Copper(II) Chelate Complex with N′-(2,4-Dichlorophenoxy)acetyl-N,N-Dimethylhydrazine: Crystal and Molecular Structure

X-ray diffraction analysis of the copper(II) chelate complex CuL₂ (where L is the deprotonated imid-ol form of N,N-dimethyl-2,4-dichlorophenoxyacetohydrazide (HL)) was performed (3826 reflections, R = 0.039, wR = 0.043). Crystals are monoclinic, a = 8.365(7) Å, b = 23.090(7)Å, c = 12.713(3) Å, = 95.12(6)°, space group P2₁/c, Z = 4. The slightly distorted square environment of the copper cation is composed of two N atoms of the dimethylamino groups and two O atoms of the deprotonated imidol groups. Both N and O atoms are located in trans-positions relative to each other. Additional coordination of electron-donor atoms is prevented by methyl groups, in which the C atoms are at a distance of 2.837 to 2.918 Å from the central ion.     

Copper(II) Complexes with N-(3-Hydroximino-2-methylbutan-2-yl)methylamine (HL): Synthesis and Properties. Crystal and Molecular Structures of [Cu(HL)Cl2] and [Cu(HL)(H2O)2SO4]n

Paramagnetic copper(II) complexes with N-(3-hydroximino-2-methylbutan-2-yl)methylamine (HL), namely, Cu(HL)Cl₂(I), Cu(HL)(SO₄) · 2H₂O (II), and Cu(HL)(NO₃)₂(III), were obtained. The crystal structures of I and II were determined. The blue crystals of these compounds are monoclinic. For I(C₆H₁₄Cl₂CuN₂O): a = 8.820(1) Å, b = 6.511(1) Å, c = 18.255(2) Å, = 92.86(1)° V = 1047.0(2) ų, space group P2₁/c, _calcd = 1.679 g/cm³, Z = 4 for R ₁ = 0.0250; for II(C₆H₁₈CuN₂O₇S): a = 9.999(2) Å, b = 9.927(2) Å, c = 12.963(3) Å, = 106.37(3)°, V = 1234.5(4) ų, space group P2₁/c, _calcd = 1.753 g/cm³, Z = 4 for R ₁ = 0.0324. Crystals of I have a molecular structure. The Cu coordination polyhedron is a square bipyramid (2N + 2Cl + Cl + Cl) due to additional contacts with two Cl atoms from the neighboring molecules. Structure II is built from polymeric chains. The environment of the Cu atom is a distorted cis-octahedron (2N + 2O(H₂O) + 2O(SO₄)). Complexes I–IIIare characterized by IR and EPR spectroscopy.     

Crystal Structure of Cesium-Sodium Molybdate Dihydrate

Structure of CsNaMoO₄ · 2H₂O crystals formed in Cs₂MoO₄–Na₂MoO₄–H₂O system is determined by X-ray diffraction study. The unit cell parameters a = 6.379(2) Å, b = 8.631(2) Å, c = 13.670(2) Å, V = 752.6(3) ų, Z = 4, M = 351.87, (calcd) = 3.105 g/cm³, space group P2₁2₁2₁. The isle crystal structure is built of MoO₄ ^2-, Cs⁺, and Na⁺ ions. The Mo–O bond lengths lie within 1.756(2)–1.769(3) Å range. The OMoO bond angle is 109.45° on average. Three oxygen atoms of MoO₄ ^2- anion are involved in hydrogen bonds with water molecules., while the fourth O atom participates in the formation of Na polyhedra only. The octahedral environment of Cs⁺ ions is formed by oxygen atoms of MoO₄ ^2- anions, without participation of water molecules. The structure contains two crystallographically independent water molecules, whose tetrahedral coordination consists of two Na⁺ ions and two MoO₄ ^2- anions.     

The W2Cl4(NHCMe3)2(PR 3)2 molecules (R 3=Me3, Et3, Pr n 3, Me2Ph) I. Their isomeric forms,interconversion proeesses,crystalline forms,and detailed molecular structures

A thorough study of compounds with the formula W₂Cl₄(NHCMe₃)2(PR₃)₂, withR ₃=Me₃, Et₃, Prg ⁿ ₃ Me₂,Ph, is reported. In addition to the previously reported crystalline compounds, namely Ia,trans-W₂Cl₄(NHCMe₃)₂(PMe₃)₂ in space group Pmmn;3a,trans-W₂Cl₄(NHCM₃)₂(PEt₃)₂ in space group P2₁/^a (or P2₁/^c); and4,cis-W₂Cl₄(NHCMe₃)₂(PMe₂Ph)₂ in Pna2₁, we have obtained and structurally characterized the following new substances,1b,trans-W₂Cl₄,(NHCMe₃)₂(PMe₂)₂, space group P2₁/^c,a= 12.233 (4) Å,b= 12.872 (4) Å,c=17.095 (5) Å,=93.52 (2)°,Z=4,V=2687 (1) ų 2,cis-W₂Cl₄(NHCMe₃)₂(PMe₃)₂, P2₁/^c,a=9.673 (4) Å,b=17.249 (4) Å,c=16.244 (5) Å,=99.63 (3),Z = 4 ,V=2669 (1) Å.3b,trans-W₂Cl₄(NHCMe₃)₂(PEt₃)₂, Pl,a=16.850 (3) Å,b=17.797 (3) Å,c= 11.459 (2)Å,= 101.02 (1),= 103.13°, y=84.23 (1)°,Z=4,V= 3279 (1) Å5,trans-W₂Cl₄(NHCM₃)₂(PMe₂Ph)₂, Fdd2,a=39.563 (8) Å at 20°C; 39.325 (10) Å at -6O°C,b = 57.543 (17) Å at 20°C; 57.186 (16) Å at -60°C,c= 8.810 (1) Å at 20°C; 8.770 (1) Å at - 60°C ,Z=24,V=20057 (7) ų (20°C), 19723 (8) ų ( - 60°C) .6,trans-W₂Cl₄(NHCMe_{3 2}(PPrⁿ ₃)₂, Pl,a= 17.287 (2) Å (20°C); 17.077 (5) Å (-60°C),b= 19.119 (2) Å (20°C); 18.952 (6) Å (-60°C),c= 12.713 (1) Å (20°C); 12.668 (4) Å (-60°C),Z=4,V= 3980 (1) ų (20°C), 3898 (2) ,ų ( - 60°C). In addition, the structure of3a was re-determined and refined so that the disorder ratio was a refined parameter, leading to a value of 0.520:0.480 instead of being arbitrarily fixed at 0.50:0.50. In all of the structures the molecules are held in eclipsed (but very distorted) rotational conformations and the W-W distances are all within the range of 2.305-2.330 Å. As will be shown in a later paper, for all phosphines, thecis andtrans isomers are of similar stability and an equilibrium mixture exists in solution. It is also shown that1a and3a do not contain unexpectedly short W-N bonds as previously reported.     

Kristallstruktur des Molybdändioxiddichlorid-Phosphoroxidtrichlorid-Addukts MoO2Cl2 · POCl3

Crystal Structure of the Molybdenum Dioxide Dichloride — Phosphorus Oxide Trichloride Adduct MoO₂Cl₂ · POCl₃ The crystal structure of MoO₂Cl₂ · POCl₃ was determined by X-ray methods (R = 0.046; 2497 independent reflexions). MoO₂Cl₂ · POCl₃ crystallizes monoclinic in the space group P2₁/c with Z = 8. It forms nearly linear chains in which the Mo atoms are linked together via weakly bent and asymmetric oxo bridges (Mo? O = 172 and 218 pm). The Mo atoms are surrounded in a distorted octahedral coordination by one O and two Cl atoms (Mo? Cl = 230–232 pm) as terminal ligands and by the POCl₃ molecule and the bridging O atoms as well. The POCl₃ molecule (Mo? O = 233 pm) is located in trans position to the terminal oxo ligand (Mo? O = 166 pm).     

Ethylenediamine-N,N"-Diacetate Ion (Edda2–) as a Tridentate Ligand: Synthesis and Structure of the [Co(Edda)(Dien)]ClO4 · H2O and [Co(Edda)(En)(CN)] · 2H2O Complexes

The cobalt(III) complexes with tridentate ethylenediamine-N,N"-diacetate ions (Edda^2–) and additional ligands, namely, diethylenetriamine (Dien) or ethylenediamine (En) and cyanide ions, were synthesized. As follows from X-ray diffraction analysis of [Co(Edda)(Dien)]ClO₄· H₂O (monoclinic crystals with a = 9.243 (2) Å, b = 14.167 (4) Å, c = 13.046 (3) Å, = 91.19 (2)°, Z = 4, space group P2₁/c), the secondary N atom of the Dien ligand occupies the trans-position relative to the N atom of the Edda^2– ligand, which contains a free acetate group. Two fac-isomers of [Co(Edda)(En)(CN)] with the CN^– ion in the cis- and trans-positions relative to the oxygen atom of the carboxyl group were isolated, and the structure of the trans-(O,CN)-[Co(Edda)(En)(CN)]· 2H₂O was determined: monoclinic crystals with a = 9.136 (3) Å, b = 15.484 (3) Å, c = 10.564 (3) Å, = 110.67 (5)°, Z = 4, space group P2₁/c.     

[Et3PH][W4O3Cl7(PEt3)3]. A 12-electron tetrahedral tungsten cluster with an interesting arrangement of ligands

From the reaction between W₂Cl₆(PEt₃)₂ and H₂O in tetrahydrofuran the dark green crystalline compound [Et₃PH][W₄O₃Cl₇(PEt₃)₃] was obtained and characterized by X-ray crystallography. At –155° the cell dimensions werea=b=c=20.392(3) Å,Z=8,d _calcd=2.36 g cm^–3 in the space group I23. The compound is a triethylphosphonium salt of the [W₄O₃Cl₇(PEt₃)₃]^– anion. The latter contains a tetrahedron of tungsten atoms with W–W=2.61 Å (ave) and may be viewed as a W₃(-Cl)₃Cl₃(PEt₃)₃ cluster capped by ad ⁰-[WO₃Cl]^– unit and this has proved useful in examining the bonding within the cluster by use of the M.O. calculational method of Fenske and Hall. The cluster anion has crystallographically imposed C_3v symmetry. Theoxo-groups bridge the tungsten atoms in a notably asymmetric manner W–O=1.87(2) Å and 2.04(2) Å with the shorter distances being involved with the capping [WO₃Cl]^– unit. The W–P bonds lie in the W₃(₃-Cl)₃ plane and the three terminal W–Cl bonds are trans to theoxo-bridges.     

Electronic structure and one-electron properties of the MoO2Cl2 molecule. Electronic spectra of the MoO2Cl2, MoO2Br2 and WO2Br2 molecules

The SCF-X -SW method in an overlapping atomic spheres approximation has been used to calculate the electronic structure, ionization potentials, energies and oscillator strengths of the allowed optical transitions and also some of the one-electron properties of the MoO₂Cl₂ molecule. The electronic absorption spectra of vapours over molybdenum and tungsten dioxodibromides have been measured. Interpretation of the experimental electronic absorption spectra of the MoO₂Cl₂, MoO₂Br₂ and WO₂Br₂ molecules is discussed.     

Darstellung und Kristallstruktur von Pb2(NO2)(NO3)(SeO3)

Crystals of Pb₂(NO₂)(NO₃)(SeO₃) were synthesized by partial reduction of nitrate ions with native copper under hydrothermal conditions. The crystal structure [a=5.529 (2) Å,b=10.357 (3) Å,c=6.811 (2) Å, space group Pmn2₁,Z=2] was determined from 1 707 independent X-ray data up to sin /=0.81 Å^–1 and was refined toR _w =0.028. The Pb(1) atom is ten coordinated to O atoms [Pb(1)-O from 2.51 Å to 2.96 Å], the Pb(2) atom has three nearest O atoms [Pb(2)-O=2.41 Å (1 ×) and 2.45 Å (2 ×)] and six next-nearest O atoms [Pb(2)-O from 2.80 Å to 3.22 Å].

Herrn Prof. Dr.K. Komarek zum 60. Geburtstag gewidmet.     

Interaction of Np(V) with N,N-Dimethylacetamide

A new Np(V) complex [(NpO₂)(NO₃)(DMAA)₂(H₂O)] was synthesized and its crystal structure was determined. Its absorption spectra were recorded in IR and near-IR regions. The unit cell parameters are a = 9.389(3) Å, b = 8.075(3) Å, c = 20.956(7) Å, = 92.53(3)°, space group P2₁/c, Z = 4, V = 1585.8(9) ų, R = 0.054, wR(F ²) = 0.170. The coordination polyhedron of the Np atom is a pentagonal bipyramid with the O atoms of two DMAA molecules, bidentate nitrate ion, and the water molecule in its equatorial plane.     

Rhodium(III) halide complexes with sulphur donors. The crystal structure ofmer-tris(o-ethylthiocarbamate)-trichlororhodium(III)acetone(1/1)

Summary The complexes [Rh(TC)₃Cl₃] · Me₂CO and [Rh(TC)₃X₃] · 0.5 Me₂CO (TC=O-ethylthiocarbamate; X=Br or I) have been prepared and characterized by i.r. and¹H n.m.r. spectroscopy.The crystal structure of [Rh(TC)₃Cl₃] · Me₂CO has been determined by x-ray diffractometer data and refined to R=0.040. Crystals are monoclinic, space group P2₁, with a=9.101(5), b=15.785(8), c=8.776(5) Å, and =103.00(3)°; Dx=1.57 gcn^–3 for Z=2. The complex is monomeric with octahedral Rh. Relevant distances are Rh-Cl (trans to one another) 2.354(2) and 2.353(2) Å, Rh-Cl (trans to S) 2.388(2) Å; Rh-S (trans to one another) 2.376(3) and 2.369(3) Å, Rh-S (trans to Cl) 2.332(3) Å. There is intramolecular, and possibly intermolecular, hydrogen bonding in the structure.     

Neptunium(V) Perrhenate Complex with 1,10-Phenanthroline [(NpO2)(ReO4)(Phen)(H2O)2]: Crystal Structure and Absorption Spectra

Neptunium(V) perrhenate complex [(NpO₂)(ReO₄)(Phen)(H₂O)₂] was synthesized with 1,10-phenanthroline as a ligand. Its composition and structure were determined by X-ray diffraction analysis. The coordination polyhedron of the Np atom is a pentagonal bipyramid. The nearest surrounding of the neptunoyl ion includes the oxygen atom of the ReO₄ anion, two nitrogen atoms of phenanthroline, and the oxygen atoms of two water molecules. The crystals of the compound are monoclinic. The main crystallographic parameters are the following: space group P2₁/c, unit cell parameters a = 7.288(1) Å, b = 10.513(2) Å, c = 20.936(4) Å, = 96.939(5)°, Z = 4, V = 1592.2(5) ų. Absorption spectra of the compound in visible and IR regions are reported.     

4,7,13,16,21,24-Hexaoxa-1,10-Diazoniabicyclo[8.8.8]hexacosane Pentaaqua[Bis(nitrato-O,O′)]yttrium(III) Dichloride Nitrate: Synthesis and Crystal Structure

A complex salt, namely, 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane pentaaqua[bis(nitrato-O,O)]yttrium(III) dichloride nitrate [Y(NO₃)₂(H₂O)₅]⁺[H₂(Crypt-222)]²⁺2Cl^–NO^– ₃ (I) was synthesized and structurally characterized by X-ray diffraction analysis (triclinic crystal system, space group P31, a = 8.443(1) Å, c = 28.110(5) Å, Z = 2). The structure was solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.072 from 2000 measured reflections (CAD4 automated diffractometer, CuK radiation). The crystal structure of I is highly disordered. All ions are located in crystallographic axes 3 and all but one Cl^– ion are disordered. In the [Y(NO₃)₂(H₂O)₅]⁺ complex cation, the coordination polyhedron of the Y atom (C.N. 9) is a distorted pentagonal bipyramid with two O atoms of two nitrato ligands as two bifurcate vertices and five O atoms of five water molecules as the base.     

Synthesis and Characterization of the Isocyanide Ligated Centered Zirconium Halide Cluster [(Zr6Be)Cl12(CNXyl)6]

The first isocyanide ligated hexanuclear zirconium halide cluster is reported. The unoxidized [(Zr₆Be)Cl₁₂(CNXyl)₆] (CNXyl = 2,6-dimethylphenyl isocyanide) was obtained from the solid state precursor K₃Zr₆Cl₁₅Be by dissolution in CH₃CN in the presence of CNXyl. The CNXyl ligands occupy all the axial positions on the cluster. The compound was recrystallized from CH₂Cl₂ and Et₂O. [(Zr₆Be)Cl₁₂(CNXyl)₆].2CH₂Cl₂ crystallizes in the space group (#2) with a = 12.092(5) Å, b=12.728(5) Å, c = 14.102(8) Å, = 104.98(4)°, =107.11°, = 100.94°, V = 1919(2) ų, Z = l, R = 11.3% and R _W = 27.0%. For the bound isocyanide ligands, v _CN increases to 2140 cm^–1.     

Synthesis and crystal structural study of ternary molybdate NaMg3In(MoO4)5

We have synthesized single crystals of a temary molybdate NaMg₃In(MoO₄)₅ and cam'ed out an X-ray structural study (a KM-4 automatic difiactometer, MoK, radiation, 4503 F, R = 0.047). The triclinic unit cell dimensions are a = 7.0476(7), b = 17.935(2), c = 6.9849(7)Å, = 87.650(9), = 100.980(8), = 92.510(9)°, V= 865.5(2) A³, Z = 2, and space group P^–1. The crystal structure involves MoO₄ tetrahedra and (Mg, In)0₆ octahedra forming a three-dimensional framework with Na atoms located in its cavities. The compound melts at 990°C with decomposition.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Institute of Physics, Siberian Branch, Russian Academy of Sciences. Buryatian Institute of Natural Sciences, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 147–151, September–October, 1993.Translated by T. Yudanova     

[Cl3Cu(I)-As(III)O3]: Ein kristallchemisch neues Bauelement in der Struktur des Pb6Cu(AsO3)2Cl7

The synthetic compound Pb₆Cu(AsO₃)₂Cl₇ crystallizes in space group R witha ₀=9.8614(4),c ₀=17.089(2)Å,Z=3. The crystal structure, determined by single crystal X-ray work, is a typical layer structure. Complex Pb₆(AsO₃)₂Cl₆ layers are combined via monovalent Cu and Cl atoms. A novel element within the structure is a [Cl₃Cu(I)-As(III)O₃] group with the interatomic distances (Å): Cu-Cl=2.44 (3×), As-O=1.76 (3×), Cu-As=2.34 (1×).

     

New uranyl complex with imidazolidine-2-one [UO<Subscript>2</Subscript>(Imon)<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Structure and some properties

A complex of uranyl perchlorate with imidazolidine-2-one as the molecular ligand, [UO₂(Imon)₄(H₂O)](ClO₄)₂ (I), was synthesized and structurally characterized by X-ray diffraction analysis. The coordination number of the uranium atom is 7. The nearest environment of the uranyl ion includes four O atoms of the imidazolidine-2-one molecules and one O atom of the water molecule. The perchlorate anions are outer-sphere ligands. The crystals are monoclinic: space group P2₁/c; a = 16.294(3) Å, b = 16.135(3) Å, c = 9.987(2) Å, = 97.69 (3)°, V = 2603.0 (9) ų, (calcd) = 2.117 g/cm³, Z = 4. The IR and luminescence spectra of the complex were recorded.Translated from Koordinatsionnaya Khimiya, Vol. 30, No. 12, 2004, pp. 919–924.Original Russian Text Copyright © 2004 by Andreev, Antipin, Budantseva, Tuchina, Serezhkina, Fedoseev, Yusov.     

The crystal structure of tetraphenylarsonium tricyanooxopyridine-2-carboxylatotungstate(IV) dihydrate

Summary The structure of (AsPh₄)₂[WO(CN)₃(Pic)] · 2H₂O has been determined from three dimensional x-ray data. The cell dimensions are:a=17.699(8),b=13.546(6),c= 13.590(6) Å, =117.39(8), = 71.54(7) and = 115.04(8)°, space group P¯1, Z = 2, The structure was solved from 5279 observed reflections. The anisotropic refinement converged to R = 0.060.The [WO(CN)₃(Pic)]^2–-ion is a distorted octahedron. The structure indicates that the aqua group in [WO(CN)₄(H₂O)]^2– was displaced by an oxygen atom of the carboxylate of 2-picolinate, while a cyanide ligand was substituted by the pyridine nitrogen atom. Themer-arrangement of the three cyanide ligands has two normaltrans W-C_av = 2.17(2) Å bond distances and a significant shorter W-C = 2.042(18) Å bond trans to the W-N [2.188(18) Å] bond. The W=O and W-O bond lengths are 1.676(9)Å and 2.171 Å, respectively.     

Synthesis,structure and bonding of 2-aminopyridinium heptamolybdate trihydrate

Summary 2-aminopyridinium heptamolybdate trihydrate crystallizes in the monoclinic system with space group P2₁/n and Z=4 (R=0.030). The unit cell dimensions area=14.8161(4) Å,b=17.5073(4) Å,c=20.8492(6) Å, =107.503(2)°, V=5157.7(2) ų. The [Mo₇O₂₄]^6– anions in the 2-aminopyridinium, ammonium⁽⁴⁾, guanidium⁽²⁾, propyl- and isopropyl-ammonium⁽¹⁾ molybdates, while similar, show slightly differences in several bond lengths and angles. The distinguishing features of 2-aminopyridinium heptamolybdate trihydrate structure is its extensive hydrogen bonding. The planar cations and the water molecules are positioned so as to be able to form hydrogen bonds with either molybdate oxygen atoms or water oxygen atoms. Four different types of hydrogen bonds have been found-: N-H... O (mono- and bifurcated), N-H... Ow (monofurcated), Ow-Hw... O (mono- and bi-furcated) and Ow-Hw...OW (monofurcated). The closest approach distances associated with 27 of these potential hydrogen bonds vary from 2.67 to 3.24 Å^(7,8)). The proposed strong hydrogen bonding interactions appear to stabilize the structure and explain the way of three water molecules are lost upon heating. Some of these hydrogen bonds can play an important role in the possible photochromism of this compound.     

Reaction of early transition metal complexes with macrocycles. II. Synthesis and structure of TiCl3(H2O) · 18-crown-6, a compound with a unique bidentate bonding mode for the 18-crown-6 molecule

18-crown-6 reacts with TiCl₃ in CH₂Cl₂ to form a complex in which the crown ether functions as a tridentate ligand. Addition of moist hexane affords a molecular complex in which the crown ether functions as a bidentate ligand. A water molecule is bonded directly to the titanium atom and is further hydrogen bonded to three of the oxygen atoms of the crown. The deep blue crystals of the CH₂Cl₂ adduct belong to the monoclinic space groupP2₁/n witha=13.481(8),b=8.021(5),c=21.425(9) Å, =97.32(5)°, and _calc = 1.51 g cm^–3 forZ=4. Refinement led to a conventionalR value of 0.040 based on 873 observed reflections. The Ti–O bond distances for the crown oxygen atoms are 2.123(8) and 2.154(9) Å, while the oxygen atom of the water molecule is bonded at 2.072(8) Å. The octahedral coordination sphere of the titanium atom is completed by the three chlorine atoms at distances of 2.340(5), 2.352(4), and 2.373(4) Å. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82034 (10 pages).