Crystal structure and molecular stereochemistry of polymeric Cu2(DMP)4(DMSO) as a platform for phosphate diester binding

Abstract

Treatment of a solution of CuCl 2 in dimethyl phosphate (DMP) in an inert solvent under nitrogen atmosphere resulted in a light blue fluorescence powder. Slow evaporation of H 2 O-DMSO solution of this powder led to the formation of blue-sky crystals of a new polymeric Cu(II) complex, with a unit cell composed of Cu 2 (DMP) 4 (DMSO), (1). The crystal and molecular structure of the complex was established crystallographically. Compound (1) crystallizes in the monoclinic space group P2 1 /n with a = 12.8920(11)Å, b = 13.1966(11)Å, c = 14.7926(13)Å, α = 90°, β = 98.943(2)°, γ = 90° and Z = 4. A square pyramidal environment for the metal center is established by coordination of oxygen atoms of four bridging DMP ligands in the basal positions and a tri-centered oxygen atom of DMSO in the apical disposition. The sixth position is also affected by a weak interaction with the sulfur atom of DMSO. The phosphorous atom in the bridging DMP is arranged in a deformed tetrahedron with gg conformation for methyl esters with C 2v symmetry. Accordingly, the angles of methoxy substituents are unexpectedly smaller than the bridging oxygens, and synchronous z-in and z-out distortions are suggested for DMP anion. The oxygen atom of SOCuCu´ fragment derived from DMSO, functions as a tri-centered nuclei lie almost in a trigonal triangle environment. This study helps provide further insights into the binding nature of phosphate esters to the active sites of enzymes, which catalyze phosphoryl transfer reactions.

Decomposition of allantoin in the presence of Cu(II) ions resulting in the formation of a coordination polymer containing oxalate species

“…Additionally, the presence of new band at 482 cm À1 in the far infrared spectrum, which has been assigned to metal-oxygen vibration coupling with (O-C@O) ring deformation of the oxalate ion [25], confirms the mode of DMSO bonding to copper(II Furthermore, the broad band region between 3500 and 2500 cm À1 can be assigned to the stretching vibrations of methyl (m(CH 3 )) groups of dimethyl sulfoxide (2997 cm À1 and 2915 cm À1 ) [29,37,38].…”

Hexaaquanickel(II) bis(dimethyl phosphate)

“…Recently, we reported the syntheses and crystal structures of [Cu 2 (DMP) 4 (DMSO)] n (Rafizadeh et al, 2005) and [UO 2 (-DMP) 4 (DMSO)] n (Rafizadeh et al, 2006), where DMP is dimethyl phosphate, [O 2 P(OCH 3 ) 2 ] À , and DMSO is dimethyl sulfoxide. In these complexes, DMP acts as an O-atom donor ligand, forming coordination polymers in the solid state.…”

Synthesis, Characterization, and Crystal Structures of a New Coordination Polymer of Manganese(II) Containing Dimethyl Phosphate

“…CCDC 632187 (1) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/datarequest/cif whereas that of O(11)-P(1)-O(12) is 119.3(2)°, according to a inspection on similar polymeric complexes [34,39], an acceptable reason is simultaneous z-in and z-out distortion for the DMP ligands. In this complex, we expectedly observed the gg (gauche, www.zaac.wiley-vch.de The unitcell-packing diagram of complex 1 is presented in Figure 2.…”