Cage-annulated thiacrown ethers and thiacryptands

Abstract

A series of cage-annulated sulfur-containing crown ethers and cryptands have been synthesized as possible specific metal host systems. The synthesis and structures of seven compounds are described, including a thiacryptand complex with Hg(II). The trishomocubane cage is essentially spherical except for a methylene group, which imparts no steric restrictions, and two disordered superimposed orientations occur in most structures. This superposition of four- and five-membered rings usually cannot be resolved into separate entities, resulting in distorted distances, angles, and thermal parameters for the cage. (3) I41cd, a = 13.207(3) A, b = 13.207(3) A, c = 35.876(12) A; (10) C2, a = 14.551(2) A, b = 10.028(1) A, c = 10.491(1) A, β = 107.108(2)°; (14) P21/n, a = 10.6277(8) A, b = 9.8488(7) A, c = 21.822(2) A, β = 97.945(2)°; (19) P21/c, a = 15.381(3) A, b = 6.667(1) A, c = 18.158(3) A, β = 94.838(4)°; (25) C2/c, a = 34.386(4) A, b = 11.318(1) A, c = 13.409(2) A, β = 110.044(2)°; (28) \(P\bar 1\), a = 10.4487(8) A, b = 11.5677(9) A, c = 13.354(1) A, α = 71.042(1)°, β = 87.344(1)°, γ = 65.839(1)°; (29) P21/c, a = 10.8138(5) A, b = 16.4949(8) A, c = 22.054(1) A, β = 96.087(1)°.