Primary to secondary sphere coordination of 15-crown-5 to lanthanide(III) chlorides: Structural analysis of [MCl{sub 3}(15-crown-5)] (M = La, Ce) and [Er(OH{sub 2}){sub 8}]Cl{sub 3} {center_dot} 15-crown-5
- Northern Illinois Univ., DeKalb, IL (United States)
Complexes of LaCl{sub 3}{center_dot}7H{sub 2}O and CeCl{sub 3} {center_dot} 7H{sub 2}O directly coordinated to 15-crown-5 were prepared by placing the reactants in 3:1 CH{sub 3}CN:CH{sub 3}OH on opposite sides of a fine porosity glass frit in a U-shaped cell and passing a 10 {mu}A current through the cell. The crystal structures of the two anhydrous 8-coordinate complexes, [MCl{sub 3}(15-crown-5)] (M = La, Ce) have been determined. Each contains the lanthanide in a bicapped trigonal prismatic geometry. The two complexes are isostructural crystallizing in the monoclinic space group P2{sub 1}/c with (at 20{degrees}C) for M = La: a =8.217(8), b = 14.298(2), c = 14.341(9){angstrom}, {beta} = 104.79(8){degrees}, and D{sub calc} = 1.90 g cm{sup {minus}3} for Z = 4; for M = Ce: a = 8.208(9), b = 14.263(6), c = 14.270(8){angstrom}, {beta} = 104.74(7){degrees}, and D{sub calc} = 1.92 g cm{sup {minus}3} for Z = 4. Direct reaction of ErCl{sub 3}{center_dot}6H{sub 2}O with 15-crown-5 in 3:1 CH{sub 3}CN:CH{sub 3}OH resulted in the crystallization of the second sphere hydrogen bonded complex [Er(OH{sub 2}){sub 8}]Cl{sub 3}{center_dot}15-crown-5. This complex is monoclinic, P2{sub 1}/n with (at 18{degrees}C) a = 9.193(3), b = 17.235(9), c = 15.216(5){angstrom}, {beta} = 92.48(3){degrees}, and D{sub calc} = 1.76 g cm{sup {minus}3} for Z = 4. The Er{sup 3+} ion is dodecahedral.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 513325
- Journal Information:
- Journal of Chemical Crystallography, Vol. 24, Issue 8; Other Information: PBD: Aug 1994
- Country of Publication:
- United States
- Language:
- English
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