Synthesis and crystal structures of binuclear complexes of cobalt(II) and cadmium(II) diisobutyldithiophosphinates with hexamethylenetetramine

Heteroligand complexes [Co₂(HMTA)(iso-Bu₂PS₂)₄] (I) (μ_eff = 4.67 μB) and [Cd₂(HMTA)(iso-Bu₂PS₂)₄] (II) have been synthesized. Single crystals of compounds I and II have been obtained. The crystals are monoclinic: a = 32.622(2) Å, b = 9.4891(6) Å, c = 21.7570(13) Å, β = 125.774(1)^o, V = 5464.3(6) Å,³, Z = 4, ρ_calcd = 1.331 g/cm³ for I; a = 34.6092(7) Å, b = 9.5595(2) Å, c = 22.3473(5) Å, β = 127.144(1)^o, V = 5893.5(2) Å, Z = 4, ρ_calcd = 1.355 g/cm³ for II; space group for both complexes C2/c. Structures I and II are based on discrete binuclear molecules. The coordination polyhedra of the Co and Cd atoms are distorted tetragonal pyramids NS₄, with the bases formed by four S atoms of two bidentate chelating ligand iso-Bu₂PS ₂ ^? and the axial vertices occupied by N atoms of bidentate bridging HMTA ligand. The character of interaction of the molecules in structures I and II is considered.     

Synthesis and crystal structure of two {M(4,4′-dpdo)<Subscript>2</Subscript>[N(CN)<Subscript>2</Subscript>]<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>} complexes (M = Co(II), Mn(II); 4,4′-dpdo = 4,4′-bipyridyl-N,N′-dioxide)

The ligand 4,4′-bipyridyl-N,N′-dioxide (4,4′-dpdo) was used in the synthesis of two complexes, {Co(4,4′-dpdo)₂[N(CN)₂]₂(H₂O)₂} (1) and {Mn(4,4′-dpdo)₂[N(CN)₂]₂(H₂O)₂} (2). The complexes were found to be isostructural, triclinic, space group P-1 with Z = 1 and the following unit cell parameters: a = 8.158(8) Å, b = 8.865(8) Å, c = 9.477(9) Å; α = 70.988(13)°, β = 78.778(13)°, γ = 71.964(10)°; V = 612.8(10) ų for 1; a = 8.247(14) Å, b = 9.001(16) Å, c = 9.707(17) Å; α = 71.02(2)°, β = 78.63(2)°, γ = 72.62(2)°; V = 646(2) ų for 2. Final R-values were 0.075 and 0.083 for 1 and 2, respectively. In the molecules of the complexes, Co(II) or Mn(II) cation is coordinated by two O-atoms of two 4,4′-dpdo ligands, two terminal N-atoms of two dicyanamides, and two O-atoms of water molecules. The crystals are molecular, with adjacent complex molecules linked through a system of O-H...N and O-H...O hydrogen bonds.     

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.     

Structure of Potassium and Cesium Barbiturates

The structures of catena-[K(μ₆-Hba?O,O,O,O′,O′,O″)] (I) and catena-[Cs(μ₆-Hba–O,O,O′,O′,O″,O″)] (II), where Н₂ba is barbituric acid C₄H₄N₂O₃, were characterized by powder X-ray diffraction. Crystallographic data: a = 14.1603 (4) Å, b = 3.68977 (9) Å, c = 10.9508 (3) Å, β = 82.226 (1)°, V = 566.90 (3) ų, space group P2₁/n, Z = 4 for I; a = 14.652 (1) Å, b = 11.7275 (7) Å, c = 3.8098 (3) Å, β = 79.140 (6)°, V = 642.90 (8) ų, space group C2/m, Z = 4 for II. The structural topologies of alkali metal complexes with barbituric acid and some its derivatives were compared. The thermal stability of complexes I and II in an air atmosphere was studied.     

Synthesis and crystal structure of zinc(II) and manganese(II) complexes of 2-(diphenylacetyl)indandione-1,3

Zinc(II) and manganese(II) complexes of 2-(diphenylacetyl)indandione-1,3 (HL) were synthesized. Crystals of [M(DMSO)₂L₂] · CHCl₃, where M= Zn^(II) (I) and Mn^(II) (II), obtained from chloroform plus dimethyl sulfoxide (DMSO) mixture were found to be isostructural based on the similarity of their unit cell parameters and unit cell volumes. The crystals are triclinic, Z = 2, space group P \(\bar 1\); a = 10.422(1) Å, b = 11.929(1) Å, c = 20.429(1) Å, α = 73.616(1)°, β = 85.095(1)°, γ = 77.586(1)° for complex I; a = 10.436(1) Å, b = 12.297(1) Å, c = 19.924(2) Å, α = 78.138(2)°, β = 87.625(2)°, γ = 82.048(2)° for complex II. X-ray structural analysis of complex I was carried out. For complex II, the structure was not refined because all of its atoms are each disordered over three to five positions. The two DMSO molecules in complex I coordinate the central metal atoms in the monodentate mode via their donor oxygen atoms to occupy an axial position and an equatorial position in an octahedral polyhedron. The other four positions are occupied by the four oxygen atoms of the two deprotonated ligands L^? coordinated in the bidentate-cyclic mode. The outer sphere of complex I contains the solvating chloroform molecule.     

Co(II) and Ni(II) complexes incorporating <Emphasis Type="Italic">N</Emphasis>-acetimidoylacetamidine ligand: Synthesis and structures

Two new square planar complexes with the formula Co(L)₂ · CH₃OH (1) and Ni(L)₂ · CH₃OH (2) (HL = HN{C(Me)=NH}₂ = N-acetimidoylacetamidine) have been synthesized by solvothermal reactions in methanol/acetonitrile. N-acetimidoylacetamidine ligand was derived from the self-condensation reaction of acetonitrile, and the reaction was promoted by the cooperation of M(II) (M = Co in 1 and M = Ni in 2) with diphenylcarbazide. 1 and 2 are characterized by single crystal X-ray diffraction, elemental analysis and infrared spectrum. Both complexes crystallize in the monoclinic space group P2₁/c with a = 9.329(6) Å, b = 11.494(7) Å, c = 13.040(8) Å, β = 92.945(11)°, V = 1396.3(16) ų and Z = 4 for 1, and a = 9.323(4)Å, b = 11.512(5) Å, c = 13.020(6)Å, β = 92.819(7)°, V = 1395.7(10)ų and Z = 4 for 2.     

<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.     

Two copper complexes with imidazole ligands: Syntheses,crystal structures and fluorescence

Two copper (imidazole) complexes, namely, [Cu(im)₆]Cl₂ · 4H₂O (1), and [Cu(im)₆]Cl₂ · 2H₂O (2) (im-imidazole) have been synthesized by hydrothermal method. Single-crystal X-ray analysis revealed that the complex 1 belongs to triclinic system, space group P \(\bar 1\) with a = 8.8097(18) Å, b = 9.0812(18) Å, c = 10.586(2) Å; α = 75.08(3)°, β = 83.14(2)°, γ = 61.84(3)°; R ₁ = 0.0562, wR ₂ = 0.1607. In compound 1, [Cu(im)₆]²⁺ cation and counter anions Cl^? alternatively array in an ABAB fashion via N-H...Cl hydrogen bonding. Compound 2 falls into monoclinic system, space group P2₁/n with a = 8.073(2) Å, b = 13.239(2) Å, c = 15.0810(10) Å; β = 97.940(10)°; R ₁ = 0.0434, wR ₂ = 0.1243. The equatorial ligands are involved into a complex hydrogen bond network that involves the chloride anions and uncoordinated water molecules. We report there synthesis, crystal structure, thermal stability, IR spectrum and fluorescent property.     

Synthesis,spectroscopic characterization,crystal structures,and theoretical studies of (<Emphasis Type="Italic">E</Emphasis>)-2-(2,4-dimethoxybenzylidene)thiosemicarbazone and (<Emphasis Type="Italic">E</Emphasis>)-2-(2,5-dimethoxybenzylidene)thiosemicarbazone

Two thiosemicarbazones, (E)-2-(2,4-dimethoxybenzylidene)thiosemicarbazone (24-MBTSC (1)) and (E)-2-(2,5-dimethoxybenzylidene)thiosemicarbazone (25-MBTSC (2)), derived from 2,4-dimethoxybenzaldehyde and 2,5-dimethoxybenzaldehyde, respectively, with thiosemicarbazide have been synthesized and their structures were characterized by elemental analyses, FT-IR, ¹H NMR spectroscopy, and X-ray single-crystal diffraction analysis. Molecular orbital calculations have been carried out for 1 and 2 by using an ab initio method (HF) and also density functional method (B3LYP) at 6-31G basis set. Compound 1 crystallizes in the monoclinic system, space group P2₁/c, with a = 8.1342(5) Å, b = 18.1406(10) Å, c = 8.2847(6) Å, β = 109.7258(17)°, V = 1150.75(12) Å³, and Z = 4, whereas compound 2 crystallizes in the orthorhombic system, space group Pbca, with a = 11.0868(6) Å, b = 13.1332(6) Å, c = 15.9006(8) Å, V = 2315.2(2) Å³, and Z = 8. The compounds 1 and 2 displays a trans-configuration about the C=N double bond.     

Synthesis and characterization of heteronuclear germanium(IV) lanthanide 1,3-diamino-2-propanoltetraacetates: Crystal and molecular structure of the [Ge(OH)(μ-Hpdta)(μ-OH) Ln(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>] · 2H<Subscript>2</Subscript>O complexes (Ln = Tb,Yb)

In the course of systematic studies, heteronuclear germanium lanthanide complexes based on 1,3-diamino-2-propanoltetraacetic acid (H₅Hpdta) have been synthesized (Ln = Pr (I), Nd (II, the structure was described in [1]), Sm (III), Eu (IV), Gd (V), Tb (VI), Dy (VII), Ho (VIII), Er (IX), Tm (X), Yb (XI), Lu (XII)). Comparative analysis of their structure as a function of the lanthanide ion has been performed. The analysis is based on a combination of physicochemical data on complexes I–XII, including X-ray crystallographic data for two heteronuclear [Ge(OH)(μ-Hpdta)(μ-OH)Ln(H₂O)₃] · 2H₂O complexes (Ln = Tb (VI) and Yb (XI). Isostructural crystals of VI and XI are monoclinic, Z = 4, space group P2₁/n, a = 9.340(4) and 9.3133(10) Å, b = 10.4839(14) and 10.4561(10) Å, c = 20.246(2) and 20.1222(10) Å, β = 95.12(3)° and 95.275(10)°, V = 1974.5(10) and 1951.2(3) A³, R1 = 0.0277 and 0.0241 for 4527 and 4751 reflections with I > 2σ(I). Crystals of VI and XI are composed of binuclear [Ge(OH)(μ-Hpdta)(μ-OH)Ln(H₂O)₃] molecules and crystal water molecules. The Ge and Ln atoms in VI and XI are linked by the bridging oxygen atom of the hydroxo group (Ge-O, 1.806(2) and 1.812(2) Å; Ln-O, 2.445(3) and 2.405(2) Å, respectively) and by the deprotonated oxygen atom of the isopropanol group of the Hpdta5-ligand (Ge-O, 1.865(2) and 1.864(2) Å; Ln-O, 2.302(2) and 2.255(2) Å in VI and XI, respectively). The coordination sphere of each of the Ge and Ln atoms involves one nitrogen atom (Ge-N, 2.097(3) and 2.096(3) Å; Ln-N, 2.670(3) and 2.628(3) Å in VI and XI, respectively) and two carboxyl oxygen atoms of four acetate arms of the completely deprotonated heptadentate Hpdta^5? ligand (av. Ge-O, 1.922(3) and 1.920(3) Å; Ln-O, 2.349(2) and 2.298(2) Å in VI and XI, respectively). The coordination polyhedron of the Ge atom is completed to a distorted octahedron by the oxygen atom of the terminal hydroxo group (Ge-O, 1.811(2) Å in VI and 1.810(2) Å in XI), and the coordination polyhedron of the Ln atom is completed to an eight-vertex polyhedron by the oxygen atoms of three water molecules (av. Ln-O, 2.378(3) Å in VI and 2.342(3) Å in XI). In the crystals of VI and XI, complex molecules and crystal water molecules are combined by a system of hydrogen bonds into a three-dimensional framework.     

Tetranuclear rhenium chalcochloride cluster complexes Cs<Subscript>3</Subscript>H[Re<Subscript>4</Subscript>Q<Subscript>4</Subscript>Cl<Subscript>12</Subscript>] · 3.33H<Subscript>2</Subscript>O (Q = Se and Te): Synthesis and structures

The tetranuclear cluster rhenium complexes Cs₃H[Re₄Q₄Cl₁₂] · 3.33H₂O (Q = Te (I) and Se (II)) with the Cl atoms as terminal ligands were obtained and structurally characterized. The structures of complexes I and II were determined by X-ray diffraction analysis. Their isostructural crystals are monoclinic; space group C2, Z = 6; a = 26.403(8) Å, b = 16.495(5) Å, c = 11.744(3) Å, β = 91.25(2)°, V = 5113(2) ų (I); a = 26.573(3) Å, b = 16.461(3) Å, c = 11.726(2) Å, β = 91.381(4)°, V = 5127.6(14) ų (II).     

Synthesis,crystal and molecular structures of 1D and 2D supramers of copper(II) with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-{bis(pyridin-2-yl) benzylidene}butane-1,4-diamine

Reaction of copper(II) perchlorate with N,N′-{bis(pyridin-2-yl)benzylidene}butane-1,4-diamine (bpbd) yielded monoclinic crystals of bluish green [Cu(bpbd)(ClO₄)]ClO₄ (1), and a similar reaction in presence of azide anion, N₃ ^? formed monoclinic crystals of dark green [Cu(bpbd)(N₃)]₂ClO₄ (2). Crystal data for 1: space group P21/c, Z=4, a=17.3968(4) Å, b=9.3182(2) Å, c=17.6794(4) Å, β=102.149(1)°. The geometry around Cu(II) centre is distorted square pyramidal with axial site occupied by O atom of perchlorate and in plane Cu is bonded to four N atoms of the organic ligand. The intermolecular C–H...π stacking in 1 forms a zigzag chain (1D) supramer. Crystal data for 2: space group C2/c, Z=4, a=22.3109(4) Å, b=17.7832(3) Å, c=14.3389(2) Å, β=92.553(1)°. In dinuclear 2, Cu(II) has tetragonally distorted octahedral geometry coordinated by four N atoms of bpbd, with the fifth and sixth positions occupied by N atoms of two end-on bridging azides. The π...π interaction leads to a two dimensional (2D) sheet within which the counter anions are embedded. Both the compounds 1 and 2 show simple paramagnetism. Cyclic voltammetry and fluorescence spectra are also reported.     

Synthesis,crystal, and molecular structure of coordination polymers constructed by self-assembly of NiN<Subscript>4</Subscript> cores with 2,2′-iminodibenzoate and nitroprusside ions

Two coordination compounds of compositions [Ni(L¹)(idba)(H₂O)]·1.5 H₂O (1) and [Ni(L²)Fe(CN)₅NO]·C₂H₅OH (2) where L¹ is N, N′-bis(3-aminopropyl)ethylenediamine, L² is 2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),2,11,13,15-pentaene, and idba^2? is 2,2′-iminodibenzoate have been synthesized and characterized by elemental analysis, IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic space group P2₁/n (No. 14) with a=9.810(2) Å, b=10.230(2) Å, c=25.350(5) Å, V=2543.6(9) Å³, Z=4, and R=0.0727. The nickel atom is six-coordinated by four N atoms of amine and two O atoms of water and idba^2?. The molecular packing of the complex comprises of an infinite one-dimensional layered network in which the molecules in the crystal are held together by a system of hydrogen bonding. Complex 2, however, crystallizes in the space group C2/c (No. 15) of the monoclinic system with a=19.7990(4) Å, b=14.9440(3) Å, c=19.8800(3) Å, V=5115.90(17) Å³, Z=4, and R=0.0540. The Ni ion in compound 2 has a slightly distorted octahedral arrangement of the N₄ donor atoms of primary ligand L² and two N-donor atoms of the secondary nitroprusside ligand. The structure of 2 displays an extended one-dimensional network formed by linear [—Ni—NC—Fe—CN—] units. A cyclic voltammetric study shows that compound 1 undergoes a quasireversible oxidation attributable to Ni²⁺ → Ni³⁺ in the range 300–420 mV vs SCE.     

Structural aspects of some organoselenium compounds

The crystal structures of four organoselenium compounds, viz. bis(2-formylphenyl)diselenide (5), bis(2-methylnaphthyl)diselenide (6), organoselenenyl sulfide (7), and spiroselenurane (8) are described. Crystal data for 5: space group Pca2₁, crystal system orthorhombic, a=7.9969(4) Å, b=20.8794(12) Å, c=15.8307(13) Å, Z=8, R=0.0292. Owing to the presence of a strong Se···O interaction in compound 5 the geometry around the selenium atom may be considered as T-shaped. Crystal data for 6: space group Pna2₁, crystal system orthorhombic, a=18.2253(12) Å, b=13.0714(8) Å, c=7.7355(5) Å, Z=4, R=0.0570. The molecule has a cisoid conformation. Crystal data for 7: space group Pbcn, crystal system orthorhombic, a=22.2144(13) Å, b=8.0255(4) Å, c=15.4496(9) Å, Z=8, R=0.0292. Due to intramolecular Se···N interaction in 7 the geometry around selenium is T- shaped. Crystal data for 8: space group P2₁/c, crystal system monoclinic, a=7.4585(5) Å, b=19.5634(13) Å, c=8.0428(5) Å, β=97.1320(10)°, Z=4, R=0.0254. The O?Se?O angle is 172.86(6)°.     

2-(diphenylphosphinylmethoxy)aniline: Synthesis,vibrational spectra,and crystal structure

The synthesis, vibrational spectra, and X-ray diffraction analysis results for 2-(diphenylphosphinylmethoxy) aniline, 2-[(C₆H₅)₂P(O)OCH₂]C₆H₄NH₂(I), are described. The crystals are monoclinic: a = 18.4515(17) Å, b = 10.5421(12) Å, c = 17.897(2) Å, β = 104.479(8)°, V = 3370.7(6) ų, Z = 8, space group P2₁/c, R = 0.0546 for 1770 reflections with I > 2σ(I). The unit cell contains two crystallographically independent molecules Ia and Ib joined by an N-H …O hydrogen bond between a hydrogen atom of the amino group of aniline in molecule Ia (Ib) and the phosphoryl oxygen atom of molecule Ib (Ia) (O…H 2.18 and 2.19 Å, N…O, 2.979(5) and 3.000(5) Å; NHO angle, 154° and 157°).     

Crystal Chemistry Study of Two Magnesium Complexes with Trifluoroacetylacetone

Single crystal X-ray diffraction at a temperature of 150(2) K is used to determine the structures of two magnesium complexes with trifluoroacetylacetone: [Mg(tfac)₂]₃I and [Mg(H₂O)₂(tfac)₂]·H₂O II. Crystallographic data for I: space group P2₁/n, a = 12.5226(10) Å, b = 13.0591(7) Å, c = 12.6034(13) Å, β = 95.243(2)°, V = 2052.5(3) ų, Z = 2; for II: space group P2₁/c, a = 10.826(2) Å, b = 7.0742(13) Å, c = 21.858(4) Å, β = 102.712(5)°, V = 1632.9(5) ų, Z = 4. The isle structure of I is formed by linear trimeric molecules; in the structure of II the molecules of the complex and crystallization water form a layered framework using hydrogen bondings; the coordinated water molecules are in a trans position. The magnesium atoms have a distorted octahedral coordination environment, the Mg–O distances are 1.991(4)- 2.146(4) Å and 2.040(5)-2.073(5) Å in molecules of I and II respectively.     

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 (2.2.2-cryptand)rubidium chloride and bromide hydrates

Two complexes, (2.2.2-cryptand)rubidium chloride and bromide hydrates [Rb(Crypt-222]Hal · 3.5H₂O (Hal = Cl (I) and Br (II)), are synthesized. The structures of isomorphic crystals of compounds I and II are studied by X-ray diffraction analysis. The crystals are trigonal: space group P \(\overline 3 \), Z = 2; I: a = 11.810 Å, c = 11.302 Å; II: a = 11.890 Å, c = 11.402 Å. The structures are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.060 (I) and 0.077 (II) for 2650 (I) and 2700 (II) independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). In crystals of complexes I and II, the [Rb(Crypt-222)]⁺ cation of the host-guest type lies on the crystallographic axis 3 and has the approximate symmetry D ₃. In complexes I and II, the coordination polyhedron of the Rb⁺ cation is a two-base-centered trigonal prism somewhat distorted to an antiprism. The crystals of compounds I and II contain H-bonded disordered cubes of the water molecules and Cl^? or Br^? anions.     

Synthesis,crystal structures,and catalytic property of dioxomolybdenum(VI) complexes with hydrazone ligands derived from 3,5-Di-<Emphasis Type="Italic">tert</Emphasis>-butylsalicylaldehyde

Two new dioxomolybdenum(VI) complexes, [MoO₂L¹(MeOH)] (I) and [MoO₂L²] (II), where L¹ and L² are the anionic forms of N'-(2-hydroxy-3,5-di-tert-butylbenzylidene)-4-methoxybenzohydrazide and 2-amino-N'-(2-hydroxy-3,5-di-tert-butylbenzylidene)benzohydrazide, respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination (CF files CCDC nos. 1448089 (I), 1487063 (II)). The crystal of I is monoclinic: space group P21/n, a = 7.353(1), b = 24.758(3), c = 13.891(2) Å, β = 101.013(2)°, V = 2482.3(6) Å3, Z = 4, R ₁ = 0.0848, wR ₂ = 0.2050. The crystal of II is monoclinic: space group P2₁/c, a = 6.752(1), b = 16.947(1), c = 19.510(1) Å, β = 96.891(2)°, V = 2216.5(4) Å3, Z = 4, R ₁ = 0.0670, wR ₂ = 0.1638. The Mo atom in complex I is in octahedral coordination, with three donor atoms of the hydrazone ligand, two oxo groups, and one methanol O atom. The Mo atom in complex II is in square pyramidal coordination, with three donor atoms of the hydrazone ligand, and two oxo groups. The complexes have interesting catalytic properties for sulfoxidation reactions.     

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.