Structure of Tl (18-crown-6){Cl_3CC(O)NP(O)(OCH_3)2}: Coordination of the Ionic Multidentate Weakens the Interaction of the Metal Atom with the Crown Ether

摘要

The thallium (I) dimethyl-N-trichloroacetylamidophosphate complex with a 18-crown-6 of the composition Tl (18-crown-6){L}(L = {Cl_3CC(O)NP(O)(OCH_3)_2}~-) has been prepared and characterized by means of IR spectroscopy and X-ray diffraction (orthorhombic, space group P2_12_12_1 with a = 8.660 (1), b = 11.557 (2), c = 26.296 (3) A, Z = 4, V = 2631.8 (6) A~3; R1 = 0.0285 and wR2 = 0.0558 for 4314 unique reflections). It was shown that (L~-) is coordinated to the central atom in a bidentate manner via oxygen atoms of phosphoryl [Tl-O(1) 2.678 (4) A] and carbonyl groups [Tl-O(2) 3.012 (6) A]. The Tl(18-crown-6)~+ moiety adopts a typical "sunrise" coordination with the metal atom laying 1.134 (2) A above the mean plane of the oxygen atoms of the macrocycle. This deviation is the highest value of the structurally examined Tl (18-crown-6)~+ complexes. The Tl-O (etheric) separations are in the range 2.913 (4)-3.198 (5) A (av. 3.030 (6) A).