Layered solids based on second-sphere coordination interactions: synthesis, spectroscopic characterization, crystal structure and packing of two copper(II) naphthalene-2-sulfonates (original) (raw)
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Crystal structures of two enantiomorphous 2-ethylpiperazinediium hexaaquacopper sulfates [(R or S)-C5H14N2]Cu(H2O)62
Journal of Structural Chemistry, 2012
Two new non-centrosymmetric copper sulfates are synthesized under slow evaporation conditions through the use of enantiomorphically pure sources of either (R)-2-methylpiperazine or (S)-2-methylpiperazine. Both crystallize in the non-centrosymmetric P2 1 space group, crystal data for [(R)-C 5 H 14 N 2 ][Cu(H 2 O) 6 ](SO 4) 2 (I), a = 6.5276(2) Å, b = 11.1955(3) Å, c = 12.4559(4) Å, E = 101.196(2)q, Z = 2, V = 892.95(5) Å 3 and [(S)-C 5 H 14 N 2 ][Cu(H 2 O) 6 ](SO 4) 2 (II), a = 6.5188(2) Å, b = 11.1786(2) Å, c = 12.4365(3) Å, E = 101.205(1)q, Z = 2, V = 888.99(4) Å 3. The three-dimensional structure networks for these compounds consist of isolated [Cu(H 2 O) 6 ] 2+ and [(R)-C 5 H 14 N 2 ] 2+ or [(S)-C 5 H 14 N 2 ] 2+ cations and 2 4 SO anions linked only by hydrogen bonds. The Cu atom is in a slightly distorted octahedral coordination environment. The crystal packings are influenced by cation-to-anion N-H…O and OW-H…O hydrogen bonds leading to an open framework structures.
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.
Acta Crystallographica Section E Crystallographic Communications, 2019
A reaction of copper(II) carbonate and potassium 4-sulfobenzoic acid in water acidified with hydrochloric acid yielded two crystalline products. Tetraaquabis(4-carboxybenzenesulfonato)copper(II) dihydrate, [Cu(O3SC6H4CO2H)2(H2O)4]·2H2O, (I), crystallizes in the triclinic space group P\overline{1} with the Cu2+ ions located on centers of inversion. Each copper ion is coordinated to four water molecules in a square plane with two sulfonate O atoms in the apical positions of a Jahn–Teller-distorted octahedron. The carboxylate group is protonated and not involved in coordination to the metal ions. The complexes pack so as to create a layered structure with alternating inorganic and organic domains. The packing is reinforced by several O—H...O hydrogen bonds involving coordinated and non-coordinated water molecules, the carboxylic acid group and the sulfonate group. Hexaaquacopper(II) 4-carboxybenzenesulfonate, [Cu(H2O)6](O3SC6H4CO2H)2, (II), also crystallizes in the triclinic space grou...
Crystals
Two new complexes, [Cu(dimpyr)2(H2O)2](NO3)2.2H2O (1) and (Hamdimpy)2[CoCl4].H2O (2), with the monodentate ligand 2-amino-6-methylpyrimidin-4-(1H)-one (dimpyr) and the countercation 4-amino-2,6-dimetylpyrimidium (Hamdimpy), respectively, were prepared and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy. In (1), the Cu(II) cation is tetracoordinated, in a square plan fashion, by two nitrogen atoms from the pyrimidine ring of the organic ligand and two oxygen atoms of two coordinated water molecules. In the atomic arrangement, the CuO2N2 square planes are interconnected via the formation of O-H…O hydrogen bonds involving both coordinated and free water molecules and NO3− nitrate anions to form inorganic layers parallel to the (a, b) plane at z = (2n + 1)/4. In (2), the central atom Co(II) is four-coordinated in a distorted tetrahedral fashion by four Cl− ions. The [CoCl4]2− tetrahedra are arranged parallel to the plane (1¯10) at x = (2n + 1)/2...
Acta Crystallographica Section E Crystallographic Communications
Two CuII complexes [Cu(C14H13N4O2)Cl] n , I, and [Cu4(C8H10NO2)4Cl4] n , II, have been synthesized. In the structure of the mononuclear complex I, each ligand is coordinated to two metal centers. The basal plane around the CuII cation is formed by one chloride anion, one oxygen atom, one imino and one pyridine nitrogen atom. The apical position of the distorted square-pyramidal geometry is occupied by a pyridine nitrogen atom from a neighbouring unit, leading to infinite one-dimensional polymeric chains along the b-axis direction. Each chain is connected to adjacent chains by intermolecular C—H...O and C—H...Cl interactions, leading to a three-dimensional network structure. The tetranuclear complex II lies about a crystallographic inversion centre and has one core in which two CuII metal centers are mutually interconnected via two enolato oxygen atoms while the other two CuII cations are linked by a chloride anion and an enolato oxygen. An open-cube structure is generated in which t...
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
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 = p-toluenesulphonate, L 2 = 5-bromo-2-methoxybenzenesulphonate) were obtained by the addition of ethylenediamine to hydrated Cu(II) sulphonates, Cu(L 1 /L 2 ) 2 ÁnH 2 O in methanol-water solution. The newly synthesized complex salts have been characterized by elemental analyses, TGA, spectroscopic techniques (electronic and FT-IR), magnetic moment determination and conductance measurements. The complex salt 1 crystallizes in the monoclinic system with space group P2 1 /c and complex salt 2 crystallizes in the triclinic system with space group P 1. X-ray structure determination revealed ionic structures consisting of one complex cation [Cu(en) 2 (H 2 O) 2 ] 2+ and two respective sulphonate anions in 1 and 2. A three dimensional hydrogen bonding network formed by N-H. . .O, C-H. . .O and O-H. . .O through second sphere interactions besides electrostatic forces of attraction stabilize crystal lattice in both complex salts.
Acta Crystallographica Section E Crystallographic Communications, 2020
In the title compound, [Cu(C16H8Br3N2O)2]·C2H6OS, the CuII atom is tetracoordinated in a square-planar coordination, being surrounded by two N atoms and two O atoms from two N,O-bidentate (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olate ligands. The two N atoms and two O atoms around the metal center are trans to each other, with an O—Cu—O bond angle of 177.90 (16)° and a N—Cu—N bond angle of 177.8 (2)°. The average distances between the CuII atom and the coordinated O and N atoms are 1.892 (4) and 1.976 (4) Å, respectively. In the crystal, complexes are linked by C—H...O hydrogen bonds and by π–π interactions involving adjacent naphthalene ring systems [centroid–centroid distance = 3.679 (4) Å]. The disordered DMSO molecules interact weakly with the complex molecules, being positioned in the voids left by the packing arrangement of the square-planar complexes. The DMSO solvent molecule is disordered over two positions with occupancies of 0.70 and 0.30.
CuII hydroxy salts: characterization of layered compounds by vibrational spectroscopy
Journal of the Brazilian Chemical Society, 2006
Hidroxo-sais lamelares de composição Cu 2 (OH) 3 X (X = NO 3-, CH 3 COOe ClO 4-) foram sintetizados através da coprecipitação (sais básicos de nitrato e acetato) e da troca iônica (sal básico de perclorato). Os sólidos cristalinos foram caracterizados por difratometria de raios X, análise termogravimétrica e espectroscopia vibracional. Bandas fracas em 336 e 345 cm-1 (espectro Raman) dos sais de nitrato e perclorato, respectivamente, foram tentativamente atribuídas ao νCu-O (ânion). Os ions nitrato possuem simetria C 2v no composto Cu 2 (OH) 3 NO 3 e, consequentemente, observa-se o desdobramento dos modos E'. A quebra da degenerescência também é observada nos modos F 2 do íon ClO 4 livre, ocasionando o desdobramento das bandas em 630 e 1100 cm-1 no espectro do hidroxo-perclorato de cobre(II). A pequena diferença de energia entre os modos ν as CO e ν s CO (Δ=143 cm-1) do sal de acetato sugere a presença de ligação de hidrogênio entre o oxigênio não coordenado do grupo carboxilato e um íon hidroxila adjacente. Os íons nitrato, acetato e perclorato estão coordenados ao cobre(II) de modo monodentado. Copper hydroxy salts with a layer-type structure and general composition Cu 2 (OH) 3 X (X = NO 3-, CH 3 COOand ClO 4-) were synthesized by co-precipitation (nitrate and acetate salts) and ion exchange (perchlorate salt) methods. The isolated polycrystalline solids were characterized by X-ray diffractometry, thermogravimetric analysis and vibrational spectroscopy. A weak band at 336 and 345 cm-1 (Raman spectrum) of the nitrate and perchlorate salts, respectively, was tentatively assigned to the nCu-O (anion). In Cu 2 (OH) 3 NO 3 the nitrate ion has a C 2v symmetry and, accordingly, a splitting in the E' modes is observed. The same happens to the hydroxy perchlorate salt with the degeneracy breakdown of the F 2 modes (free ClO 4-) at 630 and 1100 cm-1 leading to band splitting. For the carboxylate salt, the small difference in the energy of ν as CO and ν s CO (Δ=143 cm-1) suggests that hydrogen bonding with neighbor OH group may be present. Nitrate, carboxylate and perchlorate are monocoordinated to copper(II) in the investigated salts.
Blue single crystals of Cu[μ3-O3P(CH2)2COOH].2H2O (1) and Cu[(RS)-μ3-O3PCH(C2H5)COOH].3H2O (2) have been prepared in aqueous Cu2+-solutions (pH = 2.5–3.5) containing 3-phosphonopropionic acid (1) and (RS)-2-phosphonobutyric acid (2), respectively. 1: Space group Pbca (no. 61) with a = 812.5(2), b = 919.00(9), c = 2102.3(2) pm. Cu2+ is five-fold coordinated by three oxygen atomsstemming from [O3P(CH2)2COOH]2– anions and two water molecules. The Cu-O bond lengths range from194.0(3) to 231.8(4) pm. The connection between the [O3P(CH2)2COOH]2– anions and the Cu2+ cations yields apolymeric structure with layers parallel to (001). The layers are linked by hydrogen bonds. 2: Space group Pbca(no. 61) with a = 1007.17(14), b = 961.2(3), c = 2180.9(4) pm. The copper cations are surrounded by five oxygen atoms in a square pyramidal fashion with Cu-O bonds between 193.6(4) and 236.9(4) pm. The coordination between [O3PCH(C2H5)COOH]2- and Cu2+ results in infinite puckered layers parallel to (001...