Kateryna Gubina

Novel tetranuclear cubane-like Co(II) complexes involving chelate phosphoramide ligands

Abstract Interaction of cobalt(II) ions and sodium carbacylamidophosphates Na(L) (HL=PhC(O)NHP(O)(NR2)2; where NR2 are morpholyl, HL1; NMe2, HL2; NEt2, HL3) in methanol solution afforded polynuclear alkoxo complexes [Co4{L1}3(OCH3)4(OH)(H2O)5·3H2O] 1 and [Co4{L}4(OCH3)4(CH3OH)4] (L=L2 2, L3 3). Data of spectral and TGA studies are presented. Coordination compounds 1 and 3 have been characterized by means of X-ray diffraction. Both the structures consist of tetranuclear cubane alkoxo clusters with methoxide ions bridging three metal centers (CoO 2.068(3)–2.093(4) A) and phosphorylic ligands coordinated in a bidentatechelate fashion via the carbonyl oxygen atoms (CoO 1: 2.050(2); 3: 2.031(4) A) and the phosphoryl groups (2.093(2) and 2.106(4) A). Isolation of these cubane alkoxo complexes is an important proof for close resemblance in behavior of carbacylamidophosphate systems and β-diketonates towards transition metal ions.

Carbacylamidophosphates: Structure and Properties of Bis(N,N′,-morpholido)-[(N″-morpholido)-carboxamido] phosphate

The bis(N,N′-morpholido)-[(N″-morpholido)-carboxamido] phosphate: O(CH2CH2 )NC(O )-N(H)P(O)[N(CH2CH2 )O]2 [HL], has been prepared and characterized by means of IR, 31P and 1H NMR spectroscopy and X-ray diffraction (triclinic, a = 9.282(2), b = 9.308(2), c = 21.341(4) Å, α = 80.79(3)°, β = 80.92(3)° γ = 66.92(3)°, V = 1665.1(6) Å3, space group P1̄̄, Z = 4 and R = 0.0423, wR2 = 0.1303 for 6774 unique reflections used). The unit cell consists of two independent molecules connected by hydrogen bonds N-H...O=P into non-symmetric dimers. The compound behaves as a HL molecule with a protonation constant corresponding to the -C(O)N(H)P(O)- group of pK = 8.65 as determined by potentiometric studies.

2-Ureido-1,3-thia-zol-3-ium dihydrogen phosphate.

The title compound, C4H6N3OS+·H2PO4 −, (I), was obtained as a result of hydrolysis of [(1,3-thiazol-2-ylamino)carbonyl]phosphoramidic acid, (II), in water. X-ray analysis has shown that the N—P bond in (II) breaks, leading to the formation of the substituted carbamide (I). This compound exists as an internal salt. The unit cell consists of a urea cation and an anion of H2PO4 −. Protonation of the N atom of the heterocyclic ring was confirmed by the location of the H atom in a difference Fourier map. The molecules of substituted urea are connected by O⋯O hydrogen bonds into unlimited planes. In turn, those planes are connected to each other via N—H⋯O hydrogen bonds with molecules of phosphoric acid, forming a three-dimensional polymer.

Chlorido[N,N′-dibenzyl-N′′-(trichloroacetyl)phosphoramidato-κ2O,O′](1,10-phenanthroline-κ2N,N′)copper(II)

In the title complex, [Cu(C16H16Cl3N3O2P)Cl(C12H8N2)], the Cu(II) cation presents a square-pyramidal environment, where the CuO2N2 base is formed by two O atoms from carbonyl and phosphoryl groups, and by two N atoms from a 1,10-phenanthroline molecule. A coordinated Cl atom occupies the apex. N-H···Cl hydrogen bonds link the molecules into one-dimensional chains. The trichloromethyl group is rotationally disordered over two positions, with occupancies of 0.747 (7) and 0.253 (7).

Crystal structure of aqua­tris­{μ-N-[bis(diethyl­amino)phosphoryl]-2,2,2-tri­chloroacetamidato-κ3O,O′:O}calciumsodium

In the title compound, three ligands are coordinated to the Ca2+ ion in a bidentate-chelated manner via the O atoms of the CO and PO groups. The sodium ion is encapsulated between three chelated metallacycles {CaL}(where L − = Cl3CC(O)NP(O)[N(C2H5)2]2) due to the bridging function of the carbonyl O atoms and it is capped by the water molecule.

Hexa-μ2-chlorido-μ4-oxido-tetra­kis[(morpholine-κN)copper(II)] methanol disolvate

In the title solvate, [Cu4(μ2-Cl)6(μ4-O)(C4H9NO)4]·2CH3OH, each Cu2+ ion in the tetranuclear complex has a trigonal–bipyramidal coordination arising from three bridging chloride ions in equatorial positions and the central μ4-O2− ion and morpholine N atom in axial positions. The morpholine rings adopt chair conformations, with the N—Cu bonds in equatorial orientations. In the crystal, the components are linked by N—H⋯O and O—H⋯O and O—H⋯Cl hydrogen bonds, which generate a three-dimensional network. One methanol molecule is disordered over two sets of sites in a 0.642 (9):0.358 (9) ratio.

Tetra­methyl N,N′-(2,2,3,3,4,4-hexa­fluoro-1,5-dioxopentane-1,5-di­yl)bis­(phospho­ramidate)

The molecule of the title compound, C9H14F6N2O8P2, lies on a twofold rotation axis that passes through the middle C atom of the three-atom fluoromethylene unit. The carbonyl and phosphoryl groups are in an antiperiplanar conformation. In the crystal, N—H⋯O=P hydrogen bonds link the molecules into polymeric chains parallel to the c axis.