Wai-Hing Yip

Metal-phenoxyalkanoic acid interactions. Part 15. The crystal structures of diaquabis(phenoxyacetato)cadmium(II) and catena-μ-[aquabis(phenoxyacetato-O)lead(II)-bis(phenoxyacetato)lead(II)]

Abstract The crystal structures of the cadmium(II) and lead(II) complexes of phenoxyacetic acid (PAH) have been determined by single crystal X-ray diffraction techniques. The cadmium complex, [Cd(PA)2(H2O)2] (1), space group C2, with Z = 2 in a cell of dimensions, a = 11.801(2), b = 5.484(1), c = 13.431(3) A, β = 100.87(2)°, possesses a distorted trapezoidal bipyramidal coordination around the metal atom, involving two water oxygens [2.210(5) A] and four carboxyl oxygens from two symmetrical bidentate phenoxyacetate ligands [2.363(4), 2.365(4) A] with Cd lying on the crystallographic two- fold axis. The lead complex, [Pb2(PA)4(H2O)]n (2) is triclinic, space group P 1 , Z = 2, with a cell of dimensions, a = 10.135(4), b = 10.675(3), c = 19.285(9) A, α = 114.66(3), β = 91.94(3) and γ = 114.99(3)°. (2) is a two-dimensional polymer with a repeating dimer sub-unit. The first lead [Pb(1)] has an irregular MO8 coordination [2.34−2.96(2) A: mean, 2.63(2) A] involving the water molecule, two oxygens from an asymmetric bidentate carboxylate group, two from a bidentate chelate [O(ether), O(carboxylate)] group and three from bridging oxygens, one of which also provides a polymer link to another symmetry generated lead. The second lead [Pb(2)] is irregular seven-coordinate [PbO, 2.48−2.73(2) A: mean, 2.61(2) A] with three bonds from the bridging groups, two from an unsymmetrical bidentate carboxylate (O, O′) group and one from a second carboxyl group which also bridges two Pb(2) centres in the polymer.

Metal phenoxyalkanoic acid interactions—36. The preparation and crystal structures of tetraaquabis(2-phenoxybenzoato)nickel(ii) dihydrate, diaquabis(4-fluorophenoxyacetato)zinc(ii), catena-diaquabis(phenoxyacetato)cobalt(ii) and tetrakis-μ-[(pentafluorophenoxy)acetato(o,o′)] bis[aquacopper(ii)]

The structures of four complexes involving divalent first-row transition metals and phenoxy substituted carboxylic acids have been determined by X-ray diffraction. These are tetraaquabis(2-phenoxybenzoato)nickel(II) dihydrate (1), diaquabis(4-fluorophenoxyacetato)zinc(II) (2), diaquabis(phenoxyacetato)cobalt(II) (3) and tetrakis-μ-(pentafluorophenoxyacetato)bis[aquacopper(II)] (4). Complex 1 is regular octahedral with trans-related unidentate carboxylate [Ni-O (carboxylate) 2.031(1) A] and four waters [Ni-O 2.049, 2.104(2) A]. Complex 2 has a skew trapezoidal bipyramidal stereochemistry, involving four oxygens from two asymmetric bidentate carboxylates [Zn-O 2.107, 2.332(3) A] and two waters [Zn-O 1.989(4) A]. The polymeric complex 3 is isomorphous and isostructural with the manganese(II) analogue, with centrosymmetric octahedral CoO stereochemistry comprising four bonds to carboxylate oxygens (both bridging) [Co-O 2.076, 2.087(3) A] and two to waters [Co-O 2.134(3) A]. Complex 4 is a pseudo-centrosymmetric tetracarboxylate bridged dimer of the copper(II) acetate hydrate type with a Cu-Cu separation of 2.644(4) A. Bond distances to copper are 1.96(1) (average, equatorial) and 2.15(1) A (average, axial, to water).

Triphenyltin derivatives of isothiazol-3(2H)-one 1,1-dioxides. Synthesis, Mössbauer spectra, some fungitoxicity data, and crystal structure of triphenylstannyl 1,2-benziosthiazol-3-(2H)-one 1,1-dioxide·N,N-dimethylformamide

The syntheses and tin-119m Mossbauer spectroscopic data are reported for two series of stannylimides, 2-triphenylstannyl 1,2-benziosithiazol-3(2H)-one 1,1-dioxide·L (L = O-donor ligand) and 2-triphenylstannyl 4,5-substituted isothiazol-3(2H)-one 1,1-dioxides, and for the stannylester, triphenyltin 1,2-benzisothiazol-3(2H-onyl-2-acetate 1,1-dioxide. The observed quadrupole splitting (QS) values (3.12–3.25 mm s−1) are interpreted in terms of trans-C3SnNo trigonal bipyramidal structures for the (C6H5)3SnNC(O)C6H4SO2·L [ L = (C6H5)2C2CO, (CH3)2NCHO, C9H7NO, (C6H5CH2)2SO, (C6H53PO, (C6H5)3AsO] adducts. A crystal structure determination of the N,N-dimethylformamide adduct confirms the Mossbauer assignment. The ipso-carbons [Sn-C 2.120(4), 2.120(5), 2.122(5) A] comprise the equatorial girdle of the trigonal bipyramid, the apical positions being occupied by the imido nitrogen [Sn−N 2.242(5) A] and amido oxygen [Sn–O 2.402(5) A] atoms. A similar five-coordinate structure is assigned to (C6H5)3SnNC(O)C(R′)C(R″)SO2 [Qs 2.95–3.32 mm s−1; R′ = R″ = CH3; R′ = H, R″ = C6H5; = −(CH2)4−; R′R″ = −(CH2)5−], but for the R′ = CH3, R″ = C6H5 derivative, the lower QS value (2.54 mm s−1) is more consistent with a four-coordinated tetrahedral structure. A trans-C3SnO2 trigonal bipyramidal structure for the (C6H5)3SnO2CCH2NC(O)C6H4SO2 stannylester is indicated by its large QS (3.53 mm s−1). Results on fungitoxicity tests on some of the triphenyltin compounds are presented.

Organotin esters of 3-ureidopropionic acid. Crystal structure of triphenyltin(IV) 3-ureidopropionate, (C6H5)3SnOCO(CH2)2NHCONH2

Syntheses and spectroscopic (119mSn Mossbauer and infrared) data are reported for triorganotin derivatives of 3-ureidopropionic acid of the general formula, R3SnOCOCH2CH2NHCONH2 (R = Ph, nBu, cyclohexyl, and p-tolyl) and Ph2RSnOCOCH2CH2NHCONH2 (R = nBu, p-ClC6H4 and cyclopentyl). The crystal structure of triphenyltin 3-ureidopropionate has been determined. The compound adopts a trans-C3SnO2 trigonal bipyramidal geometry with the axial positions occupied by the ester oxygen and the ureido-oxygen of an adjacent molecule. The polymer units are held together by intermolecular hydrogen bonding between the group NH of the ureido fragment and the oxygen of the carboxylate carbonyl.

Metal-(phenylthio)alkanoic acid interactions— VII. The crystal and molecular structures of diaquabis[(benzylthio)acetato]-zinc(II), catena- [diaqua-tetra[(benzylthio)acetato]-bis[cadmium(II)], catena-tetra-μ-{2-methyl-3- (phenylthio)propionato-O,O′]-bis[copper(II)]} and tetra-μ-[2-methyl-2-(phenylthio)propionato-O,O′]- bis[ethanolcopper(II)]

Abstract The crystal structures of diaquabis[(benzylthio)acetato]zinc(II), [Zn(BTA)2 (H2O)2] (1), catena-[diaqua-tetra[(benzylthio)acetato)]-bis[cadmium(II)], [Cd2(BTA)4 H2O)2]n (2), catena-{tetra-μ-[2-methyl-3-(phenylthio)propionato-O,O′]-bis[copper (II)]}, [Cu2(MPTP)4]n (3) and tetra-μ-[2-methyl-2-(phenylthio)propionato-O,O′]- bis[ethanol copper(II)], [Cu2(PTIBA)4(EtOH)2] (4) have been determined using X-ray diffraction techniques. Complex (1) is monomeric with distorted octahedral stereochemistry and lies on a two-fold rotational axis. The MO6 coordination involves four oxygens from two slightly asymmetric bidentate BTA car☐yl groups [Zn O, 2.138(3), 2.28(3)A] and two cis-related waters [Zn Ow, 1.996(3)A]. The cadmium complex (2) is best described in terms of a polymer with the repeating unit consisting of two different centres, one seven, the other six-coordinate. With the first, the distorted MO6S coordination sphere has four oxygens from two asymmetric bidentate car☐ylate groups (ligands B and C) [Cd O, 2.36, 2.56(1)A; 2.26, 2.67(1)A], an oxygen and a sulphur from a bidentate chelate ligand (A) [Cd O, 2.36(1)A; Cd S, 2.773(4)A] and an oxygen from a bridging car☐yl group (ligand D) [Cd O, 2.28(1)A]. Ligands C and D also bridge two Cd centres through sulphurs [Cd S, 2.739, 2.723(4)A]. The second car☐yl oxygen of ligand A also forms a bridge to the second Cd [(Cd O, 2.30(1)A], while the distorted octahedral MO4S2 stereochemistry is completed by two waters [Cd O, 2.25(1), 2.49(1)A] and a sulphur from ligand D [Cd S, 2.723(4)A] giving a polymer structure. Complexes (3) and (4) are centrosymmetric tetra-car☐ylate bridged dimers [for (3) Cu ··· Cu, 2.586(3)A; mean Cu O(equatorial), 1.957(11)A; for the two independent dimers in (4), Cu ··· Cu, 2.596(1), 2.616(1)A; Cu O (equatorial), 1.952(4), 1.968(4)Amean]. The axial positions of the dimer in (3) are occupied by car☐yl oxygens of adjacent dimers [Cu O, 2.280(9)A] forming a polymer structure. In contrast, these positions in (4) are occupied by ethanol molecules with Cu O, 2.222(3) and 2.177(4)Arespectively for the two independent dimers.

Di-n-butyltin(IV) di-o-bromobenzoate, a weakly-bridged dimer

Abstract The six-coordinated tin in di-n-butylin di- o -bromobenzoate has a skew-trapezoidal bipyramidal geometry with a C-Sn-C angle of 140.5(3)°. The molecules are packed in the unit cell as weakly-bridged dimers (Sn···O 3.451(5) A).

Silver(I)–phenoxyalkanoates. The crystal and molecular structures of polymeric [(4-chloro-2-methylphenoxy)ethanoato-O,O′]silver(I), [(2,4-dichlorophenoxy)-ethanoato-O,O′]silver(I), and di-µ-[(2-chlorophenoxy)ethanoato-O,O′]-disilver(I)–silver(I) perchlorate (1/1)

The crystal structures of three polymeric silver(I) phenoxyalkanoates have been determined by X-ray diffraction. The isomorphous complexes, [(4-chloro-2-methylphenoxy)ethanoato]silver(I)(1) and [(2,4-dichlorophenoxy)ethanoato]silver(I)(2) are chain polymers of the type [{AgL}n] and involve only two-co-ordinate linear bonds to silver [Ag–O, 2.185(3)–2.217(3)A; O–Ag–O, 176.8(2), 177.5(2)°]. Complex (1) is monoclinic, space group P21/n, Z= 8, in a cell with a= 9.100(2), b= 13.503(6), c= 15.702(5)A, β= 100.12(2)°, and was refined to R= 0.053 for 2 743 observed reflections. Complex (2) was confirmed as isomorphous and isostructural with (1) using single-crystal and X-ray powder diffractometry. Di-µ-[(2-chlorophenoxy)ethanoato]-disilver(I)–silver(I) perchlorate, [{Ag2L2·AgClO4}n], (3), forms triclinic crystals, space group P, with Z= 2, in a cell of dimensions a= 10.245(2), b= 10.798(2), c= 11.067(2)A, α= 75.27(2), β= 68.27(2), γ= 82.70(2)°. The structure was refined to R= 0.052 for 3 661 observed reflections. Complex (3) is a sheet polymer based on bis(carboxylate) bridged Ag2L2 units [Ag–O, 2.229(4)–2.299(4)A]. In the two axial sites of the dimers are a co-ordinated perchlorate group [Ag–O, 2.454(4)A] and a bridging carboxyl oxygen [Ag–O, 2.373(4)A], while an angular bridge is also formed between the centrosymmetrically related dimer pairs by the third silver [Ag–O, 2.322(4), 2.296(4)A; O–Ag–O, 126.4(4)°].

Metal—(phenylthio)acetic acid interactions. Part 3. The crystal structures of anhydrous barium (phenylthio)acetate and the potassium (phenylthio)acetate-(phenylthio)acetic acid adduct

Abstract The crystal structures of barium and potassium complexes of (phenylthio)acetic acid (PTAH) have been determined using X-ray diffraction. The barium analogue, [Ba(PTA) 2 ] n (1) is monoclinic, space group C2 with Z = 2, a = 7.219(4), b = 5.894(2), c = 19.272(2) A, β = 91.57(4)°. [K(PTA)(PTAH)] n (2) is triclinic, space group P 1 with Z = 2, a = 6.272(1), b = 7.222(1), c = 18.459(3) A, α = 97.23(1), β = 93.64(1), γ = 97.31(1)°. The structures of (1) and (2) were refined to residuals of 0.047 and 0.053 for 844 and 2628 ‘observed’ reflections respectively. The MO 8 coordination about Ba in (1) is distorted ‘cubic’ with four oxygens from two bidentate carboxylate groups [BaO, 2.86, 2.97(3) A] and four oxygens from adjacent carboxylates [BaO, 2.68, 2.69(2) A] forming an infinite 2-dimensional polymer structure. (2) is polymeric and has bonded PTA as well as adducted PTAH species. There are seven KO contacts ranging from 2.729–3.034(3) A from both PTA and PTAH species in an irregular coordination.

Synthesis and characterization of copper(I) halide/pseudohalide adducts of 2-benzoylpyridine and X-ray crystal structure of [di-μ-iodo-bis(N,O-2-benzoylpyridine)dicopper(I)]

Abstract Dark-brown copper(I) complexes of the type CuXL, for X = Cl, Br, I, SCN and N3, and orange-yellow complexes of the type (CuX)2L, for X = Cl or Br, where L = 2-benzoylpyridine, have been prepared and characterized. All complexes exhibit strong CT bands in the visible region and gave non-conducting solutions in acetone and nitrobenzene. The IR spectral data suggest that 2-benzoylpyridine acts as a monodentate ligand in the orange-yellow complexes and as a bidentate chelating ligand in the brown complexes, whereas bridging halides and pseudohalides exist in both types. The structure of the 1 : 1 black iodide complex, as determined by X-ray crystallography, features a discrete, centrosymmetric [CuI(2-benzoylpyridine)]2 molecule with a short Cu⋯Cu distance of 2.587(1) A. Each copper atom in the dimeric molecule is tetrahedrally coordinated by two μ-iodine atoms and the carbonyl oxygen and nitrogen atoms of the chelating 2-benzoylpyridine ligand. The orange-yellow complexes display visible emission when excited in the UV region, whereas the brown complexes do not.

Preparation and characterization of gold(III) halide complexes of picolinic acid (pic-H) and X-ray crystal structure of [K(pic-H)2(H2O)2][AuBr4]·(pic-H)2

Abstract Complexes of the types MAuX4·4(pic-H)·2H2O (M = Na for X = Cl and M = K for X = Br), NaAu(pic)2K2·2H2O (where X = Cl or I) and NaAuCl4·Na(pic-H)·(pic)·2H2O (where pic-H = picolinic acid) have been prepared and characterized. Picolinic acid functions as a neutral N,O-bidentate ligand in the first type and as an O-monodentate picolinate anion in the second type. The IR results suggest that the last complex contains both neutral and anionic organic moieties. The conductivities of these complexes were measured and are discussed. X-ray single-crystal analysis of the KAuBr4 · 4(pic-H)·2H2O complex revealed that it should be formulated as [K(pic-H)2(H2O)2]·[AuBr4]·(pic-H)2. The potassium atom in the centrosymmetric cation is octahedrally coordinated by two trans-N,O-bidentate neutral picolinic acid molecules [KN = 2.790(6) A and KO = 2.888(5) A] and two aqua ligands at KO distances of 2.769(4) A. The other two picolinic acid molecules are involved in hydrogen bonding with the oxygen atoms of the coordinated pic-H and aqua molecules.