Structural diversity of lanthanoid salicylate hydrates

Behrsing, Thomas, Deacon, Glen B., Luu, Jenny, Junk, Peter C., Skelton, Brian W., and White, Allan H. (2016) Structural diversity of lanthanoid salicylate hydrates. Polyhedron, 120. pp. 69-81.

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From metathesis reactions between lanthanoid salts and sodium salicylate (Na(salH)) in water, four classes of lanthanoid salicylate hydrates have been identified. Single crystal X-ray studies established a new monomeric class [Ln(salH)3(H2O)3]·3H2O (6Ln). This new rhombohedral R3c, Z = 6 form '6Ln' has the nine coordinate metal atom on a crystallographic 3-axis, for Ln = Sm–Gd, Ho, Er, Yb, Lu, Y. We also have augmented or defined the previously known different forms, consolidating or extending their putative 'domains of existence'. The monohydrate, Ln = '1Ce', monoclinic, P21/n, has been re-examined at lowtemperature suggesting further elasticity in its formulation beyond the recently proposed '[Ln(H2sal) (Hsal)(sal)H2O)](∞|∞)' for the Ln = Gd complex, '1Gd', one of the protonic hydrogen atoms being associated with a very short phenoxyl–O···carboxylate–O distance (2.427(3) Å). With refinement and the insights from a previous Ln = Eu study, suggest the protonic disposition to be around the O···O median. The 'domain of existence' for this form embraces Ln = La (dependent on a powder diffraction study) – Gd. The tetrahydrate is manifested in two forms: triclinic, centrosymmetric binuclear Ln2(salH)6(H2O)4]·4H2O, P·1, Z = 1, '4Ln' recorded here in a 153 K determination, for Ln = Ho, consolidating the assignment of its domain of existence to be Ho–Er, Y, and 'polymeric mononuclear' [Ln(salH)3(H2O)2](∞|∞)·2H2O, '4Ln,' recorded here for Ln = Tb–Er, Yb, Lu, Y. The 6Gd hexahydrate shows paramagnetic f7 magnetic behaviour. The reaction conditions leading to the isolation of a particular structural type of lanthanoid salicylate could not be reliably identified, indicating that a fine balance exists in the preferential crystallization of the lanthanoid salicylate hydrate phases. The discovery of the monomeric class has applications for the species acting as a corrosion inhibitor in dilute aqueous solution.

Item ID: 47739
Item Type: Article (Research - C1)
ISSN: 1873-3719
Keywords: lanthanoid, carboxylate, salicylate, crystal structure, monome
Funders: Australian Research Council (ARC)
Date Deposited: 13 Mar 2017 23:48
FoR Codes: 34 CHEMICAL SCIENCES > 3402 Inorganic chemistry > 340203 F-block chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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