Structural Modulation in Lanthanide Tetracyanoplatinates Incorporating Terpyridine: Synthesis and Structures of Four Distinct One-Dimensional Variants

• Published in: Journal of chemical crystallography 2010-07, Vol.40 (7), p.616-623
• Main Authors: Maynard, Branson A., Smith, Philip A., Jaleel, Ayesha, Ladner, LeAnn, Sykora, Richard E.
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Crystallography and Scattering Methods; Inorganic Chemistry; Organometallic Chemistry; Original Paper; Physical Chemistry
• ISSN: 1074-1542; 1572-8854
• DOI: 10.1007/s10870-010-9706-x

The synthesis of four different lanthanide tetracyanoplatinates all incorporating 2,2′:6′,2″-terpyridine have been carried out in acetonitrile/water mixtures by reaction of an appropriate Ln 3+ salt with 2,2′:6′,2″-terpyridine and potassium tetracyanoplatinate. The use of different Ln 3+ salts as reactants results in the isolation of {La(tpy)(H 2 O) 3 } 2 [Pt(CN) 4 ] 3 ·2CH 3 CN·2H 2 O ( La-1 ) space group , a  = 9.3862(15) Å, b  = 12.186(1) Å, c  = 13.493(1) Å, α = 88.082(7)°, β = 80.22(1)°, γ = 74.88(1)°, {Pr(tpy)(H 2 O) 3 } 2 [Pt(CN) 4 ] 3 ·2H 2 O ( Pr-2 ) space group , a  = 9.2458(15) Å, b  = 10.8068(9) Å, c  = 13.6178(14) Å, α = 84.554(8)°, β = 74.905(10)°, γ = 79.490(9)°, Ho(tpy)(H 2 O) 2 (NO 3 )[Pt(CN) 4 ] · CH 3 CN ( Ho-3 ) space group P 2 1 / c , a  = 12.867(1) Å, b  = 15.1046(15) Å, c  = 13.651(4) Å, β = 105.39(1)°, or Yb(tpy)(H 2 O) 2 (NO 3 )[Pt(CN) 4 ]·0.5CH 3 CN·1.5H 2 O ( Yb-4 ) space group Pbcn , a  = 13.226(7) Å, b  = 15.870(2) Å, c  = 24.276(3) Å under quite similar reaction conditions. All four of these compounds have been isolated as single crystals and X-ray diffraction has been used to investigate their structural features. None of these compounds are isostructural with one another, but all contain one-dimensional, polymeric structures that contain tris chelation of the Ln 3+ cations by terpyridine and bridging of the Ln 3+ ions by tetracyanoplatinate. La-1 and Pr-2 contain both cis - and trans -bridging of Ln 3+ cations by tetracyanoplatinate resulting in double chains with a ladder-type structure. Ho-3 and Yb-4 are similar in that they contain chelation of Ln 3+ by both terpyridine and a nitrate anion and both structure types only contain cis -bridging by tetracyanoplatinate. All four structures contain Pt–Pt interactions in the form of dimeric units. Graphical Abstract The structures are presented for four non-isostructural lanthanide tetracyanoplatinates all incorporating 2,2′:6′,2″-terpyridine, all containing one-dimensional, polymeric structures, and all illustrating Pt–Pt interactions in the form of dimeric units.