Nazarenko Olga M, Rusanova Julia A, Krautscheid Harald, Domasevitch Konstantin V
Inorganic Chemistry Department, National Taras Shevchenko University of Kyiv, Volodimirska Street 64, Kyiv 01033, Ukraine.
Acta Crystallogr C. 2010 Oct;66(Pt 10):m276-9. doi: 10.1107/S0108270110034785. Epub 2010 Sep 4.
The title compound, Th(C(12)H(15)O(4))(4), 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 = 2.359 (2) Å] and four to neutral carboxyl groups [Th-O = 2.426 (2) Å], while a strong hydrogen bond between these two kinds of O-atom donor [O...O = 2.494 (3) 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 = 7.5240 (4) Å] defining the helical axis.
标题化合物[Th(C₁₂H₁₅O₄)₄]ₙ是首例均配型钍羧酸盐配位聚合物。它具有一维结构，由单电荷的3-羧基金刚烷-1-羧酸盐（HADC⁻）阴离子的双齿桥连配位作用支撑。金属离子位于四重轴上（点群对称性4），具有四方反棱柱形的ThO₈配位环境，包括与阴离子羧酸根基团形成的四条键[Th-O = 2.359 (2) Å]以及与中性羧基形成的四条键[Th-O = 2.426 (2) Å]，而这两种氧原子供体之间存在的强氢键[O...O = 2.494 (3) Å]形成了平面伪螯合的Th{CO₂...HO₂C}环。这种配位作用和氢键作用的组合导致了HADC⁻配体的四重螺旋链的形成，这些链缠绕在定义螺旋轴的Th(IV)离子线性链周围[Th...Th = 7.5240 (4) Å]。
