A >22 Å long metal-complex anion and a 1D cationic coordination polymer, both based on 4,4′-bipyridine- N, N′-dioxide, yielding a 3D and 2-fold interpenetrated fsc net of the hydrogen-bonded metal-organic 1D polymer

• Published in: Inorganica Chimica Acta 2010-06, Vol.363 (10), p.2193-2200
• Main Authors: Chamayou, Anne-Christine, Janiak, Christoph
• Format: Article
• Language: English
• Subjects: 4,4′-Bipyridine- N, N′-dioxide; Cobalt; Complex anion; Coordination polymer; fsc net; Interpenetration
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2010.03.025

The cationic one-dimensional (1D) coordination polymer chain {[Co(μ-bpdo)(H 2O) 4] 2+} n and the metal-complex anion trans-[Co(SO 4) 2(bpdo) 2(H 2O) 2] 2−, both based on the 4,4′-bipyridine- N, N′-dioxide (bpdo) ligand, form a complementary 3D-supramolecular network {[Co(μ-bpdo)(H 2O) 4] 2+} n n[Co(SO 4) 2(bpdo) 2(H 2O) 2] 2− with respect to charge balance and hydrogen bonding. The cationic one-dimensional (1D) coordination polymer chain 1 ∞ {[Co(μ-bpdo)(H 2O) 4] 2+} and the metal-complex anion trans-[Co(SO 4) 2(bpdo) 2(H 2O) 2] 2−, both based on the 4,4′-bipyridine- N, N′-dioxide (bpdo) ligand, form a complementary supramolecular pair 1 ∞ {[Co(μ-bpdo)(H 2O) 4] 2+} n n[Co(SO 4) 2(bpdo) 2(H 2O) 2] 2− ( 1) with respect to charge balance and hydrogen bonding. With a length of >22.14 Ǻ along the bpdo–Co–bpdo axis the metal-complex trans-[Co(SO 4) 2(bpdo) 2(H 2O) 2] 2− is one of the longest and anisotropic counter anions (aspect ratio 22.14:8.11:4.17) observed so far in coordination polymers. Hydrogen-bonding of the anion links the cationic metal-organic 1D polymer into a 2-fold interpenetrated three-dimensional (3D) fsc (or sqc11) 4,6-c 2-nodal net of stoichiometry (4-c)(6-c) with square-planar, 4-connected (Co in anion) and octahedral, 6-connected (Co in cation) nodes in a 1:1 ratio. The 4-c point symbol is (4 4.6 2), the 6-c one (4 4.6 10.8) yielding a point symbol for the fsc net of (4 4.6 2)(4 4.6 10.8). The synthesis of 1 requires the presence of a Schiff base. Synthesis under the same conditions in the absence of the Schiff base yields the molecular complex and cocrystal [Co(bpdo)(H 2O) 5]SO 4·1/2bpdo ( 2) which is related (as pseudo-polymorph) to the known solvate [Co(bpdo)(H 2O) 5]SO 4·2H 2O ( 3) (CSD Refcodes RAXMUZ and RAXMUZ01).