NEW HYDROGEN-BONDED STRUCTURE FORMED BY THE
ASSOCIATION OF [Zr(C2O4)4]4- ANIONS AND [H2(CH6N4S)]2+ CATIONS
IN SUPRAMOLECULAR HYBRID ARCHITECTURE INCLUDING AN
OPEN FRAMEWORK.
Monia Hamdouni,a Siwar Walha,a Ahlem Kabadou,a Carine Duhayon,b,c Jean-Pascal Sutterb,c
Laboratoire des Sciences des Matériaux et de l’Environnement ; Faculté des Sciences de Sfax, Université de
Sfax, Sfax, BP 1171, 3000, Tunisie.
a
b
CNRS ; LCC (Laboratoire de Chimie de Coordination) ; 205, route de Narbonne, F-31077 Toulouse, France.
c
Université de Toulouse ; UPS, INPT ; LCC ; F-31077 Toulouse, France.
Abstract
For the first time, a new assembly involving the tetrafunctional metallotecton [Zr(C2O4)4]4(C2O42- = oxalate) with oxalate linkers and the linear-shaped organic cation [H2(CH6N4S)]2+,
is explored. A pure phase of a new porous and charge-assisted hydrogen-bond complex
[H2(CH6N4S)2 (Zr(C2O4)4)].4H2O, has been synthesized using slow diffusion approach in a
H-shaped tube. Its crystal and molecular structure has been determined by single-crystal
diffractometry. It crystallizes in a triclinic system, space group P1̅
(no. 2) with the
dimensions of the reduced cell: a=10.077(3), b=10.81(3), c=11.1158(2) Å, α=78.136°,
β=89.232°, γ=86.707°, V=1183.05 Å3, Z=2. The crystal network is formed from [Zr(C2O4)4]4anions and [H2(CH6N4S)]2+ cations which act as bridges between anionic complexes bearing
N-H donors. Chemical moieties are involved in extensive three-dimensional (3D) hydrogen
bonding networks composed of strong and highly directional O–H----O, N–H----O and N–H---N interactions. The thermal decomposition has been studied by thermogravimetry and
temperature-dependent powder diffraction. These results have been supplemented by infrared
and Raman emission spectroscopy as a function of temperature and by chemical analysis.