Crystal and Molecular Structure of Cu(II) Bis-(2-methoxy-2,6-dimethyl-3-imino-5-heptanonate)

A new compound from the series of alkoxyketoiminates, Cu(II) bis-(2-methoxy-2,6-dimethyl-3-imino-5-heptanonate), has been synthesized and studied by X-ray crystallography. Crystal data for CuO₄N₂C₂₀H₃₆: a=10.154(1), b=9.921(1), c=11.684(2) , =96.17(1)°, space group P2₁/c, Z=2, dcalc =1.226 g/cm³, R=0.037. The structure is molecular and built from isolated trans-complexes. The copper atom has a plane square environment of two oxygen atoms (Cu–O 1.93 ) and two nitrogen atoms (Cu–N 1.90 ). The O–Cu–N chelate angle is 91.7°. The complex has an intramolecular hydrogen bond, N–H...O 2.16 , involving the alkoxy oxygen atom. The molecular packing in the crystal is close to that of copper(II) dipivaloylmethanate. The calculated van der Waals intermolecular interaction energies and thermogravimetric characteristics of the complexes are compared.     

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.     

Configurations of the [Pd(NO2)4]2- Complex Anion: Crystal Structure of Ag4A2[M(NO2)4]3 (M = Pd, Pt; A = K, Rb)

An integrated Xray diffraction study was performed on polycrystals and single crystals of three new isostructural phases with general formula Ag₄A₂[M(NO₂)₄]₃ (M = Pd, Pt; A = K, Rb). Data on the crystal structure solution (CAD4 diffractometer, MoK radiation, graphite monochromator = 2–30° are presented. In one crystallographically independent [M(NO₂)₄]^2- complex anion, the planar square coordination of the central atom is completed to 4 + 2 by two oxygen atoms at a distance of 3.02–3.12 in the other anion, it is completed to 4 + 1 + 1 by an oxygen atom at a distance of 3.12–3.30 and an Ag⁺ cation at a distance of 3.04–3.11 . Part of the Ag⁺ cations form Ag - Ag dimers with a distance of 3.03–3.07. Crystalchemical analysis of known structures containing [Pd(NO₂)₄]^2- complex anions was performed. It has been established that in none of the cases do any of the possible limiting configurations occur.     

Crystal and Molecular Structure of Platinum(II) trans-Bis-(1,1,1-trifluoro-4-iminopentan-2-onate)

This paper describes a new method for the synthesis of the -iminoketonate complex Pt(ktf)₂ using 1,1,1-trifluoro-4-iminopentan-2-one as a bidentate ligand. An X-ray study has been performed on the polycrystals and single crystals of the compound. The single crystal X-ray diffraction analysis was carried out on a CAD-4 diffractometer (MoK radiation, /2 scan mode). Crystal data: a = 10.217(2), b = 10.231(2), c = 10.924(2) , = 83.12(3), = 63.38(3), = 70.77(3)°, V = 963.4(3) ³, space group P1, Z = 2, d _calc = 1.721 g/cm³. The Pt atom has a distorted planar square environment; the average lengths of Pt–N and Pt–O coordination bonds coincide (1.97 ). The mean value of the chelate angle is 94.2°. The environment of Pt is completed to bipyramid by the hydrogen atoms of the neighboring molecules. The structure of the compound is molecular. The differently oriented molecules of the complex are linked into chains down the x axis with Pt...Pt distances of 5.10 . A comparative crystal-chemical analysis of the structures of Pt(ktf)₂ and Pd(ktf)₂ and their O,O-chelate analogs — Pt(II) and Pd(II) trifluoroacetylacetonates — has been carried out. An X-ray study of Pt(tfa)₂ and Pd(tfa)₂ has been accomplished, and crystal data are given.     

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.     

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.     

Two Modifications of the Mixed-Ligand Complex ZnPhen(i-C3H7OCS2)2 with Monodentate and Bidentate Ligands i-C3H7OCS 2 -

Two crystal modifications (m-1 and m-2) of the mixed-ligand complex ZnPhen(i-PrOCS₂)₂ have been isolated. Their crystal structures were solved using X-ray diffraction data (CAD-4 diffractometer, MoK radiation, 3141 and 3532 F_hkl, R = 0.0363 and 0.0304). For both modifications, the crystals are monoclinic with unit cell parameters a = 10.543(2), b = 13.494(3), c = 16.875(3) , = 102.08(3)°, V = 2347.6(8) ³, Z = 4, space group P2₁/n (m-1) and a = 10.931(2), b = 12.996(3), c = 16.288(3) , = 92.69(3)°, V = 2311.3(8) ³, Z = 4, space group P2₁/n (m-2). The structures basically consist of discrete monomer molecules in which the Zn atom has a tetragonal pyramidal (m-1: ZnN₂S₃, c.n. 5, bidentate and monodentate i-PrOCS ₂ ^- ligands) or distorted octahedral (m-2: ZnN₂S₄, c.n. 6, bidentate i-PrOCS ₂ ^- ligands) environment. Molecular packings and their interactions in the structures are discussed.     

Synthesis and Crystal Structure of trans-Rb2[Pd(NO2)2Cl2]. Structure Refinement of Na2[Pd(NO2)4]

The reaction products of palladium(II) nitration with sodium nitrite in the presence of rubidium salts are described. The crystal structure of rubidium dinitrodichloropalladoate(II) — trans-Rb₂[Pd(NO₂)₂Cl₂] — has been studied (KUMA automatic diffractometer, MoK radiation, graphite monochromator, /2 scan mode for 2 < 30°, 758 experimental reflections, R = 0.030; R = 0.023 for I>2(I)). Crystal data: a = 15.123(3), b = 7.750(2), c = 7.776(2) , V = 911.4(4) ³, space group Cmca, Z = 4, d _calc = 3.209 g/cm³. The structure consists of [Pd(NO₂)₂Cl₂]^2– complex anions and Rb⁺ cations. The planar square coordination of the Pd atom is completed to distorted octahedral by the chlorine atoms of the neighboring complexes at Pd...Cl distances of 3.18 . Chains of complexes with alternating orientations are formed. The geometrical characteristics of the complex anions, the coordination polyhedra of the cations, and the heavy atom sublattice are analyzed. The crystal structure of Na₂[Pd(NO₂)₄] has been refined, and refinement data are given.     

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 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.     

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.     

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.     

Synthesis and Crystal Structure Investigation of Trinitrotriamminerhodium(III) [Rh(NO2)3(NH3)3]

Synthesis of the complex [Rh(NO₂)₃(NH₃)₃] is described. The compound crystallizes as monoclinic colorless plates. Crystal data: a = 7.176(10), b = 10.407(2), c = 10.989(2) , = 93.27°, V = 819.3(2) ³, space group , Z = 4, d _calc = 2.367 g/cm³. The structure is molecular and built of neutral complexes having cis-facial configuration. The unit cell of the crystal contains two independent complexes.     

The synthesis and crystal structure of a cubane-like tungsten copper sulphur cluster, [W4CuS4 2P(OEt)2 3(I)(μ2-PhCO2)(MeCN)]

Summary The title compound [W₃C₃S₄{S₂P(OEt)₂}₃(I)(₂ ^–PhCO₂)(MeCN)] crystallized in triclinic system with space group P1 and cell dimensiona=11.645(6),b=18.565(2),c=11.292(7)Å, =96.15(3)°, =113.65(3)°, =93.77(3)°, V=2207.6ų, Z=2, Mr=1588.09, D_c=2.39 g cm^–3. MoK radiation, =0.71073 Å, =97.3 cm^–1, F(000)=1488, R=0.042 for 5588 observed unique reflections I3(I). There are some distortions in the cubane-like W₃CuS₄ core, with three W-W bonds and three weak W-Cu bonds. Two W atoms are coordinated by PhCO₂ bridge ligand, the other W atom is coordinated to the N atom of MeCN.     

Crystal and Molecular Structure of 5,7,12,14-Tetramethyl-1,4,8,11-tetraaza-4,6,11,13-tetraenatogold(III) Bromide [Au(C14H22N4)]Br

The crystal and molecular structure of [Au(C₁₄H₂₂N₄)]Br has been determined. Monoclinic crystals, a=12.592(2), b=6.309(1), c=19.628(2) ; =98.00(1)°, V=1544.1(4) ³, Z=4, d_calc=2.251 g/cm³, space group C2/c. The structure consists of virtually planar centrosymmetric [Au(C₁₄H₂₂N₄)]⁺ cations and Br^- anions. The coordination sphere of the gold atom involves four nitrogen atoms of the ligands, forming a planar square. The Au–N bond lengths are equal (the mean length is 1.982(7) ). The C–C and C–N bonds inside the -diiminate rings are delocalized. The parameters of the -diiminate rings of the [Au(C₁₄H₂₂N₄)]⁺ cation are compared with the parameters of the related complexes.     

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.     

Synthesis and crystal structure of π-complex of copper(I) with 1-allylbenzimidazolium cation [C7H5N2H(C3H5)]+ [Cu3Cl4]?

Single crystals of [C₇H₅N₂H(C₃H₅)]⁺[Cu₃Cl₄]^– were obtained for the first time by ac electrochemical synthesis from 1-allylbenzimidazolium and copper(II) chlorides in ethanol and structurally characterized. The unit cell parameters are a=8.6755(9) , b=8.846(1) , c=10.4540(7) , =85.36(1)°, =70.529(7)°, =83.29(1)° , V=750.5(3) ³, space group P , R(F)=0.0551. In the -complex, the copper and chlorine atoms form complicated infinite chains along the x axis. The 1-allylbenzimidazolium cation functions as an original bridge: it is coordinated by the Cu atom of one cuprous-chloride chain through the C=C bond of the allyl group and forms a N-HCl hydrogen bond with another inorganic chain through the N atom of the imidazole ring. The trigonal pyramidal environment of the Cu(1) atom includes three Cl atoms and the C=C bond; the environments of the Cu(2), Cu(3), and Cu(3a) are composed only of chlorine atoms. The positions of the Cu(2) and Cu(3a) atoms are partially disordered, which is manifested by the high thermal parameters for the Cu(2) atom and by the splitting of another copper atom into two equally occupied positions Cu(3) and Cu(3a).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 199–203.Original Russian Text Copyright © 2005 by Goreshnik, Schollmeyer, Myskiv.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.     

Synthesis, Formation Mechanism, and Crystal Structure of the Nitrosoruthenium(II) Nitrochloride Complex Fac-K2[RuNO(NO2)2Cl3]

Procedures for synthesis of the first nitrochloride complex of nitrosoruthenium(II), fac-K₂[RuNO(NO₂)₂Cl₃], are described and the mechanism of its formation is suggested. The compound was investigated by IR spectroscopy and X-ray phase and X-ray diffraction analyses. Crystal data for Cl₃N₃O₅K₂Ru: a = 7.050(1), b = 7.524(2), c = 10.125(2) , = 90.44(3), = 103.17(3), = 90.51(3)°, V = 522.9 ³, space group , Z = 2, d _calc = 2.589 g/cm³. The structure consists of the complex anions fac-[RuNO(NO₂)₂Cl₃]^2– and K⁺ cations. The complex crystallizes as triclinic plates and red orange prisms; it is well soluble in water, not readily soluble in KCl solutions, and insoluble in ethanol and acetone; the complex is stable when stored in air.     

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.     

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 .