Silicon and iron levels in tissues of animals treated with a “ferrimagnetic ceramic” with oncotherapeutic potential (anti-tumor) value

The stability in a biological environment of an injectable cement with oncotherapeutic potential — consisting of a glass powder of SiO₂ (35.6%), CaO (42.4%), P₂O₅ (17%), Na₂O (5%) and 30% of its weight of Fe₃O₄ dissolved in (NH₄)₂HPO₄ plus NH₄H₂PO₄ — was evaluated referring to the release of silicon and iron. The experimental model was the rat, and organs (liver, kidney, spleen, lung, heart, and brain) of the implanted and control animals were collected for quantification of these elements by electrothermal atomization atomic absorption spectrometry methods. In most of the analysed organs no significant difference in the contents of silicon and iron between the implanted and the control animals was found.     

The new enneanuclear nickel carbonyl anion [Ni9(CO)16] and its relationships with the [Ni12(CO)21] and [Ni6Rh3(CO)17] clusters

The reaction of [N(PPh₃)₂]₂[Ni₆(CO)₁₂] with Cu(PPh₃)_xCl (x=1, 2), as well as the degradation of [N(PPh₃)₂]₂[H₂Ni₁₂(CO)₂₁] with PPh₃, affords the new and unstable dark orange–brown [N(PPh₃)₂]₂[Ni₉(CO)₁₆].THF salt in low yields. This salt has been characterized by a CCD X-ray diffraction determination, along with IR spectroscopy and elemental analysis. The close-packed two-layer metal core geometry of the [Ni₉(CO)₁₆]²⁻ dianion is directly related to that of the bimetallic [Ni₆Rh₃(CO)₁₇]³⁻ trianion and may be envisioned to be formally derived from the hcp three-layer geometry of [Ni₁₂(CO)₂₁]⁴⁻ by the substitution of one of the two outer [Ni₃(CO)₃(μ−CO)₃]²⁻ layers with a face-bridging carbonyl group.     

Microspectrofluorometry of ultraviolet-inducible fluorescence in supravitally-stained ascites tumour cells

Synopsis Ultraviolet irradiation of tumour cells (Ehrlich tetraploid ascites tumour of mice, TO strain), supravitally stained with thiazine dyes (Azure II, Azure A, Methylene Blue, Toluidine Blue) or an oxazine dye (Brilliant Cresyl Blue), induces blue fluorescence in cytoplasmic bodies believed to be lipid droplets or lysosome-like bodies. Microspectrofluorometry of the inducible fluorescence in Ehrlich tumour cells gives bimodal excitation (340/394 nm) and emission (443/700 nm) curves.     

Six-coordinate phosphorus compounds. Crystal structures and dynamic NMR studies of phosphoranes containing chelating ligands

Hexacoordination of the neutral phosphorus compounds 4–6 is evidenced by their high field ³¹P NMR chemical shifts and is further substantiated by the crystal structure of 5 and 6.5 contains the potentially bis-chelating ligand Ar = (C₆H₃(CH₂NMe₂)₂-2,6) and 6 the same ligand with a protonated amino group. In both cases the compounds exhibit slightly distorted octahedral geometry. In compound 5, only one NMe₂ group is coordinated to the phosphorus atom with an N → P bond of 2.063 Å. In compound 6, the NMe₂ group is coordinated to the phosphorus atom with an N → P bond of 2.007 Å while the dimethylammonium substituent is pointing away from the phosphorus atom forming a hydrogen bridge with two oxygen atoms. The fluxional behavior of these three novel six-coordinate phosphorus compounds was studied by dynamic ¹H NMR spectroscopy.     

Interactions between thiamine and large anions. Crystal structures of (H-thiamine)[Pt(SCN)4] · 3H2O and (H-thiamine)[Pt(SCN)6] · H2O

The reaction of thiamine with K₂Pt^IICl₄ and with Pt^IVCl₄ in the presence of excess NaSCN in aqueous solution gave thiamine salts, (H-thiamine)[Pt(SCN)₄] · 3H₂O (1) and (H-thiamine)[Pt(SCN)₆] · H₂O (2), respectively, structures of which have been determined by X-ray diffraction. The thiamine molecule adopts the usual F conformation in each salt. In 1, [Pt(SCN)₄]²⁻ ions act as large planar spacers in the crystal lattice and interact scarcely with thiamine, except for a hydrogen bonding with the terminal hydroxy O(5γ). Instead, water molecules form two types of host–guest-like interactions with the pyrimidine and the thiazolium moieties of a thiamine molecule, one being a C(2)–Hwaterpyrimidine bridge and the other being an N(4′)–Hwaterthiazolium bridge. In 2, despite the much larger ion size, octahedral [Pt(SCN)₆]²⁻ ions form a C(2)–Hanionpyrimidine bridge and an N(4′)–Hanionthiazolium bridge. An additional hydrogen bonding between the anion and the terminal O(5γ) of thiamine creates a hydrogen-bonded macrocyclic ring {thiaminium–[Pt(SCN)₆]²⁻}₂, a supramolecule.     

ADP binding and ATP synthesis by reconstituted H-ATPase from chloroplasts

The H⁺-ATPase from chloroplasts, CF₀F₁, was isolated, purified and reconstituted into asolectin liposomes. The enzyme was brought either into the oxidized state or into the reduced state, and the rate of ATP synthesis was measured after energisation of the proteoliposomes with an acid—base transition ΔpH (pH_in = 5.0, pH_out = 8.5) and a K⁺/valinomycin diffusion potential, Δφ (K⁺_in = 0.6 mM, K⁺_out = 60 mM). A rate of 250 s⁻¹ was observed with the reduced enzyme (85 s⁻¹ in the absence of Δφ). A rate of 50 s⁻¹ was observed with the oxidized enzyme under the same conditions (15 s⁻¹ in the absence of Δφ). The reconstituted enzyme contained 2 ATP_bound per CF₀F₁ and 1 ADP_bound per CF₀F₁. Upon energisation the enzyme was activated and 0.9 ADP per CF₀F₁, was released. Binding of ADP to the active reduced enzyme was observed under different conditions. In the absence of phosphate the rate constant for ADP binding was 10⁵ M⁻¹·s⁻¹ under energized and de-energized conditions. In the presence of phosphate the rate of ADP binding drastically increased under energized conditions, and strongly decreased under de-energized conditions.     

Mechanistic details for metathetical exchange between XCO (X = O and RN) and the tin(II) dimer, {Sn[N(SiMe3)2] (μ-OBu)}2

Metathetical exchange between carbon dioxide and the tin(II) dimer, {Sn[N(SiMe₃)₂](μ-OBu¹)}₂ (3) has been observed to cleanly produce the two new heteroleptic tin(II) dimers, Sn[N(SiMe₃)₂](μ-OBu^t)₂Sn(OSiMe₃) (6) and [Sn(OSiMe₃)](μ-OBu^t)]₂ (7]). In addition, reaction of 3 with I equiv, of tert-butylisocyanate (8), at 25°C, quantitatively provides 6, and with 2 equiv., quantitatively provides 7. Likewise 6 reacts with 1 equiv, of 8 to quantitatively provide 7. The mechanism for these latter processes has been investigated by low temperature ¹H NMR spectroscopy which reveals that metathetical exchange does not involve the tri-coordinate tin(II) centers of the dimeric structures, but rather, it occurs, in each case, via the transient monomeric tin(II) species, Sn[N(SiMe₃)₂](μ-OBu^t) (4), that undergoes metathesis to produce, initially the open dimer intermediate, Sn(OCNBu^t)(OSiMe₃)(μ-OBu^t)Sn(OBu^t) (OSiMe₃) (12), that is observed at −10°C. Subsequent redistribution reactions then generate the final products that are observed. Together, these mechanistic details provide additional support for the ‘monomeric tin(II)’ hypothesis proposed earlier for metathetical exchange between XCO and Sn[N (SiMe₃)₂]₂ (1).     

Gold in organic synthesis Part 2. Preparation of benzyl-alkyl and-arylketones via C---C coupling

Reaction of [Au(η²-Ar){CH₂C(O)R}Cl] (Ar=C₆H₄N=N- Ph-₂, R=Me, C₆H₂(OMe)₃-3′,4′,5′; Ar=C₆H₃(N=NC₆H₄Me- 4′)-2, Me-5, R=Me) with PPh₃ and NaClO₄·H₂O (1:2:1) at room temperature, leads to reductive elimination giving [Au(PPh₃)₂]ClO₄ and the corresponding carbon-carbon coupling product ArCH₂C(O)R. A similar process takes place when complexes [Au(η²-Ar){CH₂C(O)R}(PPh₃)Cl] are refluxed in tetrahydrofuran, through elimination of [Au(PPh₃)Cl].     

Catabolism of neurotensin by neural (neuroblastoma clone N1E115) and extraneural (HT29) cell lines

The mechanisms by which neurotensin (NT) was inactivated by differentiated neuroblastoma and HT29 cells were characterized. In both cell lines, the sites of primary cleavages of NT were Pro⁷-Arg⁸, Arg⁸-Arg⁹ and Pro¹⁰-Tyr¹¹ bonds. The cleavage at the Pro⁷-Arg⁸ bond was totally inhibited by N-benzyloxycarbonyl-Prolyl-Prolinal and therefore resulted from the action of proline endopeptidase. This peptidase also contributed in a major way to the cleavage at the Pro¹⁰-Tyr¹¹ bond. However the latter breakdown was partly due to an NT-degrading neutral metallopeptidase. Finally, we demonstrated the involvement of a recently purified rat brain soluble metalloendopeptidase at the Arg⁸-Arg⁹ site by the use of its specific inhibitor N-[1(R,S)-carboxy-2-Phenylethyl]-alanylalanylphenylalanine-p-aminobenzoate. The secondary processing of NT degradation products revealed differences between HT29 and N1E115 cells. Angiotensin converting enzyme was shown to degrade NT_1–10 and NT_1–7 in N1E115 cells but was not detected in HT29 cells. A post-proline dipeptidyl aminopeptidase activity converted NT_9–13 into NT_11–13 in HT29 cells but not in N1E115 cells. Finally bestatin-sensitive aminopeptidases rapidly broke down NT_11–13 to Tyr in both cell lines. Models for the inactivation of NT in HT29 and N1E115 cells are proposed and compared to that previously described for purified rat brain synaptic membranes.     

Fluorescence characteristics of lyophilized maize chloroplasts suspended in buffer

Fluorescence transients were measured in lyophilized maize chloroplasts (suspended in Tris-maleate buffer (pH 6.6)) after extraction with heptane. (The fluorescence characteristics before extraction were qualitatively similar to those in the fresh chloroplasts.) The initial fluorescence level (m) in the (dry) heptane-extracted sample remained the same as in the unextracted material, but the variable fluorescence (Δm) was drastically diminished. A portion of variable fluorescence, however, could be restored by adding Na₂S₂O₄. If the heptane extraction was made in the presence of water (wet), the m level was almost as high as (or higher than) the final level (M) of the unextracted sample, and Δm was reduced. The “jet” of O₂ (that measures the pool size of the intersystem intermediate A) and the “microjet” (that measures the pool size of the reaction center complex E), present in the unextracted samples, were absent in both types of extracted samples. Some of the above data may be interpreted in a hypothesis in which two quenchers (Q₁ and Q₂) control the fluorescence (O → P) of chloroplasts — the reduction of Q₁ being responsible for the rapid and that of Q₂ for the slow fluorescence rise.     

The stereochemistry of Co(III)-amine complexes. The use of nOe and COSY H NMR spectroscopy to determine structure in solution

It is shown how 1D nOe and 2D COSY ¹H NMR spectroscopy can be used to assign the stereochemistry of Co(III) amine complexes. By using d₆-DMSO as solvent together with a small quantity of DCl all non-equivalent N---H hydrogens can be distinguished at 300 MHz. Through-space (nOe), and through-bond (COSY), associations with other N---H and C---H hydrogens can then be determined. This leads to a complete assignment of structure in solution. The technique is applied to the complexes syn(N), anti(N)-[Co(cyclen) (NH₃)₂] (ClO₄)₃, syn(N), anti(Cl)-[Co(cyclen) (NH₃)Cl] (ClO₄)₂, anti(N), syn(Cl)-[Co(cyclen) (NH₃)Cl](ClO₄)₂, syn(N), anti(O)-[Co(Mecyclen)-(GlyO)](ClO₄)₂ and Δ-cis-[Co(δ-en)₂(NO₂)₂](NO₂).     

The structure of the dichromium compound Cr2(μ-OH)2(μ-3,5Cl2-form)2(η-3,5Cl2-form)2

With exposure to trace amounts of air and moisture, the Cr₂(II, II) complex Cr₂(μ-3,5Cl₂-form)₄, where 3,5Cl₂-form is [(3,5-Cl₂C₆H₃)NC(H)N(3,5-Cl₂C₆H₃)⁻], undergoes an oxidative addition reaction. Structural information from the X-ray crystal structure of the edge-sharing bioctahedral (ESBO) Cr₂(III, III) product Cr₂(μ-OH)₂(μ-3,5Cl₂-form)₂(η²-3,5Cl₂-form)₂ (1) indicates 1 has a significantly longer Cr–Cr distance [2.732(2) Å] than Cr₂(μ-3,5Cl₂-form)₄ [1.9162(10) Å], but the shortest Cr–Cr distance in an ESBO Cr₂(III, III) complex recorded to date.     

Effluxes of nitrous oxide,methane and carbon dioxide and their responses to increasing nitrogen deposition in the Gurbantünggüt Desert of Xinjiang,China

Aims Desert soils play an important role in the exchange of major greenhouse gas (GHG) between atmosphere and soil. However, many uncertainties existed in understanding of desert soil role, especially in efflux evaluation under a changing environment. Methods We conducted plot-based field study in center of the Gurbantünggüt Desert, Xinjiang, and applied six rates of simulated nitrogen (N) deposition on the plots, i.e. 0 (N0), 0.5 (N0.5), 1.0 (N1), 3.0 (N3), 6.0 (N6) and 24.0 (N24) g·m^-2·a^-1. The exchange rates of N₂O, CH₄ and CO₂ during two growing seasons were measured for two years after N applications. Important findings The average efflux of two growing seasons from control plots (N0) were 4.8 μg·m^-2·h^-1, -30.5 μg·m^-2·h^-1 and 46.7 mg·m^-2·h^-1 for N₂O, CH₄ and CO_2, respectively. The effluxes varied significantly among seasons. N0, N0.5 and N1 showed similar exchange of N₂O in spring and summer, which was relatively higher than in autumn, while the rates of N₂O in N6 and N24 were controled by time points of N applications. The uptake of CH₄ was relatively higher in both spring and summer, and lower in autumn. Emission of CO₂ changed minor from spring to summer, and greatly decreased in autumn in the first measured year. In the second year, the emission patterns were changed by rates of N added. N additions generally stimulated the emission of N₂O, while the effects varied in different seasons and years. In addition, no obvious trends were found in the emission factor of N₂O. The uptake of CH₄ was not significantly affected by N additions. N additions did not change CO₂ emissions in the first year, while high N significantly reduced the CO₂ emissions in spring and summer of the second year, without affected in autumn. Structure equation model analysis on the factors suggested that N₂O, CH₄ and CO₂ were dominantly affected by the N application rates, soil temperature or moisture and plant density, respectively. Over the growing seasons, both the net efflux and the global warming potential caused by N additions were small.     

A medium optimization strategy for improvement of growth and methane production by Methanobacterium thermoautotrophicum

Methanobacterium thermoautotrophicum, strain Hveragerdi, has been cultivated in a completely defined mineral salts medium, under strictly anaerobic conditions with CO₂ and H₂ as sole carbon and energy source, respectively. During optimization of the medium an iron limitation was identified that could not be overcome by the simple addition of iron—or iron complexed with nitrilotriacetate (NTA)—to the medium, due to the formation of insoluble FeS complexes. In order to define a medium optimization strategy, and to avoid laborious empirical optimization procedures, a theoretical model has been developed in order to describe the solubility of iron and other mineral species in the medium as a function of the concentration of sulfur and NTA. This model may be applied for the optimization of any medium component. With this information sulfide has been replaced by a combination of cysteine and thiosulphate in conjunction with a non-toxic reducing agent (titanium (III) citrate). Using this defined medium precipitation was avoided and an iron limitation was overcome resulting in a 5-fold improvement of the final biomass concentration from 2–3 g l⁻¹ to 11.2 g l⁻¹ together with a 2-fold increase (from 45 to almost 100%) in the conversion of CO₂ and H₂ to CH₄, even at gas flow rates as high as 6 l min⁻¹.     

Hemoglobin and iron-evoked oxidative stress in the brain: protection by bile pigments, manganese and S-nitrosoglutathione

In the present in vitro and in vivo study we investigated the pro-oxidant effects of hemoglobin, as well as the antioxidant effects of its metabolites, in the brain. Incubation of rat brain homogenates with hemoglobin (0-10 μM) but not hemin induced lipid peroxidation up to 24 h (EC₅₀ = 1.2 μM). Hemoglobin's effects were similar to ferrous ion (EC₅₀ = 1.7 μM) and were blocked by the chelating agent deferoxamine (IC₅₀ = 0.5 μM) and a nitric oxide-releasing compound S-nitrosoglutathione (IC₅₀ = 40 μM). However, metabolites of hemoglobin — biliverdin and bilirubin — inhibited brain lipid peroxidation induced by cell disruption and hemoglobin (biliverdin IC₅₀ = 12-30 and bilirubin IC₅₀ = 75-170 μM). Biliverdin's antioxidative effects in spontaneous and iron-evoked lipid peroxidation were further augmented by maganese (2 μM) since manganese is an antioxidative transition metal and conjugates with bile pigments. Intrastriatal infusion of hemoglobin (0-24 nmol) produced slight, but significant 20-22% decreases in striatal dopamine levels. Whereas, intrastriatal infusion of ferrous citrate (0-24 nmol) dose-dependently induced a greater 66% depletion of striatal dopamine which was preceded by an acute increase of lipid peroxidation. In conclusion, contrary to the in vitro results hemoglobin is far less neurotoxic than ferrous ions in the brain. It is speculated that hemoglobin may be partially detoxified by heme oxygenase and biliverdin reductase to its antioxidative metabolites in the brain. However, in head trauma and stroke, massive bleeding could significantly produce iron-mediated oxidative stress and neurodegeneration which could be minimized by endogenous antioxidants such as biliverdin, bilirubin, manganese and S-nitrosoglutathione.     

Enhanced dye decolorization efficiency by citraconic anhydride-modified horseradish peroxidase

Bromophenol blue and methyl orange removal capabilities of citraconic anhydride-modified horseradish peroxidase were compared with those of native horseradish peroxidase. Citraconic anhydride-modified horseradish peroxidase showed higher decolorization efficiencies for both dyes than native horseradish peroxidase. Upon the chemical modification, the decolorization efficiencies were increased by 1.8% and 12.4% for bromophenol blue and methyl orange, respectively. The quantitative relationships between decolorization efficiencies of dyes and reaction conditions were also investigated. Experimental data revealed that aqueous phase pH, reaction time, temperature, enzyme concentration and ratio of dye and H₂O₂ play a significant role on the dye degradation. Lower dose of citraconic anhydride-modified horseradish peroxidase was required than that of native enzyme for the decolorizations of both dyes to obtain the same decolorization efficiencies. Citraconic anhydride-modified HRP exhibited a good decolorization of dye over a wide range of dye concentration from 8 to 24 or 32 μmol l⁻¹ at 300 μmol l⁻¹ H₂O₂, which would match industrial expectations. Kinetic constants for two different dyes were also determined. Citraconic anhydride-modified horseradish peroxidase shows greater affinity and catalytic efficiency than native horseradish peroxidase for both dyes.     

Photosynthetic photon flux effects on bean response to nitrogen dioxide

Phaseolus vulgaris L. cv. Kinghorn Wax seedlings, supplied with nutrient solution containing either 0 or 5 mM nitrate as sole N source, were exposed to 0.25 μl/l NO₂ for 6 hr each day for 10 days at continuous photosynthetic photon flux (PPF) of 100, 300, 500 or 700 μmol m⁻² sec⁻¹. There was a significant interaction of PPF and nitrate. Shoot and root dry weights increased with increasing PPFs only when nitrate was supplied. The main effects of NO₂ on plant growth were significant; none of the interactions involving NO₂ were significant. Exposure to NO₂ decreased shoot and root dry weight in both the presence and absence of nutrient N and at all PPF levels. All interactions were significant for in vitro leaf nitrate reductase activity (NRA), which increased markedly at PPFs above 100 μmol m⁻² sec⁻¹ when nitrate was supplied. Treatment with NO₂ strongly inhibited enzyme activity in the presence of nitrate, particularly at the 300 μmol m⁻² sec⁻¹ PPF level. These experiments demonstrated that PPF level does not modify the effect of NO₂ on growth but does have a major effect on NRA and on NO₂ effects on NRA in the presence of nutrient nitrate.     

Organometallic chemistry of diphosphazanes. Rhodium(I) complexes of RN(PX2)2 (R = C6H5; X = OC6H5, OC6H4Br−p, R = CH3; X = OC6H5)

Reactions of [Rh(COD)Cl]₂ with the ligand RN(PX₂)₂ (1: R = C₆H₅; X = OC₆H₅) give mono- or disubstituted complexes of the type [Rh₂(COD)Cl₂{ν²−C₆H₅N(P(OC₆H₅)₂)₂}] or [RhCl{ν²−C₆H₅ N(P(OC₆H₅)₂)₂ }]₂ depending on the reaction conditions. Reaction of 1 with [Rh(CO)₂Cl]₂ gives the symmetric binuclear complex, [Rh(CO)Cl{μ−C₆H₅N(P(OC₆H₅)₂)₂} ₂, whereas the same reaction with 2 (R = CH₃; X = OC₆H₅) leads to the formation of an asymmetric complex of the type [Rh(CO)(μ−CO)Cl{μ−CH₃N(P(OC₆H₅)₂)₂}₂ containing both terminal and bridging CO groups. Interestingly the reaction of 3 (R = C₆H₅, X = OC₆H₄Br−p with either [Rh(COD)Cl]₂ or [Rh(CO)₂Cl]₂ leads only to the formation of the chlorine bridged binuclear complex, [RhCl{ν²−C₆H₅N(P(OC₆H₄Br−p)₂)₂}]₂. The structural elucidation of the complexes was carried out by elemental analyses, IR and ³¹P NMR spectroscopic data.     

Ligand induced P---H bond formation and a comparison of the reactivity of two isomers of the carbonyl hydride [Pt2(μ-PBu2)2(H)(CO)(PBu2H)]CF3SO3

The Pt₂ ^(II) isomeric terminal hydrides [(CO)(H)Pt(μ-PBu^t ₂)₂Pt(PBu^t ₂H)]CF₃SO₃ (1a), and [(CO)Pt(μ-PBu^t ₂)₂Pt(PBu^t ₂H)(H)]CF₃SO₃ (1b), react rapidly with 1 atm of carbon monoxide to give the same mixture of two isomers of the Pt₂ ^(I) dicarbonyl [Pt₂(μ-PBu^t ₂)(CO)₂(PBu^t ₂H)₂]CF₃SO₃ (3-Pt); the solid state structure of the isomer bearing the carbonyl ligands pseudo-trans to the bridging phosphide was solved by X-ray diffraction. A remarkable difference was instead found between the reactivity of 1a and 1b towards carbon disulfide or isoprene. In both cases 1b reacts slowly to afford [Pt₂(μ-PBu^t ₂)(μ,η²,η²-CS₂)(PBu^t ₂H)₂]CF₃SO₃ (4-Pt), and [Pt₂(μ-PBu^t ₂)(μ,η²,η²-isoprene) (PBu^t ₂H)₂]CF₃SO₃ (6-Pt), respectively. In the same experimental conditions, 1a is totally inert. A common mechanism, proceeding through the preassociation of the incoming ligand followed by the P---H bond formation between one of the bridging P atoms and the hydride ligand, has been suggested for these reactions.     

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.