Four binuclear coordination polymers with a 63 net and self-assembly of 2D 63 topology into different supramolecular networks using unit-unit H-bondsElectronic supplementary information (ESI) available: XRD powder patterns, IR spectra, TGA curves. CCDC reference numbers 1045240-1045243. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5ce00264h

In this work, crystal engineering is focused on the self-assembly of 2D 6 3 topology into different supramolecular networks using unit-unit H-bonds. Four related coordination polymers, [Zn 2 (teaH 2 )(ndc) 1.5 ]·MeOH ( 1 ), [Co 2 (teaH 2 )(ndc) 1.5 ]·MeOH ( 2 ), [Zn 2 (deaH)(ndc) 1.5 ]·MeOH ( 3 ) and [Co 2 (teaH 2 )(btb)]·3EtOH ( 4 ) where ndc 2− = 2,6-naphthalenedicarboxylate, btb 3− = benzene-1,3,5-tribenzoate, teaH 3 = triethanolamine, and deaH 2 = diethanolamine, contain a well-known 6 3 subnet and the binuclear units. Furthermore, their 6 3 nets present different hexagonal windows (chair- or ship-shaped) and diversified layer arrays (ABAB or ABCABC sequence). The 6 3 subnet and symmetry-related unit-unit H-bonds as supramolecular synthons can build up different supramolecular networks. Compounds 1 and 2 show a distorted diamond supramolecular network due to formation of a square-pyramidal node. Because the formation of a seesaw-shaped node, compound 3 features a general diamond supramolecular network with 3-fold interpenetration. Compound 4 exhibits a binodal supramolecular framework in that H-bonding interactions occur between three binuclear units. In addition, the diversified layer array has endowed compound 4 with a large 1D channel, which can be characterized by standard N 2 adsorptions. Compound 4 has a type I adsorption isotherm with an appreciable adsorption of 45.04 cm 3 g −1 at 0.40 P / P 0 , whereas 1-3 do not exhibit appreciable N 2 uptake. This work reported four coordination polymers with 6 3 subnets and unit-unit H-bonds as supramolecular synthons to form different supramolecular networks.