Soft scorpionate coordination at alkali metals

Reported here are the single-crystal X-ray structure analyses of bis-mu-methanol-kappa O-4:O-bis{[hydrotris(3-phenyl-2-sulfanylidene-2,3-dihydro-1H-1,3-imidazol-1-yl) borato-kappa(3) H,S,S']-(methanol-kappa O) sodium(I)}, [Na-2(C27H22BN6S3)(2)(CH4O)(4)] (Na-Tm-Ph), bis-mu-methanol-kappa O-4:O-bis{[hydrotris(3-isopropyl-2-sulfanylidene-2,3-dihydro-1H-1,3-imidazol-1-yl) borato-kappa(3) H,S,S']-(methanol-kappa O) sodium(I)}-diethyl ether-methanol (1/0.3333/0.0833), [Na-2(C18H28BN6S3)(2)(CH4O)(4)]center dot 0.3333C(4)H(10)O center dot 0.0833-CH3OH (NaTmiPr), and a novel anhydrous form of sodium hydrotris(methylthioimidazolyl)borate, poly[[mu-hydrotris(3-methyl-2-sulfanylidene-2,3-dihydro-1H-1,3-imidazol-1-yl)borato] sodium(I)], [Na(C12H16BN6S3)] ([NaTmMe](n)). NaTmiPr and NaTmPh have similar dimeric molecular structures with kappa H-3,S,S'-bonding, but they differ in that NaTmPh is crystallographically centrosymmetric (Z' = 0.5) while NaTmiPr contains one crystallographically centrosymmetric dimer and one dimer positioned on a general position (Z' = 1.5). [NaTmMe](n) is a one-dimensional coordination polymer that extends along the a direction and which contains a hitherto unseen side-on eta(2)-C=S-to-Na bond type. An overview of the structural preferences of alkali metal soft scorpionate complexes is presented. This analysis suggests that these thione-based ligands will continue to be a rich source of interesting alkali metal motifs worthy of isolation and characterization.