Hydrogen bond network structures based on sulfonated phosphine ligands: The effects of complex geometry, cation substituents and phosphine oxidation on guanidinium sulfonate sheet formation |
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| Authors: | Nichola J. Burke Mary F. Mahon John E. Warren |
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| Affiliation: | a Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK
b CLRC Daresbury Laboratory, Daresbury, Warrington WA4 4AD, UK |
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| Abstract: | Interactions between guanidinium cations and the sulfonate groups on the phosphine [PPh2C6H4-m-SO3]− have been exploited to incorporate iridium(I) centres into hydrogen-bonded networks. The crystal structure of [C(NH2)3]2{trans-[IrCl(CO)(PPh2C6H4-m-SO3)2]} (4) contains hexagonal guanidinium sulfonate (GS) sheets in which both of the sulfonate groups from each complex anion form hydrogen bonds within the same sheet. The crystal structures of [C(NH2)2(NHMe)][PPh2C6H4-m-SO3] (5) and [C(NH2)2(NHEt)][PPh2C6H4-m-SO3] (6) reveal that the GS sheets can tolerate the loss of one hydrogen bond donor, though twisting occurs to accommodate the alkyl group. However, the crystal structure of [C(NH2)2(NMe2)][PPh2C6H4-m-SO3] (7) shows that ribbon structures are formed instead of sheets when two hydrogen bond donors are lost. The compound [C(NH2)2(NHMe)]2{trans-[IrCl(CO)(PPh2C6H4-m-SO3)2]} · 3/8H2O (8) contains hydrogen-bonded cylinders as opposed to sheets. This is a likely consequence of a mismatch between the intramolecular S?S distance present in the anion, and the closer S?S distance present in a twisted GS sheet such as that in 5. The crystal structures of [C(NH2)2(NHEt)][P(O)Ph2C6H4-m-SO3] (9) and [C(NH2)2(NMe2)][P(O)Ph2C6H4-m-SO3] · H2O (10) show that the phosphine oxide group successfully competes with the sulfonate as a hydrogen bond acceptor. The crystal structure of 9 contains hydrogen-bonded ribbons that are interlinked through the anions which act as pillars to form a layer structure. In contrast, the crystal structure of 10 contains hydrogen-bonded sheets that involve cations, sulfonate groups, phosphine oxides and the included water molecule. These sheets are linked into a three-dimensional network through the anion pillars. |
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| Keywords: | Phosphine ligands Hydrogen bonds Sulfonates X-ray structures Iridium Crystal engineering |
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