Unidentate Carboxylate Groups Research Articles

Synthesis, structure and property of diorganotin complexes with chiral N-(5-chlorosalicylidene)valinate ligand

Six new diorganotin N-[(5-chloro-2-oxyphenyl)methylene]valinates, R2SnL (R = Me, 1; Et, 2; L = 5-Cl-2-OC6H3CH = NCH(i-Pr)COO: (S)-, a; (R)-, b; (RS)-, c), have been synthesized from the reaction of R2SnCl2 with the chiral ligand KHL (potassium salt of HL) in different solvents and characterized by elemental analysis, IR, NMR (1H, 13C and 119Sn) spectra. In benzene, the configuration of the chiral ligand was retained. (S)-Enantiomers (1a and 2a) and (R)-enantiomers (1b and 2b) display discrete molecular structures with distorted trigonal bipyramidal geometries in which two C atoms of organic groups (R) and the imino N atom occupy the equatorial positions and a phenoxide O and an unidentate carboxylate group O atom are in the axial orientation. In the methanol, the chiral ligand was racemized. 1c⋅MeOH is a centrosymmetric dimers formed by (R)- and (S)- enantiomers through two SnO⋅⋅⋅Sn bridges. The coordination geometry of the Sn atom can be described as a distorted pentagonal bipyramid with two methyl groups in axial positions. The crystal of 2c is composed of two threefold symmetric trimers, a [Et2SnL-(R)]3 and a [Et2SnL-(S)]3, with a macrocyclic 12-membered ring structure formed by the bidenate bridging coordination of carboxylate group to tin atoms. Each tin atom is six-coordinated in distorted [SnC2NO3] octahedron geometry. The fluorescence properties of ligand KHL and complexes 1 (1a-1c) and 2 (2a-2c) have been measured. The results show the complexes may be explored for potential luminescent materials.

Two new metal–organic frameworks based on cyclic dodecanuclear copper units

Two new metal–organic frameworks based on cyclic-type dodecanuclear copper units, (Me4N)6[Cu12(OMe)6(pz)6(BTC)6]·18H2O 1 and (Me4N)6[Cu12(OH)6(pz)6(BTC)6]·21H2O 2 (pz = pyrazolate, BTC = 1,3,5-benzenetricarboxylate), have been prepared by the solvothermal reactions of copper salts, Hpz and H3BTC ligands. The cyclic-type Cu12 unit in 1 and 2 is constructed by twelve CuII ions linked together by μ2-OH or μ2-OMe and unidentate carboxylate groups at the inner- and μ-pz and bidentate carboxylate groups at the outer surface of the toroid. In 1 and 2, each Cu12 unit is connected to 12 other units by BTC linkers, leading to 12-connected three-dimensional porous frameworks. The photocatalytic investigations indicate that compounds 1 and 2 exhibit photocatalytic activity for the degradation of RhB.

Synthesis, characterization, single crystal X-ray structural studies and packing analyses of two novel copper(II) complexes: [Cu(2-Cl-5-FC7H3O2)2(β-picoline)2(H2O)2] and [Cu(en)2(H2O)2](2-Cl-5-FC7H3O2)2

Two novel copper(II) complexes, [Cu(2-Cl-5-FC7H3O2)2(β-pic)2(H2O)2] 1 and [Cu(en)2(H2O)2] (2-Cl-5-F-C7H3O2)22 (where β-pic=β-picoline, en=ethylenediamine) were isolated by addition of β-picoline and ethylenediamine respectively to the hydrated copper(II) aryl carboxylate, Cu(2-Cl-5-F-C7H3O2)2 suspended in water–methanol (1:4) mixture. The newly isolated complexes have been characterized by elemental analyses, TGA, spectroscopic techniques (EPR, IR and UV/Vis), conductance, magnetic susceptibility studies and single crystal X-ray structure determination. Single crystal X-ray structure determinations revealed the presence of covalently bonded 2-Chloro-5-fluorobenzoate groups in the complex, viz: [Cu(2-Cl-5-FC7H3O2)2(β-picoline)2(H2O)2] 1 and ionic 2-Chloro-5-fluorobenzoate groups in [Cu(en)2(H2O)2] (2-Cl-5-FC7H3O2)2 in 2. In 1, two β-picoline, two unidentate carboxylate groups and two water molecules are coordinated to copper(II) ion. In 2, two ethylenediamine molecules (4N) and two oxygen from water molecules are coordinated to copper(II) ion. Hexacoordination around copper(II) is achieved with distorted octahedral geometry in both the cases. The crystal network in complex 1 is stabilized by O–H⋯O, C–H⋯π, Cl⋯F, and Cl⋯H–C and in complex 2 cationic and anionic layers are held together by the N–H⋯O, O–H⋯O, C–H⋯F, C–H⋯O interactions.

Synthesis, spectroscopic characterisation of 1,1,2,3,4,5-hexahydro-1,1-dicarboxylatotellurophenes and crystal structures of 1,1,2,3,4,5-hexahydro-1,1-di(benzoato)- and 1,1-di(4-nitrobenzoato)tellurophene

1,1,2,3,4,5-hexahydro-1,1-dicarboxylatotellurophenes C 4H 8Te(OCOR) 2 (R=CH 2Cl, C 6H 5, 4-NO 2C 6H 4, 3,5-(NO 2) 2C 6H 3, 4-OCH 3C 6H 4) were obtained from the reactions of 1,1,2,3,4,5-hexahydro-1,1-diiodotellurophene with silver oxide and carboxylic acids or silver carboxylates. They were characterised by IR and ( 1H, 13C, 125Te)-NMR spectroscopy. The structures of C 4H 8Te(OCOC 6H 5) 2 and C 4H 8Te(4-NO 2C 6H 4OCO) 2 were established by single-crystal X-ray diffraction studies. In both cases the coordination geometry about the central Te atom can be described as pseudotrigonal bipyramidal in which two oxygen atoms of the unidentate carboxylate groups are in the axial positions, two methylene carbon atoms (attached to Te) of the C 4H 8 group and the stereochemically active electron lone pair occupy the equatorial positions. The molecules are packed in their unit cells as the weakly bridged dimers through intermolecular Te⋯O secondary bonds.

Formation of Nickel(II) Coordination Polymers by a Double Betaine: [{Ni(L)(H2O) 2} n] Cl2n.2nH2O and [{Ni(L)2(H2O)2} n

Two novel polymeric nickel(II) complexes of a double betaine with a rigidtris(ethylene) bridge between the pair of nitrogen atoms, namely [ {Ni(L)(H2O)4 }n]Cl2n.2nH2O(1)and [ {Ni(L)2(H2O)2} n](ClO4)2n.4nH2O(2) [L =¯O2CCH2N+(CH2CH2)3N+CH2CO2¯], have been prepared and characterized by X-ray crystallography. Thenickel(II) atom in either complex is coordinated by unidentate carboxylategroups and aqua ligands in a distorted octahedral geometry. The crystalstructure of (1) features an infinite zigzag chain composed of an alternatearrangement of metal atoms and double betaine ligands, and hydrogen bondingamong adjacent chains leads to a three-dimensional network. Complex (2)exhibits a wave-like layer structure corresponding to the (2 0 0) family ofplanes.

Bis[(2-hydroxyethyl)dimethylammonium] Tetrakis(μ-benzoato-O:O')bis[(benzoato-O)cuprate(II)

Copper(II) benzoate reacts with 2-dimethylaminoethanol in ethanol forming a green copper(II) complex, (C 4 H 12 NO) 2 [Cu 2 (C 7 H 5 O 2 ) 6 ]. The two Cu atoms, with a Cu...Cu distance of 2.670 (2)A in the centrosymmetric molecule, are held together by the four carboxylate groups. Each Cu atom is bound in a square-pyramidal configuration to five carboxylate O atoms. The (2-hydroxyethyl)dimethylammonium cation is hydrogen bonded to the uncoordinated O atom of the unidentate carboxylate group.

Preparation, IR and119mSn Mössbauer Spectral Data of Diorganotin (IV) Derivatives OP N-Phthaloylglycine

Abstract Diorganotin (IV) derivatives L2SnR2 [2:1] and (LSnR2)2O [1:1] (R = Me, n-Bu, n-oct, benzyl', L = anion of N-phthaloylglycine) have been prepared by reacting diorganotin (IV) oxides with N-phthaloylglycine. All the compounds have been characterized by elemental analyses, IR, 1H NMR AND 119mSn Mossbauer data which confirm a trans-octahedral and a trigonal bipyramidal structure with a Sn-O-Sn bridge for the 2:1 and 1:1 derivatives respectively. All the complexes have a unidentate carboxylate group and a Sn-N bond except L2Sn(n-C4H9)2 which has a bidentate carboxylate group and a linear R-Sn-R moiety with C-Sn-C bond angle equal to 180°.

Sulphonamide nitrogen-containing, nitrogen-protected amino acids interacting with the Cd2+ion. A cadmium-113 nuclear magnetic resonance and potentiometric study. X-Ray diffraction of [Cd(ts-β-alaO)2(H2O4)

α-Alanine and β-alanine, N-protected by a tosyl (toluene-p-sulphonyl) group, bind Cd2+ acting initially as a simple carboxylate at low pH, and, at increasing pH, as N,O-bidentate ligands, through the carboxylic oxygen and the deprotonated amide nitrogen atoms. In the latter case they give rise to five- and six-membered ring chelate species, respectively. Cadmium-113 n.m.r. and potentiometric measurements reveal that the stability of the complexes is almost unaffected by the chelate ring size. The five-membered ring chelate species has a more deshielded chemical shift and only a slightly greater stability than the six-membered species. The crystal and molecular structures of the [Cd(ts-β-alaO)2(H2O)4](ts-β-alao =N-tosyl-β-alaninate monoanion) complex have been solved. Crystal data are: monoclinic, space group P21/c, a= 14.956 (6), b= 5.472(2), c= 16.860(7)Å, β= 107.36(3)°, Z= 2, and R= 0.039 for 1 635 reflections. The amina acid molecule binds through the unidentate carboxylate group and the structure consists of discrete units in which the Cd2+ exhibits a nearly regular octahedral geometry.

The crystal structure of hexaaquacopper(II) bis(7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato)cuprate(II)

The crystal structure of the copper(II) complex with the herbicide endothall, (7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid = H 2 L), [Cu(H 2 O) 6 ][CuL 2 ], has been determined by X-ray methods and refined to a residual of 0.033 for 1774 observed reflections, collected at 163 K. The complex comprises centrosymmetric tetragonally distorted octahedral [Cu(H 2 O) 6 ] 2+ cations [Cu – O, 1.957, 1.972, 2.321(2) Å and [CuL 2 ] 2− anions [Cu – O, 1.959, 1.995, 2.376(2) Å]. In the complex anions, the four equatorial oxygens are from two unidentate carboxylate groups of each ligand while the axial sites are occupied by oxygens of the oxy-bridged molecular cage.

Synthesis of tris(2,4,6-trimethylphenyl) hydroxoantimony carboxylates. Crystal structure of tris(2,4,6-trimethylphenyl) hydroxoantimony 1-adamantylcarboxylate

The tris(2,4,6-trimethylphenyl)hydroxoantimony carboxylates Mes 3Sb(OH)-OOCR · nH 2O ( n = 1, Mes = 2,4,6-Me 3C 6H 2, R = H, CH 2F; n = 0, R = CH 3, CHCl 2, CF 3, C 10H 15 = 1-adamantyl) have been obtained by neutralization of tris-(2,4,6-trimethylphenyl)antimony dihydroxide with the appropriate carboxylic acid. The crystal structure of tris(2,4,6-trimethylphenyl)hydroxoantimony 1-adamantyl-carboxylate has been determined by single crystal X-ray diffraction. Antimony is in a slightly distorted trigonal bipyramidal environment, with the unidentate carboxylate group and OH being in apical positions. The SbO(H) bond length, 202.6(3) pm, is appreciably shorter than the usual value for SbO(carboxylate) bond, viz. 212.1(3) pm in tris(2,4,6-trimethylphenyl)-hydroxoantimony 1-adamantyl-carboxylate. From IR data analogous molecular structures are inferred for the other compounds Mes 3Sb(OH)O 2CR · nH 2O. The water in Mes 3Sb(OH)O 2CR · H 2O (R = H, CH 2F) is assumed to be water of crystallization.

ChemInform Abstract: Preparation and Structure of Triorganotin, Triorganolead and Tetraphenylantimony Derivatives of Acetylenedicarboxylic Acid, Terephthalic Acid and Dithioterephthalic Acid.

AbstractThe 2:1 molar reactions of R3SnOH, R3PbOH or R4SbOH with acetylenedicarboxylic acid or dithioterephthalic acid and of the appropriate chlorides with dipotassium terephthalate in MeOH yield the 2:1 products (I)‐(IV).

Preparation and structure of triorganotin, triorganolead and tetraphenylantimony derivatives of acetylenedicarboxylic acid, terephthalic acid and dithioterephthalic acid

AbstractTriorganotin, triorganolead and tetraphenylantimony derivatives of acetylenedicarboxylic acid (H2ADC), terephthalic acid (H2TER) and dithioterephthalic acid (H2DTT) (R3M)2X (M = Sn, Pb; R = Me, Ph; X = ADC, TER, DTT) and (Ph4Sb)2X (X = ADC, TER) were prepared by neutralization of R3MOH or Ph4SbOH with the appropriate acid (X = ADC, DTT) or by reaction of R3MCl or Ph4SbCl with K2TER. The crystal structures of (Me3Sn)2ADC and (Me3Sn)2TER were determined by X‐ray diffraction. The Sn atoms are in slightly distorted trigonal‐bipyramidal environments, with C(Me) in the equatorial plane and O(carboxyl) in apical positions. The carboxylate groups are bridging, leading to the formation of a two‐dimensional polymer of puckered 22‐membered [(Me3Sn)2ADC] and 26‐membered [(Me3Sn)2TER] rings. From vibrational spectra, analogous structures are inferred for solid (Ph3Sn)2ADC, (R3Pb)2ADC (R = Me, Ph), and (Me3Pb)2TER, but structures with unidentate ‐ COO and ‐ COS groups and tetracoordinated Sn or Pb and pentacoordinated Sb are proposed for the other compounds. The DTT ligands are linked by S bonds to M. According to IR and 1H NMR studies the polymeric species dissociate on dissolution so that generally species with unidentate carboxylate groups are present. Sn and Pb in (R3M)2X (X = ADC, TER) are apparently tetracoordinated in CHCl3, but pentacoordinated in DMSO by addition of a solvent molecule.

Synthesis, structure, and spectroscopic and magnetic properties of catena-µ-aqua-diaquabis(2,6-dimethoxybenzoato)metal(II) monohydrate complexes of manganese, cobalt, nickel, and zinc. X-Ray crystal structure of [Co(dmba)2(H2O)3]·H2O

Metal complexes of 2,6-dimethoxybenzoic acid (Hdmba), [M(dmba)2(H2O)3]·H2O, for M = MnII, CoII, NiII, or ZnII have been prepared and studied by means of X-ray diffraction, electronic and i.r. spectroscopies as well as magnetic measurements. The crystal and molecular structure of the cobalt complex has been determined by single-crystal X-ray diffraction and refined by least-squares methods to R= 0.0347 on the basis of 1 337 independent significant counter data. Crystals are orthorhombic, space group Pna21, with unit-cell dimensions a= 7.934(3), b= 10.652(3), c= 26.423(7)Å, and Z= 4. The compound is polymeric, the metal atoms being linked to each other by bridging water molecules to form an infinite chain. The metal ion is six-co-ordinate, the equatorial ligands being two mutually trans water molecules and two unidentate carboxylate groups of the dmba anions. The metal–oxygen bonds in the bridge [2.165(4) and 2.172(4)Å] are longer than the other metal–oxygen distances [M–O(water) 2.091(7) and 2.033(8)Å; M–O(carboxy) 2.073(5) and 2.069(5)Å] giving rise to a tetragonally distorted octahedron at the metal ion. The intra-chain Co–Co distance along the a axis is 3.97 Å, whereas the shortest inter-chain distances along the b and c axes are 10.65 and 14.28 Å, respectively. The Mn, Ni, and Zn complexes are isomorphous with the cobalt compound. Magnetic susceptibility data, in the range 4.2–300 K, for the Co, Ni, and Mn complexes are reported and discussed in relation to the structural data.

Triphenyltin(IV) 8-quinolyloxyacetate hydrate, [Ph 3SnO 2CCH 2(8-C 9H 6NO) · H 2O] n, an organotin ester derivative built of hydrogen-bonded helical chains

The X-ray crystal structure of triphenyltin(IV) 8-quinolyloxyacetate hydrate, [Ph 3SnO 2CCH 2(8-C 9H 6NO) · H 2O] n , has been determined and refined to R F = 0.066. The compound crystallizes in space group P2 1/ c with a 13.667(5), b 10.340(5), c 35.92(1) Å, β 93.01(3)° and Z = 8. The asymmetric unit consists of two independent [Ph 3SnO IC(O II)CH 2(8-C 9H 6NO III) · H 2O IV] molecular units ( A and B) which differ in the extent of the intramolecular approach of the carbonyl oxygen O II to tin (Sn ⋯ O II 3.53(1) and 3.20(1) Å, respectively). The coordination environments of tin in A and B are in each case essentially trigonal bypyramidal, with the ipso-carbons of the phenyl groups lying in the equatorial plane and the axial positions being occupied by oxygen from a unidentate carboxylate group and a water molecule. The SnO bond lengths involving coordinated water are approximately 0.22 Å longer than those involving the carboxylate groups; the axial angles, O ISnO IV, in A and B are respectively 175.9(3) and 176.6(3)°. Molecules A and B are linked sequentially by hydrogen bonds involving the coordinated water molecule and the quinolyloxyacyl O III and N atoms to form one-dimensional helical chains parallel to the a axis. The slope of the variable-temperature 119mSn Mössbauer plot ( a = dln( A T A 80 K)/d T = −1.99 X 10 −2 K −1 for 80 ≤ T ≤ 110) is consistent with the model of a weakly associated lattice.

Areneruthenium(II) carboxylates: reactions with ligands and the X-ray structure of the p-cymene pyrazine complex [Ru(η-p-MeC6H4CHMe2)Cl(pyz)2]PF6

The preparation of monomeric areneruthenium(II) acetates and trifluoroacetates [Ru(η-arene)X(O2CR)] and [Ru(η-arene)(O2CR)2](X = Cl or Br; R = Me or CF3; arene = C6H6, p-MeC6H4CHMe2, C6H3Me3-1,3,5, C6H2Me4-1,2,4,5, or C6Me6)(not all possible combinations) from the corresponding dihalides [{Ru(η-arene)X2}2] is described. Infrared spectra suggest that the complexes [Ru(η-arene)X(O2CR)] contain a bidentate carboxylate group and that [Ru(η-arene)(O2CR)2] contain one bi- and one uni-dentate carboxylate group, which are apparently equivalent on the n.m.r. time-scale at room temperature. Reaction of trifluoroacetic acid with [{Ru(η-C6Me6)Cl2}2] gives a complex of empirical formula Ru(η-C6Me6)Cl(O2CCF3)·CF3CO2H which may be a salt [(η-C6Me6)Ru(η-Cl)2(µ-O2CCF3)Ru(η-C6Me6)][H(O2CCF3)2]·CF3CO2H. Triphenylphosphine converts [Ru(η-C6Me6)(O2CR)2](R = Me or CF3) into [Ru(η-C6Me6)(O2CR)2(PPh3)] in which both carboxylate groups are unidentate. The trifluoroacetate group is completely displaced from [Ru(η-C6H6)Cl(O2CCF3)] by pyridine (py) or ethyldiphenylphosphine to give [Ru(η-C6H6)ClL2]+(L = py or PEtPh2), isolated as PF6– or BPh4– salts. The potentially binucleating ligands pyrazine (pyz), 4,4′-bipyridyl, and 1,3-dithiane react either with [Ru(η-C6H6)Cl(O2CCF3)] or with [{M(η-p-MeC6H4CHMe2)Cl2}2](M = Ru or Os) in the presence of NH4PF6 or NaBPh4 in methanol to give [M(η-arene)ClL2]+ salts in which only one donor atom of the ligand is co-ordinated, but pyz and [{Ru(η-p-MeC6H4CHMe2)Cl2}2] react in dry tetrahydrofurane to give the pyrazine-bridged species {Ru(η-p-MeC6H4CHMe2)Cl2}2(µ-pyz). The structure of the complex [Ru(η-p-MeC6H4CHMe2)Cl(pyz)2]PF6 has been verified by X-ray analysis. The crystals are triclinic, space group P, with a= 9.265(2), b= 9.684(4), c= 12.969(2)Å, α= 86.51(2), β= 72.89(2), and γ= 85.59(2)°.

Triorganozinn- und Triorganobleiderivate von N-Benzoyl- und N-Formylglycin / Triorganotin and Triorganolead Derivatives of N-Benzoyl-and N-Formylglycine

Triorganotin and -lead derivatives of X-benzoylglveine (BzGlyH) and N-formylglycine (ForGlyH), R3MBzGly and R3MForGly (M = Sn; R = Me, Ph. M = Pb; R = Ph) have been prepared from R3MOH and BzGlyH or ForGlyH, respectively. According to spectro­scopic data the Me3Sn groups are essentially planar; molecules of R3SnForGly are bridged by unidentate carboxylate groups and formyl-C = O groups in the solid state, while Ph3PbForGly and benzoylglycinates are bridged by bidentate carboxylate groups. NH does not coordinate to M. Pentacoordination and a polymeric nature in the solid state is also indicated by Mößbauer data of Me3SnForGly and Me3SnBzGly. In solution all compounds are monomeric.

Organomercury compounds. VIII. The preparation of pentafluorophenylmercury compounds by mercuration reactions

Pentafluorophenylmercuric carboxylates, C6F5HgOCOR (R = CF3, CHF2, CH2F, or CH3), have been prepared by reaction of pentafluorobenzene with the appropriate mercuric carboxylate. The compounds are monomeric in toluene, and their infrared spectra suggest the presence of unidentate carboxylate groups. Mercuration of pentafluorobenzene with mercuric trifluoroacetate, followed by reaction of the crude product with sodium iodide in aqueous ethanol, gives a good yield of bispentafluorophenylmercury.