Synthesis, characterization and ethylene polymerization activity of titanium aminopyridinato complexes

Three titanium complexes derived from 2-(2,6-difluoroanilino)pyridine and 2-(2-chloroanilino)pyridine were synthesized and characterized by X-ray diffraction or spectroscopic methods. All titanium complexes have been used to catalyze the polymerization of ethylene in the presence of MAO as cocatalyst. The mono(2,6-difluorophenylaminopyridinato) titanium catalyst was found to be more active in ethylene polymerization than the bis(2,6-difluorophenylaminopyridinato) and bis(2-chlorophenylaminopyridinato) titanium catalysts. ortho-Halogens disturbed the β-elimination transition state of ethylene polymerization and formed higher molar mass polyethylene than their unhalogenated congener. Due to fluxionality, the bis(2-chlorophenylaminopyridinato) titanium catalyst formed broader molar mass distribution than the bis(2,6-difluorophenylaminopyridinato) titanium catalysts.     

Titanium complexes with chiral amino alcohol ligands: synthesis and structure of complexes related to hydroamination catalysts

Titanium complexes with chiral amino alcohol ligands are useful precatalysts for the intramolecular hydroamination of aminoallenes. They can be synthesized via protonolysis of titanium dimethylamide starting materials with the free ligand. In most cases, the resulting materials are not isolable due to their oily nature. However, several complexes were prepared in pure form and isolated as solid materials. [Ti(Cl)(NMe₂)(-OCH₂CH(Ph)N(CHMe₂)-]₂ was prepared at room temperature from TiCl(NMe₂)₃ and the corresponding N-substituted d-amino alcohol; the dimeric nature of the complex was established by X-ray crystallography. [Ti(NMe₂)₂(-OCH₂CH(Ph)N(2-Ad)-)]₂ (2-Ad = 2-Adamantyl) was prepared from Ti(NMe₂)₄ and the corresponding N-substituted l-amino alcohol after prolonged heating. An intermediate complex that could not be purified or isolated is believed to be Ti(NMe₂)₃(-OCH₂CH(Ph)NH(2-Ad)). Two complexes with the composition TiCl₂(-OCH₂CH(R*)N(CHMe₂)-)(HNMe₂) (where R* = CH₂Ph or CHMe₂) were prepared at room temperature by protonolysis of TiCl₂(NMe₂)₂ with the corresponding N-substituted l-amino alcohols. These two complexes exhibit dynamic behavior on the NMR timescale that is believed to be a dimer-monomer equilibrium, but they decompose at elevated temperatures.     

Synthesis and characterization of 3-thiophene carboxamides containing a pyridine ring: structure, electrochemistry, and complexation

A series of new thiophene amides containing a pyridine ring has been synthesized and characterized. Single crystal X-ray structures have been determined for four of the new substances which show two distinct patterns of hydrogen-bonding. The crystal structure of the copper (II) complex of one of the ligands shows that the bonding is O,N in a square planar geometry with perchlorate ions in the axial positions. The new compounds do not undergo electropolymerization due to primary oxidation of the amide function but tuning of the amide group by introduction of an electron-withdrawing group on the pyridine ring allows electropolymerization to occur.     

Steric and counterion effects on the structure of dipicolylamine nickel complexes

Four nickel complexes each containing an R-2,2′-dipicolylamine ligand species (RDPA; R = benzyl, isopropyl, or tert-butyl) were synthesized and structurally characterized. In the absence of an interfering coordinating counterion, BzDPA and iPrDPA form 1:2 nickel:ligand complexes, with two facial ligands completing an pseudooctahedral nickel(II) coordination environment. In contrast, the sterically hindered tBuDPA ligand instead forms 1:1 metal:ligand complexes, even in the absence of associating counterions. Two novel tBuDPA nickel complexes with different counterions are described: nickel(II) chloride gives rise to an unusual 2Ni-3Cl dimer complex, while nickel(II) nitrate affords a 1:1 nickel:ligand complex which crystallizes with both fac and mer conformations in the same unit cell.     

Titanocene complexes with nonlinear pseudohalide ligands: Synthesis, spectroscopic characterization and crystal structure

Binuclear titanocene complexes [Cp₂Ti(tcm)]₂O (4), [Cp₂Ti(dca)]₂O (5) and [Cp₂Ti(dcnm)]₂O (6) (tcm⁻ = tricyanomethanide, dca⁻ = dicyanamide and dcnm⁻ = dicyanonitrosomethanide) were synthesized in moderate yields by the reaction of Cp₂TiCl₂ (1) with respective alkali metal pseudohalide salts in the aqueous solution. When the reaction was carried out in dry organic solvents, mononuclear compounds Cp₂Ti(tcm)₂ (2) and Cp₂Ti(dca)₂ (3) were isolated. Preparation of dipseudohalide complex Cp₂Ti(dcnm)₂ by this manner was unsuccessful due to decomposition of dcnm ligand resulting in formation of oxygen-bridged compound 6. All prepared compounds were characterized by elemental analysis, NMR, Raman, infrared and UV-Vis spectroscopy. Molecular structures of 2, 4 and 6 (two polymorphs) have been determined by single-crystal X-ray diffraction analysis.     

Synthesis, properties and solution speciation of lanthanide chloride complexes of triphenylphosphine oxide

The reaction of Ph₃PO with LnCl₃ · nH₂O (Ln=La-Lu ≠ Pm) in a 3.5:1 ratio in acetone produces [LnCl₃(Ph₃PO)₃], whilst from a 6:1 ratio in ethanol the products are [LnCl₂(Ph₃PO)₄]Cl · n(solvate). In the presence of [NH₄][PF₆] in ethanol solution, [LnCl₂(Ph₃PO)₄]PF₆ can be isolated. The last complexes are stable in solution but the [LnCl₃(Ph₃PO)₃] and [LnCl₂(Ph₃PO)₄]Cl partially interconvert in non-coordinating solvents, the neutral species being preferred by the lighter lanthanides, the cationic tetrakis complexes becoming more favoured towards the end of the series. The complexes have been characterised in the solid state by analysis and IR spectroscopy and in solution by ³¹P{¹H} NMR spectroscopy and conductance measurements. The crystal structures of trans-[LnCl₂(Ph₃PO)₄]Cl · nEtOH (Ln=Tb or Yb) and mer-[LnCl₃(Ph₃PO)₃] · 0.5Me₂CO (Ln=La or Ce) are reported and discussed.     

Synthesis, structures and luminescent behaviour of tridentate salicylaldiminato-type borate complexes

Treatment of the ligands 3,5-tBu₂-2-(OH)C₆H₂CHNR [R = 2-(CO₂H)C₆H₄ (1a) and 2-(CO₂H)C₁₀H₆ (1b)] with trimethylborate, B(OMe)₃, in toluene yields, after work-up, the yellow crystalline complexes {[3,5-tBu₂-2-(O)C₆H₂CHNR]B(OMe)} [R = 2-(CO₂)C₆H₄ (2a) and 2-(CO₂)C₁₀H₆ (2b)], respectively. Further treatment of these complexes with trifluoromethanesulfonic (triflic) acid, CF₃SO₃H, followed by recrystallisation from tetrahydrofuran (thf) afforded the triflate salts [{3,5-tBu₂-2-(O)C₆H₂CHNR}B(thf)][CF₃SO₃] [R = 2-(CO₂)C₆H₄ (3a) and 2-(CO₂)C₁₀H₆ (3b)]. An electroluminescent device was constructed using 2a, which produced orange-green light with broad emission spectra (maximum brightness of 5 cd/m² being observed at 13 V). Compounds 1a and 2b·2MeCN have been characterised by single crystal X-ray structure determinations.     

Mononuclear cobalt(II) carboxylate complexes: Synthesis, molecular structure and selective oxygenation study

Some cobalt carboxylate (both mononuclear as well as binuclear) complexes have been prepared by using hindered hydrotris(3,5-diisopropyl-1-pyrazolyl)borate (Tp^iPr2) as supporting ligand. The reaction of [Tp^iPr2Co(NO₃)] (2) with sodium benzoate resulted in the formation of acetonitrile coordinated complex [Tp^iPr2Co(OBz)(CH₃CN)] (3) whereas the reaction of 2 with sodium fluorobenzoate gave coordinately unsaturated five coordinate complex of the type [Tp^iPr2Co(F-OBz)] (4). The oxidation of compound 4 in the presence of 3,5-diisopropylpyrazole resulted in the formation of a unique compound (5) where only one methine carbon of isopropyl group on pyrazole ring of hydrotris(3,5-diisopropyl-1-pyrazolyl)borate oxidized and coordinated with cobalt center. In compound 5, the binding behavior of fluorobenzoate also changes from bidentate to monodentate and the nonbonded oxygen atom formed intramolecular hydrogen bond with the hydrogen atom of the NH fragment of the coordinated . X-ray crystallography and IR studies confirmed the existence of hydrogen bonding in complex 5. The pyrazolato bridged binuclear cobalt(II) complex (6) was prepared by the reaction of hydrated cobalt(II) nitrate, 3,5-diisopropylpyrazole and sodium nitrobenzoate where, each cobalt is four coordinate. The X-ray structure of 6 showed that the NH fragment of terminally coordinated formed intramolecular hydrogen bonding with nonbonded oxygen atom of monodentately coordinated nitrobenzoate.     

Synthesis, spectroscopy, structure and photophysical properties of dinaphthylmethylarsine complexes of palladium(II) and platinum(II)

Dinaphthylmethylarsine complexes of palladium(II) and platinum(II) with the formulae [MX₂L₂] (M = Pd, Pt; L = di(1-naphthyl)methylarsine = Nap₂AsMe and X = Cl, Br, I), [M₂Cl₂(μ-Cl)₂L₂], [PdCl(S₂CNEt₂)L], [Pd₂Cl₂(μ-OAc)₂L₂] and [MCl₂(PR₃)L] (PR₃ = PEt₃, PPr₃, PBu₃, PMePh₂) have been prepared. These complexes have been characterized by elemental analyses, IR, Raman, NMR (¹H, ¹³C, ³¹P) and UV-vis spectroscopy. The stereochemistry of the complexes has been deduced from the spectroscopic data. The crystal structures of trans-[PdCl₂(PEt₃)(Nap₂AsMe)] and of [Pd(S₂CNEt₂)₂], a follow-up product, were determined. The UV-vis spectra of [MX₂L₂] complexes show a red shift on going from X = Cl to X = I. The complexes [PdX₂L₂] and [PtX₂L₂] are strongly luminescent in fluid solution and in the solid at ambient temperature.     

Synthesis and structure determination of some platinum (II) complexes with hydrophilic carboxylated tertiary phosphine ligands

[Pt(COD)Cl₂] (1) reacts with PPh₂(C₆H₄COOH) (2a,b,c), PPh₂(C₆H₄COONa) (2d), PPh(C₆H₄COOH)₂ (4b,c) and P(C₆H₄COOH)₃ (6b,c) with formation of the corresponding complexes [Pt(L)₂Cl₂] (3a,b,c,d, 5b,c, 7b,c). Halide abstraction from 3a by Ag⁺ promotes coordination of the ortho-carboxylate function to platinum, yielding [ -2)}{PPh₂(C₆H₄COOH-2)}Cl] (bd8) and [ovbar|{PPh₂(C₆H₄COO-2)}₂] (bd9). Reaction of 1 with CO and 2a or 2b gives [Pt(CO)(L)Cl₂] (10a,b), wherea 1 and 2,3-bis(diphenylphosphino) maleic anhydride yields

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(bd12) and [Pt{Ph₂PC(COOH)=C(COOMe)-PPh₂}Cl₂] (13). The ¹H, ¹³C and ³¹P NMR spectra are reported and discussed. The X-ray structural analysis of 3b showed the compound to be monoclinic, space group P2₁/n, Z=4, with a=1038.5(3), B=1792.6(4), C=2311.5(4) pm, β=91.6(2)° and D_calc=1.353 g cm⁻³. The structure was solved from 4832 observed reflections with F₀ > 4 σ(F₀) and refined to a final R value of 0.0743. The Pt atom is surrounded by two Cl and two P atoms in a square planar arrangement.     

Synthesis, characterization, and reactivity of organometallic Zr(IV) carboxylate complexes

A series of zirconium(IV) complexes, [ZrX₂(XDK)], where XDK is the constrained carboxylate ligand m-xylylenediamine bis(Kemp's triacid imide), were prepared and structurally characterized. The solid state structure of the mononuclear carboxylate alkyl complex [Zr(CH₂Ph)₂(XDK)] reveals that one benzyl group is bonded in an η²-fashion to the metal center. The reactivity of [Zr(CH₂Ph)₂(XDK)] displays its electrophilic character toward nucleophiles strong enough to displace the η²-benzyl group. Thus, weak sigma donor ligands such as CO, alkynes and anilines do not react, whereas strong sigma donors, such as pyridines and isocyanides, rapidly form the monoadduct [Zr(CH₂Ph)₂(4-tert-butylpyridine)(XDK)] and [Zr{η²-2,6-Me₂PhNCCH₂Ph}₂(XDK)], an η²-iminoacyl derivative, respectively. Attempts to prepare zirconium amido complexes with H₂XDK generally afforded the eight-coordinate [Zr(XDK)₂] complex but use of the small amido ligand precursorZr(NMe₂)₄ allowed [Zr(NMe₂)₂(4-tert-butylpyridine)(XDK)] to be isolated in good yield.     

Synthesis, structure and electronic spectra of new three-coordinated copper(I) complexes with tricyclohexylphosphine and diimine ligands

Three new copper(I) complexes with tricyclohexylphosphine (PCy₃) and different diimine ligands, [Cu(phen)(PCy₃)]BF₄ (1) (phen = 1,10′-phennanthroline), [Cu(bpy)(PCy₃)₂]BF₄ (2) (bpy = 2,2′-bipyridine) and [Cu(MeO-CNN)(PCy₃)]BF₄ (3) (MeO-CNN = 6-(4-methoxyl)phenyl-2,2′-bipyridine), have been synthesized and characterized. X-ray structure reveals that complexes 1 and 3 are three-coordinated with trigonal geometry, while complex 2 adopts distorted tetrahedron geometry. Complexes 1 and 3 exhibit ligand redistribution reactions in chloromethane solution by addition of excess amount of PCy₃, in which three-coordinated 1 changes into four-coordinated [Cu(phen)(PCy₃)₂]⁺, and 3 leads to form [Cu(PCy₃)₂]BF₄ and CNN-OMe. All the three complexes display yellow ³MLCT emissions in solid state at room temperature with λ_max at 558, 564 and 582 nm for 1, 2 and 3, respectively, and red-shift to 605, 628 and 643 nm at 77 K in dichloromethane solution.     

Synthesis, crystal structures, and fluorescence properties of six complexes with thiophene derivative carboxylic acid ligand

The crystallization of 2,3-dihydro-thieno[3,4-b][1,4] dioxine-5,7-dicarboxylic acid (H₂tddc) with divalent transitional metal (Co, Ni, Zn, Cd) or with tervalent lanthanide metal (Sm) and with mixed ligand 4,4′-bipyridine (4,4′-bipy) or 1,10-phenanthroline (1,10-phen) formed six new complexes: [Co(C₈H₄O₆S) · 3H₂O] (1), [Co(C₈H₄O₆)(1,10-phen)(H₂O)] · H₂O (2), [Ni(C₈H₄O₆S)(4,4′-bipy)(H₂O)] · 3H₂O (3) [Sm(C₈H₄O₆S)(NO₃)(H₂O)₄] · 2H₂O (4), [Zn(C₈H₄O₆S)(H₂O)₃] (5), and [Cd₂(C₈H₄O₆S)₂(4,4′-bipy)₂] (6). The structures of these six crystals have been characterized by single-crystal X-ray diffraction analyses, which revealed that complexes 1, 4, 5 are all one-dimensional chain structures and they self-assemble into three-dimensional super-molecules via the hydrogen bond interactions and π-π stacking interactions, 2 is also a one-dimensional chain structure but still self-assembles into one-dimensional double-chains, the complex 3 has two-dimensional undulating parallelogram grid structure extended along the bc-plane, the crystal of 6 is a 3D threefold interpenetration topology framework with 4⁶6³8 nodes. The photoluminescent properties of the H₂tddc ligand and the six compounds have been measured in the solid state at room temperature. Free ligand has no luminescence, while its complexes 1, 4, and 6 all exhibit intense photoluminescence which implies that these complexes may be excellent candidates for potential photoactive materials.     

Syntheses, crystal structure, spectroscopic characterization and antifungal activity of new N-R-sulfonyldithiocarbimate metal complexes

Five new compounds with the general formula of (Bu₄N)₂[M(RSO₂NCS₂)₂], where Bu₄N = tetrabutylammonium cation, (M = Ni, R = 4-FC₆H₄) (1), (M = Zn, R = 4-FC₆H₄, 4-ClC₆H₄, 4-BrC₆H₄, 4-IC₆H₄), (2), (3), (4) and (5), respectively, were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO₂NCS₂K₂) with nickel(II) chloride hexahydrate or zinc(II) acetate dihydrate in metanol:water 1:1. The elemental analyses and the IR data are consistent with the formation of the expected bis(dithiocarbimato)metal(II) complexes. The ¹H and ¹³C NMR spectra showed the signals for the tetrabutylammonium cation and the dithiocarbimate moieties. The compounds 1, 2 and 5 were also characterized by X-ray diffraction techniques. The nickel(II) is coordinated by two N-4-fluorophenylsulphonyldithiocarbimato(2-) ligands forming a planar coordination. The zinc(II) exhibits distorted tetrahedral configuration in compounds 2 and 5 due to the chelation effect of two sulfur atoms of the N-R-sulfonyldithiocarbimate ligands. The antifungal activities of the compounds were tested in vitro against Colletotrichum gloeosporioides, an important fungus that causes the plant disease known as anthracnose in fruit trees. All the complexes were active.     

Synthesis and bioelectrochemical behavior of aromatic amines

Four aromatic amines 1-amino-4-phenoxybenzene (A₁), 4-(4-aminophenyloxy) biphenyl (A₂), 1-(4-aminophenoxy) naphthalene (A₃) and 2-(4-aminophenoxy) naphthalene (A₄) were synthesized and characterized by elemental, spectroscopic (FTIR, NMR), mass spectrometric and single crystal X-ray diffraction methods. The compounds crystallized in monoclinic crystal system with space group P2₁. Intermolecular hydrogen bonds were observed between the amine group and amine/ether acceptors of neighboring molecules. Electrochemical investigations were done using cyclic voltammetry (CV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV). CV studies showed that oxidation of aromatic amines takes place at about 0.9 V (vs. Ag/AgCl) and the electron transfer (ET) process has irreversible nature. After first scan reactive intermediate were generated electrochemically and some other cathodic and anodic peaks also appeared in the succeeding scans. DPV study revealed that ET process is accompanied by one electron. DNA binding study of aromatic amines was performed by CV and UV–visible spectroscopy. These investigations revealed groove binding mode of interaction of aromatic amines with DNA.     

Reactions of seven coordinate complexes. Synthesis, structure, and copper complex of the novel ligand 3-methyltriazolo(1,5-a)6-acetylsemicarbazonepyridine

The reaction of aquachloro(2,6-diacetylpyridinedisemicarbazone)copper(II) with hydrazine hydrate gave the copper complex of 3-methyltriazolo(1,5-a)6-acetylsemicarbazonepyridine. The free ligand was isolated from the copper complex. The X-ray structures of both the copper complex and the free ligand are reported. The copper complex and the free ligand both crystallize in the triclinic space group with 2 molecules per cell. The Cu complex has cell dimensions of a=8.8574(4), b=10.1764(5), c=10.4434(5) Å, α=71.956(1), β=64.913(1), and γ=81.597(1)°. The Cu ion is in a square pyramidal arrangement, with the Cu, the ligand, and a Cl in the plane and a disordered Cl and H₂O in the apical position. The ligand has cell dimensions of a=7.2696(7), b=8.0516(7), c=9.9326(9) Å, α=110.534(2), β=96.730(2), and γ=100.089(2)°. The ligand is planar with a conformation determined by an internal N-H?H hydrogen bond. The role of the Cu ion in the formation of the triazolopyridine is discussed.     

A series of pyrazolone lanthanide (III) complexes: Synthesis, crystal structures and fluorescence

A series of pyrazolone lanthanide complexes: Ln(PMPP)₃ · 2H₂O · C₂H₅OH (Ln = Nd (1), Sm (2), Gd (3), Dy (4); PMPP = 1-phenyl-3-methyl-4-propionyl-5-pyrazolone) have been synthesized by the hydrothermal method with the starting ligand PMPP-SAH (1-phenyl-3-methyl-4-(salicylidene hydrazone)-propionyl-5-pyrazolone) changed into PMPP during the formation process of complexes. All the complexes were structurally characterized by X-ray crystallography. The fluorescence of these four complexes 1-4 in solid state and DMF solution was investigated via F-4500 spectrophotometer and all of them indicate a fluorescent behavior at room temperature.     

Synthesis of amidate-hanging platinum mononuclear complexes by base hydrolysis of nitrile complexes

The “amidate-hanging” Pt mononuclear complexes, which can easily bind a second metal ion with the non-coordinated oxygen atoms in the amidate moieties, have been synthesized and characterized by ¹H NMR, MS, IR spectroscopy, and single crystal X-ray analysis. Five new complexes with various amidate ligands and co-ligands, cis-[Pt(PVM)₂(en)] · 4H₂O (1, PVM = pivaloamidate, en = ethylenediamine), cis-[Pt(PVM)₂(NH₂CH₃)₂] · H₂O (2), cis-[Pt(PVM)₂(NH₂^tBu)₂] (3), cis-[Pt(TCM)₂(NH₃)₂] (4, TCM = trichloroacetamidate), and cis-[Pt(BZM)₂(NH₃)₂] (5, BZM = benzamidate), were successfully synthesized by direct base hydrolysis of the corresponding Pt nitrile complexes, cis-[Pt(NCR)₂(Am)₂]²⁺ (P1, P2, P3, and P5) (NCR = nitrile, Am = amine). These nitrile complexes were obtained by introducing nitriles into the Pt aqua complexes, cis-[Pt(OH₂)₂(Am)₂](ClO₄)₂, whereas introduction of trichloronitrile into [Pt(OH₂)₂(NH₃)₂](ClO₄)₂ induced more facilitated water nucleophilic attack to afford [Pt(TCM)(NH(COH)CCl₃)(NH₃)₂](ClO₄) (P4). The base treatments of the precursor complexes (P1-5) lead to produce “amidate-hanging” Pt mononuclear complexes (1-5) without geometry isomerization. The ¹⁹⁵Pt chemical shifts for 1-5 exhibit subtle differences of the Pt electron densities among them.     

Synthesis and characterization of polypyridineruthenium(II) complexes containing a linear ambidentate ligand, NCO or NCS, and reaction of isocyanato complexes under acidic conditions

Isocyanato and isothiocyanatopolypyridineruthenium complexes, [Ru(NCX)Y(bpy)(py)₂]ⁿ⁺ (bpy=2,2′-bipyridine, PY=pyridine; X=O, Y=NO₂ for n=0, and Y=py for n=1; X=S, Y=NO₂ for n=0, Y=NO for n=2, and Y=py for n=1), were synthesized by the reaction of polypyridineruthenium complexes with potassium cyanate or sodium thiocyanate salt. Isocyanatoruthenium(II) complexes, [Ru(NCO)(NO₂)(bpy)(py)₂] and [Ru(NCO)(bpy)(py)₃]⁺, react under acidic conditions to form the corresponding ammineruthenium complexes, [Ru(NO)(NH₃)(bpy)(py)₂]³⁺. The molecular structures of [Ru(NCO)(bpy)(py)₃]ClO₄, [Ru(NCS)(NO)(bpy)(py)₂](PF₆)₂ and [Ru(NO)(NH₃)(bpy)(py)₂](PF₆)₃ were determined by X-ray crystallography.     

Studies of the cation complexing ability of crowns Part I. Synthesis, characterization and crystal structure of diazacrowns and their barium complexes

A number of N,N′-bis(4-substituted phenyl)-1,7-diaza-12-crown-4 and N,N′-bis(4-substituted phenyl)-1, 10-diaza-18-crown-6 (where the substituents are OCH₃, CH₃, H, Cl, respectively) have been prepared by cyclization reaction of a ditosylate with the appropriately substituted diol. These new macrocyclic ligands have been characterized by means of elemental analysis, IR, ¹H NMR and MS spectra. The crystal structures of N,N′-bis(4-chlorophenyl)-1,10-diaza-18-crown-6 (21) and its complex with barium thiocyanate Ba(SCN)₂ (22) have been determined by single crystal X-ray diffraction. The crystallographic data are as follows: 21: C₂₄H₃₂Cl₂N₂O₄, orthorhombic, P2₁2₁2₁, A=4.852(1), B=11.989(2), C=41.231(8) Å, V=2398.7(8) ų, Z=4; 22: C₂₆H₃₂Cl₂N₄O₄S₂Ba, monoclinic, P2₁/c, A=8.801(2), B=11.653(9), C=15.756(6) Å, ß=105.96(3)°, V=1553.7(14) ų, Z=2. In the complex, the Ba atom is eight-coordinate (O(1), O(2), O(1)′, O(2)′, N(1), N(1)′, N(21), N(21)′) to form a distorted D_6h geometry with the Ba atom at the center of crystallographic symmetry.