Crystal structure of disodium di-µ-hydroxo-bis(chloro-1,10-phenanthro-line-N,N'-copper(II))dihydroxide,Na2[Cu2Cl2(phen)2(OH)2](OH)2

Abstract

C24H2oCl2Cu2N4Na204, triclinic, PI (No. 2), a = 8.366(2) Ä, b = 8.832(3) Ä, c = 9.410(3) Ä, α = 101.75(2)°, β = 100.83(2)°, γ = 105.18(2)°, V = 635.2 Χ 3 , Z= 1, RgdF) = 0.065, wRteffF 2 ) = 0.148, T= 293 K. Source of materialUnder continuous stirring, 0.43 g (2.52 mmol) copper dichloride dihydrate (CuCh · 2H2O), 0.5 g (2.52 mmol) 1,10-phenanthroline monohydrate (C12H8N2 · H2O) and 0.33 g (2.52 mmol) glutaric acid (HOOC(CH2)3COOH) were successively added to 50 ml CH3OH/H2O (1:1 v/v), leading to a greenish slurry. After being filtered, the residual greenish slurry in the filter was then washed with a concentrated Na2CC>3 solution and a blue filtrate was collected. A small amount of blue crystals were grown by slow evaporation at room temperature for several weeks. DiscussionThe crystal structure of the title compound consists of Na + cations, hydrogen bonded OH -anions and dinuclear [CU2CI2 (phen)2(OH)2] complex molecules centered at the crystallographic Id positions. The Cu atoms are penta-coordinated by one bidentate chelating phenanthroline ligand, two bridging hydroxide groups and one CI atom to form a distorted square pyramid with two phen Ν atoms ant two hydroxide Ο atoms at the basal positions and the CI atom at the apical position (<f(Cu-N) = 2.022 Ä, 2. The non-coordinating OH" anions are hydrogen-bonded to the bridging OH ligands of the complex molecules with d(0-0) = 2.881 Ä. Strangely, each Na cation is bonded only to one apical CI atom with </(Na-CI) = 2.885 Ä close to 2.810 Ä observed in NaCl [3], The closest Na-Na distance is 3.351(6) Ä.

Solid State and Solution Study on the Formation of Inorganic Anion Complexes with a Series of Tetrazine-Based Ligands

“…The most salient property of these L1–L4 ligands is probably the ability of their neutral (not-protonated) forms to form stable complexes with hydroxide (OH − ) anions in water. Actually, as far as we know, these are the first reported cases of non-covalent binding of hydroxide anions in water with metal-free synthetic receptors, even if examples of OH − anions interacting with electron-poor aromatic groups in the solid state can be found in published crystal structures [25,26,27,28,29,30,31,32,33,34,35,36,37,38,39]. In only a few of them, the existence of anion–π interactions was noted [31].…”