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Vol 49, No 4 (2023)
Articles
Binuclear Vanadium(V) Complex with the Ligand Based on Isonicotinic Acid Hydrazide and 1-Phenyl-1,3-Butanedione: Synthesis and Crystal Structure
Abstract
A new molecular binuclear vanadium(V) complex [VO(L)(OCH3)]2 (I) is synthesized in which ligand H2L is prepared by the reaction of isonicotinic acid hydrazide (INAH, isoniazide) with 1-phenyl-1,3-butanedione. Ligand H2L and complex I are studied by elemental analysis, IR spectroscopy, mass spectrometry, and X-ray diffraction (XRD) (CIF files CCDC nos. 2172124 and 2172125, respectively). The composition and structure of the ligand in the free state is additionally studied by NMR spectroscopy. The bideprotonated organic ligand L2– coordinates to the metal atom via the tridentate mode through a set of donor atoms ONO to form two conjugated metallocycles. Different tautomeric forms are stabilized in H2L and in the corresponding coordinated ligand.
195-204
Preparation of Water-Soluble Zinc(II) Complexes with Ethylenediaminetetraacetic Acid: Molecular Structure of Zinc Ethylenediaminetetraacetate Trihydrate
Abstract
Poorly soluble zinc ethylenediaminetetraacetate zincate Zn[ZnL] reacts with sodium Na4L, potassium K4L, ammonium (NH4)4L, 2-ammonioethanol (H3NCH2CH2OH)4L, and hexamethylene-1,6-diammonium {H3N(CH2)6NH3}2L salts of ethylenediaminetetraacetic acid H4L to give readily soluble sodium Na2[ZnL], potassium K2[ZnL], ammonium (NH4)2[ZnL], 2-ammonioethanol (H3NCH2CH2OH)2[ZnL], and hexamethylene-1,6-diammonium {H3N(CH2)6NH3}[ZnL] ethylenediaminetetraacetate zincates. The reaction of tetrakis(triethylammonium) salt {(C2H5)3NH}4L with Zn[ZnL] does not give the expected bis(triethylammonium) ethylenediaminetetraacetate zincate {(C2H5)3NH}2[ZnL], but gives instead mono(triethylammonium) ethylenediaminetetraacetate zincate, {(C2H5)3NH}H[ZnL]; in aqueous solution, this product generates poorly soluble zinc ethylenediaminetetraacetate H2[ZnL(H2O)]·2H2O, which was studied by X-ray diffraction (CCDC no. 2172274).
205-216
Cationic Complexes of 3a,6a-Diaza-1,4-diphosphapentalenes
Abstract
The reactions of annulated 1,4-dichloro-3a,6a-diaza-1,4-diphosphapentalenes (DDPCl2) with 1 equiv. of trimethylsilyl triflate (TMSOTf) lead to replacement of one chlorine atom with the triflate group, thus giving cationic diazadiphosphapentalenes [ClDDP]+[TfO]−. In the presence of 2 equiv. of TMSOTf and 2 equiv. of 4‑dimethylaminopyridine (DMAP), the DDP dication stabilized by two DMAP molecules, [DDP(DMAP)2]2+[(CF3SO3)−]2, is formed. The DMAP molecules are located on one side of the DDP skeleton and lie in parallel planes. Free diazadiphosphapentalene was detected in solutions of [DDP(DMAP)2]2+[(CF3SO3)−]2 in CH2Cl2 by UV-Vis spectroscopy and CV. This implies that this compound disproportionates under these conditions; it is unstable in dilute solutions and decomposes to give [DMAP∙HOTf] in a quantitative yield. Crystallographic data for the obtained compounds: CCDC nos. 2182881–2182883.
217-228
Influence of the Aromatic Ligand Nature and Synthesis Conditions on the Structures of the Copper Pentafluorobenzoate Complexes
Abstract
New pentafluorobenzoate (Рfb) copper complexes with 2,3- and 3,5-lutidine (2,3- and 3,5-Lut, respectively), quinoline (Quin), and 1,10-phenanthroline (Рhen) ([Cu2(MeCN)2(Рfb)4] (I), [Cu(2,3-Lut)2(Pfb)2] (II), [Cu(3,5-Lut)4(Pfb)2] (III), [Cu(Quin)2(Pfb)2] (IV), and [Cu2(Phen)2(Pfb)4] (V)) are synthesized by the newly developed methods and characterized. The unusual heteroanionic pentafluorobenzoate benzoate (Вnz) ionic compound [Cu2(Рhen)2(Рfb)3]+(Рnz)– (VI) is synthesized. It is shown that the four-bridge binuclear metal cage of complex I is not retained in the reactions with various pyridine derivatives. In the case of such α-substituted pyridines as 2,3-lutidine and quinoline, the compositions and structures of the final products of the reactions with copper pentafluorobenzoate are independent of the initial ratio of the reagents and crystallization conditions. It is revealed by the Hirshfeld surface analysis that π···π, C–F···π, C–H···F, and F···F interactions make the major contribution to the stabilization of crystal packings of the synthesized complexes.
229-245
Crystallochemical Role of Benzoate and Phenylacetate Ions in Structures of Coordination 3d-Metal Compounds
Abstract
A crystal chemical analysis of the 3d-metal benzoate- and phenylacetate-containing compounds is carried out in terms of the stereoatomic crystal structure model using characteristics of the Voronoi–Dirichlet polyhedra. Coordination types of benzoate and phenylacetate anions toward the transition metals from Ti to Zn are considered. The influence of the coordination type on the characteristics of M–O bonds in the crystal structures is revealed. The electron-donating ability of benzoate and phenylacetate anions toward 3d metals is quantitatively estimated using the 18-electron rule.
246-256