The crystal structure of 4,4′-dipyridinium tetracyanooxothiocyanatorhenate(V)

Summary The light purple crystals of (4,4-dipyridinium) [ReO(NCS)(CN)₄] crystallize in the monoclinic space group P2₁/m witha=6.615(1),b=16.043(1),c=8.405(1) Å,=93.20(1)°,z=2. The anisotropic refinement of the 1770 observed reflections converged to R=0.041.The [ReO(NCS)(CN)₄]^2– ion has a distorted octahedral geometry. The rhenium atom is displaced by 0.30 Å out of the plane formed by the four carbon atoms towards the terminal oxo ligand. Bond distances: Re=0 =1.67(1), Re–N=2.12(1) and Re–C_av=2.11(1)Å. The thiocyanate ion is nitrogen bonded to the rhenium atom.     

Synthesis and X-ray crystal structure of tetraethylammonium bis[1,2-di(carbomethoxy)ethane-1,2-dithiolato]oxotechnetate(V)

Summary The (NEt₄)⁺[TcO{SCH(CO₂Me)CH(CO₂Me)}₂]^– compound has been prepared from technetium(V) gluconate and characterized by single crystal x-ray structural analysis (R factor=0.065).The compound crystallizes in the monoclinic space groupP2₁/c witha=12.722(3),b=13.820(4) andc=18.213(5) Å, =107.13(4)° andZ=4. In the complex the technetium atom is close to the center of the base of a square pyramid in which the oxo oxygen is at the apex and the four sulfur atoms form the basal plane. The Tc-S distances average 2.316 Å. The Tc=O distance is 1.672(6) Å. Considerations about the osteotropic behaviour of DMSA labelled with⁹⁹Tc are deduced from the reported results.     

Crystal structure of tris(2-pyridylthio-2-pyridinium)pentaisothiocyanato-dioxouranate(VI)

Summary The crystal structure of [DPSH] ₃ ⁺ [UO₂[NCS)₅]^3– (DPSH = 2 pyridylthio-2-pyridinium) has been determined by standard methods using diffractometer data. Crystals are monoclinic, space groupP2₁/a, witha=33.16 (3),b=16.68(2),c=7.85(1) Å, and=97.3(1); D_c=1.65 g · cm^–3 for Z=4. The structure has been refined to R=5.8% by least squares methods. Five thiocyanate groups are equatorially bonded to the linear uranyl group. The mean of the five U-N, N-C, and C-S bond distances are 2.45, 1.17, and 1.59 Å respectively. The protonated DPS molecules have the N,N-inside conformations.     

Molecular structure of the cobalt(ii) chloride complex with triphenyl-N-(2-pyrimidyl)phosphineimine

An X-ray structural study of the cobalt(ii) chloride complex with triphenyl-N-(2-pyrimidyl)phosphineimine has been performed (automatic diffractometer, Mo-–K , 2916 observed reflections, the heavy-atom method, the least squares method in anisotropicisotropic approximation toR=0.043). The crystals are monoclinic,a=15.979(6) Å,b=17.391(6) Å,c=14.976(6) Å, =104.21(2)°,V=4034(5) ų,d _calc=1.384 g cm^–3,Z=4, space groupP2₁/c. The Co atom has a distorted tetrahedral coordination by two Cl atoms (2.268(2) Å and 2.278(3) Å) and two N atoms (2.030(4) Å and 2.025(5) Å) of the two pyrimidine heterocycles. The Cl-Co-Cl and N-Co-N bond angles are equal to 107.7(1)° and 123.4(2)°, respectively. Additional weak coordination of the Co atom by two N atoms of the imine groups [Co...N 2.982(4) Å and 3.045(4) Å] is also observed in the molecule of the complex, and this coordination changes the nearest environment of the Co atom to distorted octahedral coordination. The lengths of the phosphorus-imine P=N bonds are 1.596(6) Å and 1.585(6) Å. The results obtained are compared with previous structural investigations of similar complexes of transition metals with iminophosphoranes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1203–1206, July, 1993.     

Synthesis and crystal structure of copper halide complexes with triethylallylammonium (teaa) chloride: [(teaa)Cu3ICl4], [(teaa)Cu3IBr3.86Cl0.14], and (teaa)2CuIICl4

The results of X-ray diffraction analysis of novel triethylallylammonium chloride compounds with copper(I) chloride, copper(I) bromide, and copper(II) chloride are reported. The [(CH₃CH₂)₃(CH₂=CHCH₂xN]Cu ₃ ^I Cl₄ and [(CH₃CH₂)₃(CH₂=CHCH₂Cu ₃ ^I Br_3.86)Cl_0.14 -complexes are isostructural: space group P2₁/a; a= 17.58(1) Å, b = 12.059(8)Å, c = 7.184(4) Å, = 98.37(5)° and a = 17.972(9) Å, b=12.479(8) Å, c = 7.290(5) Å, = 98.81(5)°, respectively. ²-Coordination of the copper atom by the olefinic bond plays a key role in the structural ordering of the tetraalkylammonium cation. In contrast, the structure of {(CH₃CH₂)₃x(CH₂=CHCH₂)N}₂Cu^IICl₄ (P4₂/nmc; a = 8.839(3) Å, c =15.660(9) Å) follows the ionic salt pattern.Original Russian Text Copyright © 2004 by L. M. Babkov, I. I. Gnatyuk, G. A. Puchkovskaya, and S. V. TrukhachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 398–405, May–June, 2004.     

Palladium Clusters Pd4(SEt)4(OAc)4and Pd6(SEt)12: Structure and Properties

Palladium clusters Pd₄(SEt)₄(OAc)₄(I) and Pd₆(SEt)₁₂(II) were synthesized and studied. Their structure was determined by X-ray diffraction analysis. For I, a= 9.774(2) Å, b= 10.821(2) Å, c= 13.061(3) Å, = 92.88(3)°, V= 1379.6(5) ų, (calcd.) = 2.182 g/cm³, space group P2₁/n, Z= 4, N _ref= 1558, and R= 0.031; for II, a= 10.581(1) Å, b= 10.584(2) Å, c= 11.478(2) Å, = 101.62(1)°, = 104.95(1)°, = 106.74(1)°, V= 1135.2(4) ų, (calcd) = 2.007 g/cm³, space group P1, Z= 1, N _ref= 2828, and R= 0.022. In cluster I, four Pd atoms form a planar cycle. The neighboring palladium atoms are bound by two acetate or by two mercaptide bridges, the Pd···Pd distances being 3.036–3.195 Å. In cluster II, Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.083–3.127 Å. The neighboring palladium atoms are bound by two mercaptide bridges. The formation of analogous clusters in solution was confirmed by IR spectroscopy.     

Urea-water-anion Lattices Part 1. Crystal structures of (C2H5)4N+X−·(NH2)2CO·2 H2O (X=Cl,Br, CN), an isomorphous series of layer-type inclusion complexes

The title ternary complexes (1, X=Cl;2, X=Br;3, X=CN) have been prepared and characterized by X-ray crystallography. Crystal data: space groupP2₁/n,Z=4;1,a=7.505(2),b=14.556(4),c=14.453(3) Å, =98.13(2)^o, andR _F=0.088 for 1831 observed MoK data;2,a=7.483(1),b=14.643(6),c=14.443 Å, =98.25(2)^o, andR _F=0.113 for 923 data;3,a=7.490(2),b=14.646(5),c=14.594(5) Å, =98.85(5)^o, andR _F=0.082 for 915 data. In the isomorphous crystal structure of1 and2, ordered (C₂H₅)₄N⁺ cations are sandwiched between puckered layers matching the (020) family of planes, each being constructed from the cross-linking of planar zigzag chains of hydrogen-bonded urea molecules by the water molecules and halide ions. Compound3 has the same structure except that its cyanide group is disordered. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82066 (30 pages).Operated under contract DE-AC02-76CH00016 with the U.S. Department of Energy, Office of Basic Energy Science.     

Molecular structure and bonding properties of bis(1-methylimidazole)bis(perchlorato)bis(pyridineN-oxide)copper(II)

Summary The crystal and molecular structure of bis(1-methylimidazole)bis(perchlorato)bis(pyridineN-oxide)copper(II) have been determined using three-dimensional x-ray diffraction data. The complex crystallizes in space group P2₁/c with Z=2. The cell dimensions area=9.355(3),b=14.363(4),c=9.698(4) Å, and =106.40(3)^o. Least-squares refinement of the structure has yielded a final R value of 0.049 for 1235 independent reflections. The centrosymmetric structure consists oftrans pairs of 1-methylimidazole and pyridineN-oxide figands forming a square planar geometry with Cu–N and Cu–O bond lengths of 1.963(4) Å and 1.948(4) Å, respectively. The two perchlorate ions are located above and below the square plane with Cu–O distances of 2.590(5) Å. The uv-vis and i.r. spectra and bonding properties of the title compound are discussed with reference to the structure.     

Reactions of 2H-3,4-dihydro-1,4-benzoxazin-6(8aH)-ones with 2,4,6-trimethylbenzonitrile oxide,III

Summary Regio-, stereo- and siteselectivity of the cycloadditions of trimethylbenzonitrile oxide with 2H-3,4-Dihydro-1,4-benzoxazin-6(8aH)-ones have been investigated. The structures of the obtained products were elucidated by means of homonuclear NOE difference spectroscopy and HMQC and HMBC spectra. The structure of 6-Benzyl-9a-methoxy-3-mesityl-9b-methyl-7,8,9a,9b-tetrahydro-3aH-1,2-oxazolo-[4,5-h]1,4-benzoxazin-4(6H)-on5 was elucidated from a single crystal X-ray structure analysis at ambient temperature: C₂₇H₃₀N₂O₄, M=446.55g/mol, monoclinic, P2₁/c,a=10.372 (34) Å,b=11.908 (21) Å,c=20.040 (34) Å, =97.16 (17)°,V=2455.8 (1.9)ų,Z=4,d _c=1.208g/cm³, =0.08mm^–1,R=0.0546.Dedicated to Prof. Ott with best wishes for his 70^th birthday     

Crystal structures and hydrogen bonding schemes in four benzamide derivatives (2-hydroxy-benzamide, 2-hydroxy-thiobenzamide, 2-hydroxy-N,N-dimethyl-benzamide,and 2-Hydroxy-N,N-dimethyl-thiobenzamide)

Summary 2-Hydroxy-benzamide, C₇H₇NO₂; monoclinic; I2/a-C _2h ⁶ ;a=12.901 (2),b=4.982 (1),c=20.987 (3) Å; =91.50 (2)°;Z=8. 2-Hydroxy-thiobenzamide, C₇H₇NOS; monoclinic; P2₁/n-C _2h ⁵ ;a=13.508 (5),b=6.780 (2),c=15.878 (6) Å; =93.74 (5)°;Z=8. 2-Hydroxy-N,N-dimethyl-benzamide, C₉H₁₁NO₂; orthorhombic; Pbca-D _2h ¹⁵ ;a=11.752 (2),b=16.680 (3),c=9.079 (2) Å;Z=8. 2-Hydroxy-N,N-dimethyl-thiobenzamide, C₉H₁₁NOS; monoclinic; P2₁/c-C _2h ⁵ ;a=6.983 (1),b=11.652 (3),c=11.704 (3) Å; =100.02 (2)°;Z=4. The crystal structures of these four compounds were determined (respectively refined: 2-hydroxy-benzamide) by single crystal X-ray data. The refinements of the structure parameters by least squares methods yielded in all casesR<0.056. The hydrogen atoms were located by means of difference Fourier summations. The O-H ... O distances are 2.513 (1) Å in 2-hydroxy-benzamide (intramolecular) and 2.625 (1) Å in 2-hydroxy-N,N-dimethyl-benzamide (intermolecular). The two O-H ... S distances in 2-hydroxy-thiobenzamide are 2.904 (2) Å and 2.918 (2) Å (intramolecular, two molecules in the asymmetric unit) and 3.228 (2) Å in 2-hydroxy-N,N-dimethyl-thiobenzamide (intermolecular). Clear N-H ... O hydrogen bonds with 2.926 (1) Å and 3.006 (1) Å occur only in the structure of 2-hydroxy-benzamide (intermolecular).

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Die Kristallstrukturen und Wasserstoffbrücken-Bindungsschemata in vier Benzamid-Derivaten

Zusammenfassung 2-Hydroxy-benzamid, C₇H₇NO₂; monoklin; I2/a-C _2h ⁶ ;a=12.901 (2),b=4.982 (1),c=20.987 (3) Å; =91.50 (2)°;Z=8. 2-Hydroxy-thiobenzamid, C₇H₇NOS; monoklin; P2₁/n-C _2h ⁵ ;a=13.508 (5),b=6.780 (2),c=15.878 (6) Å; =93.74 (5)°;Z=8. 2-Hydroxy-N,N-dimethyl-benzamid, C₉H₁₁NO₂; orthorhombisch; Pbca-D _2h ¹⁵ ;a=11.752 (2),b=16.680 (3),c=9.079 (2) Å;Z=8. 2-Hydroxy-N,N-dimethyl-thiobenzamid, C₉H₁₁NOS; monoklin; P2₁/c-C _2h ⁵ ;a=6.983 (1),b=11.652 (3),c=11.704 (3) Å; =100.02 (2)°;Z=4. Die Kristallstrukturen dieser vier Verbindungen wurden mittels Röntgen-Einkristalldaten bestimmt (bzw. verfeinert: 2-Hydroxy-benzamid). Die Verfeinerungen der Strukturparameter nach der Methode der kleinsten Quadrate ergab in allen FällenR<0.056. Die Wasserstoffatome konnten anhand von Differenz-Fourier-Summationen belegt werden. Die O-H ... O-Abstände haben folgende Werte: 2.513(1)Å in 2-Hydroxy-benzamid (intramolekular) und 2.625(1) Å in 2-Hydroxy-N,N-dimethyl-benzamid (intermolekular). Die zwei O-H ... S-Abstände sind in 2-Hydroxy-thiobenzamid 2.904(2)Å und 2.918(2)Å (intramolekular, zwei moleküle in der asymmetrischen Einheit) und 3.228(2)Å in 2-Hydroxy-N,N-dimethyl-thiobenzamid(intermollekular). Klar zuzuordnende N-H ... O-Wasserstoffbrücken mit 2.926(1)Å und 3.006(1)Å treten lediglich in der Struktur des 2-Hydroxy-benzamid auf (intermolekular).

     

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.     

Hydrogen peroxide oxidation of di(hydroxo)platinum(II) species in carboxylic acids

A facile procedure for synthesizing the mono(hydroxo)tris(carboxylato)platinum(IV) species has been achieved. The reaction of [Pt^II(OH)₂(dmpda)] (dmpda=2,2-dimethyl-1,3-propanediamine) with a 30% aqueous solution of H₂O₂ in the presence of a carboxylic acid produces a stable [Pt^IV(OOCR)₃(OH)(dmpda)] (R=Me, Et) complex in high yield. The crystal structures of [Pt^IV(OOCMe)₃(OH)(dmpda)] . H₂O (triclinic P1 bar, a=8.761(2) Å, b=9.245(3) Å, c=10.659(2) Å, =106.25(2)°, =93.90(2)°, =98.92(2)°, V=813.1(3) ų, Z=2, R= 0.0474) and [Pt^IV(OOCEt)₃(OH)(dmpda)] (monoclinic P2₁/c, a=12.777(4) Å, b=10.514(2) Å, c=14.971(3) Å, =107.40(2)°, V=1919.2(8) ų, Z=4, R=0.0611) show that the hydroxyl group has been selectively positioned at an axial site. The intramolecular hydrogen bond between the OH and C=O moiety exists (O(H)...=C, 2.83 Å for [Pt^IV(OOCMe)₃(OH)(dmpda)] · H₂O; 2.72 Å for [Pt^IV(OOCEt)₃(OH)(dmpda)]. Formation of the axial-mono(hydroxo)tris(carboxylato)platinum(IV) species may be ascribed to a combination of `reactive-equatorial effects' with `cis-addition' in the carboxylic acid.     

Crystal Structure and Luminescence of the [Eu(Phen)2(NO3)3] Complex. The Role of the Ion-Coactivator

The [Eu(Phen)₂(NO₃)₃] complex was synthesized via reaction of europium nitrate with 1,10-phenanthroline (Phen) and studied by X-ray diffraction analysis. The crystals are monoclinic: a= 11.168(1), b= 17.976(2), c= 13.053(1) Å, = 100.577(2)°, space group C2/c, Z= 4, (calcd) = 1.801 g/cm³. The central europium atom coordinates (on a two-fold axis) six oxygen atoms of three nitrate groups with distances of 2.499(2), 2.502(2), and 2.542(2) Å and four nitrogen atoms of two phenanthroline molecules with distances of 2.542(2) and 2.593(2) Å. The influence of ion-coactivators on the luminescence of Eu³⁺in the [Eu _x M_{1 - x} (Phen)₂(NO₃)₃] complexes (M = Y, La, Nd, and Lu) is discussed.     

The synthesis and structural analysis of Pt2Ru4(CO)18 and the products obtained from its reactions with 1, 2-bis(diphenylphosphino)ethane

From the reaction of Ru(CO)₅ and Pt(COD)₂, COD = 1, 5-cyclooctadiene, the new platinum-ruthenium heteronuclear cluster complex Pt₂Ru₄(CO)₁₈,1, was obtained in 60% yield.1 has a folded ladder-like structure with alternating pairs of ruthenium atoms and platinum atoms. The cluster of1 can be split to yield the known compound PtRu₂(CO)₈(²-dppe),2, (54% yield) by reaction with 1, 2-bis(diphenylphosphino)ethane, dppe, at 25°C. When1 was treated with excess dppe at 40°C, thebis-diphos compound3, PtRu₂(CO)₆(-²-dppe)₂ was obtained (39% yield). Under the similar reaction conditions,2 was converted to3 in 44% yield. All these complexes were characterized by single crystal X-ray diffraction analyses. Compounds2 and3 both contain a triangular cluster of one platinum and two ruthenium atoms, but in2 the bidentate ligand, dppe, chelates the platinum atom and in3 the two dppe ligands bridge the two Pt-Ru metal-metal bonds. Crystal data for1: space group C2/c,a=12.542(2)Å,b=15.350(4)Å,c=15.252(3)Å, =105.32(2)°,Z=4, 2192 reflections,R=0.025. For2: space group P2₁/c,a=14.351(2)Å,b=13.486(3)Å,c=19.218(3)Å, =108.48(1)°,Z=4, 3029 reflections,R=0.027. For3: space group P2₁/c,a=18.836(6)Å,b=15.559(5)Å,c=23.259(7)Å, =111.26(2)°,Z=4, 4204 reflections,R=0.038.     

Kristallstruktur von Sulfamid,SO2(NH2)2

X-ray crystal structure analyses of sulfamide were carried out at 293 K and at 100 K:M=96.10, orthorhombic, Fdd2,Z=8,F(000)=400, Mo K, =0.71069 Å (graphite monochromator). A) 293 K:a=9.127 (1) Å,b=16.857 (5) Å,c=4.579 (1) Å,V=704.50 ų,d _x =1.812 Mgm^–3, =0.648 mm^–1,R=1.77%,R _w =1.94% (384 reflections, 33 parameters). B) 100K:a=9.059 (1) Å,b=16.780 (8) Å,c=4.517 (1) Å,V=686.63 ų,d _x =1.859 Mgm^–3, =0.665 mm^–1,R=1.78%,R _w =1.95% (404 reflections, 33 parameters). The sulfamide molecule shows at 293 K S-O and S-N distances of 1.429 (1) Å and 1.620 (1) Å, respectively, which are in agreement with IR data. Hydrogen positions could be determined from differenceFourier syntheses. Strong weakening of some intense low order reflections by extinction was observed, their anisotropy depends on the crystal and on temperature.

     

The crystal structure of tetraethylammonium aquatetracyanooxorhenate(V)

Summary The crystal structure of the tetraethylammonium salt of [ReO(H₂O)(CN)₄]^– has been determined from threedimensional x-ray diffraction data. The light blue crystals are monoclinic, space group P2₁/m witha=8.760(1),b=9.518(5),c=11.718(1) Å, =102.63(1)^o with two molecules per unit cell. The final R value using 2009 observed reflections and anisotropic thermal parameters for all the non-hydrogen atoms was 0.038. The [ReO(H₂O)(CN)₄]^– ion has a distorted octahedral geometry with the rhenium atom displaced by 0.30 Å out of the plane formed by the four carbon atoms of the cyano ligands towards the oxo ligand. Bond distances: Re=O=1.667(8), Re–OH₂=2.142(7) and Re–C (average)=2.11(1) Å.     

Transition metal complexes with thiosemicarbazide-based ligands,IV: Synthesis and molecular structure of 5-nitrosalicylaldehyde S-methylisothiosemicarbazonato-piperidine-copper(II)

Summary The reaction of warmDMF solutions of Cu(II) perchlorate, 5-nitrosalicylaldehyde S-methylisothiosemicarbazone (H₂ L) and piperidine (Pip) yielded the paramagnetic (_eff=2.19 B.M.) Cu(L)Pip complex, whereL is the dianionic form of H₂ L, formed as a result of deprotonation of the phenolic hydroxyl and NH₂ group. Crystal data of the complex are: monoclinic P2₁,a=11.902(4),b=6.765(3),c=11.343(4)Å; =112.92°,V=841.20(8)ų,M=400.9,Z=2,d ₀=1.60 gcm^–3,d _c =1.58 gcm^–3,F(000)=424. The structure was refined to a residualR=0.047. The copper(II) ion is coordinated in a square-planar arrangement by the piperidine nitrogen and the NNO set of donor atoms ofL.

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Komplexe der Übergangsmetalle mit Thiosemicarbazid-Liganden, IV. Synthese und molekulare Struktur von 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazonato-piperidin-kupfer(II)

Zusammenfassung Durch die Reaktion in warmenDMF-Lösungen von Cu(II) Perchlorat, 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazon (H₂ L) und Piperidin (Pip) wurde ein paramagnetischer Komplex (_eff=2.19 B.M.) Cu(L)Pip erhalten, wobeiL nach doppelter Deprotonierung (NH₂- und Phenolhydroxyl-Gruppe) als dianionische Form von H₂ L vorliegt. Die kristallographischen Daten des Komplexes sind: monokline Raumgruppe P2₁,a=11.902(4),b=6.765(3),c=11.343(4)Å, =112.92°;V=841.20ų,M=400.9,Z=2,d ₀=1.60 gcm^–3,d _c =1.58 gcm^–3,F(000)=424. Die struktur wurde bis zu einemR-Wert von 0.047 verfeinert. Die Koordination des Kupfers wird quadratisch-planar über den Piperidin-Stickstoff und die NNO-Donorhülle der Chelatliganden gebildet.

     

Synthesis,structure, and characterization of Cu4S10(4-methylpyridine)4

The title compound, Cu₄S₁₀(4-methylpyridine)₄ · 4-methylpyridine was prepared by three different reactions: the oxidation of copper power by sulfur and the reaction of copper (I) sulfide (or CuBr-SMe₂) with cues sulfur, both in the coordinating solvent, 4-methylpyridine. Red crystals of the compound obtained by layering with hexans were subjected to single crystal X-ray diffraction. The structure was refined toR=0.026 and R _w =0.036 in a space groupP1bar (No. 2), withZ=2,a=13.983 (2) A,b=15.384( 2) Å,c=9.660 (1) Å, = 93.87 (1)°,=93.38 ==(1)°,V=2037.9 (9) ų. The commpound has approximate S₄ symmetry and consists of two pentasuffide chains linking four Cu(I) ions, each with a coordinating 2-methylpyridine. The infrared spectrum was dominated by absorption due to coodinated 4-methylpyridine with several low-energy peaks attributable to S-S stretches, which were also observed by Raman spectroscopy. A featureless electronic absorption spectrum yielded a single peak in the mar ultraviolet upon computer enhancement (=334 nm, = 10,000), most likely an intraligand transition. Cyclic voltammetry indicates that the polysulfide complex undergoes irreversible oxidation and reduction at +0.04 and –0.34 V vs. SCR respectively, at NS K in 4-methylpyridine when swept at 20 mV/sec. The electrochemical behavior was unvaried even at sweep rates as high as 100 V/sec.     

The crystal structure of tetraphenylphosphonium tetracyanohydroxooxorhenium(V)

Summary The crystal structure of (PPh₄)₂[ReO(OH)(CN)₄]·5H₂O has been determined from three-dimensional x-ray diffraction data. The light brown crystals are monoclinic, space group P2₁/n, with cell dimensionsa=16.753(2),b=19.928(2),c=15.338(2) Å and =101,894(1)°,z=4, D_m=1.45(1) g cm^–3. The anisotropic refinement of the 6088 observed reflections converged to R=0.077.The [ReO(OH)(CN)₄]^2– ion has a distorted octahedral geometry. Bond distances: Re =1.70(1), Re–OH=1.90(1) and ReC_av=2.12(2) Å. The Re atom is displaced by 0.08 Å out of the plane formed by the four carbon atoms towards the terminal oxo ligand.     

The crystal and molecular structure of a dinuclear copper(II) complex of a Robson-type macrocycle, [Cu2(C26H30N4O2)(H2O)2](BF4)2

Summary The crystal structure of the dinuclear complex [Cu₂(C₂₆H₃₀-N₄O₂)(H₂O)₂](BF₄)₂ was determined by x-ray crystallography. The crystals are triclinic, P¯1, witha = 10.945(5),b = 8.703(5),c = 8.495(5) Å, = 103.86(3)°, = 105.73(3)°, = 85.77(3)°, V = 756 ų D_c = 1.65 g cm^–3 for Z = 1. The copper(II) atoms are 5-coordinate and square-pyramidal. Selected bond distances are: Cu-N, 1.91 Å (mean); Cu-O(base) = 1.90(1) and 1.91(1) Å; Cu-O(apical) = 2.47(1) Å; There are O(water)-H ... F interionic hydrogen bonds in the structure. The Cu .. Cu distance is 2.847 Å.