Vickie McKee

Binuclear manganese(II) and nickel(II) complexes with a potentially octadentate macrocyclic ligand (H4L1): synthesis and characterisation. X-ray crystal structures of [Mn2(H2L1 )(CH3COO)2]·2CH3OH and [Ni2(H2L1 )(H2O)2Cl2]·2H20

Abstract A series of binuclear manganese(II) and nickel(II) complexes of the macrocyctic ligand H4L1 has been prepared and characterised. ([Mn2(H2L1)A2], where A=Cl−, Br−, NO3−, NCS−, CH3COO− or N3−; [Ni2(H2L1)X2Y2], where X=Cl−, Br− or NO3− and Y= H20, [Ni2(H2L1)(NCS)2(C2H5OH)] and [Ni2(H2L1)(CH3COO)2]·2H2O). The macrocycle is formed by Schiff base condensation of two molecules of 2,6-diformyl-4-methylphenol with two molecules of 1,3-diamino-2-hydroxypropane in the presence of Ni(lI) or Mn(II) as template ion. The complexes are all binuclear with the two metal ions bridged by the deprotonated phenolate donors of the macrocycle. The alcohol groups of the macrocyclic ligand do not coordinate to the metal ions. The complexes have been characterised by analytical, spectroscopic, electrochemical and magnetic susceptibility measurements and the single crystal X-ray structures of [Mn2(H2L1)(CH3COO)2]·2CH3OH (triclinic, P 1 , a=8.701, b= 10.258, c=10.612 A, α=62.44, β=67.83, γ= 77.74°, V=776.8 A3, Z=1) and of [Ni2(H2L1)(H2O)2Cl2]·2H2O (rhombohedral, R 3 , a=28.885, c=9.783 A, V=7069 A3, Z=9) have been determined.

The crystal structures of chloro mercury(II) salts found for some CrN63+ cations and their CrN bond-ruptured hydrolysis products

Abstract Cr(en) 3 3+ and isomeric forms of Cr(dien) 2 3+ produce yellow or orange-yellow chloro mercury(II) salts on crystallisation from 6 M HCl containing excess HgCl 2 . The salt formed by [Cr(en) 3 ]Cl 3 has the stoichiometric composition [Cr(en) 3 ] 2 [Hg 3 Cl 12 ] whereas the Cr(dien) 2 3+ salts are associated with various anions of empirical stoichiometry Hg 2 Cl 7 3− . With Cr(en) 3 3+ and u-fac -Cr(dien) 2 3+ , red CrN bond ruptured products, such as cis -[CrCl(en) 2 (Hen, N ) 3+ ][HgCl 5 3− ] are formed at long reaction times. The crystal structures of [Cr(en) 3 ] 2 [Hg 3 Cl 12 ] ( 1 ) (triclinic; a = 11.25, b = 11.245, c = 17.421 A, α =81.66, β = 72.25, γ = 90.01°; V = 2074.31 A 3 ; Z = 2), [CrCl(en) 2 (Hen, N )][HgCl 5 ] ( 2 ) (monoclinic; a = 13.304, b = 11.717, c = 14.040 A; α = 90, β = 119.05, γ = 90°; V = 1915.71 A 3 ; Z = 4), mer -[Cr(dien) 2 ][HgCl 5 ] ·[DMSO] 2 ( 3 ) (monoclinic; a = 11.007, b = 8.696, c = 14.305 A; α = 90, β = 91.85, γ = 90°; V = 1368.52; Z = 2), s-fac -[Cr(dien) 2 ] [Hg 2 Cl 7 ] ( 4 ) (triclinic; a = 11.011, b = 11.922, c = 17.588 A; α = 77.295, β = 78.739, γ = 83.553°; V = 2201.00 A 3 ; Z = 4), u-fac -[Cr(dien) 2 ] [Hg 2 Cl 7 ] ( 5 ) (orthorhombic; a = 8.521, b = 16.175, c = 31.914 A; α = 90, β = 90, γ = 90°; V = 4398.76; Z = 8) and s-fac -[CrCl(dien)(Hdien, N,N )] [Hg 2 Cl 7 ] ( 6 ) (monoclinic; a = 7.885, b = 18.21, c = 16.926 A; α = 90, β = 101.37, γ = 90°; V = 2382.55; Z = 4) have been determined by X-ray analyses. In 2 and 3 , the HgCl 5 3− stoichiometry comes from isolated HgCl 4 2− and Cl − units and in 1 the Hg 3 Cl 12 6− stoichiometry from three HgCl 4 2− units. The Hg 2 Cl 7 2− anions are more diverse, with linear (Hg 2 Cl 7 ) n 3 n − chains in 6 , (HgCl 3 ) n n − chains closely associated with HgCl 4 2− anions in 5 and s-fac - Cr(dien) 2 3+ cations associated with distinguishable Hg 2 Cl 6 2− , Hg 4 Cl 14 6− and HgCl 4 2− anions in 4 .

Structural systematics of the isomeric di-μ-chlorobis(N, N-dialkylbenzylamine-2,C, N)dipalladium(II) complexes. The crystal structures of the ortho-, meta- and para-methoxy substituted complexes

Abstract The crystal structures of three isomeric methoxy substituted bis-chloro bridged ( N, N -dimethylbenzylamine)palladium(II) dimers have been determined by X-ray diffraction. Both the ortho -isomer ( 1 ) and the meta -isomer ( 2 ) are monoclinic, spacegroup P 2 1 / c with Z = 2 in cells of dimensions a 5.7391(7), b 17.794(4), c 10.907(2) A, β 97.76(1)° ( 1 ), and a 9.897(1), b 11.178(2), c 10.660(2) A, β 105.76(1)° ( 2 ). The four molecules of the para -isomer ( 3 ) crystallize with two molecules of toluene of solvation in a cell of dimensions a 8.403(1), b 20.056(3), c 15.521(2) A, β = 90.54(1)°, space group P 2 1 / n . All three complexes have the expected trans -related dimeric structures about square planar palladium(II) centres, although 3 does not have the centrosymmetry of 1 and 2 . The PdC and PdN bond lengths show no significant variation across the series (range 1.967–1.986 A; mean, 1.977 A) and (range 2.068–2.075 A; mean, 2.071 A), respectively. The PdCl bridge bonds are asymmetric, consistent with the trans effect of the PdC bond (range, 2.466–2.488 A; mean 2.476 A and 2.334–2.341 A; mean, 2.337 A).

A furan-derived schiff-base crypt and incorporating the trans,trans dicarbimine link

Abstract -X-ray crystallographic structure determination shows the furan dicarbimine fragment in the hexaimino diamino tris furano cryptand L1 to have a trans,trans configuration; solution and coordination behaviour however, indicates that the more strongly coordinating cis,cis configuration is easily accessible.

Solid state structure and solution conformation of a macrobicyclic cyclophane

X-ray crystallographic structure determination of the macrobicyclic cyclophane L1 reveals a compact structure involving close edge-to-face approach of aromatic rings; 1H nmr shows that this is also the solution conformation.

The crystal structures of some chloromercury(II) anions with Co(III) complexes or protonated polyamines as cations

Abstract The crystal structures have been determined for [Co(NH3)6][Hg3Cl9]·H2O (1) (monoclinic, P21/c, a=7.943(2), b=21.070(9), c=12.413(4) A, β=90.33(2)°, V=2077.4 A3, Z=4); trans-[CoCl2(en)2]2[Hg2Cl6] (2) (monoclinic, P21/c, a=9.110(3), b=8.811(3), c=17.297(6) A, β=90.86(3)°, V=1388.4 A3, Z=2); [NH3(CH2)2NH3][Hg2Cl6] (3) (triclinic, P 1 , a=6.128(1), b=6.984(1), c=8.045(2) A, α=77.81(2), β=85.87(2), γ=66.40(2)°, V=308.4 A3, Z=1); [NH3(CH2)2NH3]2[HgCl4][Cl]2 (4) (orthorhombic, Pnma, a=122.759(4), b=6.073(2), c=19.829(7) A, V=1536.5 A3, Z=4); [NH3(CH2)3NH2(CH2)3NH3]2[Hg3Cl12] (5) (tetragonal, P41212, a= b=12.645(3), c=20.892(8) A, V=3341.5 A3, Z=4);and [NH3(CH2)2NH2(CH2)2NH2(CH2)2NH3[Hg2Cl8] (6) (monoclinic, P1/c, a=11.892(3), b=11.872(4), c=14.350(4) A, β=98.25(2)°, V=2005 A3, Z=4).Four of these six salts show unique Hg(II)-CI coordination. The anions in 2 and 3 are the previously described dimeric, chloro-bridged, bitetrahedral units, Hg2Cl63−. In 3, the HgCl42− anion is polymeric with a single Hg-Cl…Hg bridge, while in 6 two HgCl42−units are in much closer association and form linked Hg2Cl84− anions. Of the trimercury(II) anions, Hg3Cl93− in 1 forms (Hg3Cl93−) in chains while Hg3Cl126− in 5 exists as an isolated anion.

The structures of [Co(en)3][HgCl4I] and cis-[Co(en)2(NH3)(py)][Hg2Cl7] — complexes containing novel halo-mercury(II) anions

Abstract The single crystal X-ray structures of the title complexes have been determined. Racemic [Co(en)3][HgCl4I] (monoclinic, P21/a, a=13.488, b= 11.716, c=11.910 A, β=109.82°, V=1770.6 A3, Z=4, Dcalc=2.67 g/cc) consists of lel ob2 cations associated with [HgCl3I]2− and Cl− anions. Halo- mercury(II) distances within the irregular tetrahedral [HgCl3I]2− anion are HgI=2.65 A and HgCl varies from 2.46 to 2.63 A. Racemic-cis-[Co(en)2(NH3)(py)] [Hg2Cl7] (orthorhombic, Pbcn, a= 22.663, b=14.137, c=14.459 A, V=4632 A3, Z= 8, Dcalc=2.66 g/cc) consists of isolated δλ cations and weakly interacting dibridged [Hg2Cl7]3− anions. Within each [Hg2Cl7]3− unit, HgCl distances vary from 2.34–2.97 A, and the closest HgCl approach between two adjacent [Hg2Cl7]3− units is 3.36 A.

Anionopentaaminecobalt(III) complexes with polyamine ligands. 22. The formation of a novel tridentate ligands by oxidative deamination of 2-methyl-1,2-diaminopropane

Abstract [CoCl(ibn)(L)]ZnCl 4 (ibn = NH 2 CH 2 C(CH) 3 2 NH 2 , L = NH 2 CH 2 C(CH 3 ) 2 NCHC(CH 3 )NH 2 ) has been isolated from the reaction between dioxygen, CoCl 2 ·6H 2 O and ibn refluxing methanol. A single crystal X-ray structure of the dinitrate (trihydrate) salt shows that the tridentate ligand adopts a meridonal arrangements, and, in the remaining three octahedral sites, the unsymmetrical ibn ligands occupies a position such that the CH 2 NH 2 end is trans to the chloro ligand. Kinetic parameters for the H g 2+ , assisted loss of the coordinated chloro ligand from [CoCl(ibn)(L)]-ZnCl 4 (HClO) 4 , μ = 1.0 M) are 10 3 k Hg (298) = 1.33 M −1 s − , E a = 73.8 kJ mol −1 , Δ S 298 ♯ = −60.7 J K −1 mol −1 .

Photochromic formazans: X-ray crystal structure magnetic resonance and Raman spectra of 3-methyl-1,5-diphenylformazan and 3-t-butyl-l,5-diphenylformazan

The X-ray crystal structures of 3-methyl-1,5-diphenylformazan (1) and 3-t-butyl-1,5-diphenylformazan (2) have been determined. Magnetic resonance spectra, in both the solid state and in solution, and Raman spectra have been studied. C14H14N4(1) belongs to the monoclinic space group P21/c, a= 8.133(1), b= 19.085(4), c= 9.364(3)A, β= 105.93°, U= 1 397.6(5)A3, Z= 4; the anti, s-trans configuration found for the solid state is also the thermodynamically preferred configuration in solution equilibrium. C17H20N4(2) belongs to the monoclinic space group P21/c, a= 11.235(3), b= 20.117(5), c= 14.176(3)A, β= 92.14(2)°, U= 3 202(1)A3, Z= 8; the syn, s-cis configuration of the solid state is maintained in solution.

Photochromic formazans: Raman spectra, X-ray crystal structures, and 13C magnetic resonance spectra of the orange and red isomers of 3-ethyl-1,5-diphenylformazan

The X-ray crystal structures of the two isomers of a photochromic formazan have been determined. Red 3-ethyl-1,5-diphenylformazan belongs to the orthorhombic space group P212121 and adopts a syn,s-trans-configuration. The orange, light-stable isomer, belongs to the monoclinic space group P21/c and adopts an anti,s-trans-configuration. Raman and 13C n.m.r. spectra for the orange isomer both in the solid state and in solution confirm that the solution species retains the structure established for the solid state. The Raman spectrum for the red isomer in the solid state shows the shifts to lower wavenumber for the azo group stretching vibration characteristics of the syn,s-trans-configuration.