The reaction of a 1:1 molar ratio of tetraethylene glycol (EO4) with a series of lanthanide chloride hydrates and the corresponding La3+ and Y3+ salts in 3:1 acetonitrile/methanol solutions produces four types of coordination complexes: [LaCl3(EO4)]2, [MCl(OH2)3(EO4)]Cl2.H2O (M = Ce-Nd, Sm-Gd), [M(OH2)4(EO4)]Cl3 (M = Tb-Yb, Y), and [LuCl2(EO4)]Cl.H2O. The reaction involving Tm produced two additional crystalline complexes, [Tm(OH2)4-x(OHMe)x(EO4)]Cl3.(1 - x)(H2O) (x = 0.60) and [TmCl2(OH2)(EO4)]Cl. Modification of the metal ion's primary coordination sphere was possible for the middle lanthanides by the addition of excess LiCl. A 4:1:1 molar excess resulted in the formation of [MCl2(OH2)(EO4)]Cl (M = Sm-Tb). When a 6:1:1 molar excess was used, the anhydrous [EuCl3(EO4)] was isolated. All of these complexes were crystallographically characterized. The 9-coordinate dimer [LaCl3(EO4)]2 is triclinic, P1BAR, with a = 8.586 (2) angstrom, b = 9.489 (3) angstrom, c = 9.593 (3) angstrom, alpha = 86.16 (3)-degrees, beta = 72.34 (3)-degrees, gamma = 78.10 (2)-degrees, and D(calc) = 2.00 g cm-3 for Z = 1. The early and middle lanthanides form 9-coordinate tetrahydrates with one chloride ion in the primary coordination sphere. The complexes [MCl(OH2)3(EO4)]Cl2.H2O are monoclinic, P2(1)/n, with Z = 4 and cell data as follows: M = Ce, a = 9.765 (3) angstrom, b = 10.597 (4) angstrom, c = 18.427 (9) angstrom, beta = 102.20 (4)-degrees, and D(calc) = 1.83 g cm-3; M = Pr, a = 9.743 (4) angstrom, b = 10.585 (3) angstrom, c = 18.407 (9) angstrom, beta = 102.33 (6)-degrees, D(calc) = 1.84 g cm-3; M = Nd, a = 9.725 (2) angstrom, b = 10.567 (3) angstrom, c = 18.389 (8) angstrom, beta = 102.40 (3)-degrees, D(calc) = 1.86 g cm-3; M = Sm, a = 9.688 (6) angstrom, b = 10.539 (8) angstrom, c = 18.350 (9) angstrom, beta = 102.53 (5)-degrees, D(calc) = 1.90 g cm-3; M = Eu, a = 9.653 (4) angstrom, b = 10.501 (4) angstrom, c = 18.303 (6) angstrom, beta = 102.00 (3)-degrees, D(calc) = 1.92 g cm-3; M = Gd, a = 9.660 (5) angstrom, b = 10.516 (3) angstrom, c = 18.317 (8) angstrom, beta = 102.63 (4)-degrees, D(calc) = 1.94 g cm-3. The late lanthanide tetrahydrates are also 9-coordinate but have all four water molecules in the primary coordination sphere. These complexes of formula [M(OH2)4(EO4)]Cl3, are triclinic, P1BAR, with Z = 2 and cell data as follows: M = Tb, a = 8.234 (7) angstrom, b = 8.417 (3) angstrom, c = 13.725 (2) angstrom, alpha = 82.36 (2)-degrees, beta = 89.20 (4)-degrees, gamma = 71.65 (6)-degrees, D(calc) = 1.97 g cm-3; M = Dy, a = 8.234 (5) angstrom, b = 8.398 (4) angstrom, c = 13.691 (7) angstrom, alpha = 82.41 (4)-degrees, beta 89.36 (5)-degrees, gamma = 71.63 (5)-degrees, D(calc) = 1.97 g cm-3; M = Y, a = 8.215 (6) angstrom, b = 8.390 (5) angstrom, c = 13.697 (6) angstrom, alpha = 82.46 (4)-degrees, beta = 89.30 (5)-degrees, gamma = 71.58 (5)-degrees, D(calc) = 1.73 g cm-3; M = Ho, a = 8.217 (5) angstrom, b = 8.389 (4) angstrom, c = 13.701 (9) angstrom, alpha = 82.46 (5)-degrees, beta = 89.32 (6)-degrees, gamma = 71.60 (4)-degrees, D(calc) = 2.01 g cm-3; M = Er, a = 8.206 (1) angstrom, b = 8.378 (3) angstrom, c = 13.676 (6) angstrom, alpha = 82.44 (3)-degrees, beta = 89.34 (2)-degrees, gamma = 71.57 (2)-degrees, D(calc) = 2.03 g cm-3; M = Tm, a = 8.206 (4) angstrom, b = 8.364 (3) angstrom, c = 13.666 (9) angstrom, alpha = 82.43 (4)-degrees, beta = 89.38 (6)-degrees, gamma = 71. 61 (4)-degrees, D(calc) = 2.04 g cm-3; M = Yb, a = 8.201 (3) angstrom, b = 8.367 (3) angstrom, c = 13.664 (5) angstrom, alpha = 82.42 (3)-degrees, beta = 89.41 (3)-degrees, gamma = 71.59 (4)-degrees, D(calc) = 2.06 g cm-3. The smallest lanthanide, Lu3+, crystallizes as the 7-coordinate complex [LuCl2(EO4)]Cl.H2O in the monoclinic space group P2(1)/c with a = 7.602 (3) angstrom, b = 20.958 (9) angstrom, c = 10.041 (6) angstrom, beta = 103.80 (4)-degrees, and D(calc) = 2.11 g cm-3 for Z = 4. The reaction of the Tm+3 salt produced two other crystallographic forms. The 9-coordinate complex [Tm(OH2)4-x(OHMe)x(EO4)]Cl3.(1 - x)(H2O) (x = 0.60) has one coordination site disordered between a water molecule and a methanol solvent molecule. This complex is monoclinic, P2(1)/c, with a = 10.051 (1) angstrom, b = 11.764 (1) angstrom, c = 16.390 (3) angstrom, beta = 98.75 (1)-degrees, and D(calc) = 1.56 g cm-3 for Z = 4. The second additional form is the same as that obtained for M = Sm-Tb when a 4:1:1 molar excess of LiCl was added to the reaction, the 8-coordinate [MCl2(OH2)(EO4)]Cl. These complexes crystallize in the monoclinic space group Cc with Z = 4 and cell parameters as follows: M = Sm, a = 12.952 (5) angstrom, b = 9.348 (4) angstrom, c = 13.764 (6) angstrom, beta = 110.91 (4)-degrees, D(calc) = 2.00 g cm-3; M = Eu, a = 12.932 (4) angstrom, b = 9.336 (4) angstrom, c = 13.733 (2) angstrom, beta = 110.90 (2)-degrees, D(calc) = 2.02 g cm-3; M = Gd, a 12.925 (4) angstrom, b = 9.332 (1) angstrom, c = 13.724 (2) angstrom, beta = 110.96 (2)-degrees, D(calc) = 2.04 g cm-3; M = Tb, a = 12.880 (4) angstrom, b = 9.318 (8) angstrom, c = 13.696 (8) angstrom, beta = 110.90 (4)-degrees; D(calc) = 2.06 g cm-3; M = Tm, a = 12.822 (2) angstrom, b = 9.277 (1) angstrom, c = 13.608 (1) angstrom, beta = 110.94 (1)-degrees, D(calc) = 2.14 g cm-3. The anhydrous, 8-coordinate [EuCl3(EO4)], produced from a 6:1:1 molar excess of LiCl, is triclinic, P1BAR, with a = 7.590 (4) angstrom, b = 8.895 (2) angstrom, c = 11.672 (4) angstrom, alpha = 91.09 (2)-degrees, beta = 102.04 (3)-degrees, gamma = 109.48 (3)-degrees, and D(calc) = 2.08 g cm-3 for Z = 2.
