Synthesis and Crystal Structure of the (batre)[CuBr4] Complex, where Batre is bis‐1,1′‐(4‐amino‐1,2,4‐triazolio)ethane

The (batre)[CuBr₄] complex is produced by the reaction of CuBr₂ and (batre)Br₂ in concentrated HBr; its crystal structure is determined. The acentric unit cell (Pn space group) has the following parameters: a = 7.626(2), b = 8.945(2), c = 11.702(2), = 96.69(3)°, V = 792.8(3)³, and Z=1 ((batre)[CuBr₄] composition). The structure of the complex is built up of [CuBr₄]^2- tetrahedral anions and (batre)²⁺ uncoordinated cations. The Cu—Br distances are 2.362–2.385 and the BrCuBr angles are 99.73–129.79°.     

Di- and tri-nuclear osmium carbonyl chloride complexes: x-ray structures of Os2(CO)8Cl2 and Os3(CO)12Cl2

Summary Os₂(CO)₈Cl₂ (1) is orthorhombic P2₁2₁2₁ witha=9.3599(9),b=9.879(2),c=16.014(3), V=1480³, D_c=3.03 Mgm^–3 for Z=4. Structure solved by Patterson methods. Final R=0.038, R_w=0.038 [w=(²F)] for 1270 observed reflections and 141 parameters. Os₃(CO)₁₂Cl₂ (2) is monoclinic C2/m witha=12.105(3), b=10.612(3),c=8.798(1) , =117.02(2)°, V=1006³, D_c=3.22 Mgm^–3 for Z=2. Structure solved by Patterson methods. Final R=0.036, R_w=0.037 (w=(²F)^–) for 821 observed reflections and 75 parameters.Complex(1) has an osmium-osmium single bond 2.897(1), with the chloride ligands in equatorial positions,(2) has a linear triosmium chain with osmium-osmium single bonds 2.893(1) and the chloride ligands occupy equatorial sites on the terminal osmium atoms. Both(1) and(2) are isostructural with their osmium carbonyl iodide analogues.     

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 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 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.     

Disordered Crystal Structure of 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacozane perchlorate

Crystals of the ionic complex (salt) of 4,7,13,16,21,24hexaoxa 1,10diazabicyclo[8.8.8]hexacozane perchlorate, [H₂(Crypt2.2.2)]²⁺ · 2ClO₄ ^-, were synthesized and studied by Xray structural analysis: space group C2/c, a = 20.198(3), b = 10.119(2), c = 12.938(2), = 90.97(1)°, Z = 4, 3030 measured independent reflections, R = 0.067. In these crystals, all atoms of the 2.2.2 dication are disordered over two positions with occupancies of 0.518(4) and 0.482(4). Two conformations of the disordered 2.2.2 dication are such that two H atoms at two nodal N atoms point to its cavity.     

Crystal Structure of Ammonium(2.2.2‐cryptand) Thiocyanate Monohydrate

Crystals of the ammonium (2.2.2cryptand) thiocyanate monohydrate complex, [NH₄(2.2.2Crypt)]⁺ × SCN^- · H₂O, were studied by Xray structural analysis: space group P2/c, a = 11.303(2)*angst;, b = 8.313(1), c = 14.392(3), = 110.39(2)°, Z = 2, 3680 independent measured reflections, R = 0.064. This complex is of the guest–host type: the cryptand ligand cavity contains the NH₄ ⁺ cation with statistically disordered H atoms forming H bonds with each of its O and N heteroatoms. The SCN^- anions and H₂O molecules are linked by H bonds to form chains that are infinite along the z axis.     

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.     

Synthesis, Properties, and Crystal and Molecular Structures of New Ni(II) Complexes with Sterically Hindered Methoxy-β-iminoketones

This paper describes a procedure for the synthesis of two new volatile complexes, C₂₂H₄₀N₂NiO₄ and C₂₀H₃₆N₂NiO₄, based on sterically hindered methoxy--iminoketones. The compounds were investigated by IR spectroscopy and DTA. Full crystal-chemical analysis has been carried out. The structures are molecular. The complexes have close geometrical characteristics; the distances are Ni–O 1.826 and Ni–N 1.842 ; the O–Ni–N chelate angle is 93.2°. The complexes have an intramolecular hydrogen bond N–H...O, estimated at 2.54 (2.08) . In both structures, the packing of complexes is similar to that in nickel(II) dipivalylmethanate.     

Crystal and molecular structure of trans-diiodobis-(1-methyl-5-nitroimidazole)platinum(II)

Summary A new platinum complex of 1-methyl-5-nitroimidazole has been obtained and characterized by elemental analysis, i.r. and n.m.r. spectroscopy. The structure of [PtI₂-(C₄ H₅N₃O₂)₂] has been determined by single-crystal X-ray diffraction. The crystals are triclinic: P1, a = 15.640(3), b = 12.617(2), c = 6.701(1) , = 102.77(5), = 101.15(5), = 100.71(5)°, V = 1228.6(3) ³, Z = 3, D_x = 2.851(6) Mg m^–3, (MoK ) = 0.71069 , = 12.85 mm^–, F(000) = 948, final R = 0.038 for 2859 reflections. The complex consists of monomeric PtI₂(1-methyl-5-nitroimidazole)₂ units. The coordination geometry is square-planar. The two 1-methyl-5-nitroimidazole ligands are trans coordinated to platinum.     

Saturated Vapor Pressure and Crystal Structure of Bis-(2-imino-4-pentanonato)copper(II)

A comprehensive study of copper(II) bis-ketoiminate including tensimetric analysis of sublimation and structure solution has been carried out. The temperature dependence of saturated vapor pressure over Cu(ki)₂ crystals derived by the flow method is expressed by the equation lnP_(atm)} = 25.31-13750/T, H _subl = -114.2 ± 1.3 kJ· mole^-1, S_subl =210.2 ± 3.0> J· mole^-1 · K^-1. Crystal data for CuO₂N₂C₁₀H₁₆: a=15.143(3), b=16.681(8), c=13.795(32) , space group Ccca, Z=12, d _calc = 1.47 g/cm³, R=0.029. The structure is molecular and consists of crystallographically independent Cu(ki)₂ complexes of two types, one with a cis structure and the other with a cis–trans disordering. The copper atom has a plane square environment of two oxygen and two nitrogen atoms. In the cis isomer, Cu–O 1.938 and Cu–N 1.895 ; in the disordered complex, all four Cu–O(N) distances are 1.901 .     

Growth and Structure of Lanthanum Polysulfide Crystals

Single crystals of lanthanum polysulfide were grown under nearly equilibrium conditions according to the P _S ndash;T–x diagram of the LaS_1.5–LaS₂ system described in the literature, and quenched from a temperature of 820°C. The structure of these crystals was determined. Their compositions are LaS_1.96(2) and LaS_2.00(2). The crystals of both compositions belong to the rhombic Pnma space group with a slight variation in lattice parameters in the ranges a = 8.133–8.124, b = 16.345–16.334, and c = 4.128–4.131. The nonstoichiometric polysulfide LaS_1.96 is treated as a spatially averaged, disordered individual phase. Arguments are given that these polysulfide phases have compositions intermediate between LaS_1.5 and LaS₂.     

Structure of Two Crystal Modifications of Cu(II) trans-Bis-(1,1,1-trifluoro-4-iminopentan-2-onate)

Two crystal modifications of the volatile Cu(II) complex prepared from fluorinated -ketoimine (1,1,1-trifluoro-4-iminopentanon-2-one), CH₃(NH)CCH₂COCF₃, were studied by X-ray crystallography (CAD-4 Enraf-Nonius automatic diffractometer, MoK radiation, graphite monochromator). The phases have molecular structures consisting of trans complexes. In both cases, the square plane around the Cu atom is completed to a tetragonal bipyramid by the carbon atoms of the chelate rings of the neighboring complexes; the Cu...C distance equals 3.36-3.39 . For Cu–O and Cu–N distances, an anomalously large difference between the centrosymmetric and noncentrosymmetric complexes has been found.     

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.     

Crystal and Molecular Structure of 1-( p -Tolyl)-4-[4-(N-naphthalimido)butyl]piperazine

An X-ray structure analysis of 1-(p-tolyl)-4-[4-(N-naphthalimido)butyl]piperazine (I) was carried out: a=9.551(3), b=13.775(3), á=8.917(4) , =103.96(3), =101.47(4), =92.60(3)°, V=1110.4(7) ³, Z=2,_calc=1.279 g/cm³, =0.644 mm, space group P 1, 4239 nonzero reflections, R=0.056. The molecule is linear elongated. The p-tolyl and naphthalimide fragments are almost planar, while the piperazine cycle has a chair conformation. The long well-packed molecules form parallel and antiparallel chains with van der Waals interactions between them.     

X-ray study of volatile Ni(II), Cu(II), and Pd(II) complexes of β-ketoimine pivalyltrifluoroacetone

Synthesis of volatile complexes based on -ketoimine pivalyltrifluoroacetone, C(CH₃)₃C(NH)CH₂COCF₃, is described. The general formula of the complexes is M(L)₂, where M = Cu, Ni, Pd. Complexes of this kind with Ni and Pd were obtained for the first time. The Cu and Pd complexes were found to be isostructural. A comprehensive crystal-chemical study showed that all structures are molecular and built of trans-complexes. The central atom has a square plane environment. The average M-O and M-N distances are nearly equal in all compounds: 1.84 , 1.92 , and 1.98 for Ni, Cu, and Pd complexes, respectively; the mean values of the O-M-N chelate angles are 93.4°, 91.9°, and 92.7°, respectively.Original Russian Text Copyright © 2004 by I. A. Baidina, G. I. Zharkova, N. V. Pervukhina, S. A. Gromilov, and I. K. IgumenovTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 713–722, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

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.     

Synthesis, Structure, and Thermal Decomposition of Chloropentamminerhodium(III) Hexabromoplatinate(IV)

The binary complex salt [Rh(NH₃)₅Cl][PtBr₆] was synthesized and studied by Xray structural analysis. The crystallographic data are as follows: a = 12.013(2) , b = 8.401(2) , c = 15.999(3) , = 91.13(3)°, V = 1614.3(6) ³, space group P2₁/m, Z = 4, d_x = 3.70 g/cm³, R = 0.086. The thermal decomposition of the salt in a hydrogen atmosphere is shown to produce a Rh_0.5Pt_0.5 solid solution with an FCC cell [a = 3.864(2) . The thermal decomposition of the salt in a helium atmosphere proceeds via the formation of metallic Pt and RhBr₃ and finally results in a mixture of several solid solutions.     

Synthesis of β‐Chlorinated Macrocyclic [Au(C14H20N4Cl2)]X (X = AuCl2, ClO4, AuCl4) Gold(III) Complexes. Crystal and Molecular Structures of [Au(C14H20N4Cl2)]ClO4

A squareplanar [AuL₂]⁺ gold(III) complex [L₂ = 6.13dichloro5,7,12,14tetramethyl1,4,8,11tetraaza4,6,11,13tetraenato(2-)] containing two chlorine atoms in the position of the ligand hexacyclic ring was first synthesized by the reaction of the [AuL₁]⁺ tetraiminate complex [L₁ = 5,7,12,14tetramethyl1,4,8,11tetraaza4,6,11,13tetraenato(2-)] with HAuCl₄ in an acetone – DMFA solution. The complex was isolated in the form of dichloroaurite (I), perchlorate (II), and tetrachloroaurate (III). Compounds I–III were studied by elemental and Xray diffraction analyses and IR and NMR spectroscopies. Single crystals of [AuL₂]ClO₄ were obtained, and the crystal structure of this compound was determined from Xray diffraction patterns. The crystals are monoclinic: a = 10.147(2), b = 7.260(1), c = 12.519(2), = 96.70(1)°, V = 915.9(3)³, Z = 2, space group P2/c, d_calc = 2.218, d_meas = 2.209 g/cm³ The crystal structure is built of nearly planar [Au(C₁₄H₂₀N₄Cl₂)]⁺ cations and [ClO₄]^- anions. Introduction of chlorine atoms into the positions of the hexacyclic rings of the tetraazamacrocycle hardly changes the lengths of the delocalized C N and C C bonds.     

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.