Hydrogen bond network structures based on sulfonated phosphine ligands: The effects of complex geometry, cation substituents and phosphine oxidation on guanidinium sulfonate sheet formation

Nichola J. Burke, Andrew D. Burrows, Mary F. Mahon, John E. Warren

Research output: Contribution to journalArticlepeer-review

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. © 2006 Elsevier B.V. All rights reserved.
Original languageEnglish
Pages (from-to)3497-3506
Number of pages9
JournalInorganica Chimica Acta
Volume359
Issue number11
DOIs
Publication statusPublished - 1 Aug 2006
Externally publishedYes

Keywords

  • Crystal engineering
  • Hydrogen bonds
  • Iridium
  • Phosphine ligands
  • Sulfonates
  • X-ray structures

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