Synthesis and characterization of three new Cd(II) coordination polymers with bidentate flexible ligands: Formation of 3D and 1D structures (original) (raw)
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Polyhedron, 2007
(1), [Cd(3-ampy)(N 3 )Cl] n (2), and [Cd(DENA)Cl 2 (H 2 O)] n (3), (pydz = pyridazine or 1,2-diazine, 3-ampy = 3-aminopyridine, DENA = N,N-diethylnicotineamide) have been synthesized and characterized by spectral and structural methods and their network topologies analysed. Complex 1 crystallizes in monoclinic C-centred space group C2/m, the Zn(1) center is octahedrally coordinated; and simultaneously bridged by EO-azido, N,N 0 -pydz, and O,O 0 -sulphato ligands. The ZnN 4 O 2 -octahedra form a 1D anionic chain along b-axis. The Na(OH 2 ) 6 -octahedra have also common water molecules, thus also forming a 1D chain along b-axis. The cationic and anionic chains are connected via hydrogen bonds of type O-HÁ Á ÁO including lattice water molecules to form a supramolecular 3D network structure. In complex 2, the Cd(1) is six-coordinated by two EE-bridging azide groups, and two nitrogen atoms of bridging N,N 0 , 3-ampy ligand, and two bridging chloro ligands. The three different bridging ligands connect the distorted octahedra of the Cd(II) centres to form a 3D network structure with the topology of a square pyramidal net (4 3 AE 6 6 -sqp). The centrosymmetric Cd 2 Cl 2 -rings are planar and the NH 2 -of the 3-ampy groups forms additional hydrogen bonds of type N-HÁ Á ÁN to the adjacent azido groups. In complex 3, the octahedrally coordinated Cd(1) centres are occupied by alternating monodentate DENA ligand and a water molecule and the other four sites are occupied by four bridging chloro ligands. Thus the Cd 2 Cl 2 -rings form common edges to form 1D chains of Cd(II) octahedra along the b-axis of the monoclinic unit cell. 2D supramolecular sheets extended along the bc-planes of the unit cell are formed by the O-HÁ Á ÁO hydrogen bond. The IR spectra of the three complexes were measured and they confirm the X-ray structural data.
Polyhedron, 2003
Three new cadmium(II) complexes: [Cd(4-Clpy) 2 (NCS) 2 ] n (1), [Cd(3-aldpy)(H 2 O)(N 3 ) 2 ] n (2) and [Cd(3-CNpy)(N 3 ) 2 ] n (3) (4-Clpy ¼ 4-chloropyridine, 3-aldpy ¼ 3-aldehyde-pyridine, and 3-CNpy ¼ 3-cyanopyridine) have been synthesized and structurally characterized. The IR spectra of the complexes are measured and discussed. The single crystal X-ray diffraction revealed that the structure of 1 features l-1,3-thiocyanate bridges and 1D chains. It consists of alternate octahedrally coordinated Cd atoms. Both Cd(1) and Cd(2) are surrounded by pairs of 4-Clpy, S atoms and N atoms of two di-l-1,3 thiocyanato bridges in trans and cis arrangements, respectively. In complex 2 each octahedrally coordinated Cd binds two di-l-1,1 azide bridges in a zigzag 1D chain and the other two positions are occupied by O and N atoms from aqua and 3-aldpy molecules, respectively. Hydrogen bonds of the types O-HÁ Á ÁO and O-HÁ Á ÁN are formed between aqua molecules and end nitrogen atoms of the l-1,1 azide bridges generating 3D framework structure of 2. The structure of 3 consists of [Cd(N 3 ) 2 ] n chains in which each octahedrally coordinated Cd atom is linked by two di-l-1,1 azide bridges. These chains are cross-linked by l-N ; N 0 -3-CNpy bridges generating 2D systems for this complex.
Journal of Molecular Structure, 2019
Three new coordination complexes [Mn(L1)(m-azide)(azide)] 2 ,4H 2 O (1), [Mn(L1)(fum)] n (2) [L1 ¼ 2methyl-N 1 ,N 2-bis(pyridin-2yl)propane-1,2-diamine, fum ¼ Fumaric acid] and [Co(L2)(azide)] (3) [L2 ¼ 6 phenyl-1,3,5-triazine 2,4-diyl amino(pyridine-2yl)methanol] have been synthesized and X-ray crystallographically characterized. Complex 1, a dinuclear Mn(II) complex is formed by bridging azide ligand and other coordination sites are satisfied by tetradentate ligand L1 and terminal azide ligand. The overall structure is an incomplete supramolecular 3D cage structure, formed by intermolecular p … p interaction of pyridyl ligand and hydrogen bonding. Complex 2 comprised of eight coordinated Mn(II) centre where ligand L1 and fumarate is bridged between the metal centers that leads to a one dimensional chain structure which further extended to a 3D structure by p … p and CeH … p interactions. The overall structure is further stabilized by hydrogen bonding with the guest water molecules. Complex 3, a six coordinated mononuclear Co(II) discrete complex is consist of pentadentate ligand L2 and azide act as a terminal ligand. This Mononuclear complex is connected by p … p, CeH … p interactions and hydrogen bonding which ultimately leads to a supramolecular 2D architecture. All the complexes have been further characterized by elemental analysis, infrared spectroscopy (IR) and powder X-ray diffraction (PXRD) studies.
Two new 3D network structures: [Cd3(nic)4(N3)2(H2O)]n and [Zn(nic)(N3)]n (nic=nicotinate anion)
Polyhedron, 2005
Two new cadmium(II) and zinc(II) complexes: [Cd 3 (nic) 4 (N 3 ) 2 (H 2 O) 2 ] n (1) and [Zn(nic)(N 3 )] n (2) (nic = nicotinate anion) have been synthesized and characterized by spectroscopic, crystallographic and thermal methods. Both complexes 1 and 2 represent 3D network structures. Complex 1 consists of trinuclear units in which the three Cd centers are held together by four bridging l-N,O,O 0 -tridentate nicotinate anions, two bridging end-on (EO), (l 1,1 -N 3 ) groups and two aqua molecules. The water molecule is further H-bonded to the neighboring unit through an OÁ Á ÁH-O bond. Complex 2 crystallizes in the non-centrosymmetric space group P2 1 2 1 2 1 , representing a right handed chiral complex. Each zinc(II) atom forms a distorted trigonal bipyramidal structure linked through l-N,O,O 0 -tridentate nicotinate anions and di-(l 1,1 -N 3 ) groups. IR, Raman, 1 H NMR and 13 C NMR spectra of both complexes have been measured and discussed in comparison to the free ligand, in addition to the discussion of the thermal TGA and DTA curves.
Journal of Solid State Chemistry, 2018
Four new coordination polymers [Ni2(HL1)2(L1)3(BTC)2]·6H2O (1), [Ni2(L1)3(HBTC)2]·4H2O (2), [Cd2(L2)(BTC)(H2O)3]·2H2O (3) and [Cd2(HL2)(BTCA)] (4) were synthesized by reactions of nickel(II)/ cadmium(II) salts with rigid ligands of 1,4-di(1H-imidazol-4-yl)benzene (L1), 1,3-di(1-imidazolyl)−5-(4H-tetrazol-5-yl)benzene (HL2) and polycarboxylic acids of 1,3,5-benzenetricarboxylic acid (H3BTC), 1,2,4,5-benzenetetracarboxylic acid (H4BTCA), respectively. The structures of the complexes were determined by single crystal X-ray diffraction analysis. The complex 1 is one-dimensional (1D) chain while 2 is a (4, 4)-connected two-dimensional (2D) layered structure with 2D → 2D parallel interpenetration. Complex 3 is a rare tetranodal (3,4)-connected three-dimensional (3D) CrVTiSc architecture with Point (Schläfli) symbol of (4·82)(4·84·10)(42·82·102)(83), and compound 4 has the 2D network with (4,4) topology based on the [Cd2(COO)4] SBUs. The weak interactions such as hydrogen bonds and π···π stacking contribute to stabilize crystal structure and extend the low-dimensional entities into high-dimensional frameworks. The UV–vis absorption spectra of 1 – 4 are discussed. Moreover, the photo luminescent properties of 3 and 4 and gas sorption property of 2 have been investigated.
Coordination Polymers in Dicyanamido-Cadmium(II) with Diverse Network Dimensionalities
Crystals, 2021
The synthesis and structural characterization of six dicyanamido-cadmium(II) complexes are reported: catena-[Cd(μ1,3-dca)(μ1,5-dca)(3-ampy)] (1), catena-[Cd3(μ1,3,5-dca)2(μ1,5-dca)4(pyNO)2(H2O)2] (2), catena-{Cd(H2O)2(μ1,5-dca)2](2,6-lut-NO)} (3), catena-[Cd(Me2en)(μ1,5-dca)2] (4), catena-[Cd(Me4en)(μ1,5-dca)2] (5), and [Cd(1,8-damnp)2(dca)2] (6), where dca = dicyanamide anion, 3-ampy = 3-aminopyridine, pyNO = pyridine-N-oxide, 2,6-lut-NO = 2,6-lutidine-N-oxide, Me2en = N,N-dimethyl-ethylenediamine, Me4en = N,N,N′,N′-tetramethyl-ethylenediamine, and 1,8-damnp = 1,8-diaminonaphthaline. The coordination polymers have different dimensionalities: 1 and 5 form 3D networks structures; 3 and 4 form polymeric 1D chains and 1DD double chains, respectively. Ribbons of three fused polymeric chains are observed in 2. In 6, the mononuclear complex units form a hydrogen-bonded supramolecular 3D network. In the coordination polymer compounds, the dca linkers display three bonding modes: the most c...
Crystals, 2016
The three novel cadmium(II) cyanide coordination polymers with alkoxyethanols, [Cd(CN) 2 (C 2 H 5 OCH 2 CH 2 OH)] n (I), [{Cd(CN) 2 (C 4 H 9 OCH 2 CH 2 OH)} 3 {Cd(CN) 2 }] n (II) and [{Cd(CN) 2 (H 2 O) 2 }{Cd(CN) 2 } 3 •2(C 6 H 13 OCH 2 CH 2 OH)] n (III), were synthesized and charcterized by structural determination. Three complexes have three-dimensional Cd(CN) 2 frameworks; I has distorted tridymite-like structure, and, II and III have zeolite-like structures. The cavities of Cd(CN) 2 frameworks of the complexes are occupied by the alkoxyethanol molecules. In I and II, hydroxyl oxygen atoms of alkoxyethanol molecules coordinate to the Cd(II) ions, and the Cd(II) ions exhibit slightly distort trigonal-bipyramidal coordination geometry. In II, there is also tetrahedral Cd(II) ion which is coordinated by only the four cyanides. The hydroxyl oxygen atoms of alkoxyethanol connects etheric oxygen atoms of the neighboring alkoxyethanol by hydrogen bond in I and II. In III, hexyloxyethanol molecules do not coordinate to the Cd(II) ions, and two water molecules coordnate to the octahedral Cd(II) ions. The framework in III contains octahedral Cd(II) and tetrahedral Cd(II) in a 1:3 ratio. The Cd(CN) 2 framework structures depended on the difference of alkyl chain for alkoxyethanol molecules.
Polyhedron, 2014
The work in this report deals with seven compounds of composition {[Cu II (dmpn) 2 ] 3 [Fe III (CN) 6 ] 2 Á6H 2 O} n (1), {[Cu II (dmpn) 2 ] 3 [Co III (CN) 6 ] 2 Á6H 2 O} n (2), {[Cu II (dmpn) 2 ] 3 [Cr III (CN) 6 ] 2 Á4H 2 O} n (3), {[Cu II (dmpn)][Ni II (CN) 4 ]ÁH 2 O} n (4), [{Cu II (dmpn) 2 Cl}{Cu II (dmpn) 2 (H 2 O)}][Ag I (CN) 2 ]Cl 2 (5), [(Cu II (dmpn) 2 (dicyanamide) 2 ] (6) and [(Ni II (dmpn) 2 (dicyanamide) 2 ] (7), where dmpn = 2,2-dimethyl-1,3-diaminopropane. Syntheses, characterization and crystal structures of 1-7 along with variable-temperature (2-300 K) magnetic properties of 1 and 3 are described. Compounds 1-4 are cyanide-bridged two-dimensional coordination polymers. Twelve metal-membered ring is formed in 1-3, while both four and eight metal-membered rings are formed in 4. On the other hand, dicyanoargentate(I) in 5 is noncoordinated and dicyanamide in 6 and 7 behaves as monodentate terminal ligand. The coordination polymers in 1-4 and the discrete systems in 5-7 are self-assembled by hydrogen bonding interactions to generate overall three-dimensional supramolecular topologies. A novel structural aspect, two-dimensional network containing both four and eight metal-membered rings, has been observed in the copper(II)-tetracyanonickelate(II) compound 4. Magnetic studies reveal ferromagnetic interaction between Cu II and Cr III in 3. In addition, spin-orbit coupling of low-spin Fe III or weak antiferromagnetic interaction along with intermolecular antiferromagnetic interactions which exist between Cu II and Fe III are present in 1.
Journal of Molecular Structure, 2009
Three distinct coordination complexes, viz., [Co(imi) 2 (tmb) 2 ] (1) [where imi = imidazole], {[Ni(tmb) 2 (H 2 O) 3 ]Á2H 2 O} n (2) and [Cu 2 (l-tmb) 4 (CH 3 OH) 2 ] (3), have been synthesized hydrothermally by the reactions of metal acetates, 2,4,6-trimethylbenzoic acid (Htmb) and with or without appropriate amine. The Ni analogue of 1 and the Co analogue of 2 have also been synthesized. X-ray single-crystal diffraction suggests that complex 1 represents discrete mononuclear species and complex 2 represents a 1D chain coordination polymer in which the Ni(II) ions are connected by the bridging water molecules. Complex 3 represents a neutral dinuclear complex. In 1, the central metal ions are associated by the carboxylate moiety and imidazole ligands, whereas the central metal atom is coordinated to the carboxylate moiety and the respective solvent molecules in 2 and 3. In 3, the four 2,4,6-trimethylbenzoate moieties act as a bridge connecting two copper (II) ions and the O atoms of methanol coordinate in an anti arrangement to form a square pyramidal geometry, with the methanol molecule at the apical position. In all the three structures the central metal atom sits on a crystallographic inversion centre. In all the cases, the coordination entities are further organized via hydrogen bonding interactions to generate multifarious supramolecular networks. Complexes 1, 2 and 3 have also been characterized by spectroscopic (UV/Vis and IR) and thermal analysis (TGA). In addition, the complexes were found to exhibit antimicrobial activity.The magnetic susceptibility measurements, measured from 8 to 300 K, revealed antiferromagnetic interactions between the Co(II) ions in compound 1 and the Ni(II) ions in 1a, respectively.
Polyhedron, 2020
Four Cd(II) coordination polymers, formulated as {(H 2 betib) 2 [Cd(l-Hpdia) 2 ]ÁH 2 OÁMeOHÁdmf} n (1), {[Cd (l-Hpdia)(l-bipib)]Ádmf} n (2), [Cd(l-Hpdia)(H 2 O) 2 (l-betix) 0.5 ] n (3) and [Cd(l 3-Hpdia)(MeOH) (l-bipix) 0.5 ] n (4) (Hpdia: 5-(4-hydroxyphenylazo)isophthalate, betib or bipib: 1,4-bis(2-x-imidazol-1yl)butane, betix or bipix: 1,4-bis((2-x-imidazol-1-yl)methyl)benzene where x = ethyl-or isopropyl-) were synthesized under the same solvothermal conditions with 5-(4-hydroxyphenylazo)isophthalic acid and flexible or semi-flexible substituted bis(imidazole) linkers, and characterized by elemental analysis, IR spectroscopy, single crystal X-ray diffraction and thermal analysis methods. X-ray analysis results demonstrated that compounds 1-4 displayed 1D, 2D and 3D structures. In 1, the flexible betib ligand was protonated and the 2D structure formed by Hpdia was extended by hydrogen bonding to a 3D supramolecular network with the rtw topology. The hydrogen-bonded structure of 2 displayed a twofold 3D ? 3D interpenetrated supramolecular network with the tcj/hc topology. Compounds 3 and 4, synthesized using semi-flexible bis(imidazol) ligands, exhibited 1D and 3D frameworks, respectively. The thermal, optical and photoluminescence properties of the compounds were also investigated.