Vanadium(IV) dimer complexes containing [V(o-C6H4OS)3]2− fragment and caged sodium ions

Tris[o-mercaptophenolato]vanadium(IV) dimer complexes (A)₂[V(mp)₃NaLL']₂ (A = Ph₄P₊, H₂mp = o-mercaptophenol, L = MeCN, L'=EtOH, (1); L' = MeOH, (2)) were prepared by the reaction of anhydrous VC1₃, and Na₂mp in the molar ratio 1:3. Complex (3) (A = Et₄N⁺, L=L' = MeOH) was prepared by the reaction of VC1₃, Na₂mp and Li₂S in the molar ratio 1:2:1. The complexes were characterized by X-ray diffraction crystallography, infrared spectra, magnetic susceptibility, and cyclic voltammetric measurements. Complex 2 crystallizes in the triclinic space group P1 with a=12.813(6), b = 14.199(4), c = 12.790(5) Å, α = 112.72(2), β = 104.24(4). γ = 88.68(4)°, V = 2073.6 ų, and Z=1. The structure was refined to R=0.058. Complex 3 crystallizes in the mono-clinic space group P2₁/n with a=12.359(3), b=17.452(6), c=14.829(13) Å, βequals;96.51(5)°, V=3177.8 ų, and Z=2. The final R factor is 0.067. Both of the anions of 2 and 3 contain two [V(mp)₃]^2? fragments linked by sodium ions through the μ₃-O bridges with a crystallographic center of symmetry. The V(IV) atom is in a coordination environment intermediate between a trigonal prism and an ideal octahedron.     

Studies on werner clathrates. Part 131. Selective criteria in werner clathrates. Six crystal structures with bis(isothiocyanato)tetra(4-vinylpyridine)nickel(II) as host

This paper addresses the general question: what are the significant guest properties selected by this host when interacting with guest molecules in the liquid phase, resulting in cocrystallization of the host and guest? In particular, to what extent do π electrons in a guest molecule effect its potential as a guest? Werner clathrates of the host [Ni(NCS)₂(4-ViPy)₄] with mixtures of tetrahydrofuran (THF) and cyclic hydrocarbons as guests have been synthesised and their structures elucidated. Clathrate (1): [Ni(NCS)₂(4-ViPy)₄](1.78 THF)(0.22 cyclohexane), crystallizes in the orthorhombic space groupP _bcn a=9.976(6),b=20.630(25),c=19.861 (4) Å,V=4087ų,Z=4,R=0.087 for 1461 reflections; (2): [Ni(NCS)₂(4-ViPy)₄](1.76 THF)(0.24 cyclohexene),P _bcn ,a=9.987(7),b=20.614(4),c=19.898(4)Å,V=4096ų,Z=4,R=0.084 for 1304 reflections; (3): [Ni(NCS)₂(4-ViPy)₄](0.48 THF)(0.52 1,3-cyclohexadiene), tetragonalI4₁/a,a=16.898(3),b=16.898(3),c=26.463(6)Å,V=7556ų,Z=8,R=0.120 for 1698 reflections; (4): [Ni(NCS)₂(4-ViPy)₄](0.36 THF)(1.04 1,4-cyclohexadiene),I4₁/a,a=16.986(4),b=16.986(4),c=25.896(15)Å,V=7472ų,Z=8,R=0.103 for 2025 reflections; (5): [Ni(NCS)₂(4-ViPy)₄](0.35 THF)(1.05 benzene),I4₁/a,a=17.102(10),b=17.102(10),c=25.498(8)Å,V=7458ų,Z=8,R=0.118 for 2200 reflections; (6): [Ni(NCS)₂(4-ViPy)₄](3 benzene), triclinicP1,a=10.432(24),b=11.155(9),c=21.581(7)Å, α=78.70(5), β=82.60(7), γ=74.09(13)°,V=2361ų,Z=2,R=0.078 for 3427 reflections. Host-guest ratios and, for mixtures of guests, guest1/guest2 ratios, were elucidated by density and NMR. We show that the conformational freedom of the substituted pyridines is not the primary reason for the clathrating ability of Werner hosts. All six structures show no host-guest interaction at the level of van der Waals interactions. As non-bonding interactions are not observed between the host and guest, this study shows that the above host's selectivity by enclathration of particular guest molecules cannot be accounted for by solid state structural analysis.     

The Syntheses and crystal structures of trans-dichlorobis (10-thiabenzo-15-crown-5)-palladium(Ⅱ)and trans-dichlorobis-(10-selenabenzo-15-crown-5)palladium(Ⅱ)

The preparation and X-ray crystal structures of the adducts of 10-thiabenzo-15-crown-5 and 10-selenabenzo-15-crown-5 with PdCl2 are reported. [PdCl2(C14H20O4S)2] (1): or-thorhombic, space group Pbca with cell dimensions of a=17.285(5), 6=8.354(3), c=21.689(4) A, K=3131.9 A3, Z=4;R=0.0330 for 2301 reflections with I > 3o(I), [PdCl2(C14H2oO4Se)2] (2): monoclinic, space group P21/n with cell dimensions of a=18.928(4), b=8.912(3), c=9.813(2) A, β=96.90(2)0, V=1643.4 A3, Z=2; R=0.0289 for 2617 reflections with I> 3σ(I), Both complexes are monomeric, square-planar palladiurn(Ⅱ) compounds with the Pd(Ⅱ) ion situating on a crystal-lographic inversion centre, and the crown ligands all adopt the axial coordination with the Pd-S bond of 2.3233(7) A and the Pd-Se bond of 2.4357(3) A. Their complexing characteristics are discussed in brief.     

两个双核铁（Ⅲ）和三足配体的配合物的合成和晶体结构

运用三足四齿配体三（2－甲基吡啶）胺（TPA）或三（2－甲基苯丙咪唑）胺（TBA）,得到两个双核铁(III)配合物，[Fe₂L₂(μ₂-O)(μ₂-p-NH₂-C₆H₄COO)]³⁺ (L = TPA, 1 和 L = TBA, 2)。两个配合物均为单斜晶系，空间群为P2(1)/c.晶胞参数 1: a = 1.4529(4), b = 1.6622(5), c = 2.0625(6) nm, β= 100.327(5)º, V = 4.900(3) nm³, z = 4, F(000) = 2344, 分子量M_r = 1142.91, Dc = 1.549 g/cm³, R₁ = 0.0544, R₂ = 0.0962. 2: a = 1.3378(4), b = 2.1174(7), c = 2.4351(7) nm, β= 97.315(6)º, V = 6.842(4) nm³, z = 4, F (000) = 3116, 分子量M_r = 1505.08, Dc = 1.444 g/cm³, R₁ = 0.0793, R₂ = 0.1623. 在两个双核铁(III)配合物中，中心的三价铁和配体TPA或TBA上的四个氮原子和两个氧原子通过不同的桥形成一个畸变的八面体构型。     

Complexation with diol host compounds. Part 14. Inclusion compounds of 2,2′-bis(9-hydroxy-9-fluorenyl)biphenyl with acetonitrile,cyclohexanone, di-n-propylamine and dimethylformamide

Abstract

The structures of the inclusion compounds of 2,2′-bis(9-hydroxy-9-fluorenyl)biphenyl (H) with acetonitrile (1) (1:1), cyclohexanone (2) (1:2), di-n-propylamine (3) (1:1) and dimethylformamide (4) (1:2) are reported. Crystal data: (1) monoclinic, P2₁/c with a=10.500(3), b=15.598(3), c=18.344(3) Å, β=96.66(2)°, Z=4, D _C=1.24 g cm^?3. (2) monoclinic, P2₁/c with a=13.980(3), b=11.768(5), c=23.49(1) Å, β=98.77(3)°, Z=4, D_c =1.24 g cm^?3. (3) monoclinic, C2/c with a=29.57(1), b=13.485(4), c=18.17(1) Å, β=107.94(4)°, Z=8, D _C=1.16 g cm^?3. (4) monoclinic, C2/c with a=30.123(9), b=13.391(6), c=19.177(6) Å, β=111.23(4)°, Z=8, D _C=1.22 g cm^?3. Final R values for the four structures were 0.065, 0.120, 0.084 and 0.107 for 2937, 2830, 2071 and 3769 reflections, respectively. The host conformation is quite rigid and does not appear to be influenced by the shape and size of the guests studied. The host is held in a spiral conformation by means of an intramolecular hydrogen bond. In addition, host-guest hydrogen bonds are observed in all structures. Thermal analysis was used to evaluate the strength of binding of the guest molecules and confirmed that (1) is the most stable of the four compounds studied.     

Carbon-nitrogen bond formation in the reaction of the reaction of diphenyl diazomethane Ph2 CN2 with diiron-carbene complexes (Fe2(CO)7x03BD;-C(R)C(NEt2)x03BD;-C(R)C(NEtx03BC;-C(R)C(NEt2)N(NCPh2)x03BC;-C(R)C(NEtx03BC;-C(R)C(NEt2)NN(CPh2)x03BC;-C(R)C(NEt)]

The diiron ynamine complex [Fe₂(CO)₇{μ-CR)C(NEt₂)}] (1:R=Me,2:R = C₃H₅.3:R=SiMe₃.4:R = Ph) reacts at room temperature with diphenyldiazomethane Ph₂CN₂, in hexane to yield complexes [Fe₂(CO)₆{C(R)C(NEt₂)N (NCPh₂)] (5a:R=Me,6a:R=C₃H₅.7a R=SiMe₃.8a:R=Ph) resulting from the insertion of the terminal nitrogen atom into the Fe=C carbene bond. Insertion the second nitrogen atom and formation of compounds [Fe₂(CO)₆zμ-C(R)C(NEt₂)NN(CPh₂)}] (5b:R=Me,6b:R=C₃H₅,7b:R=SiMe₃,8b:R=Ph) is observed when compounds5a-5a are treated in refluxing hexane. Transformation of compoundsa tob is also obtained at room temperature within a few days. All compounds were identified by their¹H NMR spectra. Compounds6a, 7a, 8a, and8b were characterized by single crystal X-ray diffraction analyses. Crystal data: for6a: space group = P2₁/n,a=12.853(1) A,b=24.800(7) A,c=8.947(6) A,β=99.29(3)°,Z=4, 2227 rellectionsR=0,038; for7a: space group=Pl,a=ll.483(4) A,b=14.975(4) A,c = 17.890(8) A,α = 82.80(3)°,β=94.29(7)°,γ=85.42(2),Z = 4, 5888 reflectionR = 0.035: for8a: space group = Pcab.a = 31.023(8) A.b=20.137(1) A.c=9.686(2) A.Z=8. 1651 reflections,R=0.071; for8b: space group=P2₁/n,a=21.459(4),b=10,100(3) A,c=28,439(8) A,ß=103.86(4)°,Z=8. 2431 reflections.R=0.057.     

K3Na5(H2NCH2CH2NH3)2{(VO)12O6[B3O6(OH)]6}(H2O)•12H2O的合成与晶体结构

利用水热合成技术成功制备出一种新型多钒硼氧化合物， 用X射线单晶衍射分析技术对其晶体结构和分子结构进行了确定。结果表明在该化合物中多钒硼氧阴离子具有一个新颖的三明治结构。上下两个结构单元都是由六个VO₅四角锥交替地通过顺式和反式共边的方式连接起来构成的一个钒氧三角形结构。中间的结构单元是由BO₃平面三角形和BO₄四面体以共角的方式相互连接形成的一个折叠型的B₁₈O₃₆(OH)₆环。三明治结构中层与层之间通过桥氧相连。一个水分子处于它的核心位置上，与每个VO₅四角锥中的钒原子都保持几乎相等的距离。该化合物及其晶体中存在着丰富的化学结构和成键信息，同时也有作为氧化还原反应催化剂的潜能。     

Studies on solid state reactions of coordination compounds. XLVII. Solid state syntheses and crystal structures of cluster compounds {Cu3MoS3I} (PPh3)3S and {Cu3WS3Br} (PPh3)3S

Reactions of [NH⁴]₂[MS₄](M = Mo,W), CuX(X = Br, I) and PPh₃ in the solid state produced four mixed-metal sulfur containing clusters {Cu₃MS₃X}(PPh₃)₃S(M = Mo, W; X = Br, I), two of which (1: M = Mo, X = I; 2: M = W, X = Br) were structurally determined. Crystals of 1 and 2 are triclinic, space group P1 (1: a = 11.895(3), b = 13.107(1), c = 20.473(2)Å, α = 74.95(6), β = 84.87(8), γ = 64.27(7)°, Z=2, V=2776.1 ų, R_w = 0.064 for 6443 observed reflections. 2: a = 11.876 (1), b = 13.065 (2), c = 20.325(2)Å, α = 74.95(1), β= 85.39(1), γ = 64.09(1)°, Z = 2, V = 2737.3ų, R_w = 0.055 for ·5303 observed reflections). The results of the structure determination showed that the central units of the two cubane-like cluster compounds are composed of four metal atoms and four non-metal atoms situated at alternate corners. The differences of cubane-like cluster compounds obtained from solid state reactions and from solution reactions are discussed.     

The reactivities of Mo cluster — A selective substitution reaction of the bridging (dtp) ligand and the crystal structure of {Mo3S4(μ-O2CR)(dtp)3(Py)}

The reaction of trinuclear molybdenum cluster {Mo₃S₄(μ-dtp) (dtp)₃ (H₂O)} 1 [dtp= S₂P(OEt)₂] with RCO₂Na (R?H, CH₃) in the presence of Py gave the black compounds {Mo₃S₄ {μ-O₂ CR) (dtp)₃ (Py)} (2, R?H, 3, R?CH₃). Both compounds are characterized by X-ray crystallography. It is shown that crystals 2 and 3 belong to space group P&1bar; with Z=2 and a=10.519(2), b= 12.121(2), c=15.757(2)Å, α=93.27(1), β=94.63(1), γ = 105.22(1)°, V= 1925 ų for crystal 2, whereas a=9.556 (2), b=14.067(7), c=15.914 (9) Å, α=101.41 (4), β=101.44(4), γ-74.26(3)°, V=1994ų for crystal 3. The final R factors are 0.041 and 0.048 for crystal 2 and 3 respectively. The structure analysis indicates that (O₂CR)^? ligand selectively substitutes the bridging (dtp) ligand. This type of Mo, cluster molecule where structure contains two species of bidentate ligand is for the first time to be obtained by us.     

The crystal structures of α,ω-diaminoalkanecadmium(II) tetracyanonickelate(II)-aromatic molecule inclusion compounds. IV. (1,6-Diaminohexane)cadmium(II) tetracyanonickelate(II)-m-toluidine(1/1),-p-toluidine(1/1), and-2,4-xylidine(1/1) clathrates,and the coordination complex bis(p-toluidine) (1,6-diaminohexane)cadmium(II) tetracyanonickelate(II)

The crystal structures of the four title compounds have been analyzed by single crystal X-ray diffraction methods at room temperature. Three with a general formula Cd[NH₂(CH₂)₆NH₂]Ni(CN)₄·G (G=m-toluidine,Im;p-toluidine,Ip; and 2,4-xylidine,Ix) are the inclusion compounds of the respective aromatic molecules in the three-dimensional metal complex host (1,6-diaminohexane)cadmium(II) tetracyanonickelate(II). The remaining one is a coordination complex ofp-toluidine, bis(p-toluidine) (1,6-diaminohexane)cadmium(II) tetracyanonick-elate(II),II, Im, Ix, andII crystallize under similar experimental conditions;Ip is obtained using thep-toluidinemesitylene mixture at higher dilution than that used forII. Im crystallizes in the tri linic space group \(P\bar 1\) , witha=9.725(2),b=7.598(1),c=7.177(1) Å, α=90.44(1), β=98.80(1), γ=95.70(1)^o, andZ=1 (the final conventionalR=0.037 for 3526 reflections);Ip: monoclinic,P2/m,a=9.540(2),b=7.611(1),c=7.120(1) Å, β=100.95(1)^o, andZ=1 (R=0.027 for 1700 reflections);Ix: monoclinic,P2/m,a=9.628(2),b=7.613(1),c=7.122(1) Å, β=100.01(1)^o, andZ=1 (R=0.049 for 2704 reflections);II: monoclinic,P2₁/n,a=12.107(3),b=10.117(2),c=12.471(3) Å, β=113.67(2)^o, andZ=2 (R=0.037 for 2616 reflections). The structures ofIm, Ip andIx are similar to that of theo-toluidine inclusion compound of the same metal complex host. InII atrans pair of thep-toluidine molecules to the cadmium atom in the two-dimensional network formed by thecatena-μ-linkages of ?Cd?NH₂(CH₂)₆NH₂?Cd? and ?NC?Ni?CN?Cd?NC?Ni?CN?intersecting at each Cd atom; two cyanide groups of the tetracyanonickelate(II) moiety have free N-ends.     

Solid state synthesis and structure of two novel polyoxometalates [(n-Bu)4N]4[M6O19][Ag2I4](M?Mo,W)†

The reaction of [NH₄]₂[MO₂S₂], AgI and (n-Bu)₄NBr in solid state produced the polyoxometalates [(n-Bu)₄N]₄[M₆O₁₉][Ag₂I₄] (1, M? Mo; 2, M? W) which were structurally determined. The crystals of 1 and 2 are isomorphous, monoclinic, space group P2₁/c. 1, a = l.6624(2), b=1.6699(3), c=l.7217(2) nm, β=98.29(1)°, V=4.729(1) nm³, Z=2, R=0.040, R_w“0.037; 2, a = 1.6636(3), b = 1.6733(3), c = 1.7190(3) nm, β=98.25(1)°, V=4.736(l) nm³, Z = 2, R = 0.038, R_w = 0.047. The results of the structure determination showed that the two compounds had the same structures whose skeletons are composed of [Ag₂I₄]². and [M₆O₁₉]^2-. The difference of them and heteropolymetalate compounds synthesized in solution is that the title compounds contain cluster. ion, heteropolymetalate and organic cations, while the latter is only composed of heteropolymetalate and organic cations.     

X-RAY STRUCTURES OF BIS[(2-AMINOPHENYL)DIPHENYLPHOSPHINE]BIS-(ETHANOL)SILVER(I) NITRATE AND TRIS[(2-AMINOPHENYL)DIPHENYLPHOSPHINE] SILVER(I) NITRATE MONOHYDRATE

Abstract

The crystal structures of two Ag(I) salts, [Ag(LH)₂(EtOH)₂](NO₃) (1) and [Ag(LH)₃](NO₃).H₂O (2) where LH is (2-aminophenyl)diphenylphosphine, have been determined at room temperature. In 1 the Ag atom is coordinated by two P atoms derived from the phosphine ligands (Ag-P(1) 2.433(3) and Ag-P(2) 2.439(3) Å and P(1)-Ag-P(2) 160.1(1)°) and two O atoms derived from two weakly coordinating ethanol molecules (Ag-O(1a) 2.49(1) and Ag-O(2a) 2.75(1) Å). In 2 the three phosphine ligands coordinate via the P atoms (Ag-P 2.455(2), 2.462(2) and 2.484(2) Å) which define a trigonal planar geometry about the Ag atom. In neither case was any evidence found for a bonding interaction between the amino-N atom and the Ag atom. Crystals of 1 are monoclinic, space group P2₁/n with unit cell dimensions: a=10.272(4), b=16.358(2), c=23.709(3) Å, β=101.01(2)° and Z=4 and crystals of 2 are triclinic, space group P 1 with a=11.857(2), b=21.285(2), c=11.190(4) Å, α=91.77(1), β=104.50(2), γ=97.93(1)° and Z=2. The structures were each refined by a full-matrix least-squares procedure to final R=0.058 using 2433 reflections for 1 and to R=0.069 using 4428 reflections for 2.     

2,4-二硝基苯丙氨酸钠盐·2,4-二硝基苯丙氨酸的合成、分子结构和二次谐波效应

合成了一种新的有非线性光学性能的标题化合物晶体NaAP·HAP,晶体属正交晶系,空间群为P2₁2₁2₁,a=25.773(6),b=12.377(3),c=7.2037(6)Å,z=4,D_c=1.54g·cm^-3。晶体结构由HAP分子(2,4-二硝基苯丙氨酸)、AP^-离子和Na⁺离子组成。Na⁺离子由周围的六个氧原子形成扭曲的八面体配位。这些NaO₆八面体通过共点形成无限链状结构。可用晶体结构的空间因素来解释实验测定的MAP和NaAP·HAP的二次谐波相对强度的顺序。     

Synthesis and Crystal Structures of Two Zinc(II) Complexes with the Tripodal Ligand Tris(2-Benzimidazolymethyl)Amine

This article reports the synthesis and crystal structures of two new mononuclear Zinc(II) complexes, [Zn₂(NTB)₂(N₃)₂](NO₃)₂·2CH₃OH (1) and [Zn₂(NTB)₂(SCN)₂](NO₃)₂·2CH₃OH·H₂O (2). Complex 1 crystallizes in the triclinic system, space group P&1macr;, a=13.743(4), b=14.374(4), c=14.443(5) Å; α=77.053(5), β=81.824(5), γ=88.959(6)°; Z=2; R1=0.0418, wR2=0.0889. Complex 2 also crystallizes in the triclinic system, space group P&1macr;, a=12.203(10), b=14.430(12), c=18.541(15)Å; α=72.712(15), β=85.039(15), γ=73.610(14); Z=2; R1=0.0771, wR2=0.1288. In both cases the central zinc(II) metal ions are coordinated to the four nitrogen atoms of NTB and a nitrogen atom of N^- ₃(1) or SCN^-(2) to form distorted trigonal bipyramidal coordination spheres.     

Crystal and Molecular Structure of Carbonyl (1,1,4,4-Tetrafluoro-2-tert-Butyl-1,4-Disilabut-2-Ene) (η5-Cyclopentadienyl) Cobalt (II)

(C₃H₅)Co(CO)(Si₂F₄C₄H₁₀) was synthesized by the photochemical reaction between dicarbonyl (η⁵-cyclopentadienyl) cobalt and 1,1,2,2-tetrafluoro-1,2,-disilacyclobutene. Its structure was identified by IR, NMR and mass spectrometry. The single crystal structure was studied for confirmation. The compound crystalized in a monoclinic space group P2₁/n with unit cell a=7.120 (6), b=20.334. (3), c=10.682(1) Å, β=90.97(8)°, Z=4 final R=0.050 for 3667 observed reflections. The molecule has a mirror plane symmetry about the Co atom coordination sphere. The reaction between the cobalt carbonyl and the 1,2-disilacyclobutene produces only silicon-cobalt σ bonds.     

Nickel(II) 1,10-Phenanthroline complexes: cis-[Aqua(Bromo) bis (1,10-Phenanthroline)Nickel(II)] Bromide Trihydrate and ( tris (1,10-Phenanthroline)Nickel(II)] Bromide Octahydrate

[Ni(phen)₂(H₂O)Br]Br·3H₂O where phen is 1,10-phenanthroline, is a light-blue material which crystallizes in the monoclinic space group P2₁/c with Z = 4, a = 10.4300(4), b = 25.310(2), c = 9.7790(9)?Å and β = 102.932(6)°. The structure was determined at ambient temperature from 5161 reflections with R = 0.0643 and R _w = 0.1306. The structure consists of a complex cation, a bromide anion and three waters of hydration. The Ni atom is pseudo-octahedral with a cis arrangement of Br and H₂O. This cis geometry persists in solution, as evidenced by ¹H NMR spectroscopy, although the Br may be replaced by another H₂O. [Ni(phen)₃]Br₂·8H₂O is a light-red material which crystallizes in the monoclinic space group C2/m with Z = 8, a = 23.6320(11), b = 21.4880(13), c = 15.5470(9)?Å and β = 107.927(3)°. The structure was determined at 120?K from 6820 reflections with R = 0.0733 and R _w = 0.1022. The structure consists of a complex cation, two bromide anions and eight waters of hydration. The anions and waters are extensively disordered. The Ni atom is pseudo-octahedral.     

Structural studies on rare earth carboxylates: I. Studies on the crystal structure of tris(neopentanoato)-tris(neopentanoic acid)neodymium(III) dimer, [NdA3(HA)3]2

The title complex was synthesized and its structure was determined. The crystal is monoclinic with space group P2₁/n. Unit cell parameters are as follows: a=16.474(8), b=12.425(4), c=20.844(12)Å, β=109.27(4)°, Z=4. In each dimer, the two Nd atoms are connected through two pairs of bridging neopentanoate anions. The two carboxyl groups in each pair are in opposite position to Nd atom which are coplanar with them and the two planes are perpendicular with each other. In the complex each Nd atom is further coordinated with three neopentanoic acid molecules and one monodentate neopentanoate anion. The central atom is octa-coordinated in a square-antiprism arrangement.     

The synthesis and crystal structure of α-perthionaphthoatopyridinecopper(I) dimer Cu2(α-C10H7CSS2)2(Py)2

The title compound has been synthesized by the reaction of α-dithionaphthoic acid with CuCl₂ in pyridine or by recrystallizing Cu₄(α-C₁₀H₇CSS₂)₄ ? 1/2CS₂ in a mixture of pyridine and alcohol. The structure of the title compound is determined by a single-crystal X-ray diffraction analysis. The crystal belongs to triclinic space group with unit cell parameters: a=7.085(2)Å, b= 8.672(3)Å and c=13.598(5)Å; a=92.40(3)°, β=102.59(4)° and γ=105.67(4)°; V=780.6Ų; Z=1. The structure was refined to R=0.058 for 2390 reflections. The molecule of the title compound sits on a center of symmetry. The shorter Cu—Cu bond length (2.606Å) shows considerable interaction between copper atoms. If the Cu—Cu interaction is ignored, the neighbouring S and N atoms are coordinated to copper atom in a configuration of distorted tetrahedron.     

Synthesis and characterization of nickel and copper complexes with 2,2-diphenyl- N -(alkyl(aryl)carbamothioyl)acetamide: The crystal structures of HL1 and cis -[Ni(L1)2]

2,2-diphenyl-N-(R-carbamothioyl)acetamide (R = diethyl, dipropyl, dibutyl, dihexyl, diphenyl and morpholine-4) and their Ni²⁺ and Cu²⁺ complexes have been synthesized and characterized by elemental analyses, IR spectroscopy and ¹H-NMR spectroscopy. The spectroscopic data are consistent with the ligand and the metal complexes containing two O, S chelated ligands. 2,2-diphenyl-N-(diethylcarbamothioyl)acetamide, HL¹, and bis(2,2-diphenyl-N-(diethylcarbamothioyl)acetamido)nickel(II), Ni(L¹)₂, were characterized by a single crystal X-ray diffraction study. HL¹ complex, C₁₉H₂₂N₂OS, crystallizes monoclinic, space group P2₁/c, with Z = 4, and unit cell parameters a = 14.964(2), b = 13.026(2), c = 9.0123(15) Å, β = 96.314(4)°. Ni(L¹)₂ complex, C₃₈H₄₂N₄O₂S₂Ni, crystallizes in monoclinic space group P2₁/c, with Z = 4, and unit cell parameters a = 15.434(6), b = 13.464(5), c = 17.679(7) Å, β = 108.477(11)°. The ligands coordinate bidentate to metal yielding neutral complexes of the type cis-[ML₂].     

A New Bis-amidinium Calix[4]arene-difluorophosphinate Network: An Unexpected but not Unwelcome Guest

Abstract

A complex hydrogen bonded network is formed between a mono-deprotonated bis-amidinium calix[4]arene 1 and difluorophosphinate in the presence of methanol. The compound crystallises in the triclinic space group P1 with a=12.0665(5), b=12.5737(6), c=20.0201(15) å, α=86.4098(18), β=79.747(2), γ=66.816(4)°, and D _c=1.159 Mgm^?3 for Z=4.7824 independent reflections were collected and the final R1 [F ² > 2α(F ²)] was 0.1243.