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.     

X-ray diffraction study of R2[UO2(C3H2O4)2] ·H2O (R = K or Rb)

Compounds K₂[UO₂(C₃H₂O₄)₂] · H₂O (I) and Rb₂[UO₂(C₃H₂O₄)₂] · H₂O (II) are synthesized and their crystal structures are determined by X-ray diffraction. The compounds crystallize in the monoclinic crystal system; for I, a = 7.1700(2) ?, b =12.3061(3) ?, c = 14.3080(4) ?, β = 95.831(2)°, space group P2₁/n, Z = 4, and R = 0.0275; for II, a = 7.1197(2) ?, b = 12.6433(4) ?, c = 14.6729(6) ?, β = 96.353(2)°, space group P2₁/n, Z = 4, and R = 0.0328. It is found that I and II are isostructural. The main structural units of the crystals are the [UO₂(C₃H₂O₄)₂]²⁻ chains, which belong to the AT ¹¹ B ⁰¹ (A = UO₂²⁺, T ¹¹, and B ⁰¹ = C₃H₂O₄²⁻) crystal chemical group of uranyl complexes. The chains and alkali metal ions R (R = K or Rb) are connected by electrostatic interactions and hydrogen bonds. Some specific structural features of [UO₂(C₃H₂O4)₂]²⁻ complex groups are discussed.     

Structure and some properties of [UO<Subscript>2</Subscript>(C<Subscript>5</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>O)<Subscript>5</Subscript>](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

Compound [UO₂(C₅H₁₂N₂O)₅](ClO₄)₂ is synthesized and characterized by thermogravimetry, IR spectroscopy, and X-ray diffraction. The compound crystallizes in the monoclinic crystal system; a = 15.2985(9) Å, b = 26.9676(15) Å, c = 20.6962(11) Å, β = 100.697(1)°, space group P2₁/c, Z = 8, and R = 0.0445. Discrete [UO₂(C₅H₁₂N₂O)₅]²⁺ groups belonging to the AM ₅ ¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ and M ¹=C₅H₁₂N₂O) are uranium-containing structural units of the crystals.     

A Novel Polyoxometalate-Based Hybrid Materials Composed of Octamolybdate and Hexamuclear Copper Cluster Units

Self-assemble of aqueous solution of the Cu²⁺/molybdate/glyc-ine system results in {[NaCu₆(Gly)₈(H₂O)₂][Mo₈O₂₆Cu(Gly)₂]₂}_n·n{NaCu₆(Gly)₈(H₂O)₂}·n{Mo₈O₂₆[Cu(Gly)(GlyH)(H₂O)₂]₂} 15nH₂O 1, which exhibits the 0-D + 1-D supramolecular framework and in which the copper atoms show three kinds of coordination models: (1) in quadrilateral geometry, (2) in square-pyramidal geometry, and (3) in distorted octahedral geometry. The space group of the compound is P–1, with the lattice parameters: α = 89.036(5)°, β = 89.384(4)°, γ = 88.337(5) °, a = 12.559(4) Å, b = 14.441 (4)Å, c = 23.063(6) Å, and Z = 1.     

Three‐Dimensional Structure Constructed via Hydrogen Bonds and π‐π Stacking Interaction. Crystal Structure of [Cu(AFO)2(H2O)2](ClO4)2.2(AFO).2H2O (AFO = 4,5‐Diazafluoren‐9‐one)

The structure of the title complexes [Cu(AFO)₂(H₂O)₂](ClO₄)₂.2(AFO).2H₂O (AFO = 4,5‐Diazafluoren‐9‐one)has been established by single‐crystal X‐ray diffraction. The complex crystallizes in the triclinic space group P‐1 with cell constants a = 7.659(3) Å, b = 11.066(3) Å, c = 14.203(5) Å, alpha = 75.16(3)°, β = 79.87(3)°, gamma = 85.71(3)°, Z = 1. The structure was solved by direct methods and refined to R₁ = 0.0595 (wR₂ = 0.1164). The X‐ray analysis reveals that a pair of AFO ligands chelate to a Cu(II) atom in an asymmetric fashion with one Cu‐N bond being much longer than the other, the Cu(II) atom is further coordinated by a pair of aqua ligands to form an elongated octahedral geometry. In the crystal of the complex, the mononuclear complex cations [Cu(AFO)₂(H₂O)₂]²⁺, uncoordinated AFO molecules, lattice water molecules and perchlorate anions are assembled into 3‐D structure via hydrogen bonds and π‐π stacking interaction.     

Synthesis,characterization and magnetic behaviour of a linear chain poly(oxomolybdophosphate) compound

A new linear chain compound, [Cu(en)₂][Cu(en)₂(H₂O)_1.5][Cu(en)₂(H₂O)₂]_0.5[{Cu(en)₂}₅{HP₂Mo₅O₂₃}₃] · 6.5H₂O ( 1 ) (en = ethylenediamine), has been synthesized under mild hydrothermal conditions, and characterized by elemental analysis, IR, thermogravimetric analyses, magnetic susceptibility measurements and single‐crystal X‐ray diffraction. The crystals are monoclinic, C2/c, a = 42.509(2) Å, b = 25.542(2) Å, c =22.1011(14) Å, β = 102.5940(10)º, V = 23419(3) ų, Z = 8. The crystal structure of 1 features Cu‐bearing cations that are both free as well as being coordinated to the poly(oxomolybdophosphate) groups formed a linear chain that runs along the b axis. Magnetic studies show that the complex is antiferromagnetic. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X-ray Characterization of Sodium (4-dimethylamino-o-tolyl)phosphinate Trihydrate,a Phosphorus Source in Tonics

The structure of the title compound (C₉H₁₃NO₂NaP · 3 H₂O) (Toldimfos Na · 3 H₂O) has been determined at room temperature. The crystals are monoclinic, a = 38.15(2) Å, b = 4.940(3) Å, c = 14.510(8) Å, β = 109.58(4)°, V = 2576(3) ų, Z = 8, D_calc = 1.419 g cm^—3, space group C2/c. The structure was solved by direct methods and refined by full-matrix least-squares method (MoK_α radiation; R = 0.061). Indexed powder diffraction pattern for the drug is also reported.     

Synthesis and Structure of 1,4-Diazabutadiene Liquid Crystals

Abstract

Nine 1,4-diazabutadiene compounds, Ar-N=C(R)-C(R)=N-Ar, R=H, Me; Ar=H_2n+1C_nO-C₆H₄, 2,4-(H₉C₄O)(Me)-C₆H₃ were synthesized and their liquid crystal properties were studied through thermal polarizing microscopy. The X-ray single crystal structure of compound 9 (Ar-N=C(H)-C(H)=N-Ar, Ar=2,4-(Me)(H₉C₄O)C₆H₃) was tested. It is a monoclinic crystal system, space group P2₁/C with the unit cell parameters: a=7.0703(3)Å, b=8.6741(4)Å, c=18.3115(8)Å, β =95.392(1)?. V=1114.57(9)ų, z=2, Dc=1.134 Mg/m³, R=0.0490, Rw=0.1237.     

Synthesis and Structure Study of the Complex [Cu2 (μ–C2O4) (C10H8N2)2(H2O)2] (C6H4COSO2N)2 Crystal Structure Containing Cu (II) Bipy Oxalato and Saccharin

The title compound has been synthesized and its crystal structure determined at room temperature. MW = 927.86, monoclinic, space group P2₁/c, Z = 2, a = 9.283(1) Å, b = 16.239(2) Å, c = 12.209(1) Å, β = 99.848(9)°. The crystal structure consists of repeated [Cu₂(μ–C₂O₄)(C₁₀H₈N₂)₂ · (H₂O)₂]₂ cations and non-coordinated saccharin anions. Each copper ion is in a square pyrimidal environment with two oxalate oxygen and two bipyridine nitrogen atoms as a base and one water molecule at the apex. The two copper ions are bridged by oxalato and the distance is 5.138 Å.     

Synthesis,characterization of an unusual crystalline material with tartrate

An exploration of the cobalt‐tartrate system under hydrothermal conditions, has led to the isolation of crystalline framework {Co₂(H₂tar)₂]·2H₂O}_n ( 1 ) (H₂tar = tartrate dianion). Single‐crystal X‐ray analyses reveal that it crystallizes in the orthorhombic space group P2₁2₁2. a = 11.0924(11) Å, b = 7.8517(8) Å, c = 9.0171(9) Å, β = 90°. A dinuclear Co^II unit is formed via two different coordinated tartrate molecules. Further these units are united together through two bridging carboxylate groups of hexa‐coordinated H₂tar ligands to form a 2D grid layer, which exhibits a typical (6,3) topological network. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of strontium aqua(ethylenediaminetetraacetato)cobaltate(II) tetrahydrate Sr[CoEdta(H2O)] · 4H2O

The complex Sr[Co^II Edta] · 5H₂O (I) (where Edta ^4? is the ethylenediaminetetraacetate ion) has been synthesized. The crystal structure of this compound is determined by X-ray diffraction. Crystals are monoclinic, a = 7.906(2) Å, b = 12.768(2) Å, c = 18.254(3) Å, β = 95.30(3)°, V = 1834.8 ų, space group P2₁/n, Z = 4, and R = 0.036. The structure is built up of the binuclear complex fragments {Sr(H₂O)₃[CoEdta(H₂O)]}, which consist of the anionic [CoEdta(H₂O)]^2? and cationic [Sr(H₂O)₃]²⁺ units linked by the Sr-O bonds into a three-dimensional framework. The coordination polyhedra of the Co and Sr atoms are mono-and bicapped trigonal prisms. The coordination sphere of the Co atom (the coordination number is equal to 6 + 1) involves six donor atoms (2N and 4O) of the Edta ^4? ligand and the O_w atom of water molecule. One of the Co-O distances (2.718 Å) is considerably longer than the other Co-O_lig distances (2.092–2.190 Å) and the Co-O_w(1) distance (2.079 Å). The Sr coordination polyhedron (the coordination number is eight) contains three water molecules, three carbonyl O atoms of the three different anionic complexes, and two O atoms of one acetate group of the fourth anionic complex. The Sr-O distances fall in the range 2.535–2.674 Å. The structural formula of the compound is {Sr(H₂O)₃[CoEdta(H₂O)]}_3∞ · H₂O.     

Static Disorder in Hexagonal Crystal Structures of C60 at 100 K and 20 K

C₆₀ · 2C₈H₁₀ (100 K): hexagonal space group P6₃, a = 23.694(4), c = 10.046(2) Å, V = 4884(2) ų, D_x = 1.903 g cm⁻³, Z = 6, F(000) = 2856, γ(CuKa) = 1.54178 Å, μ = 0.84 mm⁻¹. C₆₀ · 2C₈H₁₀ (20 K): hexagonal space group P6₃, a = 23.67(1), c = 10.02(1) Å, V = 4862(6) ų, D_x = 1.912 g cm⁻³, Z = 6, F(000) = 2856, γ(CuKa) = 1.54178 Å, μ = 0.84 mm⁻¹. The structures were determined by Patterson syntheses and rigid-body refinements. The C₆₀ molecules show two orientations with one molecular centre in common. The solvent molecules are disordered too. Static disorder could not be overcome or influenced by cooling down. A coordination number of 10 was found for the fullerene molecules.     

Synthesis and structure of the first water-soluble chiral monomeric MnIV complex: [Δ-MnIV(biguanide)3] (ClO4)4·H2O

The reaction of KMnO₄ with alkaline biguanide sulfate solution, followed by acidification of the resulting stable filtrate with concentrated HClO₄, led to the title complex, 1. The crystal structure of the [Δ-Mn^IV(bigH)₃](ClO₄)₄·H₂O (1, bigH: biguanide, C₂H₇N₅) has a tetragonal chiral P4 ₁ 2 ₁ 2 space group with a = b = 11.416(3) ?, c = 20.742(7) ?, Z = 4. The complex consists of one chiral [Δ-Mn^IV(bigH)₃] tetracation, four ClO₄ ⁻ anions, and one water molecule. In the tetracation, six N atoms from three neutral biguanide chelate coordinate to the Mn^IV cation, forming an octahedron with Δ-optical activity. The [Δ-Mn^IV(bigH)₃] tetracation interconnects each other by numerous hydrogen bonds with N–H···O and O–H···O between biguanide moieties of the [Δ-Mn^IV(bigH)₃] tetracations and counter-anions as well as water molecules, to construct a three-dimensional network.     

Syntheses,Crystal Structures and Physical Properties of Cd(II) and Mn(II) Complexes with <Emphasis Type="Italic">Trans</Emphasis>-1,2-di(4-pyrindyl)ethylene and <Emphasis Type="Italic">P</Emphasis>-(carboxyl-methyloxy)-benzenecarboxylic Acid

Abstract  

Two complexes [Cd₂(dpe)₃(H₂O)₈]·(dpe)·(hssal)₂·(H₂O)₂ 1, [Mn(dpe)₂(Hpcmb)₂·(H₂O)₂] 2, (dpe = trans-1,2-di(4-pyrindyl)ethylene; H₂hssal = sulphosalicylic acid; H₂pcmb = p-(carboxyl-methyloxy)-benzenecarboxylic acid) has been prepared, and was characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction. Structure indicates in complex 1 that Cd(II) is a distorted octahedral coordination geometry. The hssal²⁻ anions are localized between 2-D sheets {[Cd(dpe)₂(H₂O)₄]²⁺(dpe)}n and {{[Cd(dpe)₂(H₂O)₄]²⁺}n as count anions and bridge to further connect these 2-D sheets through hydrogen bond O–H···O to form 3-D structure. The complex 2 is a single molecule structure. In 2, Each Mn(II) atom is six-coordinated with a distorted octahedral coordination geometry. The single molecule units are extended into three-dimensional structure via π–π, hydrogen bonding interactions. The thermogravimetric behavior and luminescent property of complex 1 were investigated.     

Synthesis and X-ray structural investigation of (C3N6H7)4(CN3H6)2[UO2(CrO4)4] · 4H2O and (H3O)6[UO2(CrO4)4]

Single crystals of the compounds (C₃N₆ H₇)₄(CN₃H₆)₂[UO₂(CrO₄)₄] · 4H₂O (I) and (H₃O)₆[UO₂(CrO₄)₄] (II) are synthesized, and their structures are investigated using X-ray diffraction. Compound I crystallizes in the triclinic system with the unit cell parameters a = 6.3951(8) ?, b = 10.8187(16) ?, c = 16.9709(18) ?, α = 93.674(4)°, β = 97.127(4)°, γ = 92.020(4)°, space group, P Z = 1, V = 1161.6(3) ?³, and R = 0.0470. Crystals of compound II belong to the monoclinic system with the unit cell parameters a = 14.3158(4) ?, b = 11.7477(3) ?, c = 13.1351(4) ?, β= 105.836(1)°, space group C2/c, Z = 4, V = 2125.2(1) ?³, and R = 0.0213. The uranium-containing structural units of crystals I and II are mononuclear anionic complexes of the composition [UO₂(CrO₄)₄]⁶⁻ with an island structure, which belong to the crystal-chemical group Am ₁⁴ (A = UO₂₊², M ¹ = CrO₂₋⁴) of the uranyl complexes. The [UO₂(CrO₄)₄]⁶⁻ anionic complexes are joined into a three-dimensional framework through the electrostatic interactions with outer-sphere cations and a system of hydrogen bonds. Original Russian Text ? L.B. Serezhkina, E.V. Peresypkina, A.V. Virovets, A.G. Verevkin, D.V. Pushkin, 2009, published in Kristallografiya, 2009, Vol. 54, No. 2, pp. 284–290.     

Crystal structure and properties of K<Subscript>2</Subscript>[OsO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>] · 2H<Subscript>2</Subscript>O

The synthesis and X-ray diffraction study of the compound K₂[OsO₂(C₂O₄)₂] · 2H₂O are performed. The compound crystallizes in the triclinic crystal system, space group P \(\bar 1\), a = 6.545(1) Å, b = 6.835(2) Å, c = 7.595(2) Å, α = 85.76(2)°, β = 65.33(2)°, γ = 71.14(2)°, and Z = 1. The osmium atom is located at the center of symmetry and has a distorted octahedral coordination formed by oxygen atoms: two oxygen atoms of the osmyl group occupy the apical positions [Os-O, 1.730(2) Å], and four oxygen atoms of the oxalate ions lie in the equatorial plane. The K⁺ cation is surrounded by ten oxygen atoms located at different K-O distances in the range from 2.787(2) to 3.158(2) Å. The assignment of the absorption bands in the IR spectrum of K₂[OsO₂(C₂O₄)₂] · 2H₂O is performed. The electronic absorption spectra of the compound are recorded in different solvents, and the thermal behavior in air is studied.     

Synthesis,thermal analysis,and crystal structure of manganese(II) 9-molybdocobaltate(III)

Manganese(II) 9-molybdocobaltate(III) of the composition [Mn(H₂O)₄] · [CoMo₉O₂₇(OH)₅] · 7H₂O (I) has been synthesized for the first time and investigated using X-ray diffraction and thermal gravimetric analyses. Compound I crystallizes in the trigonal system with the following unit cell parameters: a = 15.926(1) Å, c = 12.363(1) Å, V = 2715.6(4) ų, M = 1692.55, Z = 3, ρ_(calcd) = 3.105 g/cm³, space group R32.     

Diaquabis(phen)Ni(II) Complex with Vitamin B13 Counter-ions

Abstract The synthesis and crystal structure of a new Ni(II) complex of stoichiometry [Ni(phen)₂(H₂O)₂](H₂Or)₂ · 2H₂O, where phen is phenanthroline and H₂Or is oratate monoanion, are reported. The complex [Ni(phen)₂(H₂O)₂](H₂Or)₂ · 2H₂O crystallizes in the monoclinic system with space group C2/c and cell parameters a = 16.1661(8) ?, b = 12.5669(7) ? and c = 16.4752(7) ?. The coordination around Ni(II) is a distorted octahedron with two phen ligands perpendicular to each other and two aqua ligands in cis- position. Orotate ions locate themselves out of the coordination sphere and bridge the [Ni(phen)₂(H₂O)₂]²⁺ moieties through hydogen bonding with aqua ligands. The FT-IR spectrum of the complex and thermal decomposition behaviour are also briefly discussed. Graphical Abstract Diaquabis(phen)Ni(II) Complex with Vitamin B13 Counter-ions Dursun Ali K?se, Birgül Zümreoglu-Karan, Başak Koşar, Orhan Büyükgüng?r A new complex where Vitamin B13 monoanions act as counter ions and bridge the [Ni(phen)₂(H₂O)₂]²⁺ units by hydrogen bonds is described CCDC deposition number is 606339.     

Crystal structure of complexes of bivalent Co,Ni, and Cd with anions of benzoic and 2-(acetylamino)-5-nitrobenzoic acids

The structure of three complexes of bivalent metals (cobalt, nickel, and cadmium) with anions of benzoic (HL ¹) and 2-(acetylamino)-5-nitrobenzoic (HL ²) acids, namely, [Co₂¹ (H₂O)₂(μ-C₄H₄N₂)] _n (I), [NiL²(H₂O)₅]L² · 2H₂O (II), and [Cd(μ-L ²)₂(H₂O)₂] _n · 2nH₂O (III), is determined. In chainlike structure I, cobalt atoms are connected by bridging pyrazine molecules; structure II contains isolated complexes. In structure III, centrosymmetric (CdOCO)₂ cycles and polymeric ribbons are formed due to the coordination of the carboxylate group of the L ² ligand to two cadmium atoms.     

Crystal structure investigation of [Mn(3-CH3C5H4N)2(N3)2(H2O)2]

The crystal structure of the title compound has been determined by single crystal X-ray diffraction methods. [Mn(3-CH₃C₅H₄N)₂(N₃)₂(H₂O)₂] crystallizes in the space group P 1 with a = 7.444(2) Å, b = 7.691(2) Å, c = 8.926(3) Å, α = 99.82(3)°, β = 108.80(2)°, γ = 114.99(2)° and Z = 1. Least squares refinement gave a R value of R_w = 0.046 for 1414 observed reflections. The manganese atom in the title complex is octahedrally coordinated by two oxygen atoms of the water molecules and four nitrogen atoms; two N-atoms are the end atoms of azide groups and the other two nitrogen atoms belong to the 3-methylpyridine molecules. The polyhedra are linked via hydrogen bonds between the water molecules and the azide groups.