Crystalline materials have been isolated and characterized from mixing the silver carborane salts Ag(CB(11)H(12)) or Ag[Co(C(2)B(9)H(11))(2)] with nitrile ligands, either terminal acetonitrile or potentially bridging alkanedinitriles. Most of the complexes showed B-H...Ag interactions between the silver center and carborane anion. [Ag(acetonitrile)(2)(CB(11)H(12))] has a hexagonal network structure. [Ag(malonitrile)(2)(CB(11)H(12))] is a discrete dimeric complex, while [Ag(4)(succinonitrile)(5)(CB(11)H(12))(4)], [Ag(glutaronitrile)(2)][Co(C(2)B(9)H(12))(2)], and [Ag(glutaronitrile)[Co(C(2)B(9)H(11))(2)]] all show coordination chain structures. The carborane anions in [Ag(adiponitrile)[Co(C(2)B(9)H(11))(2)]] bridge between Ag centers to give a 3D CdSO(4)-related coordination polymer. The structure of [Ag(malonitrile)(2)](BF(4)) was also determined to have an unusual chiral diamondoid structure with a skewed 2-fold interpenetration.
A series of three-dimensional (3-D) hydrogen-bonded structures of lanthanide aquo ions and 4,4′-bipyridine (bpy) or protonated bpyH + as ligands and hydrogen-bonding tectons have been characterized by single-crystal X-ray crystallography, with both Cland [Co(C 2 B 9 H 11 ) 2 ]counteranions. All show related structures with unidirectional rectangular channels filled by additional bpy molecules for the complexes [Yb(H 2 O) 8 ](bpy) 2.5 Cl 3 ‚6.5(H 2 O) and [Yb(H 2 O) 8 ] 4 (bpy) 9.5 Cl 12 ‚24.5(H 2 O) or by [Co(C 2 B 9 H 11 ) 2 ]anions for the complexes [Ln(bpy)(H 2 O) 8 ] 2 (bpy) 10 [Co(C 2 B 9 H 11 ) 2 ] 6 ‚1.5(EtOH)‚15(H 2 O) where Ln ) La, Ce, [Sm(H 2 O) 5 (bpy) 2 (EtOH)]-[Sm(H 2 O) 6 (bpyH)(EtOH)](bpyH)(bpy) 10 [Co(C 2 B 9 H 11 ) 2 ] 8 ‚EtOH‚9(H 2 O), and [Ln(H 2 O) 6 (bpy)(bpyH 0.5 )] 2 [Ln(H 2 O) 7 (bpy)](bpyH) 2 -(bpy) 14 [Co(C 2 B 9 H 11 ) 2 ] 12 ‚n(EtOH)‚5(H 2 O) where Ln ) Gd, Tb, and Ho. The smaller (CB 11 H 12 )anion does not template a similar structure; instead the complex [(bpyH) 3 (bpy)(CB 11 H 12 ) 3 ] is isolated with a one-dimensional (1-D) hydrogen-bonded ladder structure.
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