New Acetylcholinesterase‐Inhibitory Pregnane Glycosides of Cynanchum atratum Roots

Three new pregnane glycosides, cynatroside A ( 1 ), cynatroside B ( 2 ), and cynatroside C ( 3 ), isolated from the roots of Cynanchum atratum (Asclepiadaceae), were characterized as 7β‐{[O‐α‐L ‐cymaropyranosyl‐(1→4)‐O‐β‐D ‐digitoxopyranosyl‐(1→4)‐β‐D ‐oleandropyranosyl]oxy}‐3,4,4a,4b,5,6,7,8,10,10a‐decahydro‐6α‐hydroxy‐4b‐ methyl‐2‐(2‐methyl‐3‐furyl)phenanthren‐1(2H)‐one ( 1 ), 7β‐{[O‐β‐D ‐cymaropyranosyl‐(1→4)‐O‐α‐L ‐diginopyranosyl‐(1→4)‐β‐D ‐cymaropyranosyl]oxy}‐3,4,4a,4b,5,6,7,8,10,10a‐decahydro‐2,6α‐dihydroxy‐4b‐methyl‐2‐(2‐methyl‐3‐furyl)phenanthren‐1(2H)‐one ( 2 ), and 7β‐{[O‐α‐L ‐cymaropyranosyl‐(1→4)‐O‐β‐D ‐digitoxopyranosyl‐(1→4)‐β‐L ‐cymaropyranosyl]oxy}‐3,4,4a,4b,5,6,7,8,10,10a‐decahydro‐2,6α‐dihydroxy‐4b‐methyl‐2‐(2‐methyl‐3‐furyl)phenanthren‐1(2H)‐one ( 3 ), respectively. In addition, ten known constituents were identified, i.e., cynascyroside D ( 4 ), glaucoside C ( 5 ), glaucoside D ( 6 ), atratoside A ( 7 ), 2,4‐dihydroxyacetophenone ( 8 ), 4‐hydroxyacetophenone ( 9 ), syringic acid ( 10 ), azelaic acid ( 11 ), suberic acid ( 12 ), and succinic acid ( 13 ). Among these compounds, 1 – 4 significantly inhibit acetylcholinesterase activity.     

A Comparative Study of (Poly)ether Adducts of Alkaline Earth Iodides – An Overview Including New Compounds

New homoligand and mixed‐ligand adducts of the heavier alkaline earth metal (Ca, Sr, Ba) halides with oxygen‐donor polyether ligands have been isolated and characterized and are compared with previously obtained compounds of the same class in order to give an overview on structures and properties. Homoligand halide adducts, discussed herein, are [CaI(DME)₃]I ( 1 ), trans‐[SrI₂(DME)₃] ( 2 ), trans‐[BaI₂(DME)₃] ( 3 ), (DME = ethylene glycol dimethyl ether), [CaI(diglyme)₂]I ( 4 ), cis‐[SrI₂(diglyme)₂] ( 5 ), trans‐[BaI₂(diglyme)₂] ( 6 ),(diglyme = diethylene glycol dimethyl ether, [SrI(triglyme)₂]I ( 7 ), and [BaI(triglyme)₂]I ( 8 ), (triglyme = triethylene glycol dimethyl ether). Introduction of the mono‐coordinating THF ligand (THF = tetrahydrofuran) in the coordination sphere of 1 , 2 , 3 , 4 allows the formation of the new mixed‐ligand compounds trans‐[CaI₂(DME)₂(THF)] ( 9 ), trans‐[SrI₂(DME)₂(THF)] ( 10 ), trans‐[BaI₂(DME)₂(THF)₂] ( 11 ), and trans‐[CaI₂(diglyme)₂(THF)₂] ( 12 ). These compounds were obtained from the metal halide salts in solution with pure or mixtures of ether solvents. While compounds 1 – 8 appear to be very stable and non‐reactive, adducts 9 – 12 present a comparable reactivity to the well known THF adducts [MI₂(thf)_n] (M = Ca, n = 4; Sr, Ba, n = 5).     

Alkyl Rearrangement of Derivatives of 2-Anilino-4,6-dialkoxy-1,3,5-triazines in the Solid- and Liquid-state

Abstract

2-Anilino-4,6-dimethoxy-1,3,5-triazine (13), 2-anilino-4,6-diethoxy-1,3,5-triazine (14), 2-(2′-nitoanilino) 4,6-dimethoxy-1,3,5-triazine (15) undergo alkyl rearrangement in the liquid-state, while 2-(4′-nito-anilino) 4,6-dimethoxy-1,3,5-triazine (16) undergoes methyl rearrangement in the solid-state. The crystal structure and thermal behavior of these compounds are described. 13 crystallizes in monoclinic P2₁/c space group, a = 11.030(4), b = 6.345(4), c = 16.315(4) Å, β = 90.76(3)°. The calculated density for Z = 4 is 1.351 Mg/m³. The number of unique reflections collected is 2092, and the final R = 0.0643 [I > 2σ(I)]. 14 crystallizes in triclinic P-1 space group, a = 7.700(2), b = 9.723(3), c = 10.154(3) Å, α = 78.78(3), β = 70.32(3), γ = 73.67(3)°. The calculated density for Z = 2 is 1.266 Mg/m³. The number of unique reflections collected is 2401, and the final R = 0.0561 [I > 2σ(I)]. 15 crystallizes in monoclinic P21/m space group, a = 11.020(3), b = 6.600(2), c = 8.409(3) Å, β = 99.72(3)°. The calculated density for Z = 2 is 1.527 Mg/m³. The number of unique reflections collected is 1153, and the final R = 0.0502 [I > 2σ(I)]. 16 crystallizes in monoclinic P21/c space group, a = 7.499(3), b = 21.846(5), c = 7.895(3) Å, β = 115.42(3)°. The calculated density for Z = 4 is 1.576 Mg/m³. The number of unique reflections collected is 2036, and the final R = 0.0757 [I > 2σ(I)].     

Formation of polymeric chain assemblies of transition metal complexes with a multidentate Schiff-base

The new multidentate Schiff-base (E)-6,6′-((1E,1′E)-(ethane-1,2-diylbis(azan-1-yl-1-ylidene))bis(methan-1-yl-ylidene))bis(4-methyl-2-((E)(pyridine-2-ylmethylimino)methyl)phenol) H₂L and its polymeric binuclear metal complexes with Cr(III), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) are reported. The reaction of 2,6-diformyl-4-methyl-phenol with ethylenediamine in mole ratios of 2:1 gave the precursor 3,3′-(1E,1′E)-(ethane-1,2-diylbis(azan-1-yl-1ylidene))bis(methan-1-yl-1-ylidene)bis(2-hydroxy-5-methylbenzaldehyde) W. Condensation of the precursor with 2-(amino-methyl)pyridine in mole ratios of 1:2 gave the new N₆O₂ multidentate Schiff-base ligand H₂L. Upon complex formation, the ligand behaves as a dibasic octadentate species with the involvement of the nitrogen atoms of the pyridine groups in coordination for all complexes. The mode of bonding and overall geometry of the complexes were determined through physico-chemical and spectroscopic methods. These studies revealed octahedral geometries for Cr(III), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Cd(II) and Hg(II) complexes of general formulae [Cr₂^III(L)Cl₂]Cl₂, [Ni₂^II(L)(H₂O)₂]Cl₂ and [M₂(L)Cl₂] and five co-ordinate Zn(II) complex of general formula [Zn₂^II(L)]Cl₂.     

Preparation and Crystal Structures of Ruthenium and Osmium Oxide Tetrahalides

RuOF₄ as the highest valence oxide fluoride exist as a molecular compound (a = 606.0(1), b = 836.1(1), c = 626.3(1) pm, β = 91.637(3), Z = 4; P2₁/n) as well as fluorine bridged polymer (a = 547.7(2), b = 928.5(3), c = 1252.4(3) pm, Z = 8, P2₁2₁2₁). A reproducible method for pure, deep blue OsOF₄ is given. Pure OsOF₄‐I is isostructural to the fluorine bridged polymeric RuOF₄ (a = 554.6(1), b = 955.4(2), c = 1278.4(2), Z = 8, P2₁2₁2₁). OsOF₄‐II is also a fluorine bridged polymer (a = 537.8(2), b = 1274.8(4), c = 555.2(2), β = 117.716(6)°, Z = 4, P2₁/c). OsOCl₄ again is a molecular species (a = 938.9(2), b = 561.3(1), c = 1192.0(2), β = 109.944(4)°, Z = 4, P2₁/c).     

Synthesis and Structural Characterization of Two New 2D Isophthalate‐bridged Copper(II) Polymers Based on Tricopper Units

Two new neutral polymeric layer compounds, [Cu₃(bpy)₂(Hip)₂(ip)₂] ( 1 ) and [Cu₃(phen)₂(Hip)₂(ip)₂] ( 2 ) (bpy = 2, 2′‐bipyridine, phen = 1, 10‐phenanthroline, ip = isophthalate), have been synthesized under hydrothermal conditions and characterized by X‐ray crystallography. Complex 1 crystallizes triclinic, P1¯ (No. 2), a = 10.352(5), b = 10.859(6), c = 11.602(6)Å, α = 83.25(1), β = 84.71(1), γ = 66.19(1)°, V = 1183.5(11)ų, Z = 1; 2 triclinic, P1¯ (No. 2), a = 10.375(1), b = 10.668(1), c = 11.758(1)Å, α = 83.179(2), β = 86.228(2), γ = 71.187(2)°, V = 1222.7(2)ų, Z = 1. The complexes consist of trinuclcear copper units that are bridged via two ip ligands forming zigzag polymeric chains. These chains are further extended into layers via aromatic π‐π interactions as well as hydrogen bonds between the free carboxyl groups and carboxylates.     

Post‐Grignard Reagents: Influence of the Coligands L on the Molecular Structures of Phenylcalcium Iodides [(L)nCa(R)I] and Calcium Diiodides [(L)nCaI2]

Iodide is a very soft and large anion and as such its extreme ability to be polarized leads to a flat energy surface with respect to the variation of the Ca–I distances in [(L)_nCaI₂] and [(L)_nCa(R)I]. The influence of the donor strength and the bulkiness of the neutral coligands L on the Ca–I distances is studied. The base adducts of calcium diiodide can be isolated after the addition of L to CaI₂ or from the Schlenk equilibrium after the direct synthesis of calcium powder with aryl iodides. As L the ethers diethyl ether (Et₂O), tetrahydrofuran (thf), tetrahydropyran (thp), 1,2‐dimethoxyethane (dme), 18‐crown‐6 (18C6), bis(methoxyethyl)ether (diglyme), and amines tetramethylethylenediamine (tmeda), and hexamethyltriethylenetetramine (hmteta) are studied yielding the adducts [(thp)₄Ca(Ph)I] ( 1a ), [(thf)₄Ca(Ph)I] ( 1b ), [(dme)₂(thf)Ca(Ph)I] ( 1c ), [(18C6)Ca(Ph)I] ( 1d ), and [(tmeda)₂Ca(Ph)I] ( 1e ), as well as [(thp)₄CaI₂] ( 2a ), [(thf)₄CaI₂] ( 2b ), [(Et₂O)₄CaI₂] ( 2c ), [(diglyme)(thf)₂CaI₂] ( 2d ), [(diglyme)(dme)CaI₂] ( 2e ), [(dme)₂(thf)CaI₂] ( 2f ), [(18C6)CaI₂] ( 2g ), [(tmeda)₂CaI₂] ( 2h ), and [(hmteta)CaI₂] ( 2i ). For comparison reasons, [(thf)₄Ca(Ph)Br] ( 3a ), [(thp)₄CaBr₂] ( 4a ), [(thf)₄CaBr₂] ( 4b ), and [(dme)₂(AcOH)CaBr₂] ( 4c ) with AcOH being acetic acid are included as well. The comparison shows that the coordination number of calcium itself only plays an insignificant role whereas bulkiness and donor strength of L represent the key influences.     

Syntheses,Characterization and x-ray Structures of Gold(III) Complexes Obtained by Addition of Bases to Gold(III)(2-Pyridinecarboxaldehyde)

Reaction of potassium tetrachloroaurate(III), KAuCl₄, with 2-pyridinecarboxaldehyde (2CHO-py) have been examined in protic HX (X=OH, OMe, OEt, OCH₂CH₂CH₂, OCH₂CH₂CH₂CH₃, OCH₂CF₃) solvents. Compounds in which the pyridine ligand is N or N-O coordinated in a newly carbonyl hydrated or in semi- and acetal-forms, derived by addition of one or two hydroxylic molecules, have been isolated; these include dichloro[pyridine-2(α-hydroxymethanolato)]gold(III) (1), dichloro[pyridine-2(α-ethoxymethanolato)] gold(III) (2), dichloro[pyridine-2[α-(2,2,2-trifluoroethoxymethanolato)]gold(III) (3), trichloro(2-pyridinecarboxaldehyde dimethyl acetal)gold(III) (4), trichloro(2-pyridinecarboxaldehyde diethyl acetal)gold(III) (5), trichloro(2-pyridinecarboxaldehyde di-1-propyl acetal)gold(III) (6) and trichloro(2-pyridinecarboxaldehyde di-1-butyl acetal)gold(III) (7). The crystal and molecular structures of (2), (5) and (7) have been determined by X-ray methods. Compound (2) crystallizes in space group Pna2₁ with Z=4, a=7.8914(4), b=17.3660(4) and c=8.3873(5)Å; (5) crystallizes in space group P&1macr; with Z=2, a=7.7779(3), b=8.2878(2) and c=13.3202(6)Å, α=96.975(2), β=95.096(2), γ=115.027(2)°; (7) crystallizes in space group P2₁/a with Z=4, a=14.5438(12), b=8.9865(7) and c=15.0362(11)Å.     

Carotenoids of Rhizobia. IV. Isolation and structure elucidation of the carotenoids of a mutant of Rhizobium lupini

The structures of the main carotenoid pigments from the mutant 1-207 of Rhizobium lupini were elucidated by spectroscopic techniques (UV./VIS., CD., 270 MHz ¹H-NMR., and MS.). Ten carotenoids were identified, namely β,β-carotene ( 1 ), β,β-caroten-4-one (echinenone, 2 ), β,β-carotene-4,4′-dione (canthaxanthin, 3 ), (3S)-3-hydroxy-β,β-caroten-4-one ((3S)-3-hydroxyechinenone, 4 ), (2R, 3R)-β,β-carotene-2,3-diol ( 5 ), (3S)-3-hydroxy-β,β-carotene-4,4′-dione ((3S)-adonirubin, 6 ), (2R, 3S)-2,3-dihydroxy-β,β-caroten-4-one ( 7 ), (2R, 3S)-2,3-dihydroxy-β,β-caroten-4,4′-dione ( 8 ), (2R, 3S, 2′R, 3′R)-2,3,2′,3′-tetrahydroxy-β,β-caroten-4-one ( 9 ) and the corresponding (2R, 3S, 2′R, 3′S)-4,4′-dione ( 10 ). Structures 5, 7, 8 and 10 have not been reported before. From the observed carotenoid pattern it is concluded that in this mutant the oxidation to 4-oxo compounds is favoured compared to the hydroxylation at C(3) and C(2).     

Synthesis and Crystal Structures of Two Zinc(II) Complexes with the Tripodal Ligand Tris(2-Benzimidazolymethyl)Amine

This article reports the synthesis and crystal structures of two new mononuclear Zinc(II) complexes, [Zn₂(NTB)₂(N₃)₂](NO₃)₂·2CH₃OH (1) and [Zn₂(NTB)₂(SCN)₂](NO₃)₂·2CH₃OH·H₂O (2). Complex 1 crystallizes in the triclinic system, space group P&1macr;, a=13.743(4), b=14.374(4), c=14.443(5) Å; α=77.053(5), β=81.824(5), γ=88.959(6)°; Z=2; R1=0.0418, wR2=0.0889. Complex 2 also crystallizes in the triclinic system, space group P&1macr;, a=12.203(10), b=14.430(12), c=18.541(15)Å; α=72.712(15), β=85.039(15), γ=73.610(14); Z=2; R1=0.0771, wR2=0.1288. In both cases the central zinc(II) metal ions are coordinated to the four nitrogen atoms of NTB and a nitrogen atom of N^- ₃(1) or SCN^-(2) to form distorted trigonal bipyramidal coordination spheres.     

Electron-transfer polymers. XXIX. Copolymerizability of vinylhydroquinone derivatives

Ten vinylhydroquinone and one vinyl resorcinol derivatives are compared, particularly with respect to NMR spectra and copolymerizability with styrene. They are vinylhydroquinone dimethyl ether (I), vinyl-O,O′-bis(1-ethoxyethyl)hydroquinone (II), vinylhydroquinone di(2-pentyl)ether (III), 4-vinyl resorcinol bismethoxymethyl ether (IV), 2-vinyl-5-methylhydroquinone dimethyl ether (V), 2-vinyl-5-methyl-O,O′-bis(1-ethoxyethyl)hydroquinone (VI), 2-vinyl-6-methylhydroquinone dimethyl ether (VII), 2-vinyl-5-tert-butylhydroquinone dimethyl ether (VIII), 2-vinyl-5-chlorohydroquinone dimethyl ether (IX), 2-vinyl-3,6-dimethylhydroquinone dimethyl ether (X), and 2-vinyl-3,5,6-trimethylhydroquinone dimethyl ether (XI). All the vinyl protons have almost the same coupling constants. Though subtle distinctions are found among all the spectra, they can in general be put into two groups on the basis of the chemical shifts. Let the hydrogen on carbon-1 of the vinyl group be A, the hydrogen cis to A be B the hydrogen trans to A be C, then in the first group, (I) through (IX), the chemical shifts (τ) are (A) 3.02 ± 0.08, (C) 4.41 ± 0.05, and (B) 4.87 ± 0.07, and in the second group, (X) and (XI), they are (A) 3.30 ± 0.03, (C) 4.49 ± 0.01, and (B) 4.59 ± 0.03. It is supposed that in (X) and (XI) the vinyl group is out of the plane of the ring, because of the two ortho substituents, and this conformation is reflected in the NMR data. Ultraviolet spectra are consonant with this interpretation, since the λ_max of (X) and (XI) correspond closely with those of nonvinyl reference compounds, while those of (II), (V), and (VIII) are shifted to longer wavelengths. When these compounds are copolymerized separately with styrene, the behaviors are classifiable into the following three groups, where r₁ and r₂ are monomer reactivity ratios with styrene as the first monomer: (i) r₁ < 1 and r₂ < 1 for compounds (II) and (III) and the reference compound O,O′-dibenzoylvinylhydroquinone, (ii) r₁ < 1 and r₂ > 1 for compounds (I), (V), (VII), (VIII), (IX), and (iii) r₁ > 1 and r₂ = 0 for compounds (X) and (XI). These behaviors are correlated with the effect of electronegativity of groups on the stability of the radical at the growing end of the chain and with the simultaneous effects of steric hindrance.     

The reactivities of Mo cluster — A selective substitution reaction of the bridging (dtp) ligand and the crystal structure of {Mo3S4(μ-O2CR)(dtp)3(Py)}

The reaction of trinuclear molybdenum cluster {Mo₃S₄(μ-dtp) (dtp)₃ (H₂O)} 1 [dtp= S₂P(OEt)₂] with RCO₂Na (R?H, CH₃) in the presence of Py gave the black compounds {Mo₃S₄ {μ-O₂ CR) (dtp)₃ (Py)} (2, R?H, 3, R?CH₃). Both compounds are characterized by X-ray crystallography. It is shown that crystals 2 and 3 belong to space group P&1bar; with Z=2 and a=10.519(2), b= 12.121(2), c=15.757(2)Å, α=93.27(1), β=94.63(1), γ = 105.22(1)°, V= 1925 ų for crystal 2, whereas a=9.556 (2), b=14.067(7), c=15.914 (9) Å, α=101.41 (4), β=101.44(4), γ-74.26(3)°, V=1994ų for crystal 3. The final R factors are 0.041 and 0.048 for crystal 2 and 3 respectively. The structure analysis indicates that (O₂CR)^? ligand selectively substitutes the bridging (dtp) ligand. This type of Mo, cluster molecule where structure contains two species of bidentate ligand is for the first time to be obtained by us.     

Synthesis,Structures, and Properties of Layered Quaternary Chalcogenides of the General Formula ALnEQ4 (A = K,Rb; Ln = Ce,Pr, Eu; E = Si,Ge; Q = S,Se)

Four related quaternary compounds containing rare‐earth metals have been synthesized employing the molten flux method and metathesis. The reactions of Eu and Rb₂S₅ with Si and Ge in evacuated fused silica ampoules at 725 °C for 150 h yielded RbEuSiS₄ ( I ) and RbEuGeS₄ ( II ), respectively. On the other hand, a reaction between CeCl₃ and K₄Ge₄Se₁₀ at 650 °C for 148 h has yielded KCeGeSe₄ ( III ) and KPrSiSe₄( IV ) was obtained by the reaction of elemental Pr, Si and Se in KCl flux at 850 °C for 168 h. Crystal data for these compounds are as follows: I , orthorhombic, space group P2₁2₁2₁ (#19), a = 6.392(1), b = 6.634(2), c = 17.001(3) Å, α = β = γ = 90°, Z = 4; II , monoclinic, space group P2₁/m (#11), a = 6.498(2), b = 6.689(3), c = 8.964(3) Å, β = 108.647(6)°, Z = 2; III , monoclinic, space group P2₁ (#4), a = 6.852(2), b = 7.025(2), c = 9.017(3) Å, β = 108.116(2)°, Z = 2; IV , monoclinic, space group P2₁ (#4), a = 6.736(2), b = 6.943(2), c = 8.990(1) Å, β = 108.262(2)°, Z = 2. The crystal structures of I ‐ IV contain two‐dimensional corrugated anionic layers of the general formula, [LnEQ₄]^? (Ln = Ce, Pr, Eu; E = Si, Ge and Q = S, Se) alternately piled upon layers of alkali cations. In addition to structural elucidation, Raman and UV‐visible spectroscopy, and magnetic measurements for compound III (KCeGeSe₄) are also discussed.     

Synthesis of novel copper compounds containing isonicotinic acid and/or 2,6-pyridinedicarboxylic acid: third-order nonlinear optical properties

Two novel compounds, [Cu₂(pydc)₂(inta)₂(H₂O)₂]·3H₂O 1 (pydc?=?2,6-pyridinedicarboxylic acid, inta?= isonicotinic acid) and [Cu(pydc)₂][Cu(H₂O)₅]·2H₂O 2, have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses and IR spectra. Compound 1 exhibits reverse saturable absorption and self-defocusing. X-ray structural analysis reveals that Compounds 1 and 2 both possess π–π stacking and hydrogen-bonding interactions forming three-dimensional (3D) networks. Crystal data for 1: a?=?7.2345(14), b?=?12.219(2), c?=?17.069(3)?Å, α?=?90.44(3), β?=?91.82(3), γ?=?93.56(3)°, Z?=?1, R1?=?0.0435, wR2?=?0.1216. Crystal data for 2: a?=?8.3708(17), b?=?27.386(6), c?=?9.6170(19)?Å, α?=?90.00, β?=?98.14(3), γ?=?90.00°, Z?=?3, R1?=?0.0742, wR2?=?0.2160.     

COPPER(I) COMPLEXES WITH N-(P-NITROPHENYL)-N′-ALKOXYCARBONYLTHIOUREA: SYNTHESES AND CRYSTAL STRUCTURES OF [Cu(H2net)2CI] · CH2CI2 AND [Cu(H2nmt)2CI]2·(CHCI3)2

Abstract

Two copper(I) complexes, [Cu(H₂net)₂Cl] · CH₂Cl₂ (1) and [Cu(H₂nmt)₂Cl]₂ · (CHCl₃)₂ (2), were synthesized by the reaction of CuCl₂ · 2H₂O with N-(p-nitrophenyl)-N′-(ethoxycarbonyl)-thiourea (H₂net) and N-(p-nitrophenyl)-N′-(methoxycarbonyl)-thiourea(H₂nmt), respectively. Both complexes crystallize in the monoclinic space group C2/c. For complex 1, a = 29.52(2), b=13.920(6), c = 14.873(3)Å; β= 101.75(2)°, V = 5984(4) ų, Z = 8 and R = 0.053; for complex 2, a = 30.68(1), b = 13.369(4), c = 14.226(7) Å, β = 99.52(4)°. V = 5754(4) ų, Z = 4 and R = 0.063. In complex 1, two H₂net molecules are bonded to Cu(I) atom through two S atoms forming a mononuclear complex with trigonal geometry for the Cu(I) ion [Cl(1)-Cu-S(1)=118.54(7), Cl(1)-Cu-S(2)=119.70(7), S(1)-Cu-S(2)=112.17(8)°, Cu-S(1) = 2.251(2), Cu-S(2) = 2.255(2), Cu-Cl(1) = 2.263(2) Å]. Complex 2 is a dimer formed by long Cu-S interactions [Cu-S* = 2.607(3) Å] from adjacent twc H₂nmt molecules; the Cu(I) ion has distorted tetrahedral coordination [Cl(1)-Cu-S(1) = 119.8(1), Cl(1)-Cu-S(2)=120.0(1), S(1)-Cu-S(2)=108.85(9)°] with unequal Cu-S [2.268(2), 2.247(2)Å] and Cu-Cl(1) [2.255(2)Å] bonds.     

Syntheses,Crystal Structures and Properties of the Tetrametaphosphimates MII2(PO2NH)4 · 8 H2O with MII = Mg,Mn, Co and Zn

Mg₂(PO₂NH)₄ · 8 H₂O ( 1 ), Mn₂(PO₂NH)₄ · 8 H₂O ( 2 ), Co₂(PO₂NH)₄ · 8 H₂O ( 3 ) and Zn₂(PO₂NH)₄ · 8 H₂O ( 4 ) were obtained as microcrystalline powders by combining aqueous solutions of K₄(PO₂NH)₄ · 4 H₂O and MX₂ · y H₂O (M = Mg, Mn, Co, Zn; X = Cl, NO₃). Single crystals were obtained by crystallization in gelatine gels in U‐tubes or test‐tubes. 2 and 4 were characterized by thermogravimetry and 4 was additionally characterized by temperature dependend in situ powder diffractometry. The structures of 1 , 2 , 3 and 4 were found to be isotypic and were solved by single‐crystal X‐ray methods: P 2₁/c, Z = 2 ( 1 : a = 645.4(2), b = 1050.1(2), c = 1283.3(3) pm, β = 104.66(3)°; 2 : a = 648.7(2), b = 1063.1(2), c = 1310.8(3) pm, β = 103.93(3)°; 3 : a = 643.3(2), b = 1049.0(2), c = 1286.7(3) pm, β = 104.28(3)°; 4 : a = 644.18(5), b = 1049.22(7), c = 1282.43(8) pm, β = 104.122(6)°). The structure is composed of MO₆ octahedra and (PO₂NH)₄^4— anions. The P₄N₄ rings of the (PO₂NH)₄^4— anions exhibit a slightly distorted chair conformation, which is supported by IR data and has been described by torsion angles, Displacement Asymmetry Parameters and Puckering Parameters. Via M²⁺ ions and hydrogen bonds, the tetrametaphosphimate anions are connected forming layers perpendicular to [100]. These layers are connected by hydrogen bonds.     

Oxidative Addition of Diethylchalcogenanes to Lappert's Germylene and Stannylene

Oxidative addition of diethyldichalcogenanes Et₂E₂ (E = S, Se, Te) to bis[bis(trimethylsilyl]amido]germylene and ‐stannylene M[N(SiMe₃)₂]₂ (M = Ge, Sn) proceed with formation of the corresponding bis(ethylchalcogenato)germanes (Me₃Si)₂N)₂Ge(EEt)₂ [E = S ( 1 ), Se ( 2 ), Te ( 3 )] and ‐stannanes (Me₃Si)₂N)₂Sn(EEt)₂ [E = S ( 4 ), Se ( 5 ), Te ( 6 )]. The solid state structures of 1 – 6 were determined by single‐crystal X‐ray diffraction.     

Synthesis,Characterization, and in vitro Cytotoxicity of Gold(I) Complexes of 2‐(Diphenylphosphanyl)ethylamine and Dithiocarbamates

Gold(I) complexes of 2‐(diphenylphosphanyl)ethylamine or (2‐aminoethyl)diphenylphosphine (AEP), and dithiocaarbamates (R₂NCS₂) were prepared by the reaction of these ligands with (CH₃)₂S‐AuCl in dichloromethane. The synthesized complexes [Au(AEP)Cl] ( 1 ), [Au(AEP)₂]Cl ( 2 ), and [Au₂(R₂NCS₂)₂]_n (R₂ = dimethyl ( 3 ), diethyl ( 4 ), and dibenzyl ( 5 )) were characterized by elemental analysis, IR, ¹H, ¹³C and ³¹P NMR spectroscopy. The complexes were evaluated for anticancer activity against three cancer cells, A549 (human lung carcinoma), HCT15 (human colon cancer), and MCF7 (human breast cancer) cell lines. Three of the five tested complexes showed significant in vitro cytotoxicity and for A549, the inhibition effect of three compounds is greater than cisplatin.     

Homo-atomic Nine-vertex Polyhedra of Group XIV Elements. Crystal structures and paramagnetic properties of [K-(2,2,2-crypt)]6E9E9 · 1.5 ethylenediamine · 0.5 toluene,E = Sn and Pb

The extractions of alloys of the nominal composition “KE_2.25” with ethylenediamine (en), (2,2,2)crypt, and toluene (tol) lead in good yields to paramagnetic compounds of the composition [K-(2,2,2-crypt)]₆E₉E₉ · 1.5 en · 0.5 tol (E = Sn ( 2 b ), Pb ( 2 c )). X-ray single crystal structure analyses show that two different E₉ clusters per asymmetric unit are present with configurations of distorted tricapped trigonal prismatic polyhedra. 2 b : space group P2₁/c (No. 14), Z = 4, a = 28.042(8), b = 23.527(5), c = 27.703(8) Å, β = 93.46(2)°; 2 c : space group P2₁/c (No. 14), Z = 4, a = 28.356(8), b = 23.757(5), c = 27.885(8) Å, β = 94.01(2)°.