Synthesis, characterization, and coordination chemistry of several novel electroneutral phosphane ligands

The reaction of fluorocarbon (R_f) reagents C₂F₅Li or C₂F₃Li with diaminochlorophosphanes (R₂N)₂PCl produced four new phosphane ligands of the type (R₂N)₂P(R_f). Addition of (Et₂N)₂PCl to ethereal solutions of C₂F₅Li or C₂F₃Li produced (Et₂N)₂PC₂F₅1 and (Et₂N)₂PC₂F₃2; treatment of (C₄H₄N)₂PCl and (C₄H₈N)₂PCl with C₂F₅Li afforded (C₄H₄N)₂PC₂F₅3 and (C₄H₈N)₂PC₂F₅4. All ligands were isolated as colorless, high-boiling liquids. Substitution reactions of 1-4 with Mo(CO)₆ in a refluxing alkane solvent yielded complexes of the type (L)Mo(CO)₅ (L = (Et₂N)₂PC₂F₅, 5; (Et₂N)₂PC₂F₃6; (C₄H₄N)₂PC₂F₅7 and (C₄H₈N)₂PC₂F₅8) as colorless solids in low to moderate (25-62%) yields. Complexes 5, 7 and 8 were structurally characterized by single crystal X-ray diffraction. A comparison of IR stretching frequencies and X-ray bond length data suggests these ligands approximate the electronic influence of phosphites.     

First isolation and characterization of 1,2-oxaphosphetanes with three phenyl groups at the phosphorus atom in typical Wittig reaction using cyclopropylidenetriphenylphosphorane

1,2-Oxaphosphetanes bearing three phenyl groups directly bound to the phosphorus atom were successfully isolated for the first time as stable crystals in the typical Wittig reaction of cyclopropylidenetriphenylphosphorane with activated carbonyl compounds. X-ray analysis of the oxaphosphetane showed that the phosphorus atom is at the center of a slightly distorted trigonal bipyramidal structure. Thermal decomposition of these oxaphosphetanes was carried out to give the starting carbonyl compounds and Wittig reaction products, olefins.     

X-ray structures of the tris(2,4-xylyl)phosphane and its trisulfonated derivative: Molecular architecture of a water-soluble sulfonated phosphane with propeller chirality

The structure of tris(2,4-xylyl)phosphane (1) is reported and supramolecular assembly of gua⁺ salt of tris(2,4-dimethyl-5-sulfonatophenyl)phosphane co-crystal with guanidine chloride (2) is analyzed in detail. Weaving hydrogen bond ribbons with polar and apolar stabilizing pillars as well as stacking interaction of phenyl rings resulting sixfold phenyl embraces interpenetrating with the polar networks were found. Both compounds are racemate, show propeller chirality and 2 crystallizes in non-centrosymmetric space group (C₃ symmetry) with the ortho-methyl groups outside of the molecular cone. According to the DFT calculations on the anion of 2, the high barrier of concerted ring rotation opens the possibility of resolving the enantiomers through hydrogen bonds to chiral donors.     

Crystallographic characterization of naturally occurring aragonite and calcite phase: Rietveld refinement

This research has comprehended the crystallographic characterization of two naturally occurring calcium carbonates phases e.g. aragonite and calcite in Pila globosa (P. globosa) and eggshells respectively. The tools employed to confirm the phases of aragonite and calcite were X-ray diffractoion (XRD) and Fourier Transform Infrared (FT-IR) spectroscopy. Several important crystallographic parameters like crystallite size, lattice parameters, dislocation density, crystallinity index, microstrain, volume of the unit cell, relative intensity of a certain plane, preference growth, and specific surface area were taken into account while assessing the desired aragonite and calcite phases. A number of well-known models e.g. Straight-line model of the Scherrer model, the Monshi-Scherrer model, the Williamson-Hall model, the Sahadat-Scherrer model, and the three-peak model aided the estimation of crystallite size. In all the cases, the observed crystallite size of calcite was larger than that of aragonite. The percentage of calcite and aragonite in eggshell and P. globosa were assessed by Rietveld refinement method. Observed results revealed that 97.4% calcite and 2.6% aragonite phases are present in eggshell while in P. globosa these percentages exist inversely, i.e. 93.2% aragonite and 6.8% calcite phases.     

Co(II), Cu(II) and Zn(II) dinuclear complexes of a polypodal ligand containing phenolate and pyridyl donor groups

Acetate and perchlorate dinuclear metal complexes of Co(II), Cu(II) and Zn(II) with the cresolate polypodal ligand having mixed phenolate and pyridyl pendant functionalities, H₃L, have been synthesized. The complexes were characterized by microanalysis, LSI mass spectrometry, IR, UV–Vis spectroscopy, magnetic studies and conductivity measurements. Crystal structures of H₃L, [Cu₂(HL)(OAc)(H₂O)₂](OAc)·1.5H₂O and [Zn₂L(CH₃OH)₃](ClO₄)CH₃OH·2H₂O complexes, have been also determined.     

Halogen Interactions in Halogenated Oxindoles: Crystallographic and Computational Investigations of Intermolecular Interactions

X-ray structural determinations and computational studies were used to investigate halogen interactions in two halogenated oxindoles. Comparative analyses of the interaction energy and the interaction properties were carried out for Br···Br, C-H···Br, C-H···O and N-H···O interactions. Employing Møller–Plesset second-order perturbation theory (MP2) and density functional theory (DFT), the basis set superposition error (BSSE) corrected interaction energy (E_int(BSSE)) was determined using a supramolecular approach. The E_int(BSSE) results were compared with interaction energies obtained by Quantum Theory of Atoms in Molecules (QTAIM)-based methods. Reduced Density Gradient (RDG), QTAIM and Natural bond orbital (NBO) calculations provided insight into possible pathways for the intermolecular interactions examined. Comparative analysis employing the electron density at the bond critical points (BCP) and molecular electrostatic potential (MEP) showed that the interaction energies and the relative orientations of the monomers in the dimers may in part be understood in light of charge redistribution in these two compounds.     

Synthesis and coordination chemistry of fluorinated xanthate ligands

Alkali metal, copper, nickel and rhodium complexes of alkylated [S₂COC₈H₁₇] and fluoroalkylated xanthate ligands [S₂COC_mH_2mC_nF_2n+1] (m = 2, n = 4, 6; m = 3, n = 1, 8) have been prepared in high yields and characterised by elemental analysis, mass spectrometry, IR and NMR spectroscopies. The structures of [Cu(S₂COC₈H₁₇)(PPh₃)₂], [Cu(S₂COC₃H₆CF₃)(PPh₃)₂], [Ni(S₂COC₃H₆CF₃)₂], [Cp^*RhCl(S₂COC₈H₁₇)] and [Cp^*RhCl(S₂COC₃H₆CF₃)] have been determined by single crystal X-ray diffraction.     

New coordination cyano-bridged polymers based on tetranuclear rhenium chalcocyanide clusters and copper(ii) ammonia complexes

The reactions of aqueous solutions of the tetranuclear chalcocyanide cluster anions [Re₄Q₄(CN)₁₂]^4–, where Q = S, Se, or Te, with an ammonia solution of copper(ii) chloride at room temperature afforded a series of polymeric cyano-bridged compounds [{Cu(NH₃)₃}₂{Re₄Q₄(CN)₁₂}]·nH₂O (Q = S (1), Se (2)) and [{Cu(NH₃)₃}_1.7{Cu(NH₃)₄}_0.3Re₄Te₄(CN)₁₂] (3) having chain structures. The structures of the compounds were established by X-ray diffraction analysis. Compounds 1 and 2 are isostructural and have ordered structures. In structurally similar compound 3, the copper atoms are disordered over two positions in such a way that the structure contains the bridging {Cu(NH₃)₃} fragments along with the terminal {Cu(NH₃)₄} fragments.     

Synthesis and coordination chemistry of perfluoroalkylated dithiophosphate ligands

Dithiophosphoric acids [HS₂P(OC₂H₄C_nF_2n+1)₂] (n = 4, 6) have been prepared in high yields. Deprotonation and reaction with transition metal substrates affords fluorous metal complexes which have been characterised by elemental analysis, mass spectrometry, IR and NMR spectroscopies. The structures of [Cu{S₂P(OC₂H₄C_nF_2n+1)₂}(PPh₃)₂] (n = 4, 6) and [Cu{-S₂P(OC₂H₄C₄F₉)₂}(PPh₃)]₂ have been determined by single crystal X-ray diffraction.     

Crystallographic and Spectroscopic Investigations on Oxidative Coordination in the Heteroleptic Mononuclear Complex of Cerium and Benzoxazine Dimer

Among lanthanide-based compounds, cerium compounds exhibit a significant role in a variety of research fields due to their distinct tetravalency, high economic feasibility, and high stability of Ce(IV) complexes. Herein, a systematic investigation of crystallographic information, chemical properties, and mechanistic formation of the novel Ce(IV) complex synthesized from cerium(III) nitrate hexahydrate and 2,2′-(methylazanediyl)bis(methylene)bis(4-methylphenol) (MMD) ligand has been explored. According to the analysis of the crystallographic information, the obtained complex crystal consists of the Ce(IV) center coordinated with two nitrate ligands and two bidentate coordinated (N-protonated and O,O-deprotonated) MMD ligands. The fingerprint plots and the Hirshfeld surface analyses suggest that the C–H⋯O and C–H⋯π interactions significantly contribute to the crystal packing. The C–H⋯O and C–H⋯π contacts link the molecules into infinite molecular chains propagating along the [100] and [010] directions. Synchrotron powder X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) techniques have been employed to gain an understanding of the oxidative complexation of Ce(IV)-MMD complex in detail. This finding would provide the possibility to systematically control the synthetic parameters and wisely design the precursor components in order to achieve the desired properties of novel materials for specific applications.     

Synthesis and coordination chemistry of perfluoroalkyl-derivatised β-diketonates

A series of fluorinated β-diketones, R_fC(O)CH₂C(O)R_f′ (R_f=C₆F₁₃, R_f′=CF₃; R_f=R_f′=C₆F₁₃, C₇F₁₅), have been prepared in reasonable yields by a two-step synthesis. On reaction with appropriate metal substrates, deprotonation and concurrent coordination of the perfluoroalkyl-derivatised β-diketonate ligands affords a range of fluorous metal complexes which have been characterised by elemental analysis, mass spectrometry, IR and NMR spectroscopies. The structures of [Cu(L-L)₂(H₂O)₂] {L-L=CF₃C(O)CHC(O)C₆F₁₃, C₆F₁₃C(O)CHC(O)C₆F₁₃} and [Cu(PPh₃)₂{C₇F₁₅C(O)CHC(O)C₇F₁₅}] have been determined by single-crystal X-ray diffraction.     

Preparation and coordination chemistry of N-diallylaminodiphenylphosphine and N-allylaminobis(diphenyl)phosphine

N-diallylaminodiphenylphosphine and N-allylaminobis(diphenyl)phosphine have been prepared by reaction of the appropriate amine with Ph₂PCl. The coordination chemistry of these phosphines has been studied with a range of metals [Pd, Pt, Rh, Ir, Au, Ru, Mo]. Whilst the majority of the complexes are simple bidentate P,P donors, in the case of N-diallylaminodiphenylphosphinecoordination can involve the CC group or the nitrogen centre.     

Crystallographic and Inclusion Properties of some Diacetylated Calix[4]arenes

Three 5,17-diacetylcalix[4]arene derivatives 3–5 have been prepared, evaluated for inclusion properties, and their single crystal X-ray structures determined. The diacetyl calixarenes 3 and 4 were obtained by acetylation of their parent dimethoxy 1 or dipropoxy 2 compounds, respectively, whereas 5,17-diacetyl-25,26,27,28-tetrapropoxycalix[4]arene 5 was prepared by alkylation of 4. Crystallisation of 3 resulted in no inclusion from chloroform, but yielded lattice inclusion compounds from acetonitrile or acetone. The calixarene 3 maintains its cone conformation in these crystals, but displays degrees of distortion depending upon the included solvent. Crystal structures of solvent-free 4 and 5 are also described. A new preparation of the monomethoxy derivative 6 is described, and its X-ray structure with chloroform guest is analysed.     

Template construction of a series of supramolecular coordination polymers via 6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium cation

Five cation-induced complexes, (phen-dzp) [ZnBr₃N₃] (1), (phen-dzp) [ZnCl₂Br₂] (2), (phen-dzp) (H₃O)₂ [Fe(CN)₆] (3), (phen-dzp)₂ [Cu₂I₆] (4), and [(phen-dzp)(Ag₂Br₄)] _n (5) [phen-dzp?=?(C₁₅H₁₄N₂)²⁺, 6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium], have been synthesized via self-assembly in solution. The crystal structures of 1–3 show that they all crystallize in monoclinic systems with mononuclear structures. Compound 4 is a binuclear coordination polymer. Complex 5 possesses a 2-D supramolecular layer with the organic cation phen-dzp trapped in it; interestingly, each inorganic polymeric planar layer is composed of large, decagon rings formed by sharing four Br^? and four [Ag₂Br₄] quadrilateral units with six adjacent decagon rings. The results provide insights into template effects of synthetic approaches on the construction of supramolecular compounds. The structures of 1–5 have been characterized by elemental analysis, infrared spectra, and single-crystal X-ray crystallography. Solid-state photoluminescence properties of 1–5 have been determined.     

A new mixed ligand coordination polymer of Mn(II): structural aspect and cryomagnetic study

A new 1-D polymeric chain complex [Mn(pydc)(1,10-phen)]_n· nH₂O (pydc = pyridine-2,3-dicarboxylate, 1,10-phen = 1,10-phenanthroline) has been synthesised and characterised by elemental analysis, FT-IR spectrum, thermal analysis and variable temperature magnetic susceptibility studies. Single crystal X-ray diffraction study reveals that the central Mn(II) ion is in a distorted octahedral coordination geometry, and is coordinated to pydc and 1,10-phen. The complex shows interesting hydrogen bond modes involving the dicarboxylates and lattice water molecules. The presence of weak antiferromagnetic coupling with J = −0.72 cm⁻¹ for the complex has been concluded from the cryomagnetic susceptibility studies.     

基于芳香酰腙配体的锰配合物的合成、晶体结构与性质

本文合成了2-羰基丙酸-2-甲氧基苯甲酰腙锰配合物,并借助X-射线单晶衍射测定了配合物的晶体结构。该晶体属于单斜晶系P-1空间群,晶胞参数为,a=0.7925(2)nm,b=1.0529(3)nm,c=1.1069(4)nm,α=68.142(6)°,β=69.053(4)°,γ=71.292(4)°,V=0.7816(4)nm~3,Z=1。在一个不对称单元中,Mn离子是七配位,且被镶嵌在一个有微弱形变的五角双锥结构内,配合物整体呈现双核的零维结构。利用红外光谱、紫外光谱、荧光光谱研究了其光谱性质。     

Synthesis and coordination chemistry of fluorinated phosphonic acids

Phosphonic acids [(HO)₂P(O)C₂H₄C_nF_2n+1] (n = 4, 6) and [(HO)₂P(O)C₆H₄-4-C_nF_2n+1] (n = 0, 1, 6) have been prepared in good yields. Deprotonation and reaction with cis-[PtCl₂(PPh₃)₂] affords fluorinated platinum complexes which have been characterised by elemental analysis, mass spectrometry, IR and NMR spectroscopies. The structures of [Pt{O₂P(O)C₆H₄-4-F}(PPh₃)₂], [Pt{O₂P(O)C₆H₄-4-CF₃}(PPh₃)₂] and [Pt{O₂P(O)C₂H₄C₆F₁₃}(PPh₃)₂] have been determined by single crystal X-ray diffraction.     

Synthesis and characterization of La4MnCu6S10

The new quaternary sulfide La₄MnCu₆S₁₀ has been synthesized by the reaction of La₂S₃, MnS, and CuS₂ at 1223 K. This compound crystallizes in a new structure type in space group of the triclinic system with one formula unit in a cell of dimensions at 153 K of a=6.6076(3) Å, b=7.3247(3) Å, c=8.7844(4) Å, α=83.457(1)°, β=74.398(1)°, γ=89.996(1)°, and V=406.61(3) Å³. The structure of La₄MnCu₆S₁₀ consists of a three-dimensional framework of interconnected LaS₇ monocapped trigonal prisms, MnS₆ octahedra, and CuS₄ tetrahedra. Band gaps of 2.49 eV in the [100] direction and 2.53 eV in the [001] direction have been derived from optical absorption measurements on a La₄MnCu₆S₁₀ single crystal.     

Formation of isolated guest dimers vs. host-guest coordination. X-Ray crystal structures of four carboxylic acid inclusion compounds formed by roof-shaped and scissor-like host molecules

The crystal structures of the inclusion compounds oftrans-9,10-dihydro-9,10-ethano-anthracene-11,12-dicarboxylic acid host (1) with formic acid (1a), acetic acid (1b), and propionic acid (1c) as guests, and of the coordinatoclathrate of the 1,1-binaphthyl-2,2-dicarboxylic acid host (2) with acetic acid as guest (2b) have been studied by single crystal X-ray diffraction. These studies show that inclusion of small carboxylic acids by carboxylic acid hosts like1 and2 results in formation of isolated, hydrogen-bonded guest dimers. Additional H-bond contacts between host and guest carboxylic groups are only formed in cases1a and2b. The dimeric acidic guest units are sitting in the cavities of the host or host-guest framework and have no other interactions than those of a weak Van der Waals' type with the neighbouring molecules. Crystal data:1·formic acid (1:2): triclinic (P),a = 11.6769(6),b = 9.4067(4),c = 9.0020(4) Å,a = 81.522(4), = 100.310(6), = 104.208(6)°,Z = 2,R = 0.048 for 2392 reflections;1·acetic acid (1:1): monoclinic (P2₁/n),a = 9.717(2),b = 14.462(2),c = 13.038(3)Å, = 104.27(1)°,Z=4,R=0.046 for 3042 observations;1·propionic acid (1:1): monoclinic (P2₁/n),a = 9.897(4),b = 14.671(7),c = 13.284(7) Å, = 105.92(6)°,Z = 4,R = 0.056 for 2302 reflections;2·acetic acid (2:3): triclinic (P),a = 12.746(1),b = 17.781(2),c = 11.010(1) Å, = 105.606(4), = 112.992(8), = 81.175(6)°,Z = 2,R = 0.067 for 4375 observations.     

Synthesis and structure of 6-chloro-2,3-trimethylene-4-phenylquinoline

An X-ray structural investigation of 6-chloro- 2,3-trimethylene-4- phe nylquinoli ne obtained by the reaction of 2-amino-5-chlorobenzophenone with cyclopentanone was carried out. At 20 °C, a = 23.750,b = 9,242, c = 14.018 A, = 112,68° space group (21c,Z = 8, 2647 reflections,R = 0.047 He five-membered ring has an envelope conformation Conjugation between the quinohne fragment and the phenyl substituent is significantly distorted dm to the rotation of the latter by -62.9°Translated fromIzvestiya Akademii Nauk. Seriva Khimicheskaya, No. 7, pp. 1800–1802, July, 1996.