Synthesis and X-ray investigation of Rb<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>] and Cs<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>]

Powder and single crystal X-ray diffraction studies have been performed for anhydrous nitrate complexes Rb₂[Pd(NO₃)₄] (I) and Cs₂[Pd(NO₃)₄] (II). Crystal data for I: a = 7.843(1) Å, b = 7.970(1) Å, c = 9.725(1) Å; β = 100.39(1)°, V = 597.9(1) Å ³, space group P2₁/c, Z = 2, d _calc = 2.918 g/cm³; for II: a = 10.309(2) Å, b = 10.426(2) Å, c = 11.839(2) Å; β = 108.17(3)°, V = 1209.0(4) ų, space group P2₁/c, Z = 4, d ^calc = 3.408 g/cm³. The structures are formed by isolated [Pd(NO₃)₄]^2? complex anions and alkali metal cations. The plane-square environment of the Pd atom is formed from the oxygen atoms of the monodentate nitrate groups. The geometrical characteristics of the complex anions are analyzed. Compound II has a short contact Pd...Cs 3.252 Å.     

Crystal structures of <Emphasis Type="Italic">trans</Emphasis>-[Re<Subscript>6</Subscript>S<Subscript>8</Subscript>(CN)<Subscript>2</Subscript>L<Subscript>4</Subscript>] complexes,L = pyridine or 4-methylpyridine

The structures of three novel octahedral rhenium cluster compounds [Re₆S₈(CN)₂(py)₄]·H₂O (1), [Re₆S₈(CN)₂(4-Mepy)₄] (2), [Re₆S₈(CN)₂(4-Mepy)₄]·4-Mepy (3) (py = pyridine, 4-Mepy = 4-methylpyridine) are determined by X-ray crystallography. Crystal data are: C2/m space group, a = 14.813(1) Å, b = 14.772(1) Å, c = 9.2122(6) Å, β = 119.085(2)°, V = 1761.7(2) ų, d _x = 3.318 g/cm³, R = 0.0585 (1); I4₁/amd space group, a = 16.0018(3) Å, c = 14.7186(5) Å, V = 3768.81(16) ų, d _x = 3.169 g/cm³, R = 0.0489 (2); P2₁/c space group, a = 9.0452(4) Å, b = 15.8065(7) Å, c = 15.2951(6) Å, β = 103.700(2)°, V = 2124.57(16) ų, d _x = 2.957 g/cm³, R = 0.0245 (3). Molecular cluster complexes interact via π-π stacking affording 3D frameworks in 1 and 2 and chains in 3.     

Synthesis and crystal structures of Schiff base oxovanadium(V) complexes [VO(Bhm)(OCH<Subscript>3</Subscript>)(CH<Subscript>3</Subscript>OH)] and [VO<Subscript>2</Subscript>(Bpp)]

Compound [VO(acac)₂] reacts with the Schiff bases N′-(5-bromo-2-hydroxybenzylidene)-2-hydroxy-3-methylbenzohydrazide (H₂Bhm) and 4-bromo-2-[(2-piperidin-1-ylethylimino)methyl]phenol (HBpp) in absolute methanol to give the oxovanadium(V) complexes [VO(Bhm)(OCH₃)(CH₃OH)] (I) and [VO₂(Bpp)] (II), respectively. Both complexes were characterized by elemental analysis, IR spectra, and single-crystal X-ray determination. The crystal of I crystallizes in the triclinic space group \(P\bar 1\) with a = 7.625(2), b = 11.240(3), c = 12.156(4) Å, α = 77.404(5)°, β = 75.770(4)°, γ = 79.922(5)°, V = 977.4(5) ų, Z = 2. The crystal of II crystallizes in the monoclinic space group P2/c with a = 26.760(3), b = 6.655(1), c = 17.570(2) Å, β = 100.335(2)°, V = 3078.2(7) ų, Z = 8. The V atom in I is in an octahedral coordination, and those in II are intervenient between square pyramidal and trigonal bipyramidal coordination.     

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.     

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.     

Palladium clusters Pd<Subscript>4</Subscript>(SR)<Subscript>4</Subscript>(OAc)<Subscript>4</Subscript> and Pd<Subscript>6</Subscript>(SR)<Subscript>12</Subscript> (R = Bu,Ph): Structure and properties

The structures of the Pd₄(SBu)₄(OAc)₄ (I) and Pd₆ (SBu)₁₂ (II) palladium clusters are determined by the X-ray diffraction method. For cluster I: a = 8.650(2), b = 12.314(2), c = 17.659(4) Å, α = 78.03(3)°, β = 86.71(2)°, γ = 78.13(3)°, V = 1800.8(7) ų, ρcalcd = 1.878 g/cm³, space group P \(\bar 1\), Z = 4, N = 3403, R = 0.0468; for structure II: a = 10.748(2), b = 12.840(3), c = 15.233(3) Å, α = 65.31(3)°, β = 70.10(3)°, γ = 72.91(3)°, V = 1767.4(6) ų, ρ calcd = 1.605 g/cm³, space group P \(\bar 1\), Z = 1, N = 3498, R = 0.0729. In cluster I, four Pd atoms form a planar cycle. The neighboring Pd atoms are bound by two acetate or two mercaptide bridges (Pd…Pd 2.95–3.23 Å, Pd…Pd angles 87.15°–92.85°). In cluster II, the Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.09–3.14 Å, the PdPdPd angles being 118.95°–120.80°. The Pd atoms are linked in pairs by two mercaptide bridges. The formation of clusters I and II in solution is proved by IR spectroscopy and calorimetry. Analogous clusters are formed in solution upon the reaction of palladium(II) diacetate with thiophenol.     

Syntheses and crystal structures of [Bi(DMSO)<Subscript>8</Subscript>][Fe(NCS)<Subscript>6</Subscript>] and [Al(DMSO)<Subscript>6</Subscript>][Al(NCS)<Subscript>6</Subscript>]

New complexes of composition [Bi(DMSO)₈][Fe(NCS)₆] (1) and [Al(DMSO)₆][Al(NCS)₆] (2) have been prepared, and an octahedral hexarodanoaluminate anion has been structurally characterized for the first time. Crystals of compound 1 are triclinic, space group \(P\bar 1\), a = 11.2368(4) Å, b = 11.4063(4) Å, c = 21.0711(9) Å, α = 92.9520(10)°, β = 99.9430(10)°, γ = 111.9290(10)°, V = 2447.69(16) ų, Z = 2, ρ_calc = 1.680 g/cm³, R ₁ = 0.0564; crystals of compound 2 are cubic, space group \(Pa\bar 3\), a = 15.8201(4) Å, V = 3959.39(17) ų, Z = 4, ρ_calc = 1.462 g/cm³, R ₁ = 0.0475. The bismuth coordination polyhedron BiO₈ in compound 1 is a distorted square antiprism with broken square faces (Bi-O, 2.368-2.582 Å). In the structure of 2, the cation disordered in a complex manner has an octahedral configuration (Al-O, 1.888(11)-1.912(11) Å).     

Crystal structure and properties of [M(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl](NO<Subscript>3</Subscript>)<Subscript>2</Subscript>, (M = Ir,Rh, Ru)

The crystal structures of compounds from the series [M(NH₃)₅Cl](NO₃)₂, (M = Ir, Rh, Ru) were described. The compounds crystallized in the tetragonal crystal system, space group I4, Z = 2. Crystal data for [Ir(NH₃)₅Cl](NO₃)₂ (I): a = 7.6061(1) Å, b = 7.6061(1) Å, c = 10.4039(2) Å, V = 601.894(16) ų, ρ_calc = 2.410 g/cm³, R = 0.0087; [Rh(NH₃)₅Cl](NO₃)₂ (II): a = 7.5858(5) Å, b = 7.5858(5) Å, c = 10.41357(7) Å, V = 599.24(7) ų, ρ_calc = 1.926 g/cm³, R = 0.0255; [Ru(NH₃)₅Cl](NO₃)₂ (III): a = 7.5811(6) Å, b = 7.5811(6) Å, c = 10.5352(14) Å, V = 605.49(11) ų, ρ_calc = 1.896 g/cm³, R = 0.0266. The compounds were defined by IR spectroscopy and XRPA and thermal analyses.     

Crystal structure of WI<Subscript>4</Subscript>

Tungsten tetraiodide WI₄ (1) is produced by a high-temperature reaction of WTe₂ and I₂ in a vacuum sealed ampoule. The crystals of 1 belong to the triclinic crystal symmetry, space group P-1, Z = 4, a = = 7.9291(3) Å, b = 10.7695(4) Å, c = 10.8117(4) Å, α = 85.668(1)°, β = 71.772(1)°, γ = 71.559(1)°, V = = 831.60(5) ų, d_calc = 5.523 g/cm³. The structure of 1 consists of tetrameric W₄I₁₆ molecules in which W atoms are in a distorted octahedral environment formed by I atoms.     

Crystal structures of polyphosphates MCs<Subscript>5</Subscript>(PO<Subscript>3</Subscript>)<Subscript>8</Subscript> (M = Pr,Eu, and Gd)

Crystals of double polyphosphates EuCs₅(PO₃)₈ (I) and GdCs₅(PO₃)₈ (II) have been studied by X-ray diffraction. The isostructural crystals of I and II are monoclinic, space group C2. Only unit cell parameters have been determined for the crystals of double Pr and Cs polyphosphate (III). This crystal is isostructural with earlier studied La₃Cs₁₅P₂₄O₇₂ · 6H₂O (IV). The crystals of compounds III and IV are triclinic, space group P1, Z = 1; a = 11.987(2) and 12.178(5) Å, b = 14.754(8) and 14.740(8) Å, c = 14.692(8) and 14.847(9) Å, α = 60.15(4)° and 60.87(5)°, β = 67.04(4)° and 66.35(4)°, γ = 78.76(3)° and 77.54(4)°, respectively. In compounds I and II, the polyphosphate anions exist as infinite chains. The M^IIIO₈ polyhedra are isolated from each other but share edges and faces with the CsO _n polyhedra.     

Synthesis and structure of coordination polymer compounds of AgReO<Subscript>4</Subscript> and AgPF<Subscript>6</Subscript> with piperazine

Coordination polymers [Ag(C₄H₁₀N₂)]ReO₄ (I) and [Ag(C₄H₁₀N₂)]PF₆ (II) (C₄H₁₀N₂ is piperazine, Ppz) were synthesized and their structures were determined. Crystals of compound I are monoclinic, space group P2₁/c, a = 6.207(1) Å, b = 12.533(1) Å, c = 11.386(1) Å, β = 93.41(1)°, V = 884.2(2) ų, ρ_calc = 3.337 g/cm³, Z = 4. Crystals of II are monoclinic, space group C2/m, a = 8.723(1) Å, b = 9.083(1) Å, c = 5.797(1) Å, β = 95.07(1)°, V = 457.5(1) ų, ρ_calc = 2.548 g/cm³, Z = 2. Structure I contains polymer chains [Ag(Ppz)] _∞ ⁺ . The silver atom is linked with two nitrogen atoms of the adjacent Ppz ligands to form a nearly linear fragment; the Ag-N_av distance is 2.173 Å, and the NAgN angle is 169.4(3)°. The chains are linked with each other by weak interactions Ag…O(ReO₄) (2.643(8) Å) and N-H…O hydrogen bonds. The structure of compound II also contains cationic polymer chains [Ag(Ppz)] _∞ ⁺ . The Ag⁺ ion is located in the inversion center and has a linear coordination (Ag-N distance is 2.171(9) Å). The central P atom of the octahedral fluorophos-phate ion is also located in the inversion center; the anion is slightly distorted and has no contacts with silver ions at a distance <3.4 Å.     

Crystal Structures of New Chalcogenide- Containing Yttrium Orthosilicates Y<Subscript>2</Subscript>SiO<Subscript>4</Subscript>Q (Q = S,Se)

Compounds Y₂SiO₄Q (Q = S, Se) are obtained by the interaction of oxides and elemental substances in cesium chloride flux. The structures of these compounds are determined by the single crystal XRD analysis. These compounds isostructural and crystallize in the space group Pbcm with the following parameters: Y₂SiO₄S (I) a = 6.0462(8) Å, b = 6.8976(9) Å, c = 10.6558(13) Å, V = 444.39(10) ų; Y₂SiO₄Se (II) a = 5.9935(7) Å, b = 6.9216(8) Å, c = 10.7688(12) Å, V = 446.74(9) ų. The measured fluxing points are 1650±15 °С for I and 1850±15 °С for II.     

Structure of a new chelate complex MO<Subscript>2</Subscript>O<Subscript>3</Subscript>(dpm)<Subscript>4</Subscript>

A new Mo₂O₃(dpm)₄ compound (I) is synthesized by the interaction of Mo(CO)₆ with 2,2,6,6-tetramethylheptanedione-3,5 (dpm). The structure of complex I determined by the XRD method is as follows: triclinic crystal system, space group P–1, a = 10.1780(7) Å, b = 10.1817(6) Å, c = 13.3255(9) Å, α = 110.562(2)°, β = 102.233(2)°, γ = 93.9041(19)°, V = 1248.17(14) ų. The compound is characterized by IR spectroscopy, mass-spectrometry and thermogravimetric analysis (TGA).     

Structure and characterization of a 1d double chain copper(II) complex {[Cu(BIX)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>](PhCOO)<Subscript>2</Subscript>}<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

A novel copper(II) complex {[Cu(BIX)₂(H₂O)₂](PhCOO)₂} _n (1) (BIX = 1,4-bis(imidazole-1-methyl))-benzene) is synthesized and characterized by elemental analysis, IR, TG, and single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic crystal system with the P-1 space group, Z = 1, a = 9.465(2) Å, b = 9.703(2) Å, c = 12.060(2) Å, α = 77.26(3)°, β = 70.37(3)°, γ = 67.14(3)°, and V = 956.1(3) ų. The crystal structural analysis of complex 1 shows that the copper center is six-coordinated in an elongated octahedral geometry by four N atoms from four different BIX and two O atoms from two water molecules; two neighboring Cu(II) cations are bridged by two BIX extending into an infinite 1D double chain structure.     

Crystal Structure of [UO<Subscript>2</Subscript>SO<Subscript>4</Subscript>{(CH<Subscript>3</Subscript>)HNCONH(CH<Subscript>3</Subscript>)}<Subscript>2</Subscript>]

The single crystals of [UO₂SO₄{(CH₃)HNCONH(CH₃)}₂] (I) were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 6.847(1) Å, b = 14.259(3) Å, c = 14.297(3) Å, β = 93.451(4)°, space group P2₁/n, Z = 4. The main structural units of crystals I are ribbons whose composition coincides with the composition of the compound. The crystal chemical formula of the complex is AT³M ₂ ¹ (A = UO ₂ ²⁺ ).     

Study of the monocarbonate complex of pentavalent neptunium (NH<Subscript>4</Subscript>)[NpO<Subscript>2</Subscript>(CO<Subscript>3</Subscript>)]

The single crystals of the Np(V) complex (NH₄)[NpO₂(CO₃)] (I) were synthesized and studied by X-ray diffraction. At 100 K, the crystals are hexagonal, space group P6₃ μmc, a = 5.0734(1) Å, c = 10.9191(2) Å, V= 243.399(11) ų, Z = 2, ρ(calcd) = 4.735 g/cm³. The absorption spectra of a crystal of I in the visible and infrared ranges were measured.     

Synthesis,crystal structures,and antibacterial activities of Schiff base zinc(II) complexes [Zn(L<Superscript>1</Superscript>)<Subscript>2</Subscript>] and [Zn(L<Superscript>2</Superscript>)<Subscript>2</Subscript>]

The reaction of cyclopentylamine with 2-hydroxy-1-naphthaldehyde and 5-nitrosalicylaldehyde, respectively, in methanol affords two new Schiff bases, 1-(cyclopentyliminomethyl)naphthalen-2-ol (HL¹) and 4-nitro-2-(cyclopentyliminomethyl)phenol (HL²). Two new zinc(II) complexes, [Zn(L¹)₂] (I) and [Zn(L²)₂] (II), derived from the Schiff bases, have been prepared and characterized by single-crystal X-ray diffraction, FT-IR, and elemental analysis. Complex I crystallizes in the monoclinic space group P2₁/c with a = 17.834(4), b = 14.738(3), c = 9.868(2) Å, β = 91.20(3)°, V = 2593.1(9) ų, Z = 4. Complex II crystallizes in the triclinic space group P \(\bar 1\) with a = 10.206(1), b = 10.502(1), c = 12.554(1) Å, α = 66.771(2)°, β = 78.133(2)°, γ = 76.292(2)°, V = 1191.8(1) ų, Z = 2. The Zn atom in each complex is coordinated by two N and two O atoms from two Schiff base ligands, forming a tetrahedral geometry. The Schiff bases and the complexes were assayed for antibacterial activities.     

Syntheses and crystal structures of (2.2.2-cryptand)potassium chloride and (2.2.2-cryptand)ammonium bromide<Subscript>(0.75)</Subscript>chloride<Subscript>(0.25)</Subscript> hydrates

Two new complexes were synthesized, namely, 7: 2 (2.2.2-cryptand)potassium chloride and (2.2.2-cryptand)ammonium bromide_(0.75)chloride_(0.25) hydrates: [M(Crypt-222)]⁺ · Hal^? · 3.5H₂O, where M = K, Hal = Cl (I) and M = NH₄, Hal = Br_0.75Cl_0.25 (II). The structures of two isomorphous crystals were studied by X-ray diffraction analysis. Trigonal (space group P \(\bar 3\), Z = 2) structures I (a = 11.763 Å, c = 11.262 Å) and II (a = 11.945 Å, c = 11.337 Å) were solved by direct methods and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.057 (I) and 0.065 (II) for all 2626 (I) and 1654 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK _α). In structures I and II, the host-guest [M(Crypt-222)]⁺ complex cation lies on the threefold crystallographic axis and has the approximate D ₃ symmetry. In complex I, the coordination polyhedron of the K⁺ cation (CN = 8) is a bicapped trigonal prism somewhat distorted toward an antiprism. Complexes I and II contain H-bonded disordered cubes of the water molecules and the Cl^? or Br^? anions.     

<Emphasis Type="Italic">cis</Emphasis>-Dioxomolybdenum(VI) complexes of sterically encumbered phenol-based tetradentate N<Subscript>2</Subscript>O<Subscript>2</Subscript> ligands: Structural,spectroscopic, and electrochemical studies

Two cis-dioxomolybdenum(VI) complexes [MoO₂L] (L: L ¹, 2 and L: L ², 3) in a phenol-based sterically encumbered N₂O₂ ligand environment have been synthesized, and their crystallographic characterizations are reported. The orange crystals of 2 are monoclinic, space group P2₁/a with unit cell dimensions as a=16.2407(17) Å, b=7.2857(8) Å, c=18.400(2) Å, β=98.002(9)°, Z=4, and d _cal=1.486 g cm^?3. The light orange crystals of 3, however, are orthorhombic, space group, Pbcn, with unit cell dimensions a=8.3110(12) Å, b=12.637(3) Å, c=34.673(5) Å, Z=4, and d _cal=1.187 g cm^?3. The structures were refined by a full-matrix least-squares procedure on F ² to a final R=0.046 (0.055 for 3) using 4944 (3677) all independent data. In both the cases, the Mo atom exists in a distorted octahedral geometry defined by a N₂O₄ donor set, which features a cis-Mo(–O)₂ and a trans-Mo(OPh)₂ arrangement. Compound 2 undergoes a quasireversible one-electron reduction at ?1.3 V vs Ag/AgCl reference due to Mo^VIO₂/Mo^VO₂ electron transfer and thus providing a rare example of steric solution to the comproportionation–dimerization problem encountered frequently in the development of valid biomimetic models for the active sites of oxomolybdenum enzymes.     

New barium bismuth oxides: BaBi<Subscript>4</Subscript>O<Subscript>7</Subscript> and BaBi<Subscript>15</Subscript>O<Subscript>23.5</Subscript>

New barium bismuth oxides have been synthesized under an argon atmosphere at 530 and 430°C, respectively: a Ba: Bi = 1 : 4 phase has a tetragonal perovskite structure, and a 1 : 15 phase has a rhombohedral structure. For the 1 : 4 phase, the unit cell parameters are a = 4.297(2) Å and c = 4.472(2) Å as determined by powder X-ray diffraction (XRD). Electron diffraction (ED) patterns show superstructure reflections with the vectors q ₁= 1/17[530], q ₂ = 1/17[3\(\bar 5\)0], and q ₃ = 1/5[002]. These reflections point to an ordered arrangement of barium and bismuth ions in the supercell with the parameters √17a and 5c. The supercell of the 1 : 4 phase includes a ten-layer stack of metal-oxygen planes along the c axis. The rhombohedral 1 : 15 phase has the following hexagonal unit cell parameters as determined by XRD: a= 6.018(2) Å, c = 4.070(2) Å. In view of the superstructure on the ED patterns, the supercell parameters of the rhombohedral phase are 4a and 2c. The supercell of the 1 : 15 phase contains a six-layer stack of planes along the c axis.