Synthesis and structure of diethylenetriammonium tetrachloroaurates(III)

The (DienH₃)[AuCl₄]₃ · H₂O (I) and (DienH₃)₂[AuCl₄]Cl₅ (II) compounds were obtained by the reaction of HAuCl₄ with diethylenetriamine trihydrochloride (DienH₃Cl₃) in hydrochloric acid. The compounds were characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. Crystals of I and II are monoclinic with space group P2₁/n. For I, a = 12.2314(3) Å, b = 14.6077(5) Å, c = 13.2680(5) Å, β = 106.7350(10)°, V = 2270.22(13) ų, Z = 8. For II, a = 6.62990(10) Å, b = 17.9026(5) Å, c = 10.3661(3) Å, β = 101.9230(10)°, V = 1203.83(5) ų, Z = 2. Both structures are ionic. The gold atoms in I and II have a 4 + 2 coordination environment. The Au-Cl bond lengths are within 2.276–2.294 Å, and the axial Au…Cl contacts are within 3.315–3.405 Å. The diethylenetriammonium cation in I and II has different conformations.     

Heteroligand zinc(II) and copper(II) complexes with naphthylacetic acid and monoethanolamine: Syntheses and crystal structures

New heteroligand Cu(II) and Zn(II) complexes with the α-naphthylacetic acid anion (NAA) and monoethanolamine (MEA), [M(NAA)₂(MEA)₂] (M = Cu²⁺, (I), Zn²⁺ (II)), are synthesized. The crystal structures of the obtained complexes are determined by X-ray diffraction analysis (CIF files CCDC 984097 (I) and 930946 (II)). The crystals are monoclinic, for I: a = 18.8140(9) Å, b = 4.82500(14) Å, c = 16.0360(7) Å, β = 115.135(6)°, V = 1317.87(11) ų, space group P2₁/c, Z = 2; for II: a = 32.9760(14) Å, b = 5.0911(3) Å, c = 15.7994(10) Å, β = 94.418(5)°, V = 2644.6(3) ų, space group C2/c, Z = 4. In the structure of complex I, the Cu²⁺ ion arranged in the symmetry center is coordinated at the vertices of the distorted octahedron by the oxygen atoms of two NAA molecules (Cu-O(2) 2.019(4) Å) and two MEA molecules. The latter is the bidentate-chelating ligand and coordinates the metal through the O and N atoms to form the five-membered metallocycle (Cu-O(3) 2.457(5), Cu-N(1) 1.986(5) Å). In complex II, the Zn atom (on axis 2) is coordinated at the vertices of the distorted tetrahedron by the oxygen atoms of two NAA molecules (Zn-O(2) 1.976(4) Å) and the nitrogen atoms of two MEA molecules (Zn-N 2.034(6) Å). The character of the interaction of coordinated NAA and MEA ligands and methods for packing complexes I and II are considered on the basis of the structural data.     

New fluorochromatouranylates of alkali metals: Synthesis and structure

Four new fluorochromatouranylates, namely, K[UO₂(CrO₄)F] · 1.5H₂O (I), Rb[UO₂(CrO₄)F] · 1.5H₂O (II), Rb[UO₂(CrO₄)F] · 0.5H₂O (III), and Cs[UO₂(CrO₄)F] · 0.5H₂O (IV), have been synthesized, and their crystallographic characteristics have been determined. All the compounds crystallize in monoclinic system, space group P2₁/c, with the unit cell parameters a = 13.1744(5) Å, b = 9.4598(3) Å, c = 13.0710(4) Å, β = 103.746(1)°, Z = 4, R = 0.0235 (I); a = 13.5902(7) Å, b = 9.5022(4) Å, c = 13.2271(6) Å, β = 102.914(2)°, Z = 4, R = 0.0247 (II); a = 24.7724(8) Å, b = 12.6671(4) Å, c = 9.4464(3) Å, β = 97.661(1)°, Z = 8, R = 0.0448 (III); a = 25.725(1) Å, b = 12.8261(5) Å, c = 9.4929(4) β = 97.208(1)°, Z = 8 (IV). The pairs of compounds I and II and compounds III and IV are isostructural. Crystals of compounds I–III have been subjected to complete X-ray diffraction study. It has been established that the structures of compounds I–III are built of [UO₂(CrO₄)F] _n ^n? layers, which are parallel to the (100) plane and linked into a framework by alkali-metal cations located between layers, together with water molecules. The effect of topological and geometric isomerism on the structural features of 34 known uranyl compounds of the AT³M² crystallochemical group, to which the studied compounds I–III also belong, is discussed.     

Diaquabromo(18-crown-6)rubidium and triaqua(18-crown-6)barium dibromide monohydrate: Synthesis and crystal structures

Two complexes are synthesized: diaquabromo(18-crown-6)rubidium [RbBr(18-crown-6)(H₂O)₂] (I) and triaqua(18-crown-6)barium dibromide monohydrate [Ba(18-crown-6)(H₂O)₃]²⁺ 2Br^? · H₂O (II). The orthorhombic structure of compound I (space group Pnma, a = 10.124 Å, b = 15.205 Å, c = 12.544 Å, Z = 4) and the monoclinic structure of compound II (space group C 2/c, a = 17.910 Å, b = 10.315 Å, c = 14.879 Å, β = 123.23°, Z = 4) are determined by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.063 (I) and 0.042 (II) for all 2293 (I) and 3363 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK _α). The complex molecule [RbBr(18-crown-6)(H₂O)₂] in compound I and the randomly disordered cation [Ba(18-crown-6)(H₂O)₃]²⁺ in compound II are of the host-guest type: their Rb⁺ or Ba²⁺ cation (its coordination number is nine) is located in the cavity of the 18-crown-6 ligand and coordinated by all six O atoms. In structure I, the coordination polyhedron of Rb⁺ is a distorted hexagonal pyramid with a triple apex at the Br^? ligand and two O atoms of the water molecules. In structure II, the Ba²⁺ polyhedron is a distorted hexagonal bipyramid with one apex at the O atom of the water molecule and the other split apex at two O atoms of water molecules.     

Acid Co(II) and Ni(II) trifluoroacetate complexes: Synthesis and crystal structure

Anhydrous and partially hydrated acid trinuclear trifluoroacetates of divalent transition metals of the composition [M₃(CF₃COO)₆(CF₃COOH)₆)](CF₃COOH) and [M₃(CF₃COO)₆(CF₃COOH)₂(H₂O)₄)](CF₃COOH)₂, respectively, where M = Co (I, III) Ni (II, IV), were synthesized and studied by X-ray diffraction. Complexes I and II were obtained by crystallization from solutions of M(CF₃COO)₂ · 4H₂O in trifluoroacetic anhydride; complexes III and IV were synthesized under the same conditions with the use of 99% trifluoroacetic acid as a solvent. Crystals I are triclinic: space group $P\bar 1$ , a = 13.199(6) Å, b = 14.649(6) Å, c = 15.818(6) Å, α = 90.04(4)°, β = 114.32(4)°, γ = 108.55(4)°, V = 2611.3(19) ų, Z = 2, R = 0.0480. Crystals II are trigonal: space group $R\bar 3$ , a = 13.307(2) Å, c = 53.13(1) Å, V = 8148(2) ų, Z = 6, R = 0.1112. Crystals III are triclinic: space group $P\bar 1$ , a = 9.001(8) Å, b = 10.379(9) Å, c = 12.119(9) Å, α = 83.67(5)°, β = 72.33(5)°, γ = 83.44(5)°, V = 1068.3(15) ų, Z = 1 Å, R = 0.1031. Crystals IV are triclinic: space group $P\bar 1$ , a = 9.121(18) Å, b = 10.379(2) Å, c = 12.109(2) Å, α = 84.59(3)°, β = 72.20(3)°, γ = 82.80(3)°, V = 1080.94(40) ų, Z = 1, R = 0.0334.     

Oxidation of coordinated ethylenediamine in platinum(IV) complexes with bromine. Crystal structures of [Pt(en)Py2Br2]Br2 · H2O, [Pt(HN-C(O)-C(O)-NH)Py2Br2] · H2O, and [Pt(en)PyBr3]NO3

Heating of an aqueous solution of [Pt(en)Py₂Cl₂]Cl₂ · 2H₂O (I) with KBr excess leads to the formation of [Pt(en)Py₂Br₂]Br₂ · H₂O (II). The interaction of a solution of II with bromine water results in the precipitation of polybromide ([Pt(en)Py₂Br₂]Br₂ · Br₂), which within a few days in the reaction solution partly transforms into oximide platinum(IV) complex, [Pt(HN-C(O)-C(O)-NH)Py₂Br₂] · H₂O (III). Complex [Pt(en)PyBr₃]Br · H₂O (IV) with an impurity of II was prepared by reacting KBr excess and the product of [Pt(en)Py₂]Cl₂ oxidation with chlorine in 0.05 N HCl. The action of HNO₃ on the solution of IV produced a nitrate derivative ([Pt(en)PyBr₃]NO₃, V). Complex IV, unlike II, does not react with bromine. The IR spectra of all the obtained compounds were recorded. Complexes II, III, and V were studied by X-ray crystallography. The crystals of II are monoclinic, space group P2₁/c, a = 15.640(2) Å, b = 9.345(1) Å, c = 14.167(2) Å, β = 102.63(1)°, V = 2020.5(5) ų, Z = 4, R _hkl = 0.033. The crystals of III are triclinic, space group P $\bar 1$ , a = 7.108(1) Å, b = 10.946(1) Å, c = 11.020(2) Å, α = 83.63(1)°, β = 80.31(1)°, γ = 75.02(1)°, V = 814.4(2) ų, Z = 2, R _hkl = 0.033. In the near-planar five-membered chelate ring (torsion angle NCCN is 7°), the C-O distances (1.23(1) Å) correspond to double bonds; the C-C (1.53(1) Å) and C-N (1.31(1) Å), distances correspond to ordinary bonds. The crystals of V are monoclinic, space group P2₁/c, a = 8.306(2) Å, b = 8.995(2) Å, c = 20.231(4) Å, β = 97.48(2)°, V = 1498.6(6) ų, Z = 4, R _hkl = 0.037.     

Structure and properties of tripyridine nitrosocomplexes of ruthenium: mer-[Ru(NO)Py3Cl(OH)]Cl·1.5H2O and mer-[Ru(NO)Py3Cl(H2O)]Cl2·2H2O·0.5HCl

The reaction of K₂[Ru(NO)Cl₅] with pyridine in aqueous ethanol at pH ～ 7–8 affords a nitrosoruthenium hydroxocomplex mer-[Ru(NO)Py₃Cl(OH)]Cl·1.5H₂O (I) (yield ～55%). Treatment of hydroxocomplex I with hydrochloric acid at room temperature gives the aqua complex mer-[Ru(NO)Py₃Cl(H₂O)]Cl₂·2H₂O·0.5HCl (II). The structures of the compounds are determined by X-ray crystallography: I, space group P2₁/n, a = 9.2292(4) Å, b = 11.7781(4) Å, c = 17.4915(7) Å, β = 90.9560(10)°, R = 4.84%; II, space group P-1, a = 7.3528(9) Å, b = 11.5793(11) Å, c = 13.6961(16) Å, α = 84.558(3)°, β = 87.668(4)°, γ = 74.146(4)°, R = 6.22%. Compounds I and II are characterized by powder XRD, ¹H and ¹³C NMR, and IR spectroscopy. The thermal decomposition of compound II in the inert atmosphere is examined by thermal analysis.     

Synthesis and structure of lithium and rubidium compounds with 2-(diphenylacetyl)-1,3-indanedione

Complexes RbL (I) and [Li₂(C₂H₅OH)L₂] (II) (L = C₂₃H₁₅O₃) have been synthesized and their crystal structures have been studied. Both compounds have monoclinic crystals with space group P2₁/c and Z = 4; I: a = 11.632(2) Å, b = 15.154(3) Å, c = 11.457(2) Å, β = 104.34(3)°; II: a = 12.982(3)Å, b = 12.083(2) Å, c = 25.317(5) Å β = 100.11(3)°. In the structure of I, dimeric groups [Rb₂O₆] with a shared edge are linked by the ligands to give infinite layers perpendicular to the x axis and cavities that form oblong channels. In the structure of II, Li₂O₇ dimers are formed by vertex sharing. The coordination of one of the lithium atoms (Li(1)) is completed to tetrahedral by the oxygen atom of the ethanol molecule. The structure of II, like that of I, is layered.     

Synthesis,crystal structures,and biological property of dinuclear oxovanadium(V) complexes derived from tridentate Schiff bases

A pair of structurally similar dinuclear oxovanadium(V) complexes, [VO₂L¹]₂ (I) and [VO₂L²]₂ (II), where L¹ and L² are the mono-anionic form of 2-[(2-isopropylaminoethylimino)methyl]-4-methylphenol (HL¹) and 4-fluoro-2-[(2-isopropylaminoethylimino)methyl]phenol (HL²), respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination. The crystal of I is monoclinic: space group P2₁/c, a = 12.528(1), b = 12.266(1), c = 9.432(1) Å, β = 104.814(3)°, V = 1401.2(3) ų, Z = 2. The crystal of I is monoclinic: space group P2₁/n, a = 12.3128(5), b = 6.5124(3), c = 17.1272(7) Å, β = 105.863(1)°, V = 1321.1(1) ų, Z = 2. The V…V distances are 3.210(1) Å in I and 3.219(1) Å in II. The V atoms in the complexes are in octahedral coordination. Biological assay indicates that complex II, bearing fluoro-substitute groups, has stronger antimicrobial activity against most bacteria than complex I which bearing methyl-substitute groups.     

Mixed-ligand complexes based on asymmetric gadolinium β-diketonates: Synthesis, crystal structure, and theoretical modeling

Mixed-ligand complexes of asymmetric gadolinium β-diketonates with 2,2′-bipyridyl (Bipy)—[Gd(Pa)₃(Bipy)] (HPa is pivaloylacetone) (I) and [Gd(Pta)₃(Bipy)] (HPta is pivaloyltrifluoroacetone) (II)-have been obtained by direct interaction of initial reagents and their structures have been studied by X-ray crystallography. Crystals of I are monoclinic: a = 9.536(1) Å, b = 15.037(1) Å, c = 13.280(1) Å, β = 109.56(1)°, V = 1798.7(3) ų, Z = 2, space group P2₁. Crystals of II are triclinic: a = 9.6696(17) Å, b = 12.1348(9) Å, c = 18.243(3) Å, α = 100.257(12)°, β = 103.997(2)°, γ = 101.438(11)°, V = 1977.4(5), Z = 2, space group P $\bar 1$ . The coordination polyhedron of the central gadolinium atom in I and II is a distorted square antiprism formed by six oxygen atoms of the three β-diketonate ligands (av. Gd-O, 2.35(2) and 2.351(5) Å in I and II, respectively) and two nitrogen atoms of the Bipy ligand (av. Gd-N, 2.47(2) and 2.584(7) Å in I and II, respectively). Although the molecular structures of these complexes are similar, they have different crystal packings. In II, the planes of the Bipy ligands of neighboring molecules related by an inversion center are bound by stacking interaction (the distance between the Bipy planes is 3.45 Å). The structure and properties of these mixed-ligand complexes have been discussed based on the results of quantum-chemical density functional theory calculations (DFT/B3PW91). The nature of the substituents in the β-diketonate ligand has an effect on the structure and properties of the complexes. The correlation between the Gd-Dik and Gd (Dik)₃-Bipy bond energies has been studied.     

Synthesis and crystal structures of dimeric schiff base oxovanadium(V) complexes with antimicrobial activity

Two new dimeric oxovanadium(V) complexes, [VO₂L₁]₂ · 2H₂O (I) and [VO₂L₂]₂ (II), where L¹ and L² are the monoanionic form of 5-methoxy-2-[(2-methylaminoethylimino)methyl]phenol (HL¹) and 5-diethylamino-2-[(2-methylaminoethylimino)methyl]phenol (HL²), respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination. The crystal of I is monoclinic: space group P2₁, a = 6.858(2), b = 16.630(3), c = 12.306(2) Å, β = 103.985(2)°, V = 1361.9(5) ų, Z = 2. The crystal of II is triclinic: space group $P\bar 1$ , a = 7.378(2), b = 8.838(2), c = 13.312(3) Å, α = 102.576(2)°, β = 92.044(2)°, γ = 113.017(2)°, V = 772.7(3) ų, Z = 2. The V...V distances are 3.140(1) Å in I and 3.254(1) Å in II. The V atoms in the complexes are in octahedral coordination. The effect of the complexes on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans was studied.     

Crystal and molecular structures of ZnPhen(C2H5OCS2)2 and Zn(2,2′-Bipy)(n-C4H9OCS2)2 mixed-ligand coordination compounds

ZnPhen(EtOCS₂)₂ (I) and Zn(2,2′-Bipy)(n-BuOCS₂)₂ (II) mixed-ligand complexes have been synthesized. The structures were solved from X-ray diffraction data (CAD-4 and X8-APEX diffractometers, MoK _α radiation, 1879 and 3637 F _hkl , R = 0.0374 and 0.0315). Crystals I are monoclinic with parameters a = 11.678(3) Å, b = 19.215(3) Å, c = 9.655(1) Å; β = 101.23(1)°; V = 2125.0(7) ų; Z = 4, space group P2₁/c; crystals II are triclinic with parameters a = 8.7875(3) Å, b = 11.833(1) Å, c = 13.3454(6) Å; α = 112.154(2)°, β = 108.503(1)°, γ = 92.787(2)°; V = 1196.2(1) ų; Z = 2, space group 1 $P\bar 1$ . The structures are composed of discrete mononuclear molecules. The polyhedra of the Zn atoms are distorted trigonal bipyramids N₂S₃ formed by coordination of the N atoms of Phen or 2,2′-Bipy molecules and sulfur atoms of the monodentate and cyclic bidentate xanthogenate ligand. In structures I and II, dimer assemblies are formed by π-π interactions of Phen or 2,2′-Bipy molecules.     

Copper(I) halide complexes with ethylenediaminium L0(H+)2, N,N,N′,N′-tetraallylethylenediaminium L4(H+)2, and N,N,N,N′,N′-pentaallylethylenediaminium L5(H+). Synthesis and crystal structures of the complexes [L0(H+)2]0.5CuCl2, [L0(H+)2]0.5CuBr1.67Cl0.33, [{L4(H+)2}0.5Cu2Cl3], and [L5(H+)Cu4Br6]

Alkylation of ethylenediamine with allyl bromide in the presence of NaHCO₃ in benzene-ethanol and acetone-ethanol gave N,N,N′,N′-tetraallylethylenediamine L⁴ and N,N,N,N′,N′-pentaallylethylenediaminium bromide (L₅(H⁺)Br₂), respectively. The ac electrochemical synthesis at copper wire electrodes in solutions of copper(II) halide and an appropriate ligand yielded single crystals of Cu(I) complexes with ethylenediaminium ([L⁰(H⁺)₂]_0.5CuCl₂ (I) and [L⁰(H⁺)₂]_0.5CuBr_1.67Cl_0.33 (II)) and its N-allyl derivatives N,N,N′,N′-tetraallylethylenediaminium ([{L⁴(H⁺)₂}_0.5Cu₂Cl₃] (III)) and N,N,N,N′,N′-pentaallylethylenediaminium ([L⁵(H⁺)Cu₄Br₆] (IV)). The crystal structures of complexes I–IV were determined by X-ray diffraction. The isostructural crystals of complexes I and II are triclinic, space group P $ \bar 1 $ , Z = 2. For I: a = 5.936(3), b = 6.387(3), c = 7.126(4) Å, α = 67.82(4)°, β = 72.98(4)°, γ = 67.55(4)°, V = 227.7(2) ų. For II a = 6.110(3), b = 6.657(3), c = 7.309(3) Å, α = 68.40(3)°, β = 72.38(3)°, γ = 67.23(3)°, V = 250.4(2) ų. In structures I and II, the organic cations are between infinite anionic chains (Cu ₂ ^? ) _n . The crystals of π-complex III are triclinic, space group P $ \bar 1 $ , a = 6.851(4), b = 8.729(4), c = 9.960(4) Å, α = 98.25(3)°, β = 102.29(3)°, γ = 107.30(3)°, V = 541.8(5) ų, Z = 2. In structure III, all the four allyl groups are π-coordinated by the metal atoms of four discrete anions Cu₄Cl ₆ ^2? . The crystals of π-complex IV are monoclinic, space group C2/c, a = 15.228(5), b = 17.095(6), c = 20.182(6) Å, β = 92.43(4)°, V = 5249(3) ų, Z = 8. Only two of five allyl groups at the same N atom are coordinated by copper(I) atoms. Structure IV contains a complex inorganic fragment of the formula (Cu₄Br ₆ ^2? ) _n .     

Copper complexes with N-allylisoquinolinium halides: Synthesis and crystal structures of [C9H7N(C3H5)]2CuIICl2.86Br1.14, [C9H7N(C3H5)CuIBr2] · H2O, and [C9H7N(C3H5)CuIBr2]

Crystals of the copper bromide complexes with N-allylisoquinolinium halides of the composition [C₉H₇N(C₃H₅)]₂Cu^IICl_2.86Br_1.14 (I), [C₉H₇N(C₃H₅)]Cu^IBr₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^IBr₂ (III) are prepared by ac electrochemical synthesis, and their structures are studied by X-ray diffraction analysis (DARCh-1 (for I) and KUMA/CCD (for II and III) diffractometers). The crystals of compound I are monoclinic: space group P2₁/n, a = 15.053(5) Å, b = 10.486(4) Å, c = 17.179(10) Å, γ = 109.77(3)°, V = 2552(4) ų, Z = 4. The crystals of complex II are triclinic: space group P $\overline 1 $ , a = 7.040(1) Å, b = 7.610(2) Å, c = 12.460(2) Å, α = 79.54(3)°, β = 86.73(3)°, γ = 89.51(1)°, V = 655.4(2) ų, Z = 2. The crystals of complex III are monoclinic: space group P2₁/n, a = 12.799(1) Å, b = 7.692(1) Å, c = 13.491(1) Å, β = 111.08(1)°, V = 1239.3(2) ų, Z = 4. The structure of compound I is built of the Cu^IIX ₄ ^2? tetrahedra and N-allylisoquinolinium cations united by the C-H···X contacts into corrugated layers. The crystal structure of π-complex II is formed of dimers of the composition [C₉H₇(C₃H₅)]₂ Cu ₂ ^I Br₄ forming layers in the direction of the z axis due to the C-H···X contacts. An important role in structure formation belongs to water molecules that cross-link the organometallic layers through the O-H···X contacts into a three-dimensional framework. When kept in the mother liquor for 6 months, the crystals of compound II transformed into crystals of compound III, whose structure consists of {[C₉H₇(C₃H₅)]₂Cu ₂ ^I Br₄} _n columns united through the C-H···Br contacts (H···Br 2.84(3)?2.92(4) Å) into a three-dimensional framework.     

Synthesis and crystal structures of Manganese(IV) complexes with tridentate schiff bases

The complexes with the formulae [Mn(L¹)₂] · 0.5H₂O (I) and [Mn(L²)₂] (II), where L¹ and L² are the dianionic form of 2,4-dichloro-6-[(2-hydroxyethylimino)methyl]phenol and 2-{[1-(3-ethoxy-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol, respectively, were obtained and characterized by elemental analysis and IR spectroscopy. The crystal structures of complexes I and II were determined using X-ray diffraction. The crystal of I is orthorhombic space group Fdd2: a = 24.170(2), b = 32.021(3), c = 11.352(2) Å, V = 8785.9(19) ų, Z = 8. The crystal of II is monoclinic space group C2/c: a = 13.931(4), b = 18.381(5), c = 12.444(5) Å, β = 121.980(3)°, V = 2702.9(15) ų, Z = 4. The Mn atom in each of the complexes is in an octahedral coordination.     

Synthesis and crystal structure of [UO2(L)(OH)], (CN3H6)2[(UO2)2CrO4(L)4 · 2H2O and [UO2(H2O)5][(UO2)2Cr2O7(L)4] (where L is picolinate ion)

[[UO₂(L)(OH)] (I), (CN₃H₆)₂[(UO₂)₂CrO₄(L)₄] · 2H₂O (II), and [UO₂(H₂O)₅][(UO₂)₂Cr₂O₇(L)₄] (III) crystals, where L is picolinate ion C₅H₄NCOO^?, have been synthesized and studied by X-ray diffraction and IR spectroscopy. Complex I crystallizes in triclinic system with the unit cell parameters a = 6.2858(5) Å, b = 7.9522(5) Å, c = 8.3598(6) Å, α = 79.527(6)°, β = 87.760(6)°, γ = 79.126(6)°, space group P $\bar 1$ , Z = 2, R = 0.0306, and complexes II and III crystalize in monoclinic system with a = 8.8630(9) Å, b = 13.4540(13) Å, c = 31.266(3) Å, β = 93.118(3)°, space group C2/c, Z = 4, R = 0.0187 (II), and a = 7.3172(4) Å, b = 15.4719(8) Å, c = 16.6534(10) Å, β = 98.943(4)°, space group P2₁/m, Z = 2, R = 0.0588 (III). The structure of complex I is built of electronegative [UO₂(L)(OH)] chains, which belong to the AT¹¹M² crystallochemical group (A = UO ₂ ²⁺ , T¹¹ = L, M² = OH^?) of uranyl complexes. The structure of complexes II and III contains [(UO₂)₂(L′)(L)₄]^2? dimers (L′ = CrO ₄ ^2? or Cr₂O ₇ ^2? ), which belong to the A₂B²B ₄ ⁰¹ group (A = UO ₂ ²⁺ ,B² = L′, B⁰¹ = L). The specifics of intermolecular interactions in the structures of complexes I–III and some their analogues have been considered using molecular Voronoi-Dirichlet polyhedra.     

Syntheses, structural determination, and binding studies of mononuclear nine-coordinate (EnH2)1.5[HoIII(Ttha)] · 4.5H2O and two dimensional unlimited network (EnH2)[HoIII(Egta)(H2O)]2 · 6H2O

Two novel complexes, (EnH₂)_1.5[Ho^III(Ttha)] · 4.5H₂O (I) (En = ethylenediamine and H₆Ttha = triethylenetetramine-N,N,N′,N″,N?,N?-hexaacetic acid) and (EnH₂)[Ho^III(Egta)(H₂O)]₂ · 6H₂O (II) (H₄Egta = ethyleneglycol-bis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid), were synthesized and their crystal structures were determined by single crystal X-ray diffraction techniques. Complex I has a nine-coordinate mononuclear structure with distorted tricapped trigonal prismatic conformation and crystallizes in the monoclinic crystal system with P2/n space group. The crystal data are as follows: a = 17.7541(18), b = 9.6810(10), c = 22.166(2) Å, β = 118.913(2)°, and V = 3335.0(6) ų. Complex II has a mononuclear nine-coordinate structure with pseudo-monocapped square antiprismatic conformation and crystallizes in the monoclinic crystal system with P2₁/n space group. The crystal data are as follows: a = 12.978(8), b = 12.685(8), c = 14.905(9) Å, β = 105.333(7)°, and V = 2366(2) ų. In I, there are two types of EnH ₂ ²⁺ anions. They connect to [Ho^III(Ttha)]^3? by hydrogen bonds leading to the formation of 3D pore structure along z axis. In II, EnH ₂ ²⁺ cation connects three adjacent [Ho^III(Egta)(H₂O)]^? complex anions through hydrogen bonds, these hydrogen bonds lead to the formation of 2D network structure in [101] plane. The results showed that ligand structures play a crucial role in crystal and molecular structure of their complexes. In addition, the protonated (EnH ₂ ²⁺ ) cations conjugating to [Ho^III(Ttha)]^3? and [Ho^III(Egta)(H₂O)]^? complex anions are reviewed, which act as an important beginning for study of Ho(III) complexes conjugating with other various amino and heterocyclic biomolecule.     

Thulium(III) trifluoroacetates Tm(CF3COO)3 · 3H2O and Tm2(CF3COO)6 · 2CF3COOH · 3H2O: Synthesis and crystal structure

Thulium trifluoroacetate compounds have been synthesized, Tm(CF₃COO)₃ · 3H₂O (I) and Tm₂(CF₃COO)₆ · 2CF₃COOH · 3H₂O (II). The structure of I has been refined by the Rietveld method on the basis of the structural data for Cd(CF₃COO)₃ · 3H₂O. The structure of II has been solved in a single-crystal X-ray diffraction study. Compound I has been studied by thermal analysis. Crystals of I and II are monoclinic: for I a = 9.062(2) Å, b = 18.678(3) Å, c = 9.687(2) Å, β = 113.93(1)°, Z = 2, space group P2₁/c, R ₁ = 0.062; for II a = 8.560(4) Å, b = 19.866(5) Å, c = 20.813(7) Å, β = 101.69(4)°, Z = 8, space group C2/c, R ₁ = 0.0392. In the molecular structure of I, thulium atoms are bonded in pairs through four bridging trifluoroacetate anions to form dimers. The coordination polyhedron of the thulium atom also includes the three O atoms of the water molecules and the O atom of the monodentate trifluoroacetate group; the coordination number of the thulium atom is eight. In the chain structure of II, there are two crystallographically independent thulium atoms with coordination numbers 8 and 9. The coordination polyhedra of the Tm(1) and Tm(2) atoms are a distorted monocapped tetragonal antiprism and a distorted tetragonal antiprism, respectively. The Tm-O bond lengths are in the range 2.28(1)–2.85(2) Å. The thulium atoms are bound into chains through carboxylate groups. These chains are linked into layers through hydrogen bonds.     

Crystal structure and magnetic properties of heterometallic trinuclear Cu2Ni complex containing macrocyclic ligands

One novel heterometallic trinuclear complex of macrocyclic oxamide [Ni(CuL)₂(HBTC)H₂O] (I) (H₂L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclopentadeca-7,13-dien; H₃BTC = 1,3,5-benzenetricarboxylic acid) has been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, XRD, and single-crystal X-ray diffraction. The crystals crystallize in the monoclinic system, space group P2₁/c, a = 11.435(3), b = 20.646(5), c = 18.430(5) Å, β = 94.131(4)°. The structure of I has oxamido-bridged trinuclear [Cu ₂ ^II Ni^II] units and consists of two-dimensional supramolecular architecture formed by strong intermolecular hydrogen bonds. Furthermore, the magnetic properties of complex I was investigated and discussed in detail.     

Study of acid pyridine-3-carboxylic acid dodecatungstenphosphate of the composition (C6NO2H5)2H[PW12O40]·2H2O

Acid pyridine-3-carboxylic acid dodecatungstenphosphate (C₆NO₂H₅)₂H[PW₁₂O₄₀]·2H₂O is synthesized. The compound is studied by chemical analysis, IR spectroscopy, X-ray crystallography, and thermogravimetry. The compound is found to crystallize at 290 K in a hexagonal crystal system (space group \(R\bar 3\) ) (I) with the unit cell parameters: a = 33.015(6) Å, c = 12.010(2) Å, γ = 120°, V = 11337(4) ų, Z = 9. When the temperature decreases to 100 K, a phase transition is observed leading to an increase in symmetry to \(R\bar 3m\) (II), with the unit cell parameters: a = 33.072(1) Å, c = 24.234(1) Å, γ = 120°, V = 22955(2) ų, Z = 18.