Studies on the Complexes of N,N′-Bis[o-(diphenylphosphino)benzylidene]ethylenediamine with Transition Metal Ions

The thermodynamic parameters for the interaction of Cu²⁺, Ni²⁺, Co²⁺, Cd²⁺, andAg⁺ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag⁺ exhibited remarkably higher complexation selectivity.Ag⁺ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg⁺–M²⁺ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag⁺ was observed in both single and competitiveAg⁺–M²⁺ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P₂N₂) with silver,[Ag(P₂N₂)] (NO₃), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P2_1/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) ³ and Z = 4.     

Synthesis and Crystal Structure of Rubidium Uranyltricarbonate

A procedure for the synthesis of uranyltricarbonatetetrarubidium Rb₄UO₂(CO₃)₃ was developed. Its crystal structure was determined by X-ray diffraction analysis: space group C2/c; a=10.778(5) , b=9.381(2) , c=12.509(3) . =94.42(3)°, Z=4; 1178 independent reflections, R=0.0662.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 5, 2005, pp. 387–390.Original Russian Text Copyright © 2005 by Chernorukov, Mikhailov, Knyazev, Kanishcheva, Zamkovaya.     

Crystal Structures of [Ni(Phen)(i‐Bu2PS2)2] and [Ni(Phen)3](i‐Bu2PS2)2 Complexes and Interaction between Coordinated 1,10‐Phenanthroline Molecules

Single crystals of [Ni(Phen)(iBu₂PS₂)₂] (I) and [Ni(Phen)₃](iBu₂PS₂)₂ (III) compounds were grown, and their structures were determined by Xray diffraction analysis (CAD4 diffractometer, MoK radiation, 3336 F _hkl , R = 0.0373 for I and 2575 F _hkl for III). The crystals of complex I have a triclinic unit cell with the following parameters: a = 11.097(1) , b = 14.903(2) , c = 22.650(3); = 75.18(1)°, = 80.50(1)°, = 75.07(1)°, V = 3479.2(7)³, Z = 4, _calc = 1.255 g/cm³, and space group 1; the crystals of III have a monoclinic unit cell with the following parameters: a = 19.010(3), b = 15.481(1) , c = 17.940(3); = 97.58(1)°, V = 5233.5(12)³, Z = 4, _calc = 1.292 g/cm³, and space group C2/c. The structure of complex I is built from mononuclear molecules, and the structure of III, from [Ni(Phen)₃]²⁺ complex cations and i Bu₂PS₂ ^- outersphere anions. The NiN₂S₄ coordination polyhedra in the structure of I and NiN₆ in the structure of III are distorted octahedra. Based on structural data, the interaction between the coordinated Phen molecules of complexes I, [Ni(Phen)₂(iBu₂PS₂)](iBu₂PS₂) (II), and III is considered, as well as the packing modes of these complexes.     

Crystal structure of the synthetic analog of radtkeite Hg<Subscript>3</Subscript>S<Subscript>2</Subscript>Cl<Subscript>1.00</Subscript>I<Subscript>1.00</Subscript>

The results of structural studies of the synthetic analog of the radtkeite mineral Hg₃S₂Cl_1.00I_1.00 are analyzed. The crystal structure of the compound has been refined; the unit cell parameters are a _m = 16.827(4) , b _m = 9.117(1) , c _m = 13.165(5) , = 130.17(2)°, V = 1543.3(8) ³, space group C2/m, Z = 8, R = 0.0527. A possible transition a ₀ = a _m; b ₀ = a _m + 2c _m; c ₀ = –b _m to the pseudo-orthorhombic F cell previously determined for radtkeite, where one of the angles ( ₀ ) is slightly different from 90° (89.55°), has been found. Each sulfur atom in the structure is bonded to three mercury atoms, forming SHg₃ umbrellas with distances 2.240(6) –2.474(8) and angles HgSHg 94.7(2)°–102.9(2)°. The SHg₃ fragments are linked through Hg vertices to form corrugated [Hg₁₂S₈] layers. The halogen atoms lie inside and between the [Hg₁₂S₈] layers; the distances are Hg-Cl and Hg-I 2.783(7) , 2.961(7) , and 3.083(4) –3.311(3) , respectively.Original Russian Text Copyright © 2004 by N. V. Pervukhina, S. V. Borisov, S. A. Magarill, D. Yu. Naumov, V. I. Vasiliev, and B. G. NenashevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 755–758, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

X-Ray Diffraction Study of Piperidine Octamolybdate

Piperidine octamolybdate [C₅H₅NH₂]₄[Mo₈O₂₆]·4H₂O (I) has been synthesized and characterized by X-ray diffraction analysis. Crystals I are monoclinic, space group P2₁/n, a=12.892(3), b=9.283(2), c=19.184(4) , =92.50(3)°, V=2293.7(9) ³, Z=2,_calc = 2.317 g/cm³.     

Crystal and molecular structures of (<Emphasis Type="Italic">trans</Emphasis>-3,4-Diamino-2,2,6,6-tetramethylpiperidine-1-oxyl-N<Superscript>3</Superscript>,N<Superscript>4</Superscript>)(oxalato-O,O′)platinum(II)

The crystal and molecular structures of (trans-3,4-diamino-2,2,6,6-tetramethylpiperidine-1-oxyl-N³, N⁴)(oxalato-O,O)platinum(II) (C₁₁H₂₀N₃O₅Pt) are studied by X-ray diffraction analysis. The crystals are monoclinic: a=15.210 , b=7.222 , c=14.520 , =118.14°, Z=4, and space group P2₁/c. The structure is solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R=0.05 against 3227 independent reflections (CAD4 automated diffractometer, MoK ). A molecule of the complex is mononuclear with two different bidentate ligands. The coordination of the Pt²⁺ cation is a distorted square. The crystal contains intermolecular hydrogen bonds.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 179–182.Original Russian Text Copyright © 2005 by Chekhlov.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Crystal Structure Study of the Metastable β-modification of Glycine and its Transformation into the α-modification

Crystal structure refinement was performed of the metastable modification of glycine (space gr. P2₁, a = 5.092(2) , b = 6.273(3) , c = 5.384(3), = 113.17(4)°, Z = 2, R = 0.0274). The crystals were obtained by a new method (not described in the literature): they were precipitated from a water solution with the addition of glacial acetic acid. The crystal structure of the glycine modification [space gr. P2₁/n, a =5.106(1) , b = 11.979(5) , c = 5.463(2) , = 111.75(2)°:, Z =4] was refined for comparison. Transition from the to the modification in a damp atmosphere was revealed, resulting in the formation of a strongly strained crystal of a mosaic structure. The orientation of the crystallographic axes in the newly formed crystal of the modification relative to the axes in the initial crystal of the modification was determined. It is shown that as in glycine, the lengths of the intramolecular C—O bonds in the modification are fairly similar [1.248(2) and 1.253(2) ] and the previously found significant difference between them is most likely due to the errors of the photomethod. A comparative analysis of the crystal structures of the and glycine modifications (glycine zwitterion packings and structure of intermolecular hydrogen bond networks) was performed. Data of the analysis are used to discuss the properties of the glycine modifications, the possible reasons for the stability of the modification in dry air, the difficulties of crystal growth from solutions, and the ease of crystallization of the modification under various conditions.     

Molecular and crystal structure of 1∶1 guest-host bis(hexafluoroacetylacetonato)calcium complex with 18-crown-6

We have carried out an X-ray structural study of the title complex (a CAD-4F diffractometer, MoK, graphite monochromator, /2 scan mode, _max, direct methods, 1465 reflections, R=0.036). Crystals are monoclinic with a=17.971(13), b=13.475(3), c=13.379(8) , =106.67(5)°, Z=4CaO₁₀C₂₂H₂₆F₁₂, space group C2/c, d _calc =1.537 g/cm³. The complex (C₂ symmetry) has a molecular structure and belongs to the guest-host type. The Ca atom is located in the center of the 18-crown-6 cavity; bidentate hexafluoroacetylacetonate guest ligands occupy the trans-positions relative to the plane of a maxidentate macrocycle. The Ca–O distances in a ten-vertex Ca polyhedron are 2.474–2.666 . The macrocycle conformation is characterized by six gauche C–C bonds and two gauche and ten trans C–O bonds. The dihedral COCC angle differs significantly (by 38.1°) from the angle of 60°, which is common to a gauche conformation. The six-membered cycle formed by oxygen atoms has a twist form with the annular O–O distances of 5.132–5.329 . Structural features explaining an easy sublimation of the compound are discussed.X-ray structural analysis and the interpretation of results.Synthesis of single crystals.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 6, pp. 56–65, November–December 1993.Translated by T. Yudanova     

Distortion of the Cucurbituril Molecule by an Included 4‐Methylpyridinum Cation

The crystal and molecular structures of a guest–host complex of cucurbituril with 4methylpyridinium, {(4MePyH) (C₃₆H₃₆N₂₄O₁₂)}(NO₃) · 4H₂O, were determined by Xray structural analysis. The crystals are monoclinic with a = 26.276(3) , b = 25.861(2) , c = 17.375(2) , = 124.17(1)°, V_cell =9768.6(18) ³, space group Cc, and Z = 8. The structure contains two crystallographically independent supramolecular complexes. They are arranged in pillars oriented along the a axis. In each pillar, the complexes are parallel to each other. The pillars are shifted with respect to each other by onehalf of the crystallographic translation. The centers of the supermolecules are arranged according to a pseudobodycentered motif. Distortions of the cucurbituril molecule depending on the guest type have been analyzed with the use of results obtained in the present and previous studies.     

Novel chromium trinuclear trifluoroacetate complexes Cr3(μ3-O)(CF3COO)6(CH3COOH)2(CF3COO) and Cr3(μ3-O)(CF3COO)6(CH3COOH)2(THF): Synthesis and crystal structure

Novel anhydrous trinuclear ₃-oxo complexes of Cr(III), Cr₃(₃-O)(CF₃COO)₆(CH₃COOH)₂(CF₃COO) (I) and of Cr(III,III,II), Cr₃(₃-O)(CF₃COO)₆(CH₃COOH)₂(THF) (II) (where THF is (CH₂)₄O) are synthesized by anodic dissolution of metallic chromium in solutions of trifluoroacetic acid in acetonitrile and in tetrahydrofuran and their structures are studied by X-ray diffraction analysis. Complex I forms orthorhombic crystals with space group Pna2₁, a = 9.778(1) , b = 16.042(2) , c = 22.851(4) , Z = 4, R ₁ = 0.0332; complex II crystallizes in monoclinic system: space group P2₁/c, a = 9.866(1) , b = 17.895(2) , c = 21.167(4) , = 100.75(2)°, Z = 4, R = 0.0422. The average Cr-(₃-O) distances in compounds I and II are almost equal (1.943(3) and 1.927(3) ). An average length of the Cr-O bond in octahedral surrounding of metal atoms is different in complexes I and II (1.985(4) and 2.003(3) , respectively), which is specified by different oxidation states of the metal atom. The CrCr distances lie in an interval of 3.366(1)–3.337(1) .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 266–272.Original Russian Text Copyright © 2005 by Glazunova, Boltalin, Troyanov.     

Crystal and molecular structure of copper(II) <Emphasis Type="Italic">trans</Emphasis>-bis-(2-(methylimino)-4-pentanonate)

Synthesis and X-ray diffraction study of trans-bis-(2-(methylimino)-4-pentanonato)Cu(II), which is methyl-substituted ketoiminate, is reported. Crystal data for CuN₂O₂C₁₂H₂₀: a = 7.374(1) , b = 9.171(1) , c = 10.823(2) ; = 96.51(1)°, = 106.12(1)°, = 96.81(1)°, space group P , Z = 2, d _calc = 1.38 g/cm³, d _exp = 1.37 g/cm³, R = 0.037. The structure is molecular and consists of isolated trans-complexes. The coordination polyhedron of the copper atom is intermediate between the square and tetrahedron; the average distances are Cu-O 1.91 and Cu-N 1.95 , the O-Cu-O and N-Cu-N trans bond angles are 145.5° and 150.3°, respectively. The O-Cu-N chelate angle is 94.6°. The calculated energies of van der Waals intermolecular interactions are compared with the thermogravimetric characteristics of the complex with ketoiminate and copper(II) ethylenediamine-bis-acetylacetonate.Original Russian Text Copyright © 2004 by I. A. Baidina, P. A Stabnikov, A. D. Vasiliev, S. A. Gromilov, and I. K. IgumenovTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 706–712, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Crystal and Molecular Structure of 2‐nitro‐1‐ureidoguanidine

An Xray structural investigation of 2nitro1ureidoguanidine has been carried out. The crystals are monoclinic: a = 4.4690(2), b = 15.566(1), c = 9.4131(7), = 94.896(5)°, V = 652.4(3)> ³, space group P2₁/n, Z = 4, _calc = 1.650 g/cm³. The molecule consists of two planar fragments: carbamide and nitroguanidine. The geometrical characteristics of the molecule are analyzed. The system of intra and intermolecular hydrogen bonds in the crystal is considered.     

Crystal Structure of Dehydrated Wairakite

Singlecrystal Xray analysis was employed to study dehydrated wairakite Ca_0.97Na_0.06K_0.03×[Al_1.95Si_4.04O₁₂] with the following parameters: a = 18.260(4) , b = 18.284(4) , c = 13.432(3) , = 90.28(3)°, V = 4989(3) ³, Z = 16, space group B2₁/d. A comparison was carried out with the structure of the hightemperature (600°) phase, space group I4₁/acd. The coordination of the Ca cations increased from 4 to 4 + 1. Additional ligands were acquired from the fourmember ring of the framework upon its deformation and a pairwise countershift of the cations along the c axis. This resulted in a pseudotetragonal unit cell with a doubled volume and lowered symmetry.     

Monodentate and Bridging Bidentate Functions of 4,4′-Bipyridine in the Crystal Structures of [Zn(4,4′-Bipy){(n-C3H7)2NCS2}2] and [Zn2(4,4′-Bipy){(n-C3H7)2NCS2}4]

The structures of the mixed-ligand complexes Zn(4,4-Bipy){(n-C₃H₇)₂NCS₂}₂ (I) and Zn₂(4,4-Bipy){(n-C₃H₇)₂NCS₂}₄ (II) were determined by single crystal X-ray diffractometry (CAD-4 diffractometer, MoK radiation, 2479 and 1616 F_hkl, R = 0.0550 and 0.0523). The crystals are monoclinic with cell parameters a = 16.560(2), b = 11.423(1), c = 15.319(2) , = 94.27(1)°, V = 2889.8(6) ³, Z = 4, space group P2₁/c (for I) and a = 8.515(1), b = 10.965(1), c = 27.816(3) , = 95.860(1)°, V = 2583.5(5) ³, Z = 2, space group P2₁/n (for II). The structure of I is composed of discrete mononuclear molecules; the structure of II consists of discrete centrosymmetric binuclear molecules. The coordination polyhedra of the Zn atoms (c.n. 5) are formed by four S atoms of the two cyclic bidentate dithiocarbamate ligands and the N atom of the 4,4-Bipy ligand, which is monodentate in I and bridging bidentate in II. Molecular packings and interactions in the structures are considered.     

Crystal and Molecular Structure of Monoammonium Salt of 5‐nitroaminotetrazole

Xray structural investigation of the monoammonium salt of 5nitroaminotetrazole was performed. The crystals are orthorhombic: a = 10.077(1), b = 17.009(1), c = 6.6472(6), V = 1139.33(17)³, space group Pbca, Z =8, _calc = 1.715 g/cm³. Monodeprotonation of 5nitroaminotetrazole during formation of the salt occurs at the N(4) nitrogen atom of the heterocycle. The anion has an almost flat structure; the bond lengths suggest delocalization of electron density in the molecule. The negative charge is distributed among three nitrogen atoms and two oxygen atoms of the anion. Changes in the geometrical parameters of 5nitroaminotetrazole on monodeprotonation are considered.     

Crystal Structure of Hexa(μ-bromo)-#x03BC;4-oxo-tetrakis-(1-ethyltetrazole)-tetracopper(II)

The structure of the [Cu₄(-Br)₆(₄-O)(ettz)₄] complex of the monoclinic crystal system was investigated by X-ray diffraction analysis: a = 45.016(12), b = 9.363(4), c = 15.698(5) , = 100.28(2)°, V _cell = 6510(4) ³, space group C2/c, Z = 8,_calc = 2.330 g/cm³, R1 = 0.0697 for 714 F_hkl 4 (F). The copper atoms form a tetrahedron with an oxygen atom in the middle and bromine atoms on the edges. The coordination polyhedron around the copper atom is a distorted trigonal bipyramid (CuOBr₃N unit). All tetrazole ligands are monodentate and coordinated by the N⁴ atoms.     

Polydentate coordination of the thallium atom in complexes with chiral amidinylcyclopentadienyl ligands

The chiral thallium amidinium cyclopentadiene-N-ylide complexes [C₅(CO₂Me)₄{ArNC(Ar")NAr}]Tl were synthesized and structurally characterized by X-ray diffraction analysis and NMR spectroscopy. In these complexes, an unusual mode of coordination of the thallium atom was found, viz., the thallium atom is coordinated by both the side-chain nitrogen atom (N—Tl, 2.833(6) ) and the system of the cyclopentadienyl ring (Tl—Cp, 2.887(4) ⁵-bonding).     

Crystal Structures of Two Re(V) Complexes of 3,5-Dimethylpyrazole with Linear and Bent [OReOReO]4+ Fragments

The crystal structures of two new dimer compounds of Re(V) containing an [OReOReO]⁴⁺ fragment have been studied. Re₂O₃Cl₄(3,5-Me₂pzH)₄ (I): space group P2¹/n, Z = 4, a = 10.180(3), b = 18.132(3), c = 16.601(2) , = 94.60(2)°, V = 3054.4(1) ³, d _calc = 2.059 g/cm³, R ₁ = 0.0513, wR₂ = 0.1493 for 4701 I_hkl > 2 _I of 4926 measured reflections; Re₂O₃Cl₂(-3,5-Me₂pz)₂(3,5-Me₂pzH)₂2[(3,5-Me₂pzH₂)Cl] (II): space group P2₁/n, Z = 4, a = 16.904(2), b = 14.573(1), c = 17.401(2) , = 107.23(1)°, V = 4094.2(7) ³, d _calc = 1.848 g/cm³, R ₁ = 0.025, wR₂ = 0.0514 for 6102 I_hkl > 2 _I of 6315 measured reflections (Enraf-Nonius CAD-4 diffractometer, MoK, graphite monochromator). Compound I has a molecular structure, where molecules are dimers Re₂O₃Cl₄(3,5-Me₂pzH)₄ with a bridging O atom. In II, the dominant motif is the ReOCl(3,5-Me₂pzH) fragments bridged by the pyrazole molecules and the O atom.     

Preparation and Structure Characterization of 4-Amino-1,2,4-triazol-5-one Hydrate

4-Amino-1,2,4-triazol-5-one hydrate (ATO·H₂O) was prepared and its structure was analyzed by four-circle diffraction measurement. The obtained results show that the crystal belongs to the triclinic crystal system, space group P 1 with crystal parameters a = 6.432(1), b = 6.551(1), c = 6.740(1) ; = 68.04(1), = 82.18(1), = 81.90(1)°, V = 259.7(7) ³; Z = 2; Dc = 1.510 g/cm³; = 0.131 mm^-1; F(000) = 124. ATO·H₂O was characterized by FT-IR analysis, X-ray diffraction analysis, and single crystal diffraction analysis.     

Coordination chemistry of alkali and alkaline earth cations: Synthesis and X-ray crystal structure of cesium (picrate) (benzo-15-crown-5) Cs+C6H2N3O 7 − (C14H20O5)

Crystals of the Cs⁺ Pic^– (B15C5) complex (Pic=picrate; B15C5=benzo-15-crown-5) (M _r =629.3) are yellow prisms which belong to the triclinic space groupP witha=7.377(4),b=11.372(2),c=14.806(2) , =90.31(1), =91.06(2), =108.32(2)⁰,Z=2,D _x =1.77, andD _m =1.77 g cm^–3. FinalR=0.055 for 3575 observed reflections out of a total of 4004 measured reflections. Cesium forms a 1:1 anion paired complex with B15C5 like sodium rather than a charge separated sandwich structure as found for potassium and expected for cesium in view of the ion-cavity radius concept. The Cs cation is 9-coordinate involving the five crown oxygens (Cs...O, 3.00(1) to 3.24(1) ), the phenoxide (Cs...O^–, 3.03(1) ) and anortho nitro group oxygen (Cs...O, 3.01(1) ) of the picrate counteranion and, uniquely, with two additional oxygens (Cs...O, 3.17(1) and 3.40(1) ) from apara nitro group of the picrate belonging to the adjacent molecule in the lattice. The Cs⁺ ion lies 2.07 out of the mean plane formed by the crown oxygens. This system provides the first structural evidence that the interaction stoichiometry of an alkali cation with a cyclic multidentate ligand is not a function of the ion and cavity size alone but also of its Lewis acid strength as modified by the charge neutralizing anion. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82027.