Eric J. O'Reilly

The Crystal Structure of Silver(i) (2-Carbamoylphenoxy)acetate

The crystal structure of anhydrous silver(i) (2-carbamoylphenoxy)acetate has been determined by X-ray diffraction and refined to a residual of 0.041 for 1532 observed reflections. The complex forms crystals with space group C 2/c and Z 4 in a unit cell of dimensions a 20.789(6), b 5.202(1) c 17.318(6) A, s 105.89(2)°. The structure is based on a centrosymmetric bis-carboxylate bridged dimer [Ag-O 2.228(3), 2-266(3) A, O-Ag-O 155.8(1)° Ag…Ag 3-001(1) A] which is extended into an infinite zigzag polymer through the axial positions via the carbamoyl oxygens of adjacent ligands [Ag-O 2.494(3) A]. Symmetrical long-range interactions of phenyl-carbon to silver are also found in the structure [Ag-C 3.094, 3.078(4) A].

Metal-phenoxyalkanoic acid interactions. Part 3. Crystal and molecular structures of tetra-μ-(2,4-dichlorophenoxyacetato)bis[aquacopper(II)] dihydrate and tetra-μ-(2,4,5-trichlorophenoxyacetato)bis[pyridinecopper(II)]

The crystal structures of tetra-μ-(2,4-dichloropehonxyacetato)bis[aquacopper(II)] dihydrate (1) and tetra-μ-(2,4,5-trichlorophenoxyacetato)bis[pyridinecopper(II)] (2) have been determined by X-ray diffraction from diffractometer data and refined by leasi-squares to R 0.11 (2218 reflections) and 0.0068 (2268 reflections) for (1) and (2) respectively. For (1), crystals are monoclinic, space group C2/c with Z = 4 in a cell of dimensions a = 36-98(3), b = 7.582(2), c = 14.972(5) A, β = 105.52(5)° while for (2) the space group si P1 with Z = 1 with a cell of dimensions a = 12.184(8), b = 13.719(7), c = 8.687(6) A, α = 99.69(5), β = 99.15(5), γ = 114.01(4)°. Both compounds (1) and (2) consist of centrosymmetric tetra-carboxylate birdged dimer units of copper acetate type, with CuCu separations of 2.639(5) A (1) and 2.716(7) A (2). The copper and carboxylate oxygens lie approximately in the smae plane in both (1) and (2) with a mean CuO distance of 1.972(10) A and 1.973(12) A respectively while the co-ordination sphere is completed in the axial positions by water oxygens [2.120(10) A] in (1) and pyridine nitrogens [2.142(12) A] in (2).

Metal-phenoxyalkanoic acid interactions. Part 6. Crystal and molecular structure of tetraaquabis(2,4-dichlorophenoxyacetato) zinc(II)diaquabis(2,4-dichlorophenoxyacetato)zinc(II)

Abstract The crystal structure of tetraquabis(2,4-dichlorophenoxyacetato)zinc(II) diaquabis(2,4-dichlorophenoxyacetato)zinc(II) has been determined by direct methods from three-dimensional X-ray diffraction data and refined by least squares to a residual value of 0.068 for 2703 ‘observed’ reflections. Crystals are orthorhombic, space group Pna21 with 4 molecular ‘dimers’ in a cell of dimensions a = 19.302(2), b = 6.051, c = 36.325(6) A. The molecular units, {[Zn(H2O)4(2,4-D)2][Zn(H2O)2(2,4-D)2]} consist of two discrete and stereochemically different complexes, one octahedral, the other tetrahedral about the zinc centres. The six-coordination about the first Zn comprises four oxygens from aqua ligands [ZnO, 2.069(10)–2.147(9) rA] and two from the carboxyl groups of trans-related unidentate 2,4-dichlorophenoxyacetato ligands [ZnO, 2.071(9), 2.121(9) A]. The un-complexed carboxylate oxygens are tied into the complex unit by intramolecular hydrogen bonds to the water ligands (O⋯O, 2.66, 2.64 A). The four-coordination about the second Zn comprises two aqua ligands [ZnO, 2.003(10), 2.001(9) A] and two unidentate carboxyl oxygens from 2,4-dichlorophenoxyacetato ligands [ZnO, 1.915(10), 1.956(9) A]. The two units are not formally bonded but have inter-molecular O⋯O associations ranging from 2.68 to 2.85 A.

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—XXIII. Complexes of copper(II) with the phenoxyisobutyric acids. The crystal structures of tetra-μ-[2-methyl-2-(4-chlorophenoxy)propanoato-O,O′)]-bis[(2-aminopyrimidine)copper(II)] and two polyaquacopper(II) tri-μ-[2-methyl-2-phenoxypropanoato-O,O′]-bis[(2-methyl-2-phenoxypropanoato)copper(II)] polymorphs

Abstract The crystal structures of three copper(II) complexes with phenoxyisobutyric acid (PIBAH) and p-chlorophenoxyisobutyric acid (PCIBAH) have been determined by X-ray diffraction. Tetra-μ-[2-methyl-2-(4-chlorophenoxy)-propanoato-O,O′]-bis[2-amino-pyrimidine)copper(II)], [Cu2(PCIBA)4(2-aminopyrimidine)2]2 (1) is a centrosymmetric tetracar☐ylate bridged dimer [Cu⋯Cu, 2.689(2)A] with the nitrogens of the 2-aminopyrimidine molecules occupying the axial positions [Cu N, 2.198(7)A]. Tetraaquacopper(II) tri-μ-[2-methyl-2-phenoxypropanoato-O,O′]-bis[(2-methyl-2-phenoxypropanoato(copper(II)], [Cu(H2O)4]2+] {[Cu2(PIBA)5]−}2, (2), is a disordered precursor of the stable structure (3), [Cu(H2O)5]2+ {[Cu2(PIBA)5]−·4H2O, consisting of centrosymmetric square planar [Cu(H2O)4]2+ cations and tris(car☐ylate)-bridged dimer anions [Cu⋯Cu, 2.85(1)A] (2). The fourth position of each square planar dimer ‘end’ is occupied by a car☐ylate oxygen of a PIBA molecule which also provides the ether oxygen capping each axial dimer site [Cu O, 2.15(4), 2.19(5)A]. This completes a five-membered chelate ring. A symmetrical array of eight hydrogen bonds link the four waters of the [Cu(H2O)4]2+ cation to the car☐yl oxygens of both the capping PIBA ligands of the two dimeric anions. Structure (3) has essentially identical [Cu2(PIBA)5]− dimer anions [Cu⋯Cu, 2.929(1)A] and hydrogen-bonding interactions with the tetraaquacopper(II) cations. However, water molecules partially occupy the octahedral sites of these cations [Cu O, 2.46(1)A], as well as a number of lattice sites in the crystal.

Metal–phenoxyalkanoic acid interactions. Part 13. Copper(II)–(2-chlorophenoxy)ethanoic acid complexes. Crystal and molecular structures of catena-tetra-µ-[(2-chlorophenoxy)ethanoato-O,O′]-dicopper(II), catena-(2-aminopyrimidine-N,N′)-tetra-µ-[(2-chlorophenoxy)ethanoato-O,O′]-dicopper(II), and 1,2,2,2,2-penta-aqua-tetra-µ-[(2-chlorophenoxy)-ethanoato-O,O′]-copper(II)calcium(II)

The crystal structures of three copper(II) complexes of (2-chlorophenoxy)ethanoic acid have been determined by X-ray diffraction. Anhydrous [{Cu2(O2CCH2OC6H4Cl-2)4}n](1) is monoclinic, a= 11.587(3), b= 5.084(2), c= 29.600(6)A, β= 103.76(2)°, Z= 2, space group P21/c. The adduct [{Cu2(O2CCH2OC6H4Cl-2)4(ampym)}n](ampym = 2-aminopyrimidine)(2) is triclinic, a= 17.543(5), b= 13.344(5), c= 8.459(3)A, α= 77.89(3), β= 81.43(3)°, γ= 87.61(3)°, Z= 2, space group P. [CaCu(O2CCH2OC6H4Cl-2)4(H2O)5](3) is orthorhombic, a= 13.800(4), b= 8.426(3), c= 32.558(10)A, Z= 4, space group C2221. (1), (2), and (3) were refined to residuals of 0.051, 0.060, and 0.046 for 1 752, 3 399, and 1 042 observed reflections respectively. All three complexes have tetracarboxylate bridged dimer systems [Cu–Cu, 2.583(2)A(1); 2.700(3), 2.730(3)A(2); and Ca–Cu, 3.480(3)A(3)]. In both (1) and (2), the centrosymmetric dimer units are extended into polymer structures via axial groups which in (1) are carboxyl oxygens from adjacent dimer units while in (2) they are the meta-related nitrogens of the pyrimidine rings. Complex (3) is monomeric with ‘half’ the dimer comprising a conventional CuO4(OH2) unit, the other ‘half’ being an eight-co-ordinate CaO4(OH2)4 unit, with two-fold rotational symmetry.

MetalPhenoxyalkanoic acid interactions. Part 4. The crystal structure of tetraaquabis(2,4,5-trichlorophenoxyacetato)manganese(II)-Bis(2,4,5-trichlorophenoxyacetic acid) adduct

Abstract The crystal structure of tetraaquabis(2,4,5-trichlorophenoxyacetato)manganese(II)-bis(2,4,5-trichlorophenoxyacetic acid) adduct has been determined by X-ray diffraction from diffractometer data and refined by least-squares to R 0.054 using 2142 ‘observed’ reflections. The crystals are triclinic, space group P 1 with Z = 1 in a cell of dimensions a = 7.456(5), b = 20.841(12), c = 7.175(4) A, α = 90.70(4), β = 99.18(5), γ = 77.11(5)°. The complex consists of slightly distorted centrosymmetric octahedral MnO6 units involving four aqua ligands [MnO, 2.190(5), 2.232(5) A] and two oxygens from unidentate trans-related 2,4,5-trichlorophenoxyacetate ligands [MnO, 2.146(5) A]. The uncoordinated carboxyl oxygens are bound via very short hydrogen bonds [C⋯⋯O, 2.459(8) A] to two adducted 2,4,5-trichlorophenoxyacetic acid molecules which layer in the structure with their benzene rings approximately parallel to those of the coordinated acid ligands.

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.

Metal-phenoxyalkanoic acid interactions Part 10. Crystal and molecular structures of catena-[tetraaqua(4-carboxylato-phenoxyacetato)manganese(II)], tetraaquabis(4-carboxyphenoxyacetato)nickel(II) and tetraaquabis(4-carboxyphenoxyacetato)cobalt(II)

Abstract The crystal structures of two metal(II) complexes of 4-carboxyphenoxyacetic acid have been determined by X-ray methods. The first, catena[tetraaqua(4-carboxylato-phenoxyacetato)manganese(II), (1) forms crystals which are orthorhombic, space group Pbca, with 8 molecules in a unit cell of dimensions a = 10.356(2), b = 9.086(2), c = 25.673(8) A. It has a polymeric structure involving both cis-related carboxylate groups and four water molecules about a slightly distorted octahedron. The mean MnO (water) distance is 2.214(7) A, while the MnO (carboxylate) distances are 2.147(6) and 2.111(7) A. Tetraaquabis(4-carboxyphenoxyacetato)nickel(II) (2) is triclinic, space group P 1 with one molecule in the cell, dimensions a = 4.896(2), b = 5.679(2), c = 18.403(6) A, α = 93.75(3), β = 91.78(3), γ = 95.76(2). The centrosymmetric complex units are discrete monomers with unidentate trans-related acid ligands bonded through the phenoxy carboxylate oxygen [NiO, 2.058(3) A]. The NiO (water) distance is 2.055(4) A. Single crystal diffractometry and elemental analysis have been used to prove that the Co(II) (3) analogue is isomorphous and isostructural with the Ni(II) complex. The p-carboxy group of one molecule is hydrogen bonded about a centre of symmetry to another p-carboxy group.

Metal-phenoxyalkanoic acid interactions. Part 7. The x-ray crystal and molecular structures of pentaaqua-(2,4,5-trichlorophenoxyacetato)manganese(II)(2,4,5-trichlorophenoxyacetate), and pentaaqua-(2,4,5-trichlorophenoxyacetato)magnesium(II)(2,4,5-trichlorophenoxyacetate)

Abstract The room temperature crystal structure of the complex species of empirical formula Mn(II)(2,4,5-T**)2(H2O)5, (1) has been determined by X-ray diffraction from diffractometer data and refined by least squares to R 0.101 using 964 observed reflections. The crystals are triclinic, space group P 1 with Z = 2 in a cell of dimensions a = 23.122(8), b = 7.560(2), c = 7.066(2) A, α = 90.72(2), β = 86.37(2), γ = 88.98(2)°. The complex units have a distorted octahedral coordination comprising five waters [Mn-O, 2.21(2) A, mean] and one oxygen from a unidentate 2,4,5-T ligand [MnO, 2.072(2) A]. Charge balance in the complex is maintained by the presence of the second 2,4,5-T anion which is fixed in the structure by hydrogen bonding and π-π interactions with the ligand anions. On the basis of chemical analysis, single crystal and powder X-ray diffraction data, the Mg(II) complex (2) of the same empirical formula has been proved isostructural and isomorphous with [Mn(2,4,5-T)(H2O)5] (2,4,5-T). The triclinic crystals have the cell dimensions a = 23.00(7), b = 7.54(2), c = 7.07(2) A, α = 90.0(3), β = 86.4(1), γ = 88.8(1)°.