Structure of an I- x (H2O)6 anion cluster in a 3D anion crystal host [I x (H2O)6Fe(CN)6 x H2O]4-

A planar structure of an anion cluster I- x (H2O)6 in a 3D supramolecular complex [Ru(bpy)3]2[I x (H2O)6Fe(CN)6 x H2O] has been determined by single-crystal X-ray analysis. In the supramolecule, the anion cluster I- x (H2O)6, together with the anion [Fe(CN)6 x H2O]2-, acts as a 3D crystal host, and the [Ru(bpy)3]2+ cations, as the guest molecules, occupy the vacancies of the 3D host framework. This is the first crystal example of the anion cluster I- x (H2O)6.     

Synthesis and Crystal Structure of （H3O）2[Cu3Cl3（H2O）3（NC9H12.5O6）2]

1 INTRODUCTION The polydentate ligand nitrilotripropionic acid, H3ntp[N(CH2CH2COOH)3], has attracted conside- rable research interest in constructing coordination polymers, designing organic-inorganic hybrid mate- rials[1], synthesizing supramolecular compounds[2], etc. due to its high degree of flexibility with three carboxylic acid moieties allowing for a variety of coordination through oxygen atoms[3]. It also pro- vides other versatile properties such as the possibili- ty of inter-…     

Bimetallic cyanide-bridged complexes based on the photochromic nitroprusside anion and paramagnetic metal complexes. Syntheses, structures, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O, [Ni(en)2][Fe(CN)5NO]x3H2O, [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO], and [Mn(5-Brsalen)]2[Fe(CN)5NO

The synthesis, crystal structure, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O (1), [Ni(en)2][Fe(CN)5NO]x3H2O (2), [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO] (3), and [Mn(5-Brsalen)]2[Fe(CN)5NO] (4) are presented. 1 crystallizes in the monoclinic space group P2(1)/n (a = 7.407(4) A, b = 28.963(6) A, c = 14.744(5) A, alpha = 90 degrees, beta = 103.26(4) degrees, gamma = 90 degrees, Z = 2). Its structure consists of branched linear chains formed by cis-[Ni(en)2]2+ cations and ferrocyanide and nitroprusside anions. The presence of two kinds of iron(II) sites has been demonstrated by M?ssbauer spectroscopy. 2 crystallizes in the monoclinic space group P2(1)/c (a = 11.076(3) A, b = 10.983(2) A, c = 17.018(5) A, alpha = 90 degrees, beta = 107.25(2) degrees, gamma = 90 degrees, Z = 4). Its structure consists of zigzag chains formed by an alternated array of cis-[Ni(en)2]2+ cations and nitroprusside anions. 3 crystallizes in the triclinic space group P1 (a = 8.896(5) A, b = 10.430(5) A, c = 12.699(5) A, alpha = 71.110(5) degrees, beta = 79.990(5) degrees, gamma = 89.470(5) degrees, Z = 1). Its structure comprises neutral trinuclear bimetallic complexes in which a central [Fe(CN)5NO]2- anion is linked to two [Mn(3-MeOsalen)]+ cations. 4 crystallizes in the tetragonal space group P4/ncc (a = 13.630(5) A, c = 21.420(8) A, Z = 4). Its structure shows an extended 2D neutral network formed by cyclic octameric [-Mn-NC-Fe-CN-]4 units. The magnetic properties of these compounds indicate the presence of quasi-isolated paramagnetic Ni2+ and Mn3+. Irradiated samples of the four compounds have been studied by differential scanning calorimetry to detect the existence of the long-lived metastable states of nitroprusside.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O and [La(DMSO)4(H2O)3Co(CN)6]·H2O (DMSO = Dimethylsulfoxide)

Two new bimetallic cyano-bridged complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O 1 and [La(DMSO)4(H2O)3Co(CN)6]·H2O 2 have been prepared by the ball milling reaction method and structurally characterized by X-ray single-crystal structure analyses. Crystallographic data for 1:C14H32CeFeN6O8S4, Mr = 736.67, monoclinic, space group P21/n, a = 14.952(1), b =13.7276(9), c = 15.392(1) (A), β = 108.288(1)°, V = 2999.6(4) (A)3, Z = 4, Dc= 1.631 g/cm3,μ =2.304 mm-1, F(000) = 1480, R = 0.0593 and wR = 0.1611; and those for 2: C14H32CoLaN6O8S4,Mr=738.54, monoclinic, space group P21/n, a = 14.945(3), b = 13.731(3), c = 15.300(3) (A), β=107.806(1)°, V= 2989.3(11) (A)3, Z = 4, Dc = 1.641 g/cm3,μ = 2.288 mm-1, F(000) = 1480, R =0.0383 and wR = 0.1132. In both complexes the lanthanide ion is eight-coordinated in a square antiprism arrangement, and the Fe(Ⅲ) or Co(Ⅲ) ion in a nearly regular octahedral environment.The [LnM(CN)6(DMSO)4(H2O)3]·H2O (Ln = Ce and M = Fe for 1; Ln = La and M = Co for 2)species are held together via hydrogen bonds by coordinated water molecules, lattice water molecules and nitrogen atoms of cyanide groups to form a three-dimensional framework.     

Chloroselenate(IV): Darstellung,Struktur und Eigenschaften von [As(C6H5)4]2Se2Cl10 und [As(C6H5)4]Se2Cl9

Chloroselenates(IV): Synthesis, Structure, and Properties of [As(C₆H₅)₄]₂Se₂Cl₁₀ and [As(C₆H₅)₄]Se₂Cl₉ The Se₂Cl₁₀^2? and Se₂Cl₉^? anions were prepared, as the first dinuclear haloselenates(IV), from the reaction of (SeCl₄)₄ with stoichiometric quantities of chloride ions in POCl₃ solutions; they were isolated as yellow crystalline As(C₆H₅)₄⁺ salts. Complete X-ray structural analyses at ?130°C of [As(C₆H₅)₄]₂Se₂Cl₁₀ ( 1 ) (space group P1 , a = 10.296(7), b = 11.271(6), c = 12.375(8) Å, = 74.17(5)°, α = 81.38(5)°, β = 67.69(4)°, V = 1276 ų) and of [As(C₆H₅)₄]Se₂Cl₉ ( 2 ) (space group P2₁/n, a = 12.397(5), b = 17.492(6), c = 14.235(4) Å, α 93.25(3)°, V = 3082 ų) show in both cases two distorted octahedral SeCl₆ groups connected through a common edge in 1 and a common face in 2 . The terminal Se? Cl bonds (average 2.317 Å in 1 , 2.223 Å in 2 ) are much shorter than the Se? Cl bridges (av. 2.661 Å in 1 , 2.652 Å in 2 ). The stereochemical activity of the Se^IV lone electron pair causes severe distortion of the central Se₂Cl₂ ring in the centrosymmetric Se₂Cl₁₀^2? ion. The vibrational spectra of the anions are reported.     

Darstellung von trans-[Mo6Cl8]Cl4Br22−ausgehend von kristallisierten [Mo6Cl8]Cl4(H2O)2 und die Kristallstruktur von [(C6H5)4As]2[Mo6Cl8]Cl4Br2

Preparation of trans-[Mo₆Cl₈]Cl₄Br₂^2? Starting from Crystalline [Mo₆Cl₈]Cl₄(H₂O)₂ and Crystal Structure of [(C₆H₅)₄As]₂[Mo₆Cl₈]Cl₄Br₂ The synthesis of the title compound is successful if the crystallized [(Mo₆Cl₈)Cl₄(H₂O)₂] containing the H₂O molecules in trans-position reacts with HBr + [(C₆H₅)₄As]Br in ethanol in a heterogeneous reaction. The X-ray structure investigation confirms the existence of discrete trans-Br-substituted cluster anions of composition [(Mo₆Cl₈)Cl₄Br₂]^2? in the crystal. The reaction in homogeneous solutions proceeds to Br-enriched compounds. [(C₆H₅)₄As]₂[(Mo₆Cl₈)Cl₄Br₂] crystallizes in the triclinic space group P¯1 with a = 11.071(2), b = 11.418(2), c = 12.813(2) Å, α = 116.10(2), β = 95.27(2) and γ = 94.41(2)° (?133°C). The crystal structure at ?133°C was determined from single crystal X-ray diffraction data (R₁ = 0.026). The [(Mo₆Cl₈)Cl₄Br₂]^2?-anions are not completely ordered but distributed statistically among the three positions which are possible within the limits of the ordered [Mo₆Cl₈]-cores (ratio 11:5:4). The frameworks of the anions consist of Mo₆ cluster units with (slightly distorted) octahedral arrangement of the metal atoms (d(Mo? Mo): 2.600(1) up to 2.614(1) Å), which are coordinated by the halogeno ligands in a square-pyramidal manner. The details of the structure will be discussed and compared with similar [(Mo₆X₈)Y₄] cluster units (X, Y ? Cl, Br).     

Syntheses and structural study of trinuclear iron acetates [Fe3O(CH3COO)6(H2O)3]Cl· 6H2O and [Fe3O(CH3COO)6(H2O)3] [FeCl4]· 2CH3COOH

The structure of two trinuclear iron acetates [Fe₃O(CH₃COO)₆(H₂O)₃]Cl· 6H₂O (I) and [Fe₃O(CH₃COO)₆(H_2O)₃][FeCl₄] · 2CH₃COOH (II) was determined by X-ray diffraction analysis. Crystals I and II are ionic and belong to the orthorhombic system with parameters a = 13.704(3), b = 23.332(5), c = 9.167(2) Å, R = 0.0355, space goup P2₁2₁2 for I and a = 10.145(4), b = 15.323(6), c = 22.999(8) Å, R = 0.0752, space group Pbc2₁ for II. The complex cation [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ has a μ₃-O-bridged structure typical for trinuclear iron (III) compounds. As shown by Mössbauer spectroscopy, the iron(III) ions are in the high-spin state. In trinuclear cations, antiferromagnetic exchange interaction takes place between the Fe(III) ions with the exchange parameter J = -26.69 cm^?1 for II (Heisenberg-Dirac-Van Vleck model for D_3h, symmetry).     

4-Methyl-1,2,3,5-dithiadiazoliumsalze Die Kristallstrukturen von (CH3CN2S2)5[CoCl4]Cl3 und (CH3CN2S2)Cl

4-Methyl-1,2,3,5-dithiadiazolium Salts. Crystal Structures of(CH₃CN₂S₂)₅[CoCl₄]Cl₃ and (CH₃CN₂S₂)Cl 4-Methyl-1,2,3,5-dithiadiazolium tetrachlorocobaltate trichloride, (CH₃CN₂S₂)₅[CoCl₄]Cl₃, was obtained by reaction of trithiazyl chloride, (NSCl)₃, with CoCl₂ in acetonitrile; it forms brown, moisture sensitive crystals. With tetraphenylarsonium chloride in CH₂Cl₂ it yields yellow crystalline (CH₃CN₂S₂)Cl and (AsPh₄)₂CoCl₄. The IR spectra of the title compounds are reported and assigned. Theit crystal structures were determined by X-ray diffraction. Crystal data: (CH₃CN₂S₂)₅[CoCl₄]Cl₃, orthorhombic, P2₁2₁2₁, Z = 4, a = 830, b = 1603, c = 2443 pm at 180 K (structure determination with 1787 observed independent reflexions, R = 0.070); (CH₃CN₂S₂)Cl, triclinic, P2₁2₁2₁, Z = 4, a = 749, b = 819, c = 1015 pm, α = 84.9, β = 67.4, γ = 84.6° at 296 K (2653 reflexions, R = 0.040). Both compounds are ionic, having chloride and distorted tetrahedral CoCl₄^2? anions and planar 4-methyl-1,2,3,5-dithiadiazolium cations which nearly fulfill C_2v symmetry. The (CH₃CN₂S₂)₅[CoCl₄]Cl₃ structure contains five symmetry independent cations, (CH₃CN₂Cl has two symmetry independent cations, all being nearly equal. No nitrogen atom but all sulfur atoms of the cations have contact with three to five chlorine atoms, and as a rule there is one chloride ion which is coplanar with the cation and exhibits rather short distances to both S atoms (288 to 309 pm); therefore, the positive charge of the cations must be concentrated on the sulfur atoms.     

Structural Characterization of trans-[Cr(NH3)4(H2O)Cl]Cl2 and trans-[Cr(NH3)4Cl2]l

Trans-[Cr(NH₃)₄(H₂O)Cl]Cl₂ (A) crystallizes in the monoclinic space group P2₁/m (No. 11) with a = 6.556(1), b = 10.630(5), c = 6.729(2) Å and β = 96.15(3)°. Trans-[Cr(NH₃)₄Cl₂]I (B) has monoclinic C2/m (No. 12) space group and a = 9.877(2), b = 8.497(2), c = 6.047(2) Å and β = 108.98(2)°. Both unit cells contain two formula units. Cr? Cl, Cr? O(H₂O) and three independent Cr? N(NH₃) distances for A are 2.98(1), 2.023(2), 2.067(2), 2.086(3) and 2.064(3) °. Cr? Cl and Cr? N(NH₃) bonds in B are 2.325(1) and 2.071(2) °. All octahedral angles are close to 90 and 180°. Both structures were refined to very low R values. Water molecule from trans-[Cr(NH₃)₄(H₂O)Cl]²⁺ is hydrogen bonded to both ionic chlorides. Cation and two anions form the motive which repeats itself in the crystal. Cations and anions of the second structure are distributed in layers. Each cation and anion have coordination number eight.     

Thiocyanate Compounds of [Nb6Cl12]2+: The structure of A4[Nb6Cl12(NCS)6](H2O)4 (A = K,Rb, NH4)

New compounds of the general formula A₄[Nb₆Cl₁₂(NCS)₆](H₂O)₄ (A = K, Rb, NH₄) were synthesized from Nb₆Cl₁₄ and ASCN in aqueous solutions. X-ray structure refinements were performed on single-crystal data of the three compounds. They are isotypic and crystallize with the space group P1 (Z = 1) and the lattice parameters: a = 877.9(3) pm, b = 1176.6(3) pm, c = 1187.0(3) pm, α = 114.29(1)°, β = 98.96(2)°, γ = 100.91(2)° for K₄[Nb₆Cl₁₂(NCS)₆](H₂O)₄ ( 1 ); a = 887.6(3) pm, b = 1184.0(4) pm, c = 1195.4(4) pm, α = 114.95(2)°, β = 98.84(2)°, γ = 101.31(2)° for Rb₄[Nb₆Cl₁₂(NCS)₆](H₂O)₄ ( 2 ) and a = 886.0(4) pm, b = 1181.1(6) pm, c = 1183.9(6) pm, α = 114.49(2)°, β = 99.48(3)°, γ = 101.53(1)° for (NH₄)₄[Nb₆Cl₁₂(NCS)₆](H₂O)₄ ( 3 ). Each centrosymmetric [Nb₆Cl₁₂(NCS)₆]^4? ion of the isotypic compounds contains six terminal thiocyanate groups being bound to the corners of the octahedral niobium cluster through the nitrogen atoms (d_{Nb? N} = 221.5(6)–224.3(6) pm, bond angles Nb? N? C 168.6(5)–176.4(6)°). The [Nb₆Cl₁₂(NCS)₆]^4? ions are linked via A? S and A? Cl interactions with the A cations. Half of the cations occur to be disordered along two crystallographic sites.     

Synthesis and Crystal Structure of an Ionic Compound [Fe(CN)6(phCH2NC5H5)3]·(H2O)4

A novel ionic compound [Fe(CN)6(phCH2NC5H5)3]·(H2O)4(Mr = 794.71) has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 10.837(2), b = 16.551(3), c = 23.402(5) (A), β = 97.531(4)°V = 4161.0(15)(A)3, Z = 4, Dc = 1.269 g/cm3, F(000) = 1668, μ = 0.414 mm-1, R = 0.0479 and wR = 0.1232. The building unit of the title compound consists of three (phCH2N C5H5) ions, one [Fe(CN)6]3- anion and four water molecules. According to the structural analysis, [Fe(CN)6]3- are linked together by O-H…N and O-H…O hydrogen bonds, but [Fe(CN)6]3- and [(phCH2N C5H5)3] ions are bound by electrostatic force to form an ionic compound.Keywords: N-benzyl-pyridine, ferricyanic anion, crystal structure, supramolecular, ionic compound.     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).