Crystal structure of [Mn(bpy)3](ClO4)2·0.5(bpy) (bpy=2,2′-bipyridine)

A new monomeric manganese(II) complex with 2,2′-bipyridine (bpy), [Mn(bpy)₃-] (ClO₄)₂·0.5(bpy), has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space group $P\bar 1$ witha=9.535(2),b=13.194(3),c=14.854(3) Å, α=96.50(3), β=107.26(3), γ=91.19(3)°,V=1770.2(7) ų, andZ=2. The structure comprises discrete [Mn(bpy)₃]²⁺ cations in which the metal atom is coordinated in a highly distorted octahedral environment by three chelate bpy ligands [Mn?N=2.229(3)–2.289(2) Å]. The solvate bpy molecule and a pair of coordinated bpy ligands each from the adjacent cations are arranged in an off-set fashion, showing significant intermolecular stacking interaction with close interplanar contacts ofca. 3.47 Å.     

Carbonyl Displacement Reaction in Diiron Propane-Dithiolate Complex by Triphenylstibine: Crystal Structure of [Fe2(CO)6-n(SbPh3)n(μ-S2C3H6)] (n = 1 and 2)

Treatment of [Fe₂(CO)₆(μ-S₂C₃H₆)] (1) with triphenylstibine in a 1:1 molar ratio at room temperature in presence of Me₃NO resulted compound [Fe₂(CO)₅(SbPh₃)(μ-S₂C₃H₆)] (2) in 88% yield as red crystals. When the reaction was carried out under a 1:5 molar ratio in presence of Me₃NO, it resulted a monosubstituted compound [Fe₂(CO)₅(SbPh₃)(μ-S₂C₃H₆)] (2) in 63% yield along with a disubstituted compound [Fe₂(CO)₄(SbPh₃)₂(μ-S₂C₃H₆)] (3) in low yield (8%) as red crystals. Reaction of 2 with triphenylstibine in a 1:5 molar ratio under same condition resulted 3 in moderate yield (46%). Compounds 2 and 3 were characterized by elemental analyses, IR, ¹H NMR and ¹³C NMR spectroscopic data. Crystal structures of the compounds were unambiguously determined by single crystal X-Ray diffraction studies. Compound 2 crystalized as monoclinic crystal system with the space group P2₁/c, a?=?9.464(4) Å, b?=?16.902(7) Å, c?=?17.081(7) Å, β?=?101.216(13)° and Z?=?4. Compound 3 was triclinic, space group P-1, a?=?9.552(3) Å, b?=?13.985(5) Å, c?=?16.487(6) Å, α?=?78.372(16)°, β?=?89.976(14)°, γ?=?71.638(11)° and Z?=?2.

Graphic Abstract

Two new diiron propane-1,3-dithiolate complexes, [Fe₂(CO)₅(SbPh₃)(μ-S₂C₃H₆)] (2) and [Fe₂(CO)₄(SbPh₃)₂(μ-S₂C₃H₆)] (3), were synthesized by the displacement of carbonyl groups from [Fe₂(CO)₆(μ-S2C₃H₆)] (1) with triphenylstibine, and the resulting complexes were structurally characterized.

Solid state molecular structure of compound 2 (left) and compound 3 (right)

     

X-ray diffraction analysis of (Ph2PO)2

The title compound (Ph2PO)2 is analyzed by single crystal X-ray diffraction analysis. The crystals are monoclinic, space group P2(1)/n with a = 9.5112(19) Å, b = 11.161(2) Å, c = 9.5487(19) Å, α = 90°, β = 91.65(3)°, γ = 90°, V = 1013.2(3) ų, Z = 2, F(₀₀₀) = 420, Dc = 1.319 g cm^–3, μ = 0.232 mm^?1, the final R = 0.0818, and wR = 0.2259. A total of 7954 reflections were collected, of which 1758 were independent (R_int = 0.0542). In the crystal packing diagram, intermolecular C—H···O hydrogen bonds stabilize the solid state of the title compound.     

Synthesis,crystal structure,magnetic characterization and spectroscopic properties of a new dinuclear iron(III) complex asymmetrically bridged by a phenoxo and methoxo groups

Dinuclear iron(III) derivative of Fe₂L¹(OCH₃)Cl₂ (L¹=1,3‐bis[N‐(5‐bromo‐2‐hydroxybenzylidene)‐2‐aminoethyl]‐2‐(5‐bromo‐2‐hydroxyphenyl)imidazolidine) has been synthesized, its crystal structure determined and magnetically characterized. The title compound crystallizes in orthorhombic space group Pbcn with cell parameters a = 12.9770(10), 18.7930(10), 25.2950(10) Å, V = 6168.9(6)ų, Z = 8, D_cal = 1.951 Mg/m³. The two iron(III) ions are asymmetrically bridged by a phenoxo and methoxo groups in the compound. The iron(III) centers are separated by 3.166(3) Å. Magnetic susceptibilities of the complex were measured over the range 5 – 298 K and the observed data were successfully simulated by the equation based on the spin‐Hamiltonian operator. Magnetic susceptibility measurements indicate very weak antiferromagnetic coupling between the iron(III) ions with J = – 11.5 cm^‐1. The comparison of the magnetic and structural parameters of the investigated compound is given and the nature of the magnetic super‐exchange interaction of the title compound is compared with similar dinuclear iron(III) complexes. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Iron-Chloranilate Intercalation Compounds: Synthesis,Crystal Structures,and Thermal Properties

Abstract

Hydrogen bond supported new iron-chloranilate assemblies, {(Hpy)[Fe(CA)₂(H₂O)₂](H₂O)}_n (py = pyridine, H₂CA = chloranilic acid, C₆H₂O₄Cl₂) (1), and [(phz)₂[Fe(CA)₂(H₂O)₂](H₂O)₂]_n (phz = phenazine, C₁₂H₈N₂) (2) have been synthesized and characterized. Compound 2 crystallizes in the monoclinic, space group C2/m (#12), with a= 29.135(6) Å, b= 16.886(6) Å, c = 15.017(5) Å, ß = 165.907(1)°, V= 1798(2) ų, Z = 2. In both the compounds two chloranilate dianions and two water molecules are coordinated to the iron ion making anionic monomers [Fe(CA)₂(H₂O)₂]^?, which are the building blocks of the compounds. The coordination environment around the iron ion in the building block is a distorted octahedron, where two water molecules sit on the trans position to each other. [Fe(CA)₂(H₂O)₂]^? anions form common layer structures, supported by hydrogen bonds. Hpy⁺ are intercalated in between the layers of 1 by electrostatic and hydrogen bonding interactions and phz are intercalated in that of 2 by electrostatic interactions. DSC traces of 1 show anomaly at 174 K, indicating phase transition in the compound.     

Crystal structures of four inclusion compounds of 2,2′-dithiosalicylic acid and tetraalkylammonium

Herein four inclusion compounds of 2,2′-dithiosalicylic acid and tetraalkylammonium, 2(CH₃)₄N⁺·C₁₄H₈O₄S₂^2?·H₂O (1), (C₂H₅)₄N⁺·C₁₄H₉O₄S₂^?·0.25H₂O(2), (n-C₃H₇)₄N⁺·C₁₄H₉O₄S₂^? (3) and (n-C₄H₉)₄N⁺·C₁₄H₉O₄S₂^?(4) are prepared and characterized by X-ray single crystal diffraction. As shown in the results, compounds 1 and 3 belong to orthorhombic crystal system with different space groups of P2₁2₁2₁ and Pca2₁, and 2 and 4 are monoclinic system with similar groups of P2₁/n and P2₁/c. The crystallography data are displayed below: 1: a = 10.5903(7) Å, b = 10.6651(7) Å, c = 21.9476(13) Å, V = 2478.9(3) ų, Z = 4, R₁ = 0.0359; 2: a = 8.13340(1) Å, b = 22.0741(3)Å, c = 13.2143(2)Å, β = 101.6360(1) °, V = 2323.70(6) ų, Z = 1, R₁ = 0.0385; 3: a = 15.7857(2) Å, b = 8.24830(1) Å, c = 20.2599(2) Å, V = 2637.94(5) ų, Z = 4, R₁ = 0.0308_degree4: a = 11.7476(2) Å, b = 17.1346(1) Å, c = 16.3583(3)Å, β = 109.4560(1) °, V = 3104.74(9)ų, Z = 4, R₁ = 0.0562. Interestingly, although the carbon chains of the guest templates vary from methyl group to butyl group, the host molecules of 2,2′-dithiosalicylic acid all construct the similar 2D hydrogen-bonded host layers with or without the existence of water molecules to contain the guest templates to yield analogous sandwich-like inclusion compounds. Obviously, although the guest templates will have certain effects on the ultimate formation of these crystal structures, the host molecule of 2,2′-dithiosalicylic acid is a controlling factor to form these four inclusion compounds.     

Synthesis and structure of the three‐dimensional coordination polymer [Ag3hmt3(μ3 ‐btc)]·5H2O

A new coordination polymer, [Ag₃hmt₃(μ₃ ‐btc)]·5H₂O (1) (hmt = hexamethylenetetramine, btc=1,3,5‐benzenetricarboxlic), has been successfully synthesized. Crystal data: P2₁/a, a = 11.9906(2) Å, b = 17.3689(2) Å, c = 16.96100(10) Å, β = 101.9820(14)°, V = 3455.40(7) ų, Z = 4, Dc = 2.002 Mg/m³. In the hexagonal structure of Ag‐hmt unit, each Ag‐hmt unit comprises three Ag atoms and three hmt ligands. The μ₃ ‐btc ligands bridge adjacent two‐dimensional honeycomb‐like Ag‐hmt layers to form three‐dimensional networks. Structure analysis show that hydrogen bonds play a key role for the stable structure in the compounds. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,Structure and Characterizations of a Molybdenum Sulfide Complex with inorganic Cluster [Mo3S13]2‐ and Organic Amine Me4N+

The complex of (Me₄N)₂Mo₃S₁₃ ( I ) has been synthesized under mild hydrothermal condition. The crystal structure was determined by single crystal X‐ray diffraction at room temperature. Crystal data: M = 854.91, Trigonal, space group P3 (No. 143), a = 11.2351(8) Å, c = 5.8885(6) Å, and Z = 1, There is an inorganic [Mo₃S₁₃]^2‐ core composed of a Mo₃‐triangle, a μ₃‐S atom, three doubly bridging disulfide and three terminal disulfide. Two organic amine ions act as the positive charge to balance the [Mo₃S₁₃]^2‐ cluster.     

Crystal structure and electrochemical property of one‐dimensional complex: [K(cis‐syn‐cis‐ dicyclohexyl‐18‐crown‐6)]2[Cu(mnt)2]

One metalorganic complex [K(cis‐syn‐cis‐ dicyclohexyl‐18‐crown‐6)]₂[Cu(mnt)₂] (mnt = maleonitriledithiolate) has been obtained by the reaction of dicyclohexyl‐18‐crown‐6 with K₂mnt and CuCl₂·2H₂O. The title complex has been characterized by elementary analysis, FT‐IR, UV‐Vis spectroscopy and x‐ray single crystal diffraction. The title complex crystallizes in the triclinic space group P1 with crystallographic data: a = 10.870(6) Å, b = 11.536(6) Å, c = 12.904(7) Å, α = 101.541(10)°, β = 110.573(9)°, γ = 99.441(9)°, V = 1435.2(13) ų, Z = 1, D_calcd = 1.350 g/cm³, F(000) = 615, R₁ = 0.0641, wR₂ = 0.1475. It displays one‐dimensional chain‐like structure formed by [K(cis‐syn‐cis‐ dicyclohexyl‐18‐crown‐6)]⁺ complex cations and [Cu(mnt)₂]^2‐ complex anions through N‐K‐N interactions. Its electrochemical behavior has also been studied by the cyclic voltammetry. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Magnetic Susceptibility of Deintercalated Tunnel Compound of KxCr5Se8 and Mössbauer Spectra of Kx(Cr0.95 57Fe0.05)5Se8

Abstract

KCr₅Se₈ has a TIV₅S₈-type structure, containing K ions in one-dimensional tunnels. Deintercalated samples of K_xCr₅Se₈ (0.32 ≤ x ≤ 0.93) were prepared by leaching method using Alc₃/FeCl₃ aqueous solution. These samples showed a broad peak of magnetic susceptibility at ca. 130 K. ⁵⁷Fe-Mössbauer spectra of K_x(Cr_0.95 ⁵⁷Fe_0.05)₅Se₈ (x = 1.0, 0.49) showed a quadrupole doublet at 300 K. Magnetic sextets appeared at 4.2 K in both samples, indicative of magnetic ordering. The observed isomer shift indicated that the charge of Fe is +3 in both samples. It was proposed that Se^2- was partially oxidized by the deintercalation.     

Increase in the Fluorine-Ion Conductivity of Single Crystals of Tysonite-type CeF<Subscript>3</Subscript> Superionic Conductor by Substituting Polarized Cd<Superscript>2+</Superscript> Ions for Ce<Superscript>3+</Superscript> Ions

The fluorine-ion conductivity of single crystals with a tysonite (LaF₃) structure with heterovalent isomorphic substitutions of highly polarizable Cd²⁺ cations with a 18-electron shell for rare earth ions Ce³⁺ have been studied for the first time. Ce_0.995Cd_0.005F_2.995 single crystals have been grown from melt by the Bridgman technique in a fluorinating atmosphere. The fluorine-ion conductivity of single crystal is measured by impedance spectroscopy in the temperature range from 153 to 1073 K, where it increases by a factor of 10⁹, approaching the value σ_dc = 5 × 10^–2 S/cm at 1073 K. At T₀ = 450 ± 20 K, the dependence σ_dc(T) is split into two portions with the ion-transport activation enthalpy ΔH_σ = 0.39 ± 0.01 eV (T < T₀) and ΔH_σ = 0.23 ± 0.02 eV (T > T0). It is found that at T = 293 K the conductivity σ_dc = 3 × 10^–5 S/cm of Ce_0.995Cd_0.005F_2.995 crystal is higher by a factor of 10 than the conductivity of the tysonite matrix CeF₃ and close to the σ_dc value for Ce_0.995Sr_0.005F_2.995 crystal. This finding indicates a significant effect of the substitutions of Cd²⁺ ions for Ce³⁺ on the σdc value and the advantage of Cd²⁺ ions over Ca²⁺ and Ba²⁺ from the viewpoint of increasing σ_dc.     

Molecular structure of [(tBu)2Al(μ-Cl)]2

The crystal and molecular structure of [(^tBu)₂Al(μ-Cl)]₂ has been determined. The bond lengths and geometry about aluminum are similar to that in [Me₂Al(μ-Cl)]₂ and [(Mes)₂Al(μ-Cl)]₂ suggesting that the geometry about the aluminum is defined by the steric repulsion between the alkyl groups on adjacent aluminum centers and not steric congestion between ligands on individual aluminum centers. Crystal data: Triclinic, $P\bar 1$ ,a=6.514(1),b=8.628(2),c-11.236(2)c=11.236(2) Å, α=102.05(3), β=105.32(3), γ=103.47(3)°,V=567.2(3) ų,Z=1,R=0.063,R _w =0.067.     

X-ray and neutron diffraction studies of the hydridotriruthenium cluster complex (μ-H)Ru3(CO)7(μ-As(C6H5)CH2As(C6H5)2) ((C6H5 2AsCH2As(C6H5)·CH2Cl2: an example of dibridged metal-metal bond M(μ-H)(μ-X)M,involving a heavy bridgehead atom

The title compound is (μ-H)Ru₃(CO)₇(μ-As(C₆H₅)CH₂As(C₆H₅)₂)((C₆H₅)₂ AsCH₂As(C₆H₅)₂)·CH₂C1₂. Crystal data: monoclinic,P2₁/n, cell parameters (X-ray)a=12.82(2) Å,b=22.91(2) Å,c=17.83(2) Å, β=99.1(3)°; (neutron)a=12.94(1) Å, β=22.95(2)Å,c=17.93(3)Å,β=99.55(5)°. The structure was solved from X-ray data. FinalR indices areR(F)=0.051,R _w (F)=0.049 (X-ray);R(F)=0.064,R _w (F)=0.048,R(F ²)=0.072,R _w (F²)=0.088 (neutron). The complex is derived from Ru₃(CO)₈(dpam)₂ through reaction with hydrogen. The structure consists of a triangular array of metal atoms involving three metal-metal bonds[Ru(1)?Ru(2)=2.912(7)Å;Ru(1)?Ru(3)=2.829(3) A; Ru(2)?Ru(3)=2.845(6) Å]. The metal-metal edge Ru(1)?Ru(2) is supported by a bridging bis(diphenylarsino)methane ligand which lies in the equatorial plane. Activation of the second dpam ligand has generated the new face-bridging ligand unit μ-As(C₆H₅)CH₂As(C₆H₅)₂. In this unit, the bridgehead As atom spans over the Ru(1)?Ru(2) bond, while the second As atom is only bonded to Ru(3). The metal environment is achieved by CO ligands. The hydride ligand is bridging the Ru(1)?Ru(2) vector [Ru(1)?H=1.791(10) Å; Ru(2)?H=1.818(8) Å]. Geometric features of the dibridged Ru(μ-H)(μ-As)Ru bond are discussed.     

Naphthaceno[5,6-cd]-1,2-dithiole,C18H10S2

C₁₈H₁₀S₂,M=290.34, monoclinic,P2₁,a=20.556(5),b=15.843(3),c=3.963(1) Å,β=92.79(2)° at 18°C,Z=4,D _x =1.496 g cm^?3,μ(Cu Kα)=3.53 mm^?1. Full-matrix least-squares refinement resulted in a final conventionalR value of 0.036 for 2030 observed reflections. The average C-S bond distance is 1.747(16) Å, the S-S bond length is 2.074(1) Å. The torsion angles at the disulfide group are close to zero, at 3.5 and 0.8°. The carbon frameworks are nearly planar, and closely approximate symmetrymmm. Bond distances are comparable with those in related molecules.     

Structure of N-5-Anilino-pentadien-(2,4)-ylidenaniliniumperchlorate,C17H17N2O4Cl

M_r=348.65, monoclinic, P2₁/n, a=11.088(2), b=17.521(3), c=8.845(2) Å, β=98.87(3)⁰, Z=4, V=1697.8(8) ų, D_x=1.368(1) Mgm⁻³, μ(MoKα)=0.256 mm⁻¹, λ(MoKα)=0.71069 Å, T=296 K. Final R=0.040 for 2454 independent reflections excluding those with |F₀|<4σ(|F₀|). Intensities were measured with an automatic diffractometer. The structure belongs to the openchained cyanines. Characteristic for this class of compounds is their nearly ideal polymethinic electron structure with its main geometrical features: equalisation of bond lengths, alternation of bond angles, planarity of the polymethinic chain. All three features are significantly to be observed in the structure. The bond angle alternation determines essentially the shape of the molecules and the molecular packing.     

Observation of Strong Antiferromagnetic Exchange Interactions in [1-(4′-methobenzyl)isoquinolinium][Ni(mnt)<Subscript>2</Subscript>]: Crystal Structures,Magnetic Properties

Abstract  

An new ion-pair compound, [CH₃BzQl][Ni(mnt)₂] (1), (CH₃BzQl = 1-(4′-methobenzyl)isoquinolinium and mnt²⁻ = maleonitriledithiolate), has been synthesized, structurally and magnetically characterized. The [Ni(mnt)₂]⁻ anions (A) and [CH₃BzIQl]⁺ cations (C) of 1 alternate to form a mixed columnar stack in the manner of ···ACAC··· along the a-axis, and the neighboring columns connect together to generate a three-dimensional (3D) network structure via intermolecular H-bonding interactions and van der Waals forces. Variable-temperature magnetic susceptibility measurements in the temperature range 2–300 K show that 1 is a spin gap system with strong antiferromagnetic interaction.     

Alkali metals in beryl and their role in the formation of derivative structural motifs: Comparative crystal chemistry of vorobyevite and pezzottaite

The crystal structures of high-alkali beryl, i.e., vorobyevite Cs_0.08Na_0.42(H₂O)_{0.18 + y} × [Al₂(Be_2.35Li_0.65)Si₆O₁₈], (a = 9.2102(14) Å, c = 9.2179(14) Å, space group P6/mcc, Z = 2, ρ_calcd= 2.74 g/cm³) and pezzottaite Cs_0.75Na_0.23(H₂O)_0.24[Al₂Be₂Li(Si₆O₁₈)] (a = 15.955(3) Å, c = 27.810(8) Å, space group, R $ \bar 3 The crystal structures of high-alkali beryl, i.e., vorobyevite Cs_0.08Na_0.42(H₂O)_{0.18 + y} × [Al₂(Be_2.35Li_0.65)Si₆O₁₈], (a = 9.2102(14) ?, c = 9.2179(14) ?, space group P6/mcc, Z = 2, ρ_calcd= 2.74 g/cm³) and pezzottaite Cs_0.75Na_0.23(H₂O)_0.24[Al₂Be₂Li(Si₆O₁₈)] (a = 15.955(3) ?, c = 27.810(8) ?, space group, R c, Z = 18, ρ_calcd= 3.13 g/cm³), are determined at a temperature of 100 K. It is confirmed that, at a high lithium content in minerals of the beryl group, lithium is selectively incorporated into Be tetrahedra. The positive charge deficit due to the replacement of Be²⁺ cations by Li⁺ cations is compensated by incorporating large alkali cations into the “zeolite” channel. It is shown that, when the lithium content becomes close to unity per the corresponding formula, the Li and Be atoms are ordered and the rhombohedral structure of pezzottaite is formed. It is proposed to retain the historical name vorobyevite for the lithium- and cesium-containing variety of beryl with a disordered distribution of Be and Li atoms. Original Russian Text ? O.V. Yakubovich, I.V. Pekov, I.M. Steele, W. Massa, N.V. Chukanov, 2009, published in Kristallografiya, 2009, Vol. 54, No. 3, pp. 432–445.