Structural investigation of [Au(en)<Subscript>2</Subscript>]Cl(ReO<Subscript>4</Subscript>)<Subscript>2</Subscript> and [Au(en)<Subscript>2</Subscript>](ReO<Subscript>4</Subscript>)<Subscript>3</Subscript> complexes

Novel complex salts [Au(en)₂]Cl(ReO₄)₂ (I) and [Au(en)₂](ReO₄)₃ (II), en = ethylenediamine, are obtained. Their crystal structures are determined by single crystal X-ray diffraction. Complex I crystallizes in the triclinic crystal system: a = 6.2172(7) Å, b = 7.1644(8) Å, c = 8.8829(8) Å, α = 96.605(4)°, β = 110.000(4)°, γ = 97.802(4)°, P-1 space group, Z = 1, d _x = 3.905 g/cm³; complex II crystallizes in the monoclinic crystal system: a = 15.244(2) Å, b = 7.6809(8) Å, c = 9.3476(12) Å, β = 127.004(3)°, C2 space group, Z = 4, d _x = 4.057 g/cm³.     

Crystal structure of [CuL](NO<Subscript>3</Subscript>)(ReO<Subscript>4</Subscript>) and [CuL](ReO<Subscript>4</Subscript>)<Subscript>2</Subscript> (L = 4,6,6-trimethyl-1,9-diamino-3,7-diazanon-3-en)

The crystal structures of [CuL](NO₃)(ReO₄) and [CuL](ReO₄)₂ (L is 4,6,6-trimethyl-1,9-diamino-3,7-diazanon-3-en) are studied. The square coordination of the copper atom in [CuL](NO₃)(ReO₄) is completed to a distorted octahedron by two oxygen atoms: Cu…O (ReO ₄ ^? ) 2.393 Å and Cu…O (NO ₃ ^? ) 2.685 Å, and that in [CuL](ReO₄)₂, by Cu…O(ReO ₄ ^? ) 2.468 Å and 2.697 Å. The products of thermolysis of the salts in a hydrogen atmosphere at 800°C are mixtures of nanocrystalline metal powders with coherent scattering regions of ～45 nm.     

Supramolecular 2D structure of [Co(2-Me-Pyz)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>](NO<Subscript>3</Subscript>)<Subscript>2</Subscript>

The complex [Co(2-Me-Pyz)₂(H₂O)₄](NO₃)₂ is synthesized and its structure is determined. The crystals are monoclinic: space group P2₁/n, a = 10.685(2) Å, b = 6.837(1), c = 12.515(3) Å, β = 91.84(3)°, V = 913.8(3) ų, ρ_calcd = 1.042 g/cm ³, Z = 2. The Co²⁺ ion (in the inversion center) is coordinated at the vertices of the distorted octahedron by two nitrogen atoms of methylpyrazine and four oxygen atoms of the water molecules (Co(1)–N(1) 2.180(3), average Co(1)–O(w) 2.079(3) Å, angles at the Co atom 87.9(1)–92.1(1)°). Supramolecular pseudometallocycles are formed in the structure through the O(w)–H…N(1) hydrogen bonds between the coordinated H₂O molecules and the terminal nitrogen atoms of the 2-methylpyrazine molecules. Their interaction results in the formation of supramolecular layers joined by the NO₃ groups into a three-dimensional framework.     

Supramolecular structure organization and the biological properties of [Co(DH)<Subscript>2</Subscript>(PP)<Subscript>2</Subscript>][BF<Subscript>4</Subscript>]

The coordination compound [Co(DH)₂(PP)₂][BF₄]₂ · 2H₂O (DH⁻ is the dimethylglyoxime residue, PP is nicotinamide) was synthesized and studied by X-ray diffraction. The equatorial plane of the octahedral Co(III) complex contains two DH⁻ residues combined by intramolecular hydrogen bonds O-H…O, while the apical positions are occupied by two PP molecules. A method for the optimal use of the complex for enhancement of the biosynthesis of standard and acid-stable amylases of the micromycete Aspergillus niger 33–19 CNMN FD 02A and lipases of the micromycete Rhizopus arrhizus Fischer CNMN FD 03L was depeloped. The introduction of the complex in a concentration of 1–5 mg/l into the culture medium of Aspergillus niger 33-19 CNMN FD 02A reduces the process cycle by 24 h. The stimulating effect of the introduction of the complex (5 mg/l) into the culture medium of the Rhizopus arrhizus Fischer CNMN FD 03L strain is 55.5%.     

Double helix of the coordination polymer of silver with 1,3-bis(4-pyridyl)propane: Synthesis and crystal structure of [Ag(C<Subscript>13</Subscript>H<Subscript>14</Subscript>N<Subscript>2</Subscript>)](CF<Subscript>3</Subscript>CO<Subscript>2</Subscript>)

The [Ag(Bpp)](CF₃CO₂) complex (Bpp is 1,3-bis(4-pyridyl)propane, C₁₃H₁₄N₂) is synthesized, and its structure is determined. The crystals are monoclinic, space group C2/c, a = 26.169(5), b = 10.521(2), c = 12.906(3) Å, β = 117.99(3)°, V = 3137.7(11) ų, ρ_calcd = 1.775 g/cm³, Z = 8. The structure contains double helices of-Ag-Bpp-Ag-Bpp-cationic chains with a helix period of 21.042 Å. The Ag…Ag distance between a pair of silver atoms from different chains in the helix is 3.201 Å, and the distance between the adjacent helices is 3.279 Å. The silver atom is linked with two bridging nitrogen atoms of two Bpp ligands in an almost linear coordination: Ag-N_avg 2.142 Å; NagN, 171.3(4)°. The CF₃C ₂ ^? anion has a weak contact with the silver ion (Ag…O 2.62(2) Å).     

Three- and four-coordinated silver(I) ions in the coordination polymers [Ag(Me<Subscript>4</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript> and [Ag(2,3-Et<Subscript>2</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript>

The coordination polymers [AgPF₆(Me₄Pyz)₂] (I) and [AgPF₆(2,3-Et₂Pyz)₂] (II) were synthesized, and their structures were determined. Crystals of I are monoclinic, space group C2/c, a = 10.213(2) Å, b = 16.267(3) Å, c = 12.663(3) Å, β = 92.90(3)°, V = 2102.1(7) ų, ρ_calcd = 1.660 g/cm³, Z = 4. The structure of I is built of polymeric zigzag [Ag(C₈H₁₂N₂)] _∞ ⁺ chains and octahedral [PF₆] anions. The coordination polyhedron of the Ag⁺ ion is a flat triangle. Crystals of II are tetragonal, space group P \(\bar 4\)2(1)/c,a = b = 10.641(1) Å, c = 18.942(1) Å, V = 2144.6(2) ų, ρ_calcd = 1.627 g/cm³, Z = 4. In the structure of II, 2D cationic layers of fused square rings exist; the rings consist of four Ag⁺ cations linked by four bridging ligands of diethylpyrazine Et₂Pyz. The coordination polyhedron of the Ag⁺ ion is an irregular four-vertex polyhedron.     

Synthesis and crystal structure of a 1D coordination polymer [Cd(NITpPy)<Subscript>2</Subscript>(N(CN)<Subscript>2</Subscript>)<Subscript>2</Subscript>)]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

A novel one-dimensional chain complex [Cd(NITpPy)₂(N(CN)₂)₂)] _n (NITpPy = 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and characterized structurally. It crystallizes in the triclinic space group P \(\bar 1\) with a = 7.1742(13), b = 9.4913(17), c = 13.208(2) Å, α = 71.020(2)°, β=87.308(2)°, γ = 70.503(2)°, V = 799.8(3) ų, C₂₈H₃₂CdN₁₂O₄, Mr = 713.06, Z = 1, ρ _c = 1.48 g/cm³, μ(MoK _α) = 0.736 mm^?1, F(000) = 364, R = 0.0275 and wR = 0.0605 for 2702 observed reflections with I > 2σ(I). The crystal structure consists of infinite chains of [Cd(NITpPy)₂(N(CN)₂)₂)] units linked by dicyanamide anions [N(CN)₂]^?. Each Cd²⁺ ion is six-coordinated with the geometry of a distorted octahedron.     

Crystal structure of Li(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>[GaEdta]

The ethylenediaminetetraacetate complex Li(H₂O)₃[Ga(Edta)] was synthesized and its crystal structure composed of octahedral (Ga(Edta)⁻ anions connected to the Li(H₂O)₃⁺ ion through the oxygen atom was studied. Five of the six hydrogen atoms of water molecules are involved in weak hydrogen bonds with the oxygen atoms of four Ga(Edta)⁻ complexes, the complex anion is hydrogen-bonded to five water molecules. In addition, shortened contacts C(221)–H(22A)…O(112) between the Ga(Edta)⁻ anions were found. As a result, the molecular packing in the crystal is determined by the three-dimensional lace of hydrogen bonds. The results are compared with published data for the lithium salts of Bi(III), Sb(III), Fe(III), Ni(II), and Hg(II) ethylenediaminetetraacetates.     

X-ray diffraction study of the monoclinic modification of [Cu(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>](ReO<Subscript>4</Subscript>)<Subscript>2</Subscript> in the range 100-410 K

The monoclinic modification of [Cu(NH₃)₄](ReO₄)₂ complex salt in the range 100-410 K is studied by single crystal X-ray diffraction. The crystallographic data for 300 K are as follows: a = 10.6123(3) Å, b = 7.5443(2) Å, c = 15.2261(4) Å, β = 108.406(1)°, V = 1156.67(5) ų, space group Р2₁/n, Z = 4, d_x = 3.623 g/cm³. The coordination environment of the Cu atom, being a distorted square formed by four nitrogen atoms with Cu–N of 1.997-2.018 Å, is completed by the contacts with two oxygen atoms Cu…O of 2.472 Å and 2.598 Å. The comparative crystal chemical analysis with the triclinic modification of [Cu(NH₃)₄](ReO₄)₂ known in the literature is performed.     

Crystal structure and EPR spectra of (Bu<Subscript>4</Subscript>N)<Subscript>2</Subscript>[V(dmit)<Subscript>3</Subscript>]

The tris-chelate complex of vanadium(IV) (Bu₄N)₂[V(dmit)₃] is prepared from VCl₃ and (Bu₄N)₂[Zn(dmit)₂] (dmit = isotrithionedithiolate C₃S₅ ^2–) and characterized by single crystal XRD and mass spectrometry. The complex crystallizes in the space group Pna2₁ and has a distorted octahedral environment of vanadium. The complex is paramagnetic and gives a characteristic EPR spectrum in both solution and solid phase. The g factors and hyperfine interaction constants are determined.     

Synthesis and crystal structure of two complexes [Cu<Subscript>2</Subscript>(NiL)<Subscript>2</Subscript>Cl<Subscript>4</Subscript>] and [Cd<Subscript>2</Subscript>(CuL)<Subscript>2</Subscript>Cl<Subscript>4</Subscript>]

Macrocyclic and supermolecular complexes [Cu₂(NiL)₂Cl₄] (I) and [Cd₂(CuL)₂Cl₄] (II) (H₂L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-diene) have been synthesized and structurally determined by X-ray diffraction and IR spectrum. Complex I crystallizes in the monoclinic system with P2₁/n group, a = 10.9019(15), b = 14.3589(19), c = 12.4748(17) 0A, β = 108.645(2)°, Z = 4. Complex II crystallizes in the monoclinic system with P2₁/n group, a = 10.9784(16), b = 14.580(2), c = 12.8904(18) Å, β = 109.339(2)°, Z = 4.     

Synthesis and structure of [UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>){CONH<Subscript>2</Subscript>N(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

The single crystals of [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 7.461(2) Å, b = 8.828(2) Å, c = 11.756(2) Å, β = 107.21(3)°, space group Pc, Z = 2, R = 2.94%. The structure comprises infinite chains [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] extended along [001] and corresponding to the AT¹¹M ₂ ¹ crystallochemical group (A = UO ₂ ²⁺ , T¹¹ = C₂O ₄ ^2? , M¹ = N,N-CONH₂N(CH₃)₂) of uranyl complexes. The chains are connected into a three-dimensional framework by hydrogen bonds involving the oxygen atoms of oxalate and uranyl ions and the N,N-dimethylcarbamide methyl groups.     

Molecular Structure of Tetrahydroxycalix[4]arene [-(C<Subscript>6</Subscript>H<Subscript>3</Subscript>OH)-CH<Subscript>2</Subscript>-]<Subscript>4</Subscript> in the Gas Phase

Gas-phase electron diffraction and HF/6-31G*, HF/6-31G**, and B3LYP/6-31G* ab initio calculations were used to find that in the gas phase at 242°C the calix[4]arene [-(C₆H₃OH)-CH₂-]₄ molecule possesses a C₄ conformation. Geometric parameters of the molecule were determined, and the energies of C-H?O hydrogen bonds (7.3 kcal mol^?1) were estimated by the AM1 method.     

Iron(II) complexes [Fe(DfgH)<Subscript>2</Subscript>(3-CONH<Subscript>2</Subscript>-Py)<Subscript>2</Subscript>] and [Fe(DfgH)<Subscript>2</Subscript>(4-COOC<Subscript>2</Subscript>H<Subscript>5</Subscript>-Py)<Subscript>2</Subscript>]: Synthesis and structures

The complexes [Fe(DfgH)₂(3-CONH₂-Py)₂] (I) and [Fe(DfgH)₂(4-COOC₂H₅-Py)₂] (II), where DfgH₂ is α-benzyl dioxime, were obtained and examined by X-ray diffraction analysis. The equatorial planes of the coordination octahedra of the metal ions consist of two monodeprotonated α-benzyl dioxime residues united through intramolecular hydrogen bonds O-H…O into a pseudomacrocyclic system. The neutral molecules 3-CONH₂-Py and 4-COOC₂H₅-Py are coordinated to the Fe²⁺ ion through the N atom of the heterocycle. Structure I is layered and structure II is molecular. Intermolecular interactions N-H…O are responsible for the formation of layers in crystal structure I.     

Zinc(II) complexes of 4-aminoantipyrine (AAP). Crystal structure of [Zn(AAP)<Subscript>2</Subscript>Cl<Subscript>2</Subscript>]

Zinc(II) complexes of 4-aminoantipyrine (AAP), [Zn(AAP)₂X₂] (X = Cl^–, I^–) and [Zn(AAP)(CN)₂] · 2H₂O were prepared and characterized by elemental analysis, IR and NMR (¹H & ¹³C) spectroscopy. The crystal structure of [Zn(AAP)₂Cl₂] (1) was determined by X-ray crystallography. The structural analysis of 1 shows that the complex exists as a monomeric nonionic molecule with zinc atom bound to two AAP ligands and two chloride ions adopting a distorted tetrahedral geometry. In [Zn(AAP)₂(CN)₂] · 2H₂O, the appearance of a band at 2162 cm^–1 in IR and resonances around 142 ppm in the ¹³C NMR spectra indicated the binding of cyanide to zinc(II).     

Crystal structure and triboluminescence of centrosymmetric complex [Eu(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>(HMPA)<Subscript>3</Subscript>]

By single crystal X-ray analysis, the atomic structure of the crystals of [Eu(NO₃)₃(HMPA)₃] complex (HMPA is hexamethylphosphorotriamide) possessing intense triboluminescence is determined. Symmetry of centrosymmetrical crystals is monoclinic: a = 13.785(1) Å, b = 19.746(2) Å, c = 14.723(1) Å, β= 102.143(2)°, P2₁/n space group, Z = 4, d _x = 1.484 g/cm³. The crystal structure is represented by separate C₁₈H₅₄EuN₁₂O₁₂P₃ complexes linked by van der Waals interactions with pronounced cleavage planes. The coordination polyhedron of Eu(III) atom reflects the state of distorted square antiprism. The possible causes of spectral differences in the Stark structure of photo- and triboluminescence are discussed.     

Hydrothermal synthesis and crystal structure of [Ni(Bptc)<Subscript>2</Subscript>(Bimb)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]

In the compound [Ni(Bptc)₂(Bimb)₂(H₂O)₂] (I), where H₄Bptc is 3,3′,4,4′-biphenyltetracarboxylic acid; Bimb is 4,4′-bis(1-imidazolyl)biphenyl), Ni(II) has a distorted octahedral coordination geometry, which was bonded with two N atoms from two Bimb ligands, two O atoms from two H₂Bptc²⁻ ligands and two water O atoms. The crystal structure of compound I is stabilized by the π-π-stacking and hydrogen bonds interaction.     

Structure and some properties of [UO<Subscript>2</Subscript>CrO<Subscript>4</Subscript>{CH<Subscript>3</Subscript>CON(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

A new complex [UO₂CrO₄{CH₃CON(CH₃)₂}₂] (I) was studied by thermal analysis, IR spectroscopy, and X-ray crystallography. The crystals are monoclinic: a = 13.8108(11) Å, b = 8.6804(7) Å, c = 13.0989(10) Å, β = 104.777(1)°, V = 1518.4(2) ų, space group P2₁/c, Z = 4, R = 2.39%. The structure of I contains infinite chains of the [UO₂CrO₄{CH₃CON(CH₃)₂}₂] composition running along [001]; the complex belongs to the AT¹¹M¹ ₂ crystal-chemical group (A = UO ₂ ²⁺ , T¹¹ = CrO ₄ ^2? , M¹ = CH₃CON(CH₃)₂) of uranyl complexes. The chains are linked into a three-dimensional framework due to hydrogen bonds between oxygen atoms of chromate ions and hydrogen atoms of methyl groups of the dimethylacetamide.     

Phase equilibria in the liquid ternary system [Th(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>(TBP)<Subscript>2</Subscript>]-[Gd(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>(TBP)<Subscript>3</Subscript>]-TBP-isooctane at different temperatures

The phase diagrams of the ternary system [Th(NO₃)₄(TBP)₂]-[Gd(NO₃)₃(TBP)₃]-TBP-isooctane in the temperature range 298.15–333.15 K were constructed.