Second sphere coordination complexes: Synthesis, characterization, single crystal structure and packing analyses of trans-Cu(en)2(H2O)22 where L1=p-toluenesulphonate, L2=5-bromo-2-methoxybenzenesulphonate (original) (raw)
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Journal of Molecular Structure, 2010
Two new copper(II) complexes of composition [trans-Cu(en) 2 (H 2 O) 2 ](L 1 ) 2 , 1 and [trans-Cu(en) 2 (H 2 O) 2 ](L 2 ) 2 , 2 (L 1 = 3-methoxybenzoate, L 2 = 3,4,5-trimethoxybenzoate) were obtained by the addition of ethylenediamine to hydrated Cu(II) benzoates, Cu(L 1 /L 2 ) 2 ÁH 2 O in methanol-water mixture. The newly synthesized complexes have been characterized by elemental analyses, spectroscopic techniques (electronic and FT-IR), magnetic moment determination and molar conductance studies. The complex 1 crystallizes in the triclinic system with space group P1 and complex 2 crystallizes in the monoclinic system with space group P2 1 /c. X-ray structure determination revealed ionic structures consisting of one complex cation [Cu(en) 2 (H 2 O) 2 ] 2+ and two respective aryl benzoate anions in 1 and 2. There is a slight difference in the interplanar (plane passing through the Cu centers) distance between two cationic layers of both the complexes due to presence of two more AOCH 3 groups on the anionic moiety in 2. A three dimensional hydrogen bonding network formed by NAHÁ Á ÁO and OAHÁ Á ÁO through second sphere and CAH. . .p interactions besides electrostatic forces of attraction stabilizes crystal lattice in both the complexes.
A study of the second coordination sphere in 8-azaxanthinato salts of divalent metal aquacomplexes
Inorganica Chimica Acta, 2009
The interaction of the 4,6-dimethyl and 4-monomethyl derivatives of 1,2,3-triazolo[4,5-d]pyrimidin-5,7dione (which may be named also as purine derivatives, 1,3-dimethyl-8-azaxanthine, Hdmax and 3-methyl-8-azaxanthine, H3max) with the divalent cations of Mn, Co, Ni, Zn and Cd in aqueous media generate solids with formulation ML 2 Á 6H 2 O. The crystal structure of the Mn and Cd compounds with dmax and the Cd compound with 3max have been determined by single-crystal X-ray diffraction revealing that the compounds are salts with [M(H 2 O) 6 ] 2+ as cations and dmax À or 3dmax À as anions. The second-sphere interactions in these compounds have been analysed, consisting in a network of very welldefined hydrogen bonds, with all available potential donor and acceptor positions involved. The topology of the motifs generated by these hydrogen bonds has been characterised, adapting to the second coordination sphere concepts usually applied to the first (chelate, bridge, monodentate, . . .). Monodimensional (tapes) superstructures with the building blocks rather tightly bounded appear in the compounds with dmax À as anion, whereas the corresponding superstructure in the Cd compound with 3max À is bidimensional. These superstructures further interact among them in a less tight fashion to generate the three dimensional crystal structures. Powder X-ray diffraction strongly suggests that Mn, Co, Zn and Cd compounds of each ligand are isostructural, so the results of the samples determined by single-crystal X-ray diffraction may be extended to all these compounds. On the other hand, powder X-ray diffraction indicates that the nickel compounds have a different structure and the spectroscopic data for these compounds suggest that the ligand is directly attached to the metal for them.
Inorganic Chemistry, 1990
The synthesis and structural characterization of six new copper(I1) squarate complexes of formula [Cu(bpy)(H20)(C404)].H,0 (1). [CUZ(~PY)Z(HZO)Z(C,O,)~ (N W Z (3, [C~(P~~~)(HZO)~(C~O~)I.~HZO (3), [C~(~~~PY)(HZO)(C~~~)I.H~O (4), [Cudter-PY)z(H~O)~(C~O~)I(CIO~)Z (9, and [Cu2(pmdien)2(Hz0)2(C404)1(N03)~ (6) (where bpy, phen, terpy, pmdien, and C4042-are 2,2'-bipyridine, I , IO-phenanthroline, 2,2':6',2"-terpyridine, 1 ,I ,4,7,7-pentamethyldiethylenetriamine, and the dianion of 3,4-dihydroxycyclobutenedione, respectively), are described. The crystals of 1 are orthorhombic, space group Pbca, with 2 = 8, a = 17.182 (3) A, b = 13.094 (3) A, c = 12.321 (2) A, and R = 0.053 (R , = 0.058) for 1874 observed reflections. The crystals of 2 are monoclinic, space group P2,/n, with 2 = 2, a = 14.478 (3) A, b = 9.932 (2) A, c = 9.321 (2) A, fl = 98.09 (2)", and R = 0.040 (R , = 0.049) for 2867 observed reflections. The crystals of 3 are triclinic, space group P i , with Z = 2, a = 10.484 (3) A, b = 10.368 (2) A, c = 8.288 (2) A, a = 95.30 (2)O, f l = 83.48 (2)O, y = 110.45 (2)O, and R = 0.042 (R , = 0.049) for 2614 observed reflections. The crystals of 4 are monoclinic, space group P2,/a, with Z = 4, a = 19.626 (3) A, b = 11.291 (2) A, c = 8.436 (2) A, 6 = 99.69 (2)O, and R = 0.045 (R , = 0.050) for 1972 observed reflections. The crystals of 5 are monoclinic, space group P2,/n, with 2 = 2, a = 14.857 (3) A, b = 13.990 (3) A, c = 8.736 (2) A, @ = 93.19 (2)O, and R = 0.059 (R, = 0.064) for 2355 observed reflections. The crystals of 6 are monoclinic, space group P2,/n, with Z = 2, a = 15.802 (3) A, b = 12.975 (2) A, c = 8.207 (2) A, fl = 98.52 (2)O, and R = 0.041 (R , = 0.048) for 2013 observed reflections. The structures of 2,5, and 6 are made of PI ,3-squarato-bridged copper(I1) binuclear units. The structure of 4 consists of one-dimensional chains of p-I ,2-squarato-bridged copper(I1) complex units. The structure of 3 is built by mononuclear complex units in which the squarate acts as a monodentate ligand, whereas it acts as in 1,2,3-trismonodentate fashion in 1, giving a two-dimensional network parallel to the plane (100). The copper(I1) ion displays a pyramidal coordination in the discrete structures and a distorted octahedral coordination in the polymeric ones. The squarate ligand is planar in all these complexes. Infrared, UV-visible, and EPR spectra of these compounds are discussed, taking into account their crystal structures. Magnetic susceptibility data for 2, 4, and 5 as a function of the temperature show weak exchange interactions as expected from the structures. The ability of the squarate anion to act as a bridging ligand in copper(I1) complexes with different terminal ligands is structurally demonstrated. Simple stereochemical considerations allow us to predict that this ligand cannot coordinate to copper(I1) and most probably to first-row transition-metal ions either in a bisbidentate or even in a 1,2-bidentate fashion.
Journal of Molecular Structure, 2005
[Cu(H 2 O) 6 ](C 10 H 7 SO 3) 2 1 was obtained from reaction of CuCO 3 $Cu(OH) 2 and naphthalene-2-sulphonic acid in aqueous medium in 1:4 molar ratio. It crystallizes in the monoclinic space group P2 1 /n with aZ7.0582(3) Å , bZ6.2666(3) Å , and cZ27.1420(10) Å , bZ 92.678(4)8, ZZ2. The structure was determined from 1986 observed reflections and refined to RZ0.033. When ethylenediamine was added to hexaaquacopper(II) naphthalene-2-sulfonate dissolved in water, [Cu(en) 2 (H 2 O) 2 ](C 10 H 7 SO 3) 2 2 was obtained which crystallizes in the triclinic space group P 1 with aZ7.1491(5) Å , bZ7.1949(5) Å , and cZ14.6500(10) Å , aZ99.025(6)8, bZ98.976(6)8, and gZ104.262(6)8, ZZ1. The structure was determined from 2296 observed reflections and refined to RZ0.0313. X-ray structure determination of 1 revealed an ionic structure consisting of [Cu(H 2 O) 6 ] C2 and two naphthalene-2-sulfonate anions while that of 2 contains [Cu(en) 2 (H 2 O) 2 ] 2C cation and two naphthalene-2-sulfonate anions. Characteristic for the studied crystals is the alternated-layer arrangement of complex cations and naphthalene-2-sulfonate anions, linked together via hydrogen bonding, and the presence of a particularly robust R 2 2 ð8Þ hydrogen-bonding motif that joins the complex cation with two oxygen atoms of the same sulfonate group. Elemental analyses, IR, UV/vis spectroscopic studies are consistent with the structures revealed by X-ray structure determination.
Inorganic Chemistry, 1983
Simple and mixed-ligand copper(I1) complexes were synthesized and characterized by crystallographic and spectroscopic techniques. The N,S-and 0-donor chelating agents used include the following: 1,5-bis(benzimidazol-2-yl)-3-thiapentane, BBES; 1,5-bis(N-methylbenzimidazol-2-yl)-3-oxopentane, Me,BBEO; 2,5,8-trimethyl-2,5,8-triazanonane, pmeta; pentane-2,4-dionate anion, acac-; 2,2'-bipyridyl, bpy; 2,2'-biimidazole, biim. The perchlorate of Cu(BBES) crystallizes from methanol as the salt [CU(BBES)(M~OH)(OH,)](C~O~)~, with the symmetry of the space group Pi, Z = 2, a = 9.306 (3) A, 6 = 10.072 (5) A, c = 14.194 (5) A, a = 92.23 (2)O, @ = 96.63 (4)O, y = 108.56 (3)O, and pal& = 1.66 g~c m-~. The structure was solved with the Patterson method, incorporating 3088 of the 3884 independent reflections, to final R values of 5.6% and 6.1% (Rw). The complex cation has a distorted tetragonal pentacoordinate structure (T = 0.27) with the BBES occupying three equatorial positions, with a Cu-S linkage of 2.297 A, and the methanol bound axially. This contrasts with the perchlorate salt of a similar ligand's complex, obtained from ethanol, which has a perchlorate coordinated at this axial position. [Cu(BBES)(acac)]PF6-H20-EtOH was recrystallized from ethyl acetate to give the ester solvate, [ C U (B B~) (~C~C) ] P F~-C~H~~~. This complex also crystallizes with symmetry Pi, and Z = 2, a = 13.961 (3) A, 6 = 12.892 (3) A, c = 10.154 (3) A, a = 101.57 (4)O, @ = 104.99 (4)O, y = 104.34 (4)O, and peal& = 1.160 ~c m-~. The structure was solved by the Patterson method, using 2939 of the 3243 independent reflections, to final R values of 6.3% and 6.1% (R,J. The complex cation is of regularly tetragonal pyramidal geometry (T = 0.02) with an equatorial N,Oz-donor set and the thioether bound axially at 2.696 A, in contrast to the Cu(BBES) perchlorates. There are hydrogen-bonding interactions with benzimidazole and water protons in the lattices of the complexes. ESR spectroscopy shows that the Cu(BBES),+ and Cu(Me2BBE0)2+ complexes retain their distorted structures in solution; both give single-line ESR spectra in solution at ambient temperatures. The [Cu(BBES)(acac)]+ salts exhibit pairwise dipolar coupling in their crystalline states. Substitution of ether by thioether as donor causes absorptivity enhancement throughout the visible-near-UV spectrum, and difference spectroscopy has been used to assign sulfur-to-copper charge-transfer transitions. Unlike [Cu(bpy)(acac)]+ and [Cu-(BBES)(acac)]+, the complex cations [Cu(Me2BBEO)(acac)]+ and [Cu(biim)(acac)]+ are unstable toward coordinative disproportionation in the solvents used. The Cu(BBES),+ cation in solution is in equilibrium between thefac-BBES and mer-BBES isomers, the latter being dominant. (1) (a) Drexel University. (b) The Polytechnic of North London. (c) University of Virginia.
Journal of Coordination Chemistry, 2008
In an effort to explore [trans-Co(en) 2 Cl 2 ] C as anion receptor for tetrabromocadmate and tetraiodocadmate ion, green coloured single crystals of [trans-Co(en) 2 Cl 2 ]CdBr 4 I and [trans-Co(en) 2 Cl 2 ]CdI 4 II have been obtained by slowly mixing the separately dissolved transdichlorobis(ethylenediamine)cobalt(III) chloride with potassium tetrabromocadmate and tetraiodocadmate in aqueous medium in 2:1 molar ratio. The newly synthesized complex salt was characterized on the basis of elemental analysis and spectroscopic techniques (IR, UV/visible, 1 H and 13 C NMR). Single crystal X-ray structure determination of [trans-Co(en) 2 Cl 2 ] 2 CdBr 4 revealed that it crystallizes in the orthorhombic space group Pbca with aZ18.6201(10), bZ12.0872(6), cZ24.0877(12) Å , VZ5421.3(5) Å 3 , ZZ8, RZ0.0727. Supramolecular hydrogen bonding networks between ionic groups: bromide ions of tetrabromocadmate group and NH groups of coordinated ethylenediamine molecules, i.e. N-H/Br K interactions by second sphere coordination besides electrostatic forces of attraction have been observed. This suggests that [trans-Co(en) 2 Cl 2 ] C is a promising anion receptor for the tetrabromocadmate. q
Polyhedron, 2001
The nickel and platinum complexes [MX 2 (dppe)] (X = Cl, Br) react with bi-and tri-valent metal diethyldithiocarbamates [M%(S 2 CNEt 2 ) n ] (M%=Pb, Zn, Cd, Hg, Ni, MoO 2 , VO, n =2; M%=Co, Fe, Mn, n=3) to afford salts [M(S 2 CNEt 2 )(dppe)] 2 [M%X 4 ]; reactions involving [Cu(S 2 CNEt 2 ) 2 ] and [Ag(S 2 CNEt 2 )] gave salts of the form [M(S 2 CNEt 2 )(dppe)][M%X 2 ] (M%= Cu, Ag). The complexes cis [RuCl 2 (dppm) 2 ], [CoCl 2 (dppe)] and [PdX 2 (bipy)] likewise react with the same dithiocarbamates to form salts [Ru(S 2 CNEt 2 )(dppe) 2 ] 2 [M%Cl 4 ] [Co(S 2 CNEt 2 ) 2 (dppe)] 2 [M%Cl 4 ] and [Pd(S 2 CN n Bu 2 )(bipy)] 2 [M%X 4 ], respectively. Sample reactions involving other S-chelate ligands-S 2 COEt − , S 2 PPh 2 − and S 2 P(OEt) 2 − -appear to follow the same general pattern. However, the O-ethyldithio carbonates (ethylxanthates) are partly converted to the corresponding dithiocarbonates. An anomalous reaction between [CoCl 2 (dppe)] and [Zn(S 2 CNEt 2 ) 2 ] in the presence of (S 2 CNEt 2 ) 2 affords the novel complex [Co(S 2 CNEt 2 ) 2 (dppe)] 2 [Cl 3 ZnO:(Ph) 2 PCH 2 CH 2 P(Ph) 2 :OZnCl 3 ]. A selection of these salts have been fully characterised by elemental analysis and spectroscopic techniques, the remainder have been identified by spectroscopic methods alone. X-ray crystal structures are reported for the salts [Ni(S 2 CNEt 2 )(dppe)] 2 [HgBr 4 ], [Pt(S 2 CNEt 2 )(dppe)] 2 [CdCl 4 ], [Co(S 2 CNEt 2 ) 2 (dppe)] 2 -[Cl 3 ZnO:(Ph) 2 PCH 2 CH 2 P(Ph) 2 :OZnCl 3 ] and [Pd(S 2 CN n Bu 2 ) (bipy)] 2 [CdCl 4 ].
Journal of Fluorine Chemistry, 2005
cis-diazidobis(ethylenediamine)cobalt(III) mesitylenesulphonate hemihydrate, [cis-Co(en) 2 (N 3 ) 2 ]C 9 H 11 SO 3 $0.5H 2 O was crystallized from a solution of cis-diazidobis(ethylenediamine) cobalt(III) nitrate and sodium mesitylenesulphonate in aqueous medium in 1:1 molar ratio. Elemental analysis, spectroscopic studies (IR, UV/visible, 1 H and 13 C NMR) and conductance studies were undertaken for characterizing the complex salt. The compound crystallizes in the triclinic space group PK1 with aZ7.15220(10), bZ14.5218(3), cZ20.6925(5), VZ 2058.48 , ZZ4. X-ray structure determination revealed an ionic structure consisting of [cis-Co(en) 2 (N 3 ) 2 ] C cation, mesitylenesulphonate anion and half water molecule. In the complex cation [cis-Co(en) 2 (N 3 ) 2 ] C , the cobalt(III) is bonded to six nitrogen atoms, originating from two ethylenediamines, and two azide groups showing an octahedral geometry around cobalt. The crystal lattice is stabilized by electrostatic forces of attraction and hydrogen bonding interactions predominantly N-H.O K , suggesting that [cis-Co(en) 2 (N 3 ) 2 ] C is a promising anion receptor for the mesitylenesulphonate ion. This is the first report of a sulphonate salt containing the present cationic cobaltammine. q