The reaction of the mononuclear complex [PhenCu(OOCtBu)2(H2O)] (I) with [PhenCu(CH3CN)(Otf)2] (Phen = 1,10-phenanthroline, Otf = CF3S O_3^ - ) in dichloromethane at room temperature gave the binuclear complex [Phen2Cu2(µ-OOCtBu)2(Otf)2] (II). The reaction of II with pyrazole (PzH) involved the displacement of the triflate anions to the outer sphere and gave the ionic complex [Phen2Cu2(µ-OOCtBu)2(PzH)2](Otf)2 (III), while a similar reaction with 3,5-bis(trifluoromethyl)pyrazole ((CF3)2PzH) was accompanied by its deprotonation and gave the heteroleptic complex [Phen2Cu2(µ-OOCtBu)(µ-(CF3)2Pz)(µ-Otf)]Otf (IV). Compounds I–IV were characterized by X-ray diffraction (CCDC nos. 2332399 (I), 2332400 (II), 2332402 (III), and 2332401 (IV)), IR spectroscopy, and elemental analysis. According to X-ray diffraction data, the copper atoms in I–IV occur in a square pyramidal environment. The crystal packing of complexes I–III involves stacking interactions between phenanthroline molecules giving rise to supramolecular chains.

The reactions of [Zn(Piv)2]n and [Gd(Piv)3]n or Gd(NO3)3∙6H2O with 2-hydroxypyridine (Hhp) or its 6-methyl derivative (Hmhp) afford heterometallic complexes [ZnGd(Рiv)5(Hhp)2]·0.5H2O (I), [Zn2Gd(Рiv)6(Hhp)2NO3]∙2C6H6 (II), [Zn3GdO(Рiv)7(Hmhp)2]∙MeCN (III), and [Zn2Gd(Рiv)6-(Hmhp)2NO3]∙0.5MeCN (IV), respectively. In the carboxylate metal cage of the synthesized complexes, the Hhp and Hmhp molecules in the form of 2-pyridone are coordinated by the metal atoms via the monodentate mode through the oxygen atoms. The introduction of Et3N into the reaction with [Zn(Рiv)2]n, Gd(NO3)3∙6H2O, and Hhp is found to result in the formation of compound [Zn4Gd2(OH)2-(Рiv)6(hp)6(Hhp)2] (V) in which the 2-hydroxypyridine anions perform the bridging function. The molecular structures of complexes I‒V are determined by XRD (CIF files CCDC nos. 2365419–2365423).

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The reaction of copper(II) and zinc(II) acetates with 3-furancarboxylic (HFur) and 2-thiophenecarboxylic (HTph) acids with subsequent addition of 3,5-dimethylpyrazole (HDmpz) gave mononuclear complexes [M(L) 2 (HDmpz) 2 ] (M = Cu(II), L = Fur – ( I ), Tph – ( II ); Zn(II), L = Fur – ( III )). The structures of compounds I – III were determined by X-ray diffraction. According to X-ray diffraction data, I and II are isostructural: the central Cu(II) atom occurs in a square planar environment formed by two oxygen atoms of carboxylate anions and HDmpz nitrogen atoms; in III , the Zn atom is in the tetrahedral environment of two furoate anions and HDmpz molecules, thus forming the {MO 2 N 2 } groups. The complexes are additionally stabilized in the crystal by inter- ( I and II ) and intramolecular ( III ) hydrogen bonds. The biological activity of I – III was determined in relation to the non-pathogenic Mycolicibacterium smegmatis.

A series of polymer complexes of Gd(III) and Eu(III) with 3-furancarboxylic (HFur) and 5-nitro-2-furancarboxylic (HNfur) acids differed in the composition and coligands presented by solvent molecules (CH 3 OH/C 2 H 5 OH/H 2 O) is synthesized: [Gd(Fur) 3 (CH 3 OH)(C 2 H 5 OH)] n ( I ), [Gd(Nfur) 3 (CH 3 OH) 2 ] n · CH 3 CN ( II ), [Eu(Fur) 3 (C 2 H 5 OH)] n ( III ), and [Eu(Nfur) 3 (H 2 O) 2 ] n ·3CH 3 CN ( IV ). According to the X-ray diffraction (XRD) data, all complexes are 1D coordination polymers in which the lanthanide cation has the coordination number 8 (LnO 8 ) to form the environment as a doubly augmented triangular prism ( I , II ) or a square antiprism ( III , IV ). The supramolecular levels of the polymers are stabilized due to intra- and intermolecular hydrogen bonds between the coordinated solvent molecules and O atoms of the chelate-bound anions of the acid and via two types of noncovalent C–H…O and N–O…π interactions that significantly contribute to an additional stabilization of the crystal packings. The biological properties of complexes I , II , and IV are studied with respect to the model nonpathogenic strain Mycolicibacterium smegmatis .

It was shown that refluxing of europium(III) acetate hydrate with trifluoroacetic acid in a dioxane–acetonitrile mixture gives the polymer {[Eu(μ-OOCCF 3 ) 3 (OH 2 ) 2 ]} n ( I ) containing dioxane solvate molecules. The reaction of I with [phen(µ-OOC t Bu) 2 (OOC t Bu) 2 ] ( II ) (phen = 1,10-phenanthroline) in CH 2 Cl 2 at room temperature gives a precipitate, the recrystallization of which from acetonitrile affords an unusual trinuclear heterometallic heteroanionic phen 2 Zn 2 Eu(µ 3 -OH)(OOC t Bu) 4 (OOCCF 3 ) 2 complex ( III ). The structure of the products was established from X-ray diffraction data (CCDC no. 2235937–2235939). The optical properties of complex III were studied.

A series of polymer complexes of Gd(III) and Eu(III) with 3-furancarboxylic (HFur) and 5-nitro-2-furancarboxylic (HNfur) acids differed in the composition and coligands presented by solvent molecules(CH3OH/C2H5OH/H2O) is synthesized: [Gd(Fur)3(CH3OH)(C2H5OH)]n (I), [Gd(Nfur)3(CH3OH)2]n·CH3CN (II), [Eu(Fur)3(C2H5OH)]n (III), and [Eu(Nfur)3(H2O)2]n·3CH3CN (IV). According to the X-raydiffraction (XRD) data, all complexes are 1D coordination polymers in which the lanthanide cation has thecoordination number 8 (LnO8) to form the environment as a doubly augmented triangular prism (I, II) or asquare antiprism (III, IV). The supramolecular levels of the polymers are stabilized due to intra- and intermolecularhydrogen bonds between the coordinated solvent molecules and O atoms of the chelate-boundanions of the acid and via two types of noncovalent C–H…O and N–O…π interactions that significantly contributeto an additional stabilization of the crystal packings. The biological properties of complexes I, II, andIV are studied with respect to the model nonpathogenic strain Mycolicibacterium smegmatis.

It has been shown that boiling aqueous europium(III) acetate with trifluoroacetic acid in a dioxane-acetonitrile mixture leads to the formation of a polymer {[Eu(μ-OOCCF3)3(OH2)2]}n (I) containing solvate dioxane molecules. The interaction of I in CH2Cl2 with [Phen2Zn2(µ-OOCBut)2(OOCBut)2] (II) at room temperature forms a precipitate, recrystallization of which from acetonitrile gives an unusual trinuclear heterometallic heteroanionic complex Phen2Zn2Eu(µ3-OH)(OOCBut)4(OOCCF3 )2 (III). The structure of the obtained compounds was established according to X-ray diffraction data (CCDC No. 2235937-2235939). The optical properties of complex III were studied.

The reactions of 3,5-bis(trifluoromethyl)pyrazole ((CF 3 ) 2 PzH) with the binuclear complex [Phen 2 Co 2 (μ-OH 2 )(μ-OOCMe) 2 (OOCMe) 2 ] were studied. The reaction in dichloromethane under mild conditions gave the complex [Co 2 (Phen) 2 (µ-H 2 O)(µ-OOCMe) 2 (OOCMe) 2 ]((CF 3 ) 2 PzH) 4 ( I ). Refluxing of I in ortho -xylene resulted in deprotonation of pyrazole giving two mononuclear complexes: pyrazolate [Co(Phen) 2 (H 2 O)(OOCMe)]((CF 3 ) 2 Pz) ( II ) and pyrazolate acetate [Co(Phen) 2 ((CF 3 ) 2 Pz) 2 ] ( III ). Compounds I – III were studied by X-ray diffraction (CCDC nos. 2159355–2159357), IR spectroscopy, and elemental analysis. The thermal behavior of I was investigated by TGA.

New coordination polymers with lanthanide ions [Ln(Fur)3(H2O)x]n⋅Solv (Ln = Gd (I), Sm (II); Fur = 2-furoic acid anion; x = 2 (I), 3 (II); Solv = MeCN (I)) are synthesized. The structures of the synthesized compounds are determined by X-ray diffraction (CIF files CCDC nos. 2130014 (I) and 2130015 (II)). The coordination environment of the complexing agent (LnO8) corresponds to a distorted square antiprism (I) or a distorted triangular dodecahedron (II). Complexes I and II represent polymeric chains in which the Fur– anions perform the bridging function. The crystal lattice is stabilized by intra- and intermolecular hydrogen bonds between the coordinated water molecules, acid anions, and solvate molecules. The study of the thermal behavior of compound I by simultaneous thermal analysis in an argon atmosphere shows a low stability of the complex: its decomposition starts at 69°С, and the organic moiety destructs gradually without pronounced thermal effects. According to the data of X-ray photoelectron spectroscopy, gadolinium(III) oxide is the final product of thermal decomposition.

The reaction of cymantrenates M[(OOС5CH4)Mn(CO)3]2(MeOH)4 (M = Zn, Co(II), Ni(II)) with pyrazole (HPz) results in replacement of labile methanol molecules by the heterocyclic ligand and gives mononuclear complexes Zn[(OOCC5H4)Mn(CO)3]2(HPz)2 (I), Ni[(OOCC5H4)Mn(CO)3]2(HPz)4 (II), and Co[(OOCC5H4)Mn(CO)3]2(HPz)4 (III). A similar reaction of cobalt cymantrenate with more basic and sterically bulky 3,5-dimethylpyrazole (HDmpz) gives the complex Co[(OOCC5H4)Mn(CO)3]2(HDmpz)2 (IV). Compounds I–IV were characterized by X-ray diffraction (CCDC nos. 2157671 (I), 2157672 (II), 2157669 (III), and 2157670 (IV)), IR spectroscopy, and elemental analysis.

The reaction of manganese(II) acetate hydrate with cymantrenecarboxylic acid under inert atmosphere gave the complex [Mn(Thf)2(OH2)4][OOCC5H4Mn(CO)3]2 (I), which was highly unstable to air oxygen and temperature of the adduct, in which the anions occupy the outer-sphere positions. The oxidation of the mother liquor after isolation of the single crystals of I afforded the complex Mn6(µ4-O)2[µ,η2-OOCC5H4Mn(CO)3]2[µ-OOCC5H4Mn(CO)3]8(OH2)4·5C6H6·THF·3H2O (II). According to X-ray diffraction data, the metal core of II was a hexanuclear cluster $${\text{Mn}}_{4}^{{{\text{II}}}}{\text{Mn}}_{2}^{{{\text{III}}}}$$ containing mixed-valence metal atoms. Apart from X-ray diffraction, the obtained unstable complexes were characterized by elemental analysis and IR spectroscopy (powders).

The dissolution of aqueous copper(II) acetate in coordinating bidentate 1,4-dioxane (reflux) affords anhydrous mononuclear complex Cu 2 (µ-OOCMe) 4 (dioxane) 2 ( I ) (Cu…Cu 2.5781(3) Å). The crystal of complex I contains contacts of the α-H atom of the CH 2 fragments of coordinated dioxane with the oxygen atom of the bridging anion with the formation of the 2D metal-organic framework (MOF). The anionic exchange reactions of the acetate bridges by pivalate or trifluoroacetate groups with the corresponding acids in boiling dioxane give 1D MOF {Cu 2 (µ-OOCR) 4 (dioxane)} n (R = t Bu ( II ), Cu…Cu 2.5493(7) Å; CF 3 ( III ), Cu…Cu 2.6391(12) Å) characterized by the step and linear geometry, respectively. A similar reaction of Cu 2 (µ-OOCMe) 4 (OH 2 ) 2 with HOOCCF 3 but at room temperature in the presence of crude benzene affords mononuclear complex Cu(OOCCF 3 ) 2 (OH 2 ) 3 ·2 dioxane ( IV ). Complexes I – IV are studied by elemental and X-ray diffraction analyses (CIF files CCDC nos. 2052618 ( I ), 2052619 ( II ), 2052620 ( III ), and 2052617 ( IV )). The influence of the electronic and steric factors of substituents R on the compositions and structures of the mononuclear complexes and MOFs with 1,4-dioxane are discussed for the synthesized and known copper(II) tetracarboxylates.

The reactions of zinc, nickel(II), and manganese(II) acetate hydrates with excess trifluoroacetic acid in boiling 1,4-dioxane give coordination polymers (CPs): {[Zn3(µ-OH2)2(µ-OOCCF3)4(OOCCF3)2(OH2)2] [µ-O(CH2CH2)2O)]·3O(CH2CH2)2O}n (1, 81% yield), {[Ni2(µ-OH2)(µ-OOCCF3)2(OOCCF3)2 (OH2)2(O(CH2CH2)2O)]2[µ-O(CH2CH2)2O)]·5O(CH2CH2)2O}n (2, 89% yield), and {[Mn2(µ-OOCCF3)3(OOCCF3)(OH2)][µ-O(CH2CH2)O]2}n (4, 79% yield). According to X-ray diffraction data, the CP structure is determined by the nature of the transition metal. In polymer 1, the trinuclear Zn3(µ-OH2)2(µ-OOCCF3)4(OOCCF3)2(OH2)2 moieties (Zn···Zn, 3.6490(3) Å) are linked by bridging dioxane molecules to give zigzag-like 1D-CP, while the hydrogen atoms of coordinated water molecules form 2D-CP via intermolecular hydrogen bonds (HBs) with oxygen atoms of solvation solvent molecules. In CP 2, two binuclear Ni2(µ-OH2)(µ-OOCCF3)2(OOCCF3)2(OH2)2(O(CH2CH2)2O moieties (Ni···Ni, 3.5388(13) Å) in the tetranuclear Ni4 complex are linked by a bridging dioxane molecule, while the terminal and solvation solvent molecules form intermolecular HBs with the hydrogen atoms of the peripheral water molecules, thus giving 2D-CP. In the case of most electron-deficient Mn(II) ion, each metal atom in the binuclear complex Mn2(µ-OOCCF3)3(OOCCF3)(OH2) (Mn···Mn, 4.2487(5) Å) is bound to two bridging dioxane molecules to give 2D-CP, the dimensionality of which increases to 3D via the formation of intermolecular HBs between the terminal water molecule and the oxygen atom of the terminal and bridging carboxylate anion. It was also shown that in a similar reaction of Ni(OOCMe)2(OH2)4 with 2 moles of HOOCCF3 at room temperature, only anion exchange takes place, resulting in the polymer {Ni(OOCCF3)2(OH2)4⋅[O(CH2CH2)2O]}n (3). Apart from X-ray diffraction, the CPs were studied by chemical analysis and IR spectroscopy.

It has been found that the reactions of a suspension of 1D-coordination polymers (CPs) {(µ-dipy)2Mn2[µ-(OOCC5H4)Mn(CO)3]2[η2-(OOCC5H4)Mn(CO)3]2·2MeOH}n and {[µ-dipy)Co[(OOCC5H4)Mn(CO)3]2[O(H)Me]2}n (where dipy is 4,4'-dipy) with monodentate pyrazole (Hpz) and 3,5-dimethylpyrazole (Hdmpz) upon boiling in CH2Cl2 lead to the formation of 1D-CPs {µ-dipy)Mn[(OOCC5H4)Mn(CO)3]2(Hpz)2}n (1) and {(µ-dipy)Co[η2-(OOCC5H4)Mn(CO)3][(OOCC5H4)Mn(CO)3](Hdmpz)· Hdmpz}n (2), respectively. In the initial manganese(II) polymer, a binuclear fragment with coordination of two Hpz molecules by a metal atom in 1 is destroyed, and in the case of cobalt(II), two alcohol molecules are replaced by an Hdmpz molecule, and one of the anions becomes η2-coordinated. As a result of the reaction of the initial cobalt(II) CP with 1,10-phenanthroline (Phen) containing a water molecule, binuclear complex Co2[(OOCC5H4)Mn(CO)3]4(Phen)2(µ-dipy)(OH2)2 (3) is formed. The synthesized compounds 1–3 were studied by chemical analysis, IR spectroscopy, and X-ray diffraction analysis.