Synthesis and Crystal Structure of Mixed-valence Hexanuclear Manganase Oxide Complex,Hexakis(μ<Subscript>2</Subscript>-pivalato)-tetrakis(μ<Subscript>3</Subscript>-pivalato)-mono(pyridine)-tris(pivalic acid)-bis(μ<Subscript>4</Subscript>-oxo)dimanganese(III) tetramanganase(II)

Abstract  The complex, [Mn₆O₂(OOCCMe₃)₁₀(HOOCCMe₃)₃(py)], has a hexanuclear structure with a Mn₆O₂ core. This complex crystallizes in the monoclinic space group P2₁/n with a = 17.757(5) ?, b = 27.413(5) ?, c = 22.348(5) ?, β = 90.233(5)°, V = 9,040(4) ?³ and Z = 4. It contains a [Mn₆O₂]¹⁰⁺ core that can be described as two edge-sharing Mn₄ tetrahedra at the centre of each of which tetrahedron lies a μ₄-O²⁻ ion. All Mn atoms are six-coordinate and possess distorted octahedral geometry. Mn₄ exhibits butterfly arrangement with both μ₄-O atoms on the same side of the molecule. The complex is mixed-valence , and the Mn^III centers are assigned as the two central metal ions bridged by two O²⁻ ions. Index abstract  The complex, [Mn₆O₂(OOCCMe₃)₁₀(HOOCCMe₃)₃(py)], has a hexanuclear structure with a Mn₆O₂ core. This complex crystallizes in the monoclinic space group P2₁/n with a = 17.757(5) ?, b = 27.413(5) ?, c = 22.348(5) ?, β = 90.233(5)°, V = 9040(4) ?³ and Z = 4. It contains a [Mn₆O₂]¹⁰⁺ core that can be described as two edge-sharing Mn₄ tetrahedra at the centre of each of which tetrahedron lies a μ₄-O²⁻ ion. All Mn atoms are six-coordinate and possess distorted octahedral geometry. Mn₄ exhibits butterfly arrangement with both μ₄-O atoms on the same side of the molecule. The complex is mixed-valence , and the Mn^III centers are assigned as the two central metal ions bridged by two O²⁻ ions.      

Synthesis and Crystal Structures of the Coordination Polymers Pb(PYTAC)<Subscript>2</Subscript> and Pb<Subscript>2</Subscript>(PYTAC)<Subscript>3</Subscript>(NO<Subscript>3</Subscript>) (PYTAC = 2-(pyridin-4-yl)thiazole-5-carboxylate)

Abstract  

Two lead coordination compounds, Pb(PYTAC)₂ (1), and Pb(PYTAC)₂(NO₃) (2), were grown as single crystals via hydrothermal synthesis (PYTAC = 2-(4-pyridyl) thiazole-4-carboxylate). Both compounds have been identified via single crystal X-ray diffraction. Coordination polymer 1 crystallizes in a triclinic space group P-1 (a = 5.5097(4) ?, b = 7.2822(5) ?, c = 11.3134(8) ?, α = 103.5580(10)°, β = 99.4330(10)°, γ = 97.1050(10)°), and forms 2-D layers parallel to the crystallographic (ac) plane. Coordination polymer 2 crystallizes in a triclinic space group P-1 (a = 9.8102(5) ?, b = 10.5972(6) ?, c = 14.8076(8) ?, α = 91.9350(10)°, β = 100.8050(10)°, γ = 103.1350(10)°), and forms an infinite 1-D chains along the a axis.     

Structural phase transition in crystals of the molecular conductor α′-(BDH-TTP)<Subscript>6</Subscript>[Hg(SCN)<Subscript>3</Subscript>][Hg(SCN)<Subscript>4</Subscript>]

Single crystals of the organic conductor α′-(BDH-TTP)₆[Hg(SCN)₃][Hg(SCN)₄] are studied by low-temperature X-ray diffraction at 100–300 K. It is shown that, in the temperature range 250–200 K, the compound undergoes a phase transition, which is accompanied by the appearance of superstructure reflections and a rapid increase in their intensity due to the partial anion and cation ordering. The superstructure is observed down to a temperature of 100 K, at which the set of diffraction data is collected. The temperature dependence of the electrical resistance exhibits a minimum in the range of the structural transition temperature. Under a pressure of up to 10 kbar, the general behavior of the dependence remains unchanged and only the minimum is shifted toward the low-temperature range. The phase transition is completely reversible.     

Synthesis,Crystal Structure and Bioactivities of <Emphasis Type="Italic">N</Emphasis>-(2,6-Difluorobenzoyl)-<Emphasis Type="Italic">N</Emphasis>′-[5-(Pyrid-4-yl)-1,3,4-Thiadiazol-2-yl]Urea

Abstract N-(2,6-difluorobenzoyl)-N′-[5-(pyrid-4-yl)-1,3,4-thiadiazol-2-yl]urea, 3, has been synthesized by reaction of 2-amino-5-(pyrid-4-yl)-1,3,4-thiadiazole with 2,6-difluorobenzoyl isocyanate, and its structure was characterized with X-ray crystallographic, NMR, MS and IR techniques. It crystallizes in the triclinic space group P − 1, with a = 7.0821(9) ?, b = 9.4896(13) ?, c = 11.6594(15) ?, α = 82.311(2)°, β = 82.328(2)°, and γ = 87.641(2)°. In the title compound, the urea scaffold in each molecule is essentially planar due to the presence of intramolecular N–H···O hydrogen bond. The molecules are linked by intermolecular complementary N–H···O hydrogen bonds into centrosymmetric R ₂²(8) dimers. Intermolecular π–π stacking interactions are also present. The preliminary bioassay shows that the title compound exhibits excellent fungicidal activities against Rhizoctonia solani, Botrytis cinerea and Dothiorella gregaria. Index Abstract N-(2,6-difluorobenzoyl)-N′-[5-(pyrid-4-yl)-1,3,4-thiadiazol-2-yl]urea has been synthesized and characterized with X-ray crystallographic, NMR, MS and IR techniques. The preliminary bioassay shows that the title compound exhibits excellent fungicidal activities.      

Preparation,characterisation, and crystal structure analysis of (2<Emphasis Type="Italic">E</Emphasis>,2′<Emphasis Type="Italic">E</Emphasis>)-3,3′-(1,4-phenylene)bis(1-(2-aminophenyl)prop-2-en-1-one

A novel bis-chalcone, (2E,2′E)-3,3′-(1,4-phenylene)bis(1-(2-aminophenyl)prop-2-en-1-one) is synthesized through a base catalyzed Claisen-Schmidt condensation reaction of terephthalaldehyde with 2-aminoacetophenone. Its structure (sp. gr. P\(\bar 1\), Z = 2) is determined from single crystal X-ray diffraction data. There are two independent centrosymmetric molecules with no significant differences in bond lengths and angles between them. The NMR, IR, HRMS, and UV spectral data of the prepared bis-chalcone are presented.     

Syntheses,Characterization and Crystal Structures of <Emphasis Type="Italic">N′</Emphasis>-(5-Chloro-2-Hydroxybenzylidene)-4-Dimethylaminobenzohydrazide and <Emphasis Type="Italic">N′</Emphasis>-(2,4-Dichlorobenzylidene)-4-Dimethylaminobenzohydrazide

Abstract  

The hydrazone compounds, N′-(5-chloro-2-hydroxybenzylidene)-4-dimethylaminobenzohydrazide (1) and N′-(2,4-dichlorobenzylidene)-4-dimethylaminobenzohydrazide (2), have been synthesized by the condensation reaction of equimolar quantities of 4-dimethylaminobenzohydrazide with 5-chlorosalicylaldehyde and 2,4-dichlorobenzaldehyde, respectively, in methanol. The compounds were characterized by elemental analysis, IR, ¹HNMR spectra, and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 35.014(3) ?, b = 10.407(2) ?, c = 18.505(2) ?, β = 112.046(2)°, V = 6250.0(15) Ǻ³, Z = 16, R ₁ = 0.0624, and wR ₂ = 0.1187. Compound 2 crystallizes in the triclinic space group P-1 with unit cell dimensions a = 12.625(2) ?, b = 12.688(3) ?, c = 13.005(2) ?, α = 101.271(2)°, β = 112.945(1)°, γ = 104.966(2)°, V = 1747.6(6) Ǻ³, Z = 2, R ₁ = 0.0523, and wR ₂ = 0.1138. In the asymmetric unit of each compound, there exists two hydrazone molecules linking together by an N–H⋯O hydrogen bond. Furthermore, compound (2) contains one methanol molecule and one water molecule of crystallization.     

Synthesis and Crystal Structure of (PzCH<Subscript>2</Subscript>CHOHCH<Subscript>2</Subscript>PzH)·(Ph<Subscript>2</Subscript>SnCl<Subscript>3</Subscript>) (Pz = 3,5-dimethylpyrazol-1-yl)

Abstract  

Reaction of Ph₂SnCl₂ with 1,3-bis(3,5-dimethylpyrazol-1-yl)-2-propanol (L) in a 1:1 ratio yields L(SnPh₂Cl₂)₂ adduct, which partly hydrolyzes to the title complex (C₂₅H₃₁Cl₃N₄OSn, Mr = 628.58) during crystal growing in the air. The title complex is of monoclinic, space group P2₁/n with a = 9.0338(9), b = 17.890(1), c = 17.340(1) ?, β = 95.533(1)^o, V = 2798.9(5) ?³, Z = 4, Dc = 1.492 Mg/m³, λ(MoKα) = 0.71073 ?, μ = 1.224 mm⁻¹, F(000) = 1272, R = 0.023, wR = 0.054 for 4212 observed reflections with I ≥ 2σ(I). The crystal structure indicates that there is no direct interaction between the pyrazolyl ligand and the tin atom, but this complex forms a supramolecular structure through weak intermolecular C–H⋯Cl and O–H⋯Cl hydrogen bonds.     

The coordination of 2-(hydroxymethyl)pyridine to oxorhenium(V). Synthesis and crystal structure of [ReOCl(C<Subscript>5</Subscript>H<Subscript>4</Subscript>N–CH<Subscript>2</Subscript>O)<Subscript>2</Subscript>]

The title compound was prepared from the reaction of (n-Bu₄N)[ReOCl₄] with a twofold molar excess of 2-(hydroxymethyl)pyridine in benzene. It has a distorted octahedral coordination geometry, and it crystallizes in the monoclinic space group P2₁/n, with cell dimensions a = 14.4545(4), b = 7.0168(2), c = 14.5269(4) Å, = 116.995(1), V = 1312.85(7) ų, and Z = 4.     

Synthesis and Structure of a One-Dimensional Copper(II)–Potassium(I) Complex of (<Emphasis Type="Italic">S</Emphasis>)-2-Hydroxy-3-Phenylpropanoic acid

Abstract  

Evaporation of the mixture solution of Cu(ClO₄)₂·6H₂O, KOH and (S)-2-hydroxy-3-phenylpropanoic acid affords a Cu(II)–K(I) coordination compound 1. Single-crystal X-ray diffraction analysis reveals that 1 is a one-dimensional comb-like coordination polymer in the P2₁2₁2₁ space group with crystal cell parameters a = 10.989(2) ?, b = 15.939(3) ?, c = 22.511(5) ?, V = 3943(1) ?³ and Z = 4.     

Crystal and molecular structures of <Emphasis Type="Italic">trans</Emphasis>-2-(4′-dimethylaminobenzylideneacetyl)-5,5-dimethylcyclohexane-1,3-dione

The crystal and molecular structures of a cyclic β-triketone, namely, trans-2-(4′-dimethylaminobenzylideneacetyl)-5,5-dimethylcyclohexane-1,3-dione (I), are determined using X-ray diffraction analysis. It is established that the compound in the crystalline state exists in a diketo-enol form stabilized by intramolecular hydrogen bonds. The specific features of the structure and the physicochemical and fluorescence properties of the compound are discussed.     

Synthesis and Structure of a CdI<Subscript>2</Subscript> Coordination Polymer with 1,1′-(1,4-Butanediyl)bis-1<Emphasis Type="Italic">H</Emphasis>-benzotriazole(bbbt)

Abstract  

In this article, solution reaction of cadmium iodide with organic multifunctional ligand 1,1′-(1,4-butanediyl)bis-1H-benzotriazole(bbbt) generated a 1D polymer [CdI₂ (bbbt) (CH₃OH)]_n 1, and the crystal structure has been determined (C₁₇ H₂₀ Cd I₂ N₆ O), Mr = 690.59 a = 10.032(2), b = 13.503(3), c = 16.706(3) ?, space group C2/c, Z = 4, and V = 2223.1(8) ?³. In 1 the tetrahedral coordination of Cd(II) and the conformation of bbbt ligand make it a wave-shaped structure.     

Separation of (<Emphasis Type="Italic">S</Emphasis>)-(−)-3-Methyl-2-pyrrolidinone as an Inclusion Complex with (<Emphasis Type="Italic">R</Emphasis>)-(+)-4,4′,6,6′-Tetrachloro-2,2′-bis(hydroxydiphenylmethyl)-1,1′-biphenyl Host and its X-ray Structural Study

Abstract By inclusion complexation with the chiral host compound (R)-(+)-4,4′,6,6′-tetrachloro-2,2′-bis(hydroxydiphenylmethyl)-1,1′-biphenyl, racemic 3-methyl-2-pyrrolidinone was resolved and its (S)-(−)-enantiomer was isolated as a 1:1 inclusion complex, which crystallises in the orthorhombic crystal system in the space group P2₁2₁2₁ (a = 14.1163(2) ?, b = 14.7140(3) ?, c = 17.2025(3) ?). By the inclusion complexation, the keto–enol equilibrium of the guest was frozen and the keto-form was isolated in a pure form. By X-ray structural study of the complex, the guest molecule included was elucidated to be the keto-form and its absolute configuration was determined to be (S). Index Abstract By inclusion complexation with (R)-(+)-4,4′,6,6′-tetrachloro-2,2′-bis (hydroxydiphenylmethyl)-biphenyl, racemic 3-methyl-2-pyrrolidinone was resolved and its (S)-(−)-enantiomer isolated and in addition the keto–enol equilibrium of the guest was frozen and the keto-form isolated. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis and Crystal Structure of a Compound with Two Conformational Isomers: <Emphasis Type="Italic">N</Emphasis>-(2-methylbenzoyl)-<Emphasis Type="Italic">N</Emphasis>′-(4-nitrophenyl)thiourea

Abstract  The single crystal of the title compound (C₁₅H₁₃N₃O₃S) with two conformational isomers was obtained from the solution of the title compound dissolved in the N,N-dimethylformamide (DMF) by slow evaporation at room temperature. The crystal is triclinic, space group P-1 with a = 10.418(2), b = 10.758(2), c = 14.494(3) ?, α = 71.07(3), β = 81.56(3), γ = 85.61(3)o, V = 1519.2(5) ?³, Z = 2, C₃₀H₂₆N₆O₆S₂, D _c  = 1.379 g/cm³, μ(MoKα) = 0.229 mm⁻¹, S = 0.994, F(000) = 656, R = 0.0688 and wR = 0.1695. In the unit cell, there are two independent molecules having only slightly different bond lengths and angles, but the corresponding dihedral angles of the two molecules are different. Intermolecular N–H···S and N–H···O hydrogen bonds forming R ² ₂(8) and R ² ₂(12) rings, respectively, link the molecules into ribbons. Index Abstract  In the unit cell, there are two independent molecules having only slightly different bond lengths and angles between them, but different corresponding dihedral angles.      

Crystal Structure of Antitubercular Complex: <Emphasis Type="Italic">cis</Emphasis>-(chloro)-[<Emphasis Type="Italic">N,N</Emphasis>′-<Emphasis Type="Italic">bis</Emphasis>-(diethyl-2,2′-bipyridine-3,3′-dicarboxylate)]ruthenium(II) Monohydrate

Abstract  Diethyl-2,2′-bipyridine-3,3′-dicarboxylate (3 or L) reacts with RuCl₃ · 3H₂O to give cis-(Cl)-[Ru(L)₂Cl₂] · H₂O (4) and structure of the complex was determined by spectral (IR, ¹H-NMR), and mass spectroscopic data, elemental analyses and X-ray crystallography. The structure is solved in triclinic, space group p-1 with a = 10.658 (2), b = 12.446 (3), c = 14.186 (5) ?, α = 104.856 (3), β = 108.704 (3), γ = 94.973 (2)°, V = 1693.2 (8) ?³, Z = 2 with final R = 0.012. The geometry of the complex is shown to be a distorted octahedral with four nitrogens of two 2,2′-bipyridyl ligands in two different planes with Ru–N distance as 2.021 (2)−2.071 (3) ?. The cis-position is occupied by two chloride atoms with Ru–Cl distance as 2.4156 (12) and 2.4167 (13) ?. The trans-axial Cl2–Ru1–N and Cl1–Ru1–N4 angles are respectively, 172.42 (7) and 174.12 (7)°. A weak hydrogen bonding is observed between the two chlorides and hydrogens of neighbouring molecule [C–H···Cl distance as 2.72, 2.77 (4) ?]. A second type of weak hydrogen bonding is also observed between the oxygens of carboxylate groups and hydrogens of a neighbouring molecule [C–H···O distance as 2.53, 2.56 and 2.34 (4) ?]. Graphical Abstract  The structure of anti-tubercular precursor complexes, cis-(chloro)-[N,N′-bis-(diethyl-2,2′-bipyridine-3,3′-dicarboxylate)]ruthenium(II) monohydrate is solved by single crystal X-ray diffraction analysis which reveals geometry of the complex to be a distorted octahedral with four nitrogens of two 2,2′-bipyridyl ligands in two different planes. The cis-position is occupied by two chloride atoms.      

Study of Hydrogen Bonding in <Emphasis Type="Italic">N</Emphasis>′-(4,6-disubstituted-pyrimidin-2-yl)-<Emphasis Type="Italic">N</Emphasis>-[2-(2,4-dichlorophenoxypropionyl)]thiourea

Abstract  

Two of N′-N′-(4,6-disubstituted-pyrimidin-2-yl)-N-[2-(2,4-dichlorophenoxypropionyl)]thiourea (4a-4b) had been synthesized and their crystal structures had been determined by X-ray diffraction method. 4a crystallizes in the triclinic space group P-1, with a = 8.053(12) ?, α = 102.84(2)°, b = 10.541(16) ?, β = 106.99(2)°, c = 12.461(19) ?, γ = 94.615(19)°, and D _c  = 1.470 mg/m³ for Z = 2. 4b crystallizes in the triclinic space group P-1, with a = 7.939(5) ?, α = 105.302(10)°, b = 10.183(7) ?, β = 105.729(9)°, c = 12.764(9) ?, γ = 90.698(11)°, and D _c  = 1.517 mg/m³ for Z = 2.     

Crystal Structure of a Novel One-dimensional Chain-like Compound,Catena(μ<Subscript>2</Subscript>-4,4′-Bipyridyl)-bis(Formato-<Emphasis Type="Italic">O</Emphasis>,<Emphasis Type="Italic">O′</Emphasis>)-Copper(II)

Abstract  

The title compound, [Cu(C₁₀H₈N₂)(HCO₂)₂]_n, in which the asymmetric unit contains one crystallographically independent copper(II) ions, one formate and half of 4, 4′-bipy molecules, has a linear polymeric structure, with the bridging ligand 4, 4′-bipyridine connecting the Cu^II ions. Each ion lies on an inversion center and has a distorted octahedral environment, being coordinated by two bipy ligands and four oxygen atoms from two formate groups. The O1 in the formate group is disordered over two sites with occupancy of 0.55 and 0.45. In the crystal structure, the linear polymeric chains are linked by intermolecular C–H···O hydrogen bonds, resulting in a two-dimensional supramolecular network.     

Synthesis and crystal structure of <Emphasis Type="Italic">N</Emphasis>-(6methoxylbenzothiazol-2-yl)-1-(4-fluorophenyl)<Emphasis Type="Italic">O</Emphasis>,<Emphasis Type="Italic">O</Emphasis>-dipropyl-<Emphasis Type="Italic">α</Emphasis>-aminophosphonate

Molecular and crystal structure of N-(6-methoxybenzothiazol-2-yl)-1-(4-fluorophenyl)-O,O-dipropyl-α-aminophosphonate, C₂₁H₂₆FN₂O₄PS, have been determined by single-crystal X-ray diffraction study. The title compound is tetragonal, with a = 21.35(3) Å, c = 20.16(5) Å, Z = 16, D _x = 1.308 Mg/m³, μ(MoKα) = 0.247 mm^?1, and space group is I4₁/a. The structure was solved by direct method and refined to a final R = 0.0687 for 2370 reflections with I > 2σ(I). The compound shows a fully delocalized benzothiazole system with a sp² hybridization of the N(2). There is a strong intermolecular hydrogen bond between P=O and NH. The crystal structure is stabilized by a strong intermolecular N–H?sO hydrogen bond.     

Synthesis and crystal structure of <Emphasis Type="Italic">catena</Emphasis>-bis(nicotinamide)aqua(μ-phthalato)copper(II) hemihydrate

The copper(II) phthalate complex with nicotinamide [CuL ₂(μ-Pht)(H₂O)] · 0.5H₂O(I) (where L is nicotinamide and Pht ^2? is an anion of phthalic acid) is synthesized and investigated using IR spectroscopy and X-ray diffraction. The crystals of compound I are monoclinic, a = 13.368(2) Å, b = 7.891(3) Å, c = 20.480(2) Å, β = 108.69(2)°, Z = 4, and space group P2₁/c. The structural units of crystal I are linear chains formed by bridging phthalate anions and crystallization water molecules. The copper atom is coordinated by two pyridine nitrogen atoms of two nicotinamide ligands (Cu-N, 2.001 and 2.045 Å), two oxygen atoms of different phthalate anions (Cu-O, 1.964 and 2.235 Å), and the oxygen atom of the H₂ O molecule (Cu-O, 2.014 Å). The coordination polyhedron of the copper atom is completed to an elongated (4 + 1 + 1) tetragonal bipyramid by the second (chelating) oxygen atom of the carboxyl group (Cu-O, 2.587 Å), which is one of the anions of phthalic acid. The linear polymer molecules are joined into complex macromolecular dimers with the closest internal contacts of the specific type. The macromolecular dimers are the main supramolecular ensembles of the crystal structure.     

Synthesis and Crystal Structure of a Cyanido-Bridged Bimetallic Copper(II)–Silver(I) Complex of Imidazole and [Ag(CN)<Subscript>2</Subscript>]<Superscript>−</Superscript>: [Cu(Imidazole)<Subscript>4</Subscript>{Ag(CN)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

Abstract  

A cyanido-bridged Cu(II)–Ag(I) bimetallic complex, [Cu(Imidazole)₄{Ag(CN)₂}₂] has been prepared and structurally characterized. The compound crystallizes in the orthorhombic space group Pmna. The crystal structure of the complex consists of trinuclear molecules made up of one [Cu(Imidazole)₄]⁺² and two [Ag(CN)₂]⁻ units. The trinuclear molecules are interlinked to each other through N–H–N and C–H–N hydrogen bonds. The Cu(II) ions are located on mirrors and assume distorted octahedral geometry with the basal plane consisting of four imidazole N-atoms.     

Synthesis and Crystal Structure of <Emphasis Type="Italic">Tris</Emphasis>-(<Emphasis Type="Italic">N</Emphasis>–<Emphasis Type="Italic">N</Emphasis> dimethyl benzylammonium)-hexachlorobismuthate(III)

Abstract  The salt tris-(N–N dimethyl benzylammonium)-hexachlorobismuthate(III) crystallizes in the triclinic system P1 with unit cell parameters: a = 9.0300(12), b = 9.9220(3), c = 19.575(2) ?, α = 79.955(5), β = 89.952(2), γ = 88.108(6)°, V = 1726.0(3) ?³, Z = 2. The examination of the structure shows an alternate stacking of inorganic layers of hexachlorobismuthate(III) anions and organic layers of [C₆H₅CH₂NH(CH₃)₂]⁺ cations parallel to the a-axis. The cohesion forces of the packing of N–N dimethyl benzylammonium units in the layer and between two adjacent layers are provided by hydrogen bonds (N–H⋯Cl) and van der Waals contacts. Index Abstract  The examination of the structure shows a layer arrangement parallel to the a-axis: planes of octahedral anions [BiCl₆]³⁻ alternate with planes of [C₆H₅CH₂NH(CH₃)₂]⁺ cations (Fig. 3). The cohesion forces of the packing of the N–N dimethyl benzylammonium units in the layer and between two adjacent layers are provided by hydrogen bonds (N–H⋯Cl) and van der Waals contacts. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.