ABSTRACT
In poly[[bis(µ-4,4'-bi-1H-pyrazole-κ(2)N(2):N(2'))bis(3-carboxyadamantane-1-carboxylato-κO(1))cobalt(II)] dihydrate], {[Co(C12H15O4)2(C6H6N4)2]·2H2O}n, (I), the Co(2+) cation lies on an inversion centre and the 4,4'-bipyrazole (4,4'-bpz) ligands are also situated across centres of inversion. In its non-isomorphous cadmium analogue, {[Cd(C12H15O4)2(C6H6N4)2]·2H2O}n, (II), the Cd(2+) cation lies on a twofold axis. In both compounds, the metal cations adopt an octahedral coordination, with four pyrazole N atoms in the equatorial plane [Co-N = 2.156â (2) and 2.162â (2)â Å; Cd-N = 2.298â (2) and 2.321â (2)â Å] and two axial carboxylate O atoms [Co-O = 2.1547â (18)â Å and Cd-O = 2.347â (2)â Å]. In both structures, interligand hydrogen bonding [N...O = 2.682â (3)-2.819â (3)â Å] is essential for stabilization of the MN4O2 environment with its unusually high (for bulky adamantanecarboxylates) number of coordinated N-donor co-ligands. The compounds adopt two-dimensional coordination connectivities and exist as square-grid [M(4,4'-bpz)2]n networks accommodating monodentate carboxylate ligands. The interlayer linkage is provided by hydrogen bonds from the carboxylic acid groups via the solvent water molecules [O...O = 2.565â (3) and 2.616â (3)â Å] to the carboxylate groups in the next layer [O...O = 2.717â (3)-2.841â (3)â Å], thereby extending the structures in the third dimension.
ABSTRACT
The title compound, [Th(C(12)H(15)O(4))(4)](n), is the first homoleptic thorium-carboxylate coordination polymer. It has a one-dimensional structure supported by the bidentate bridging coordination of the singly charged 3-carboxyadamantane-1-carboxylate (HADC(-)) anions. The metal ion is situated on a fourfold axis (site symmetry 4) and possesses a square-antiprismatic ThO(8) coordination, including four bonds to anionic carboxylate groups [Th-O = 2.359â (2)â Å] and four to neutral carboxyl groups [Th-O = 2.426â (2)â Å], while a strong hydrogen bond between these two kinds of O-atom donor [O...O = 2.494â (3)â Å] affords planar pseudo-chelated Th{CO(2)...HO(2)C} cycles. This combination of coordination and hydrogen bonding is responsible for the generation of quadruple helical strands of HADC(-) ligands, which are wrapped around a linear chain of Th(IV) ions [Th...Th = 7.5240â (4)â Å] defining the helical axis.