Crystal structure of bis($2-chloro)-tris(triphenylphosphine)dicopper(I) dimethylformamide solvate, Cu2Cl2[P(C6H5)3]3 ·C3H7NO

Abstract

C 57 H 52 Cl 2 Cu 2 ONP 3 ,monoclinic, P12 1 /c1(no. 14), a =19.670(7) Å, b =14.340(4) Å, c =20.516(7) Å, b =114.333(5)°, V =5272.9 Å 3 , Z =4,R gt (F) =0.066, wR ref (F 2 ) =0.188, T =293 K. Source of materialCuCl (40 mg, 0.4 mmol) and PPh 3 (triphenylphosphine, 210 mg, 0.8 mmol) were dissolved in DMF (N,N-dimethyformamide, 10 ml), and the solution was stirred for 30 min. Vapor of isopropanol was diffused slowly into the resulting solution. After about two weeks, colorless prism-like crystals were formed. Experimental detailsHatoms were positioned geometrically and refined as riding atoms, with d(C-H) =0 .93 Å (aromatic) or 0.96 Å (methyl), U iso(H) =1.2Ueq(C) (aromatic) or 1.5 Ueq(C) (methyl). The highest peak is located 0.52 Å from atom H57A and deepest hole is located 0.61 Å from atom O1, which was refined only isotropically. DiscussionAl ong lasting interest in polynuclear copper(I) complexes has been manifest for years for their diverse structural and rich photoluminescent and potential applications in materials science. The structures of the copper(I) complexes are formed by coordinating phosphine or bulky nitrogen base ligands to CuX. These complexes are polynuclear copper(I) species with m 2-, m3-orm4-bridging Xatoms, and their structures are affected by the ligand and method of preparation [1][2][3][4][5].The crystal structure of the title complex is composed of neutral dinuclear molecule, Cu 2Cl2(PPh3)3,and one DMF solvent. There are two Cu + ions with asymmetrical coordination fashions. Cu1 is coordinated in distorted triangular geometry by one Patom from PPh 3 and two m 2 -Cl − ions with an average triangular angle of 119.99°. Cu2 is surrounded by two Patoms from two different PPh 3 and two m 2 -Cl − ions in distorted tetrahedral environment with an average angle of 108.49°. The Cu-P and Cu-Cl distances are 2.174(2) -2.251(1) Å and 2.228(2) -2.466(2) Å,respectively. The triangle and tetrahedron are bridged by two m 2 -Cl − ions to form the dinuclear copper(I) structure with the Cu···Cu distance of 3.023(1) Å indicating no Cu-Cu interaction existing [6]. The presence of DMF may have asignificant influence on the structure of the dinuclear copper compound and the molecular packing.

11/15/17 Complexes as Molecular Models for Metal Halide Double Perovskite Materials

“…Bi–Cl interatomic distances lie between 2.490 and 3.050 Å, a large range that is nonetheless typical for bismuth halide compounds and can be observed in a similar fashion for the anionic building block in [PPh 4 ] 2 [Bi 2 Cl 8 ­(Me 2 CO) 2 ] (Bi–Cl distances from 2.515 to 2.854 Å) . A close inspection of the bond lengths reveals two very different Cu–Cl interatomic distances of 2.335 and 2.798 Å, indicating that the latter is better described as a contact than a bond, since Cu-μ-Cl bonds in copper chloride phosphine complexes typically range between 2.23 and 2.50 Å. , This accords well with the overall coordination sphere of the Cu atoms, which is nearly trigonal. A similar Cu···Cl contact has been observed in the adduct [(InCl 3 )­(Cu­(SEt)­(PPh 3 ) 2 ] …”

“…55 A close inspection of the bond lengths reveals two very different Cu−Cl interatomic distances of 2.335 and 2.798 Å, indicating that the latter is better described as a contact than a bond, since Cu-μ-Cl bonds in copper chloride phosphine complexes typically range between 2.23 and 2.50 Å. 56,57 This accords well with the overall coordination sphere of the Cu atoms, which is nearly trigonal. A similar Cu•••Cl contact has been observed in the adduct [(InCl 3 )(Cu(SEt)(PPh 3 ) 2 ].…”