Coordination Networks with Flexible Ligands Based on Silver(I) Salts: Complexes of 1,3-Bis(phenylthio)propane with Silver(I) Salts of PF 6 - , CF 3 COO - , CF 3 CF 2 COO - , CF 3 CF 2 CF 2 COO - , p-TsO - , and CF 3 SO 3 - Mohamed Osman Awaleh, Antonella Badia, and Franc ¸ ois Brisse* De ´ partement de chimie, UniVersite ´ de Montre ´ al, C.P. 6128, Succursale Centre-Ville, Que ´ bec, Canada H3C 3J7 Received April 21, 2005 The synthesis and characterization of nine coordination networks based on 1,3-bis(phenylthio)propane, L 3 , and silver(I) salts of PF 6 - (1), CF 3 COO - (2), CF 3 CF 2 COO - (3), CF 3 CF 2 CF 2 COO - (4), p-TsO - (5, 6), and CF 3 SO 3 - (7-9) are reported. Only 1 and other “isostructural” complexes with weakly coordinating anions such as ClO 4 - and SbF 6 - are of the host-guest type. In all the other complexes, the anions and the acetone molecules, when present, are coordinated to the metal. Most of the complexes studied here form a 2D-coordination network. Only 4 and 5 adopt a polymer-like chain structure. The packing of the chains of 4 is pseudohexagonal compact, while that of 5 is of the centered type. In complex 1, the silver atom is tetrahedrally coordinated to the sulfur atoms of four different ligands. The PF 6 - anions and acetone molecules, sandwiched between silver-ligand cationic sheets, are held through van der Waals interactions. In each of the three perfluorocarboxylates (2-4), two silver atoms are joined by the anions in a diatomic bridging mode. The Ag‚‚‚Ag distances are sufficiently short to indicate weak metal‚‚‚metal interactions. The dimeric units in 2 and 3 are interconnected through the ligands, thereby generating a 2D-network of neutral sheets, while, in 4, the dimeric units are bound to four ligands and a 1D-coordination polymer is generated. In the case of the sulfonate anions (p-TsO - and CF 3 SO 3 - ), the crystallization solvent influences the structure adopted. Thus, in 5, 7, and 9 obtained from petroleum ether, or other nonpolar solvents, two silver atoms are bound in a double-bridge fashion, while a monobridge mode is noted for 6 and 8, both recrystallized from diethyl ether. In 8, both bridging types are observed. The thermogravimetric investigation, in the room temperature-450 °C interval, of complexes 1, 3, and 7, which incorporate acetone molecules in their crystal structures, reveals a two-step weight loss for 1 (the acetone molecules are lost first followed by the ligands, leaving behind the silver salt), while complexes 3 and 7 decompose in a single step to metallic silver. Introduction In the last two decades, there has been considerable activity in the design and synthesis of solid frameworks. 1 The self- assembly of metal-organic coordination polymers has at- tracted a great deal of attention because of their potential applications as functional materials. 2 The properties of coordination polymer materials are to some extent dependent on their network topology. Thus, it is of interest to understand and control the subtle factors that influence the formation of these supramolecular networks. Moreover, the strategy consisting of varying the coordination site and/or the size and shape of the ligand is usually employed in crystal engineering to synthesize new coordination polymers. The metal centers are linked with rigid bridging ligands 3 or less frequently by flexible building blocks. 4 However, for a given * To whom correspondence should be addressed. E-mail: francois.brisse@ umontreal.ca. Fax: (+)-(514) 343-7586. (1) (a) Hagrman, P. J.; Hagrman, D.; Zubieta, J. Angew. Chem., Int. Ed. 1999, 38, 2638. (b) Khlobystov, A. N.; Blake, A. J.; Champness, N. R.; Lemenovskii, D. A.; Majouga, A. G.; Zyk, N. V.; Schro ¨der, M. Coord. Chem. ReV. 2001, 222, 155. (c) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1461. (d) Swiegers, G. F.; Malefetse, T. J. Chem. ReV. 2000, 100, 3483. (2) (a) Stumpf, H. O.; Ouahab, L.; Pei, Y.; Grandjean, D.; Kahn, O. Science 1993, 261, 447. (b) Yaghi, O. M.; Li, G.; Li, H. Nature 1995, 378, 703. (3) (a) Blake, A. J.; Champness, N. R.; Hubberstey, P.; Li, W. S.; Withersby, M. A.; Schro ¨der, M. Coord. Chem. ReV. 1999, 183, 117. (b) Sharma, C. V. K.; Broker, G. A.; Huddleston, J. G.; Baldwin, J. W.; Metzger, R. M.; Rogers, R. D. J. Am. Chem. So. 1999, 121, 1137. (c) Abrahams, B. F.; Batten, S. R.; Hoskins, B. F.; Robson, R. Inorg. Chem. 2003, 42, 2654. (d) Abrahams, B. F.; Jackson, P. A.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 2656. Inorg. Chem. 2005, 44, 7833-7845 10.1021/ic050617n CCC: $30.25 © 2005 American Chemical Society Inorganic Chemistry, Vol. 44, No. 22, 2005 7833 Published on Web 09/30/2005