Di­chloro­[(6R,7S,8S,14S)‐(–)‐sparteine‐κ2N,N′]­nickel(II)

In the title compound, [NiCl₂(C₁₅H₂₆N₂)], the chiral alkaloid (6R,7S,8S,14S)‐(−)‐l ‐sparteine acts as a bidentate ligand, with two chloride ligands occupying the remaining coordination sites, producing a slightly distorted tetrahedron. The N—Ni—N plane in the title complex is twisted by 81.31 (11)° from the Cl—Ni—Cl plane. Other distortions of the tetrahedron are discussed.     

Density functionals in the presence of magnetic field

In this article, density functionals for Coulomb systems subjected to electric and magnetic fields are developed. The density functionals depend on the particle density ρ and paramagnetic current density j^p. This approach is motivated by an adapted version of the Vignale and Rasolt formulation of current density functional theory, which establishes a one‐to‐one correspondence between the nondegenerate ground‐state and the particle and paramagnetic current density. Definition of N‐representable density pairs (ρ,j^p) is given and it is proven that the set of v‐representable densities constitutes a proper subset of the set of N‐representable densities. For a Levy–Lieb‐type functional Q(ρ,j^p), it is demonstrated that (i) it is a proper extension of the universal Hohenberg–Kohn functional to N‐representable densities, (ii) there exists a wavefunction ψ₀ such that , where H₀ is the Hamiltonian without external potential terms, and (iii) it is not convex. Furthermore, a convex and universal functional F(ρ,j^p) is studied and proven to be equal the convex envelope of Q(ρ,j^p). For both Q and F, we give upper and lower bounds. © 2014 Wiley Periodicals, Inc.     

2‐Ethyl‐1‐[5‐(4‐methylphenyl)pyrazol‐3‐yl]‐3‐(thiophene‐2‐carbonyl)isothiourea: molecular ribbons containing three types of hydrogen‐bonded ring

The title compound, C₁₈H₁₈N₄OS₂, was prepared by reaction of S,S‐diethyl 2‐thenoylimidodithiocarbonate with 5‐amino‐3‐(4‐methylphenyl)‐1H‐pyrazole using microwave irradiation under solvent‐free conditions. In the molecule, the thiophene unit is disordered over two sets of atomic sites, with occupancies of 0.814 (4) and 0.186 (4), and the bonded distances provide evidence for polarization in the acylthiourea fragment and for aromatic type delocalization in the pyrazole ring. An intramolecular N—H...O hydrogen bond is present, forming an S(6) motif, and molecules are linked by N—H...O and N—H...N hydrogen bonds to form a ribbon in which centrosymmetric R₂²(4) rings, built from N—H...O hydrogen bonds and flanked by inversion‐related pairs of S(6) rings, alternate with centrosymmetric R₂²(6) rings built from N—H...N hydrogen bonds.     

Ein Beitrag zu Rhenium(II)‐, Osmium(II)‐ und Technetium(II)‐Thionitrosylkomplexen vom Typ [M(NS)Cl4py]—: Darstellung,Strukturen und EPR‐Spektren

A Contribution to Rhenium(II)‐, Osmium(II)‐, and Technetium(II)‐Thionitrosyl‐Complexes: Preparation, Structures, and EPR‐Spectra The reaction of [Re^VINCl₄]^— and [Os^VINCl₄]^— with S₂Cl₂ leads to the formation of the thionitrosyl complexes [M^II(NS)Cl₄]^— (M = Re, Os) which could not be isolated as pure compounds. Addition of pyridine to the reaction mixture results in the formation of the stable compounds trans‐(Ph₄P)[Os^II(NS)Cl₄py], trans‐(Hpy)[Os^II(NS)Cl₄py], trans‐(Ph₄P)[Re^II(NS)Cl₄py], and cis‐(Ph₄P)[Re^II(NS)Cl₄py]. The crystal structure analyses show for trans‐(Ph₄P)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 12.430(3)Å, b = 18.320(4)Å, c = 15.000(3)Å, β = 114.20(3)°, Z = 4), trans‐(Hpy)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 7.689(1)Å, b = 10.202(2)Å, c = 20.485(5)Å, β = 92.878(4)°, Z = 4), trans‐(Ph₄P)[Re^II(NS)Cl₄py] (triclinic, P1¯, a = 9.331(5)Å, b = 12.068(5)Å, c = 15.411(5)Å, α = 105.25(1)°, β = 90.23(1)°, γ = 91.62(1)°, Z = 2), and cis‐(Ph₄P)[Re^II(NS)Cl₄py] (monoclinic, P2₁/c, a = 10.361(1)Å, b = 16.091(2)Å, c = 17.835(2)Å, β = 90.524(2)°, Z = 4) M‐N‐S angles in the range 168‐175°. This indicates a nearly linear coordination of the NS ligand. The metal atom is octahedrally coordinated in all cases. The rhenium(II) thionitrosyl complexes (5d⁵ “low‐spin” configuration, S = 1/2) are studied by EPR in the temperature range 295 > T > 130 K. In addition to the detection of the complexes formed during the reaction of [Re^VINCl₄]^— with S₂Cl₂ EPR investigations on diamagnetically diluted powders and single crystals of the system (Ph₄P)[Re^II/Os^II(NS)Cl₄py] are reported. The ^{185, 187}Re hyperfine parameters are used to get information about the spin‐density distribution of the unpaired electron in the complexes under study. [Tc^VINCl₄]^— reacts with S₂Cl₂ under formation of [Tc^II(NS)Cl₄]^— which is not stable and decomposes under S₈ elimination and rebuilding of [Tc^VINCl₄]^— as found by EPR monitoring of the reaction.     

Hydroboration of Alkenes and Alkynes with Aza‐nido‐decaboranes

The 6‐aza‐nido‐decaboranes RNB₉H₁₁ ( 1a—d ; R = H, Ph, 4‐C₆H₄Me, 4‐C₆H₄Cl) act as 1, 2‐hydroboration agents via their 9‐BH vertex, giving products RNB₉H₁₀R′. The boranes 1a, b and 3‐hexyne yield the 9‐(1‐ethyl‐1‐butenyl)‐6‐aza‐nido‐decaboranes 2a, b (R′ = CEt = CHEt). 2, 3‐Dimethyl‐2‐butene is hydroborated by 1a—d under formation of the 9‐(1, 1, 2‐trimethylpropyl)‐6‐aza‐nido‐decaboranes 3a—d (R′ = —CMe₂ —CHMe₂). With the boranes 1a—c and (trimethylsilyl)ethene, a 85:15 mixture of the products (RNB₉H₁₀)CH₂CH₂(SiMe₃)( 4a—c ) and their chiral isomers (RNB₉H₁₀)CH(SiMe₃)CH₃ ( 5a—c ) is obtained. The action of BH₃(SMe₂) on the mixtures 4b/5b or 4c/5c results in a closure of the nido‐NB₉ skeleton of 4b or 4c , respectively, with a closo‐NB₁₁ skeleton of the products RNB₁₁H₁₀R′ ( 6b or 6c;R′ = CH₂CH₂(SiMe₃)); R′ is found in position 7 of 6b, c . All products of the type 2—6 are characterised by NMR.     

The conformations of two copper(I) complexes of 1H‐benzimidazole‐2(3H)‐thione and thiosaccharinate

(Acetonitrile‐1κN)[μ‐1H‐benzimidazole‐2(3H)‐thione‐1:2κ²S:S][1H‐benzimidazole‐2(3H)‐thione‐2κS]bis(μ‐1,1‐dioxo‐1λ⁶,2‐benzothiazole‐3‐thiolato)‐1:2κ²S³:N;1:2κ²S³:S³‐dicopper(I)(Cu—Cu), [Cu₂(C₇H₄NO₂S₂)₂(C₇H₆N₂S)₂(CH₃CN)] or [Cu₂(tsac)₂(Sbim)₂(CH₃CN)] [tsac is thiosaccharinate and Sbim is 1H‐benzimidazole‐2(3H)‐thione], (I), is a new copper(I) compound that consists of a triply bridged dinuclear Cu—Cu unit. In the complex molecule, two tsac anions and one neutral Sbim ligand bind the metals. One anion bridges via the endocyclic N and exocyclic S atoms (μ‐S:N). The other anion and one of the mercaptobenzimidazole molecules bridge the metals through their exocyclic S atoms (μ‐S:S). The second Sbim ligand coordinates in a monodentate fashion (κS) to one Cu atom, while an acetonitrile molecule coordinates to the other Cu atom. The Cu^I—Cu^I distance [2.6286 (6) Å] can be considered a strong `cuprophilic' interaction. In the case of [μ‐1H‐benzimidazole‐2(3H)‐thione‐1:2κ²S:S]bis[1H‐benzimidazole‐2(3H)‐thione]‐1κS;2κS‐bis(μ‐1,1‐dioxo‐1λ⁶,2‐benzothiazole‐3‐thiolato)‐1:2κ²S³:N;1:2κ²S³:S³‐dicopper(I)(Cu—Cu), [Cu₂(C₇H₄NO₂S₂)₂(C₇H₆N₂S)₃] or [Cu₂(tsac)₂(Sbim)₃], (II), the acetonitrile molecule is substituted by an additional Sbim ligand, which binds one Cu atom via the exocylic S atom. In this case, the Cu^I—Cu^I distance is 2.6068 (11) Å.     

Dichloro­[(6R,7S,8S,14S)‐(–)‐sparteine‐κ2N,N′]mercury(II)

In the title compound, [HgCl₂(C₁₅H₂₆N₂)], the chiral alkaloid (6R,7S,8S,14S)‐(−)‐l ‐sparteine acts as a bident­ate ligand, with two Cl⁻ ligands occupying the remaining coordination sites, producing a distorted tetra­hedron. The N—Hg—N plane is twisted by 81.1 (2)° from the Cl—Hg—Cl plane. The mid‐point of the N⋯N line does not lie exactly on the Cl—Hg—Cl plane but is tilted towards one of the N atoms by 0.346 Å. Similarly, the mid‐point of the Cl⋯Cl line is tilted toward one of the Cl atoms by 0.163 Å. The packing structure shows that the complex is stabilized by two inter­atomic Cl⋯H contacts involving both Cl atoms and the methyl­ene or methine H atoms of the (−)‐sparteine ligand.     

Partially oxidized ruthenium phosphine thiol­ates: [Ru(pySO2)0.33(pyS)1.67(dppe)] and [Ru(pySO2)0.355(pyS)1.645(dppp)]

The crystal structures of [1,3‐bis­(diphenyl­phosphino)ethane‐κ²P,P′](pyridine‐2‐sulfinato‐κ²N,S)(pyridine‐2‐thiol­ato‐κ²N,S)ruthenium(II), [Ru(C₅H₄NO₂S)_0.33(C₅H₄NS)_1.67(C₂₆H₂₄P₂)] or [Ru(pySO₂)_1−x(pyS)_1+x(dppe)] (x = 0.67), (I), and [1,3‐bis­(diphenyl­phosphino)propane‐κ²P,P′](pyridine‐2‐sulfinato‐κ²N,S)(pyridine‐2‐thiol­ato‐κ²N,S)ruthenium(II), [Ru(C₅H₄NO₂S)_0.355(C₅H₄NS)_1.645(C₂₇H₂₆P₂)] or [Ru(pySO₂)_1−x(pyS)_1+x(dppp)] (x = 0.645), (II), are composed of neutral distorted octa­hedral Ru^II complexes with chelating pyridine‐2‐thiol­ate, pyridine‐2‐sulfinate and biphosphine ligands. The S atoms are trans to each other, while pairs of P and N atoms are in cis positions. Partial double‐bond character is observed for C—S. The crystal packing consists of monolayers stabilized by C—H⋯O and C—H⋯S inter­actions, and is affected by the alkyl‐chain lengths.     

Die Kristallstruktur von Aza-closo-decaboran NB9H10

The Crystal Structure of Aza-closo-decaborane, NB₉H₁₀ Aza-closo-decaborane(10), NB₉H₁₀, crystallizes in the space group P2₁/n. The NB₉ skeleton forms a distorted bicapped tetragonal antiprism with the N atom in a capping position. The structural data are compared to those of aza-closo-dodecaborane(12), NB₁₁H₁₂.     

Intermolecular interactions in the chiral and racemic forms of 3‐­hydroxy‐2‐(1‐oxoisoindolin‐2‐yl)­butanoic acid derived from threonine

The title compounds, C₁₂H₁₃NO₄, are derived from l ‐threonine and dl ‐threonine, respectively. Hydro­gen bonding in the chiral derivative, (2S/3R)‐3‐hydroxy‐2‐(1‐oxoisoindolin‐2‐yl)­butanoic acid, consists of O—H_acid?O_alkyl—H?O=C_indole chains [O?O 2.659 (3) and 2.718 (3) Å], Csp³—H?O and three C—H?π_arene interactions. In the (2R,3S/2S,3R) racemate, conventional carboxylic acid hydrogen bonding as cyclical (O—H?O=C)₂ [graph set R₂²(8)] is present, with O_alkyl—H?O=C_indole, Csp³—H?O and C—H?π_arene interactions. The COOH group geometry differs between the two forms, with C—O, C=O, C—C—O and C—C=O bond lengths and angles of 1.322 (3) and 1.193 (3) Å, and 109.7 (2) and 125.4 (3)°, respectively, in the chiral structure, and 1.2961 (17) and 1.2210 (18) Å, and 113.29 (12) and 122.63 (13)°, respectively, in the racemate structure. The O—C=O angles of 124.9 (3) and 124.05 (14)° are similar. The differences arise from the contrasting COOH hydrogen‐bonding environments in the two structures.     

A one‐dimensional platinum mixed‐valence complex with bridging thiocyanate S atoms: [[PtII(en)2](μ‐SCN)[PtIV(en)2](μ‐SCN)](ClO4)4 (en is ethane‐1,2‐diamine)

A new one‐dimensional platinum mixed‐valence complex with nonhalogen bridging ligands, namely catena‐poly[[[bis(ethane‐1,2‐diamine‐κ²N,N′)platinum(II)]‐μ‐thiocyanato‐κ²S:S‐[bis(ethane‐1,2‐diamine‐κ²N,N′)platinum(IV)]‐μ‐thiocyanato‐κ²S:S] tetrakis(perchlorate)], {[Pt₂(SCN)₂(C₂H₈N₂)₄](ClO₄)₄}_n, has been isolated. The Pt^II and Pt^IV atoms are located on centres of inversion and are stacked alternately, linked by the S atoms of the thiocyanate ligands, forming an infinite one‐dimensional chain. The Pt^IV—S and Pt^II...S distances are 2.3933 (10) and 3.4705 (10) Å, respectively, and the Pt^IV—S...Pt^II angle is 171.97 (4)°. The introduction of nonhalogen atoms as bridging ligands in this complex extends the chemical modifications possible for controlling the amplitude of the charge‐density wave (CDW) state in one‐dimensional mixed‐valence complexes. The structure of a discrete Pt^IV thiocyanate compound, bis(ethane‐1,2‐diamine‐κ²N,N′)bis(thiocyanato‐κS)platinum(IV) bis(perchlorate) 1.5‐hydrate, [Pt(SCN)₂(C₄H₈N₂)₂](ClO₄)₂·1.5H₂O, has monoclinic (C2) symmetry. Two S‐bound thiocyanate ligands are located in trans positions, with an S—Pt—S angle of 177.56 (3)°.     

(S,S)‐Lactoyllactic acid and (S,S,S)‐lactoyllactoyllactic acid

The dimeric condensation product of lactic acid, namely (S,S)‐2‐[(2‐hydroxypropanoyl)oxy]propanoic acid, C₆H₁₀O₅, (I), crystallizes with two independent molecules in the asymmetric unit, which both have an essentially planar backbone. The trimeric condensation product, namely (S,S,S)‐3‐hydroxybut‐3‐en‐2‐yl 2‐[(2‐hydroxypropanoyl)oxy]propanoate, C₉H₁₄O₇, (II), has one molecule in the asymmetric unit and consists of two essentially planar parts, with the central C—O bond in a gauche conformation. Both molecules of the dimer are involved in intermolecular hydrogen bonds, forming chains with a C(8) graph set. These chains are connected by D(2) hydrogen bonds to form a two‐dimensional layer. The trimer forms hydrogen‐bonded C(10) and C₂²(6) chains, which together result in a two‐dimensional motif. The Hooft method [Hooft, Straver & Spek (2008). J. Appl. Cryst. 41 , 96–103] was successfully applied to the determination of the absolute structure of (I).     

Synthesis of Silver Complexes in DMSO–HX and DMSO–HX–Ketone Systems

Comparative analysis of the oxidizing and complexing properties of the DMSO–HX (X = Cl, Br, I) and DMSO–HX–ketone (X = Br, I; the ketone is acetone, acetylacetone, or acetophenone) systems toward silver was performed. The reaction products are AgX (X = Cl, Br, I), [Me₃S⁺]Ag _n X^– _m (n= 1, 2; m= 2, 3; X = Br, I) and [Me₂S⁺CH₂COR]AgX^– ₂(R = Me, Ph; X = Br, I). The composition of the obtained complexes depends on both the DMSO : HX ratio and the nature of HX, as well as on the methods used to isolate solid products from the solution. It was noted that the formation of the [Me₂S⁺CH₂COMe]AgBr^– ₂complex in the Ag⁰–DMSO–HBr–acetylacetone system occurs with cleavage of the acetylacetone C–C bond and follows a specific reaction course. The optimum conditions for production of the silver compounds in the title systems are determined.     

Stereochemisch kontrollierte Cope-analoge Zerfallsprozesse von Sulfinylverbindungen im Massenspektrometer

The extent of elimination of HX (X = SOCH₃, SCH₃) from the [M? STol]⁺ as well as [MH? HSTol]⁺ cations (Tol = CH₃C₆H₄) from 2-sulfinyl substituted cyclopentane thiocarbonic acid S-aryl esters under electron impact and chemical ionization is strongly influenced by the stereochemical relationship of the vicinal substituents.     

Di­bromo­[(–)‐sparteine‐κ2N,N′]­zinc(II)

In the title compound, di­bromo­[(6R,7S,8S,14S)‐1,3,4,7,7a,8,9,10,11,13,14,14a‐dodeca­hydro‐7,14‐methano‐2H,6H‐dipyrido­[1,2‐a:1′,2′‐e][1,5]­diazo­cine‐κ²N,N′]­zinc(II), [ZnBr₂(C₁₅H₂₆N₂)], the chiral nitro­gen‐chelating alkaloid (?)‐l ‐sparteine acts as a bidentate ligand, with two bromide ligands occupying the remaining coordination sites, producing a slightly distorted tetrahedral structure. The dihedral angle between the N—Zn—N and Br—Zn—Br planes is 82.4 (1)°. The distortion of the tetrahedral coordination is demonstrated by the fact that the midpoint of the N?N line does not lie in the Br—Zn—Br plane, but is tilted towards one of the N atoms by 0.164 Å. Similarly, the midpoint of the Br?Br line is tilted towards one of the Br atoms by 0.117 Å.     

Die Akzeptoreigenschaften der Metall—Metall-Einheit in den zweikernigen Komplexen cis-M2(O2CCH3)2Cl4L2, M = Tc,Re; L = neutrale Base

The Acceptor Properties of the Metal—Metal Unit in the Dinuclear Complexes cis-M₂(O₂CCH₃)₂Cl₄L₂, M = Tc, Re; L = neutrale Base The weakly bound H₂O molecules in axial positions of the dimetalates cis-M₂(O₂CCH₃)₂Cl₄L₂, M = Tc, Re, are easily substituted on reaction with stronger donor bases. With increasing donor number D_N or donor strength D_S of the axial ligands, the metal—metal stretching frequency v₁ is lowered. The linearity between v₁ and the hard D_N scale shows, that the M₂ unit acts as a hard Lewis acid in the axial direction, according to the observation that no coordination of soft donor bases takes place. The trans influence of the metal—metal multiple bond is estimated from the ratio of the shifts observed for v₁ and the equatorial metal-ligand stretching modes after formation of adducts. The ratio is about 5: 1 in the ditechnetates and thus considerable higher than in the dirhenates with about 2: 1.     

Synthesis and crystal structure of [V_2(μ-S_2)_2(S_2CNEt_2)_4]·2CH_3Cl

[V_2(μ-S_2)_2(S_2CNEt_2)_4].2CH_3Cl was synthesized by the reaction of NaS_2CNEt_2,Li_2S andVOCl_3 at room temperature.Crystal data:M=1061.3,space group Pbca,with the orthorhombicparameters:a=20.123(3),b=20.485(4),c=10.911(3),V=4497.7,Z=4,D_c=1.57g/cm~3,Mo Kσradiation(λ=0.71069()?),μ=13.2 cm~(-1),F(000)=2168.Final R=0.041 and R_w=0.047 for 2288 ob-served reflections with I>3σ(1).The coordination sphere of each V atom in title compound is a dis-torted tetragonal prism composed of two bidentate dithiocarbamate and two S_(2~((2-)) ligands.The V—Vdistance is 2.890 while the V—S distances fall in the range of 2.422—2.505.     

1,2‐Di­cyano‐1,2‐bis­(imidazolidine‐2‐thione)­digold(I) and 2,2‐di­cyano‐1,1‐bis­(di­methyl­thio­urea)­digold(I)

Gold(I) cyanide forms complexes with imidazolidine‐2‐thione (etu) and di­methyl­thio­urea (dmtu) with the formula [Au₂(CN)₂L₂], i.e. the title complexes di­cyano‐1κC,2κC‐bis(imidazolidine‐2‐thione)‐1κS,2κS‐digold(I)(Au—Au), [Au₂(CN)₂(C₃H₆N₂S)₂], and di­cyano‐1κ²C‐bis(N,N′‐di­methyl­thio­urea)‐2κ²S‐digold(I)(Au—Au), [Au₂(CN)₂(C₃H₈N₂S)₂]. In the etu complex, two approximately linear (etu)AuCN groups are held together by a weak homopolar Au—Au bond [3.117 (1) Å], with a torsion angle of 61 (3)° between the two groups. In the dmtu complex, an approximately linear Au(dmtu)₂ group is bound to an approximately linear Au(CN)₂ group by a weak heteropolar Au—Au bond [3.091 (1) Å], with a torsion angle of 83 (5)° between the two groups.     

K3Cr2(PS4)3: A New Chromium Thiophosphate with a One‐Dimensional [Cr2(PS4)]3— Anion Chain

A new chromium thiophosphate, K₃Cr₂(PS₄)₃ has been prepared and characterized by single‐crystal diffraction, temperature dependent magnetic susceptibility measurements and optical spectroscopy. K₃Cr₂(PS₄)₃ crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 9.731(2) Å, b = 11.986(2) Å, c = 17.727(4) Å, β = 96.52(2)°, V = 2054.2(2) ų, Z = 4, and R = 0.044. The anionic part of the structure consists of dimeric Cr₂(μ₃‐S₃PS)₂ units which are linked by bidentate PS₄ groups to form infinite one‐dimensional [S₂P_S2Cr₂(μ₃S₃P_S)₂]^3— chains separated by K⁺ cations. The Cr^III centers of the Cr₂(μ₃‐S₃PS)₂ units are antiferromagnetically coupled. The magnetic susceptibility data may be fitted using a D‐Heisenberg model for S = 3/2 with g = 2.02 and J/k = 10K. K₃Cr₂(PS₄)₃ is semiconducting with an optical band gap of 1.35 eV.