Synthesis,crystal structure and magnetic properties of a novel manganese(II)-nitronyl nitroxide-azido(μ<Subscript>1,1</Subscript> and μ<Subscript>1,3</Subscript>) one-dimensional complex

A novel one-dimensional manganese(II) complex containing nitronyl nitroxide radical [Mn₂(IM2-py)₂(Ac)₂(μ_1,1-N₃)(μ_1,3-N₃) · EtOH] _n was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group p2₁/n. Each Mn(II) ion is six-coordinated in a distorted octahedral environment. The two N atoms of the nitronyl nitroxide radical and the two O atoms of acetate ligands are in the equatorial plane, whereas the two different azido bridging ligands are in trans axial position. Mn(II) ions are linked by nitrogen atom of μ_1,1-azido and oxygen atoms of two carboxy groups to form a Mn-Mn unit. Mn-Mn units are linked by azido ligands through μ_1,3 bridging style to form a one-dimensional chain. The compound is connected by the coordination bonds, π-π interactions and hydrogen bonds as a three-dimensional structure. Magnetic susceptibility data support that there are stronger antiferromagnetic interactions between the radical and Mn(II) ion, weak antiferromagnetic interactions between the Mn-R units, and very weak antiferromagnetic interactions between the R-Mn-Mn-R units.     

Erbium(III) and lutecium(III) complexes [Ln(H<Subscript>2</Subscript>O)<Subscript>8</Subscript>][Cr(NCS)<Subscript>6</Subscript>] · 5H<Subscript>2</Subscript>O: Synthesis and crystal structure

[Ln(H₂O)₈][Cr(NCS)₆] · 5H₂O aqua complexes, where Ln = Er (1), Lu (2), have been found in an aqueous solution instead of binary complex salts with an organic ligand in their cation, when crystal products of the reaction between Ln(NO₃)₃ · 6H₂O (Ln = Er, Lu), K₃[Cr(NCS)₆] · 4H₂O, and 8-oxyquinoline (C₉H₇NO) were studied by X-ray diffraction. Crystals of complexes 1 and 2 are isostructural and crystallize in triclinic system, space group P\(\bar 1\), Z = 2. For complex 1: a = 9.0677(4) Å, b = 9.3115(4) Å, c = 16.9595 Å, α = 81.526(2)°, β = 86.153(2)°, γ = 83.879(2)°, V = 1406.33(10) ų, ρ_calc = 1.894 g/cm³; for complex 2: a = 9.0438(3) Å, b = 9.2880(3) Å, c = 16.9181(3) Å, α = 81.7250(10)°, β = 86.1600(10)°, γ = 83.8850(10)°, V = 1396.38(7) ų, ρ_calc = 1.926 g/cm³.     

[Ca(OPPh<Subscript>3</Subscript>)<Subscript>5</Subscript>][Mo<Subscript>6</Subscript>(μ<Subscript>3</Subscript>-Cl)<Subscript>8</Subscript>Cl<Subscript>6</Subscript>] · OPPh<Subscript>3</Subscript>: Synthesis and crystal structure

A solvatothermal reaction of the octahedral cluster molybdenum complex (H₃O)₂[Mo₆(μ₃-Cl)₈Cl₆] · 6H₂O with CaCl₂ · 6H₂O and OPPh₃ in acetonitrile gave the known polymeric complex trans-[{Ca(OPPh₃)₄}{Mo₆(μ₃-Cl)₈Cl₆}]_∞. However, a closer examination revealed that this system also produces a novel cluster complex, [Ca(OPPh₃)₅][Mo₆(μ₃-Cl)₈Cl₆] · OPPh₃, which was isolated and characterized by X-ray diffraction.     

Synthesis,characterization, spectroscopic,and thermal studies of imidazole complexes of metal benzenesulfonates. Crystal structure of [M(imH)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]·(BS)<Subscript>2</Subscript> [M=Ni(II) and Co(II)]

Four novel transition metal benzenesulfonate (BS) complexes of imidazole (im) with a general formula [M(imH)₃(H₂O)₃]·(BS)₂ [M=Mn(II) (1), Ni(II) (2), Co(II) (3)] and [Cu(BS)(imH)₃]·(BS) (4) have been synthesized and characterized by physicochemical and spectroscopic methods. The complexes 2 and 3 have also been characterized by single X-ray diffraction technique. The BS anion in complexes 1–3 acts as a counter anion, while in complex 4, it acts as both ligand and counter anion. The Ni and Co complexes are isomorphous, crystallizing in the monoclinic crystal system with C2/c space group. Each metal(II) atom in 2 and 3 is octahedrally coordinated by three imidazole and three aqua ligands, adopting a mer-coordination mode with Ni(II) or Co(II) centers. In both 2 and 3, the H2C atom has bifurcated donor (O3 and O5) atoms, forming a bifurcated hydrogen bond. This hydrogen bond links the complex cation and BS anion, forming one-dimensional hydrogen-bonded supramolecular chains. The complexes exhibit different decomposition characteristics. Magnetic susceptibility measurement shows that complex 3 has orbital interactions.     

Reactions of 2,2′-Pyridyl with the cadmium(II) compounds: Synthesis,crystal structure,and luminescence properties of [Cd(Pic)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · H<Subscript>2</Subscript>O

The reactions of 2,2'-pyridyl, (2-Py)C(O)C(O)(2-Py), with the Cd(II) compounds under various conditions are studied. The medium and nature of the anions exert a decisive effect on the compositions and structures of the formed cadmium complexes. The reaction of cadmium diacetate with 2,2'-pyridyl in an aqueous-alcohol medium in air affords coordination compound [Cd(Рic)₂(H₂O)₂] · H₂O (I) (Pic^? is picolinate ion, CO₂C₅H₄N), and its crystal structure is determined. The crystals are monoclinic: space group P2₁/c, a = 7.499(1), b = 15.676(1), с = 12.719(1) Å, β = 94.79(1)°, V = 1490.0(2) Å3, Z = 4, ρ_calcd = 1.502 g/cm³. The molecular packing of compound I is a supramolecular 3D framework consisting of discrete complexes [Cd(Pic)₂(H₂O)₂] linked by hydrogen bonds O–H…O. The coordination sphere of Cd²⁺ contains two O atoms and two N atoms of the ligand and two water molecules. The coordination polyhedron of Cd²⁺ is a distorted octahedron.     

New binuclear copper(II) complexes [Cu<Subscript>2</Subscript>(L)<Subscript>4</Subscript>(μ-CO<Subscript>3</Subscript>)][B<Subscript>12</Subscript>H<Subscript>12</Subscript>] (L = bipy,phen): Synthesis,structure, and magnetic properties

The processes taking place in the Cu^I/L/solv system (L = bipy, phen) in the presence of the [B₁₂H₁₂]^2– anion, which exhibited the lowest reducing ability among the [B _n H _n ]^2– cluster anions (n = 6, 10, 12), were studied. The binuclear complexes [Cu₂(L)₄(μ-CO₃)][B₁₂H₁₂] · n(solv) were found to be formed upon the redox reaction of (C₆H₅)₄P[Cu[B₁₂H₁₂]] with a twofold excess of L or the reaction of copper(II) complex [(Cu₂(phen)₄(CO₃)]Cl₂ with [(C₄H₉)₃NH]₂[B₁₂H₁₂]. The Cu(II) complexes were characterized by X-ray diffraction; their EPR-spectra were studied at 295 K and the magnetic measurements were performed in the 300–2 K range. In the [Cu₂(phen)₄(μ-CO₃)][B₁₂H₁₂] · DMF dimer with the anti-anti coordination of the (μ-CO₃)-group, strong antiferromagnetic interactions occur between the Cu(II) atoms (Cu?Cu = 5.107 Å).     

Synthesis and structure of the pyrazolate-bridged cobalt(II) benzoate Co<Subscript>2</Subscript>(μ-dmpz)<Subscript>2</Subscript>(Hdmpz)<Subscript>2</Subscript>(OOCPh)<Subscript>2</Subscript>

The reaction between Co(Hdmpz)₂(OOCPh)₂ and cobalt acetate hydrate leads to the deprotonation of coordinated pyrazole and formation of pyrazolate-bridged Co₂(μ-dmpz)₂(Hdmpz)₂(OOCPh)₂ binuclear complex. The structure of the complex was determined by X-ray crystallography.     

[H<Subscript>4</Subscript>(4,4′-Bipy)<Subscript>3</Subscript>][Sc(OH)(H<Subscript>2</Subscript>O)<Subscript>5</Subscript>]<Subscript>2</Subscript>Cl<Subscript>8</Subscript>: Synthesis,structure, and solid-phase thermal transformation

The reaction of [Sc(OH)(H₂O)₅]₂Cl₄ · 2H₂O in isopropanol with 4,4′-Bipy in CHCl₃ produced a crystalline compound, which was identified as [H₄(4,4′-Bipy)₃][Sc(OH)(H₂O)₅]₂Cl₈ (I) by elemental analysis, IR spectra, and single-crystal X-ray diffraction. In the structure of compound I, the three protonated diimine molecules form a centrosymmetric trimer via N...N hydrogen bonds. The polyhedron around the Sc atom is an octahedron with one split vertex. The excursion of the Sc atom from the plane formed by the oxygen atoms (water molecules) toward the hydroxo bridges is 0.5 Å. The thermolysis of compound I generates ScCl₃, whereas the final decomposition product of the precursor dimer is ScOCl.     

Synthesis,IR-spectroscopic study and crystal structure of tris(benzohydrazide)nickel(II) dichloride dihydrate [Ni(L)<Subscript>3</Subscript>]Cl<Subscript>2</Subscript> · 2H<Subscript>2</Subscript>O

Coordination compound [Ni(L)₃]Cl₂ · 2H₂O (L is benzohydrazide) has been synthesized and studied by IR spectroscopy and X-ray diffraction analysis. According to X-ray diffraction, one of the Cl^– ions is disordered over two nonequivalent positions. The crystals are monoclinic, a = 15.423(3) Å, b = 9.697(2) Å, c = 18.893(4) Å, ß = 105.99(3)°, space group P2₁/c, Z = 4. The structural units of the crystal are complex cations [Ni(L)3]2+, in which ligands L are coordinated to the central atom bidentately chelating the metal atoms through the O and N atoms of the hydrazide moiety (Ni–O 2.036(4), 2.051(5), 2.047(5); Ni–N 2.095(5), 2.089(6), 2.097(6) Å). The structural units of the crystal are joined together by cation–anion electrostatic interactions and hydrogen bonds, which involve both H₂O molecules, both Cl^– anions and the N atoms of chelate rings of the complex cation.     

Synthesis and structure of cobalt(III) dimethylglyoximate with [FeF<Subscript>5</Subscript>(H<Subscript>2</Subscript>O)]<Superscript>2−</Superscript> anion

A new complex [Co(DH)₂(Thio)₂]₂[FeF₅(H₂O)] · 2CH₃OH (where DH^? is dimethylglyoxime monoanion, Thio is thiourea molecule) was synthesized and its structure was determined. The coordination polyhedron of the Co(III) atoms in two centrosymmetric complex cations is an octahedron, formed by four N atoms of two dimethylglyoxime residues and two S atoms of coordinated Thio molecules. One of the Thio molecules is almost perpendicular to a metal cycle (the dihedral angle 87.8(1)°), which is responsible for realization of intermolecular hydrogen bond N-H···O (N···O 2.990(3) Å). The second Thio molecule is almost parallel to the equatorial CoN₄ fragment (the dihedral angle 159.4(1)°) to give rise to intramolecular π-π interaction between practically planar Thio molecule and one of the π-delocalized metal cycle. The Fe(III) coordination polyhedron is an octahedron, formed by five F atoms and by the O atom of coordinated water molecule. The key role in the crystal structure organization is played by intermolecular hydrogen bonds N-H···F, N-H···O, N-H···S, the intramolecular bonds O-H···O, formed by the donor NH₂ groups of a complex cation with the F atoms of the [FeF₅(H₂O)]^2? and the donor-acceptor groups of the Thio fragments.     

Synthesis of [MnCl<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>(Hatz)]·H<Subscript>2</Subscript>O and investigation of its structure via X-ray diffraction,spectroscopic measurements and DFT calculations

The 3-amino-1,2,4-triazole (atz)-based manganese complex was prepared and characterized through single-crystal X-ray diffraction, IR, EPR, and UV–visible spectroscopy. In the crystal structure, individual complex are interconnected through N(O)–H…Cl hydrogen bonds into 1D undulating chains running parallel to the [110] direction of the unit cell. Chains further grow into 2D supramolecular layers by way of the lattice water molecules of coordination and the chloride anions (O–H…Cl). Layers pack along the b-axis of the unit cell mediated by O–H…Cl(N) and N–H…O(Cl) hydrogen bonds forming a 3D supramolecular architecture. The theoretical calculations were also performed to optimize the structure of the complexes in the gas phase to confirm the structures proposed by X-ray crystallography. In addition, IR and UV–visible spectra of complex were calculated and compared with the corresponding experimental spectra to complete the experimental structural identification. The three-dimensional Hirshfeld surface (3D-HS) and their relative two-dimensional fingerprint plots (2D-FP) reveal that the structure is dominated by H…Cl/Cl…H (50.5%), H…O/O…H (11.3%) and N…O/O…N (10.2%) contacts.     

Synthesis,structure, and some reactions of the cluster complex [(μ-H)<Subscript>2</Subscript>Fe<Subscript>5</Subscript>(μ<Subscript>3</Subscript>-Se)<Subscript>2</Subscript>(CO)<Subscript>14</Subscript>]

In the reaction of Na₂Se with [Fe(CO)₅] in isopropanol with subsequent acidification with HCl, which is used to synthesize [(μ-H)₂Fe₃(μ₃-Se)(CO)₉] (II), the cluster [(μ-H)₂Fe₅(μ₃-Se)₂(CO)₁₄] (I) was detected. In assumption that compound I could serve as a suitable synthon for preparing the bulky heterometallic clusters, its reactions with the Rh-containing complexes were studied. The reaction of I with [Rh(CO)₂Cp*] (Cp* is pentamethylcyclopentadienyl) was found to give a mixture of the products. The main reaction products were isolated and their structures were determined: [Fe₂Rh(μ₃-Se)₂(CO)₆Cp*], [Fe₂Rh(μ₃-Se)(μ₃-CO)(CO)₆Cp*], [FeRh₂(μ₃-Se)(μ-CO)(CO)₃Cp ₂ ^* ], [Fe₂Rh₂(μ₄-Se)(μ-CO)₄(CO)₂Cp ₂ ^* ]. Potassium hydride treatment of II with subsequent addition of [Cp*Rh(CH₃CN)₃](CF₃SO₃)₂ leads to the well-known cluster complex [Fe₃Rh(μ₄-Se)(CO)₉Cp*]. A set of the reaction products indicates that the {Fe₅Se₂} core cannot be used as one-piece “building block” in the synthesis of heterometallic clusters.     

Manganese(II) 9-Molybdomanganate(IV), [Mn(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>]<Subscript>3</Subscript> · [MnMo<Subscript>9</Subscript>O<Subscript>32</Subscript>] · 2H<Subscript>2</Subscript>O: Synthesis,thermal analysis,IR spectra,and crystal structure

The [Mn(H₂O)₄]₃ · [MnMo₉O₃₂] · 2H₂O complex was synthesized and studied by X-ray diffraction, thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are trigonal: space group R32, a = 14.811(2) Å, c = 14.232(2) Å, V = 2703.7(8) ų, M = 1848.5, Z = 3, ρ(calcd.) = 3.419 g/cm³.     

Synthesis and Structure of Cobalt(III) α-Dimethylglyoximate [Co(DH)<Subscript>2</Subscript>(Py)<Subscript>2</Subscript>][H<Subscript>2</Subscript>F<Subscript>3</Subscript>]

The [Co(DH)₂(Py)₂][H₂F₃] complex (DH^? is the dimethylglyoxime residue) is synthesized and studied by X-ray diffraction analysis. Structural units of the crystal are complex cations [Co(DH)₂(Py)₂]⁺ and anions [H₂F₃]^?. Two residues of α-dimethylglyoxime linked by intramolecular hydrogen bonds O-H?O lie in the equatorial plane of the octahedral Co(III) complex, and two pyridine molecules occupy the apical positions. The H₂F ₃ ^? anion is formed due to the association of the F^? ion with two HF molecules through hydrogen bonds F-H?F. Weak intermolecular interactions C-H?F and C-H?O are observed in the crystal. The problem of the influence of these interactions on the packing of the complexes in crystal is discussed.     

Synthesis,Structure and Property of Oxo-Bridged Binuclear Iron(III) Complex [Fe(phen)(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]<Subscript>2</Subscript>O⋅2SO<Subscript>4</Subscript>

An oxo-bridged binuclear iron(III) complex, [Fe(phen)(H₂O)₃]₂O2SO₄, has been synthesized and structurally characterized by elemental analysis (EA), IR, TG-DSC and X-ray. Its crystal structure has been determined by X-ray crystallography. It crystallizes in the orthorhombic system, space group P2₁2₁2, with lattice parameters a = 17.650(4), b = 8.5133(17), c = 9.971(2) Å; V = 1498.2(5) ų, _calcd = 1.763 g/cm³ and Z = 4 for R₁ = 0.0601. The crystal structure indicated that two octahedrally coordinated iron(III) ions bridged with oxygen atoms formed a non-linear complex. The bond angle of Fe–O–Fe is 163.9(4). The data of EA and IR are in good agreement with the crystal structure. The thermal gravity (TG) data indicate that there are four decomposition steps with three endothermic peaks. The final product of the thermal decomposition may be Fe(C₂H₈N₂)SO₄.     

Crystal structure and spectroscopic properties of ciprofloxacinium pentachloroantimonate(III) monohydrate (C<Subscript>17</Subscript>H<Subscript>19</Subscript>N<Subscript>3</Subscript>O<Subscript>3</Subscript>F)SbCl<Subscript>5</Subscript> · H<Subscript>2</Subscript>O

Synthesis, X-ray diffraction, IR and luminescence spectroscopic studies of the monohydrate of pentachloroantimonate(III) of doubly protonated ciprofloxacin (C₁₇H₁₉N₃O₃F)SbCl₅ · H₂O (I) were performed. The structure of I is formed by SbCl₆ octahedra combined into polymeric chains [SbCl₅] _n ^2n? through common vertices, ciprofloxacinium cations (CfH₃)²⁺, and water molecules linked by hydrogen bonds. CfH is protonated at the carbonyl oxygen atom and the terminal nitrogen atom of the piperazinyl group. The electronic and geometric aspects determining the luminescence properties of I and of related compounds are discussed.     

Clathrate [Zn(C<Subscript>6</Subscript>H<Subscript>5</Subscript>COO)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 2CH<Subscript>3</Subscript>COOH: Synthesis and crystal structure

The clathrate [Zn(C₆H₅COO)₂(H₂O)₂] · 2CH₃COOH (I) was obtained for the first time from zinc(II) benzoate. The individuality, the unit cell parameters, and the number of “guest” molecules in complex I were determined from X-ray diffraction and derivatographic data. Its crystal structure was solved.     

Synthesis,crystal structure of new linear trinuclear isovalence Co(II)([Co<Subscript>3</Subscript>(H–L)<Subscript>2</Subscript>(L)<Subscript>2</Subscript>]), and visualizing intermolecular interactions with Hirshfeld surface method

S-allyl-β-N-[(2-hydroxyphenyl)methylene]hyrazinecarbodithioate) (1, H₂L), the Schiff base of dithiocarbazate with unsaturated allyl substitution, can act as a new tridentate SNO ligand H₂–L and react with cobalt(II) nitrate hexahydrate to form the novel linear trinuclear isovalence Co(II) complex, [Co₃(H–L)₂(L)₂] 2C₂H₅OH (2). The compounds were characterized by elemental analysis, infrared, and ultraviolet spectroscopy. Compound 2 was also characterized by single-crystal X-ray analysis and crystallizes in the orthorhombic space group, Pbcn, with a = 30.643(1) Å, b = 9.118(4) Å, c = 19.017(7) Å, α = β = γ = 90°, V = 5312.95 Å³, Z = 4, and R ₁ = 0.0790, (wR ₂) = 0.1223. The six-coordinate central Co(II) atom is bonded to two deprotonated metal-containing ligands. The terminal Co(II) atoms are in a square planar SNON four-coordinate environment and connected to the central Co(II) by N-atoms from the ligand backbone. For quantifying the intermolecular interactions in crystal lattice, the new d _norm surface and the breakdown of fingerprint plots have been used for visualizing and exploring the compound 2.     

Iridium–Ruthenium Cluster Complexes with SnPh<Subscript>3</Subscript> Ligands from the Reaction of IrRu<Subscript>3</Subscript>(CO)<Subscript>13</Subscript>(μ-H) with HSnPh<Subscript>3</Subscript>

The reaction of IrRu₃(CO)₁₃(μ-H), 1 with HSnPh₃ in hexane solvent at reflux has provided the new mixed metal cluster compounds Ir₂Ru₂(CO)₁₁(SnPh₃)(μ-H)₃, 2 and IrRu₃(CO)₁₁(SnPh₃)₃(μ-H)₄, 3 containing SnPh₃ ligands. Compound 2 which was obtained in low yield (3%) contains one SnPh₃, two iridium atoms and two ruthenium atoms. The increase in the number of iridium atoms must have resulted from a metal–metal exchange process. The major product 3 (19% yield) contains an open cluster of one iridium and three ruthenium atoms with three SnPh₃ ligands and four hydride ligands. Both compounds were characterized structurally by single crystal X-ray diffraction analysis.