sixth Cl site, Cl(6) is bonded to one Na(1), one U(4), and two equivalent U(2) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the seventh Cl site, Cl(7) is bonded to one Na(1), one U(1), and two equivalent U(3) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the eighth Cl site, Cl(8) is bonded to one Na(2), one U(2), and two equivalent U(3) atoms to form a mixture of distorted edge and corner-sharing ClNaU3 tetrahedra. In the ninth Cl site, Cl(9) is bonded to one Na(1), one U(2), and two equivalent U(4) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the tenth Cl site, Cl(10) is bonded to one Na(2), one U(4), and two equivalent U(2) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the eleventh Cl site, Cl(11) is bonded to one Na(2), one U(2), and two equivalent U(4) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the twelfth Cl site, Cl(12) is bonded to one Na(1), one U(1), and two equivalent U(4) atoms to form a mixture of distorted edge and corner-sharing ClNaU3 tetrahedra.
NaU2Cl6 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one Cl(1), one Cl(12), one Cl(4), one Cl(6), one Cl(7), and one Cl(9) atom. The Na(1)-Cl(1) bond length is 2.90 Å. The Na(1)-Cl(12) bond length is 2.88 Å. The Na(1)-Cl(4) bond length is 2.86 Å. The Na(1)-Cl(6) bond length is 2.92 Å. The Na(1)-Cl(7) bond length is 2.91 Å. The Na(1)-Cl(9) bond length is 2.92 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one Cl(10), one Cl(11), one Cl(2), one Cl(3), one Cl(5), and one Cl(8) atom. The Na(2)-Cl(10) bond length is 2.88 Å. The Na(2)-Cl(11) bond length is 2.89 Å. The Na(2)-Cl(2) bond length is 2.90 Å. The Na(2)-Cl(3) bond length is 2.90 Å. The Na(2)-Cl(5) bond length is 2.91 Å. The Na(2)-Cl(8) bond length is 2.88 Å. There are four inequivalent U sites. In the first U site, U(1) is bonded in a 9-coordinate geometry to one Cl(12), one Cl(3), one Cl(7), two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(4) atoms. The U(1)-Cl(12) bond length is 3.09 Å. The U(1)-Cl(3) bond length is 3.08 Å. The U(1)-Cl(7) bond length is 2.98 Å. Both U(1)-Cl(1) bond lengths are 2.95 Å. There is one shorter (2.90 Å) and one longer (2.93 Å) U(1)-Cl(2) bond length. There is one shorter (2.93 Å) and one longer (2.96 Å) U(1)-Cl(4) bond length. In the second U site, U(2) is bonded in a 9-coordinate geometry to one Cl(11), one Cl(8), one Cl(9), two equivalent Cl(10), two equivalent Cl(5), and two equivalent Cl(6) atoms. The U(2)-Cl(11) bond length is 3.01 Å. The U(2)-Cl(8) bond length is 3.08 Å. The U(2)-Cl(9) bond length is 3.02 Å. There is one shorter (2.92 Å) and one longer (2.94 Å) U(2)-Cl(10) bond length. Both U(2)-Cl(5) bond lengths are 2.96 Å. There is one shorter (2.91 Å) and one longer (2.93 Å) U(2)-Cl(6) bond length. In the third U site, U(3) is bonded in a 9-coordinate geometry to one Cl(2), one Cl(4), one Cl(5), two equivalent Cl(3), two equivalent Cl(7), and two equivalent Cl(8) atoms. The U(3)-Cl(2) bond length is 3.09 Å. The U(3)-Cl(4) bond length is 3.04 Å. The U(3)-Cl(5) bond length is 3.00 Å. Both U(3)-Cl(3) bond lengths are 2.90 Å. There is one shorter (2.95 Å) and one longer (2.96 Å) U(3)-Cl(7) bond length. There is one shorter (2.95 Å) and one longer (2.96 Å) U(3)-Cl(8) bond length. In the fourth U site, U(4) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(10), one Cl(6), two equivalent Cl(11), two equivalent Cl(12), and two equivalent Cl(9) atoms. The U(4)-Cl(1) bond length is 3.00 Å. The U(4)-Cl(10) bond length is 3.09 Å. The U(4)-Cl(6) bond length is 3.02 Å. There is one shorter (2.94 Å) and one longer (2.96 Å) U(4)-Cl(11) bond length. There is one shorter (2.91 Å) and one longer (2.95 Å) U(4)-Cl(12) bond length. Both U(4)-Cl(9) bond lengths are 2.93 Å. There are twelve inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Na(1), one U(4), and two equivalent U(1) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the second Cl site, Cl(2) is bonded to one Na(2), one U(3), and two equivalent U(1) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the third Cl site, Cl(3) is bonded to one Na(2), one U(1), and two equivalent U(3) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the fourth Cl site, Cl(4) is bonded to one Na(1), one U(3), and two equivalent U(1) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the fifth Cl site, Cl(5) is bonded to one Na(2), one U(3), and two equivalent U(2) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the sixth Cl site, Cl(6) is bonded to one Na(1), one U(4), and two equivalent U(2) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the seventh Cl site, Cl(7) is bonded to one Na(1), one U(1), and two equivalent U(3) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the eighth Cl site, Cl(8) is bonded to one Na(2), one U(2), and two equivalent U(3) atoms to form a mixture of distorted edge and corner-sharing ClNaU3 tetrahedra. In the ninth Cl site, Cl(9) is bonded to one Na(1), one U(2), and two equivalent U(4) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the tenth Cl site, Cl(10) is bonded to one Na(2), one U(4), and two equivalent U(2) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the eleventh Cl site, Cl(11) is bonded to one Na(2), one U(2), and two equivalent U(4) atoms to form a mixture of edge and corner-sharing ClNaU3 tetrahedra. In the twelfth Cl site, Cl(12) is bonded to one Na(1), one U(1), and two equivalent U(4) atoms to form a mixture of distorted edge and corner-sharing ClNaU3 tetrahedra.