865-38-3Relevant articles and documents
De, Goutam,Chaudhuri, Nirmalendu Ray
, p. 151 - 158 (1985)
Supramolecular Cd(II) complexes with (E)-N, N′-bis(2-pyridyl) iminoisoindoline (2-pyimiso): Synthesis, X-ray structures, hirshfeld surface analyses, and DFT study of [CdX2(2-pyimiso)2] (X = Cl or NCS)
Bitzer, Rodrigo S.,Visentin, Lorenzo C.,Nascimento, Marco A. C.,Filgueiras, Carlos A. L.
, p. 3261 - 3283 (2016)
The paucity of coordination entities bearing (E)-N,N′-bis(heteroaryl)iminoisoindolines has prompted us to investigate coordination modes and supramolecular features of (E)-N,N′-bis(2-pyridyl)iminoisoindoline (2-pyimiso), a versatile iminobis(pyridyl) ligand. In this article we report the synthesis, spectroscopic characterization and crystal structure analysis of two Cd(II): 2-pyimiso (1?:2) bis-adducts, [CdX2(2-pyimiso)2] [X = Cl (1) or NCS (2)]. Our X-ray structural results reveal that 1 exhibits distorted tetrahedral coordination (four-coordinate geometry index τ4 = 0.92), whereas 2 displays six-coordinate Cd(II) and two four-membered chelate rings (bite angles = 52.5°), each comprising one Cd–Npy [2.247(2) ?] bond and one Cd?Nimine [2.809(21) ?] secondary interaction. Remarkably, in 2 each 2-pyimiso unit binds to Cd(II) according to an unusual bidentate coordination. The contributions of the Cd–N and Cd–Cl bond valences to the total metal valence for both 1 and 2 have been evaluated to confirm the coordination modes of 2-pyimiso, which can be interpreted in terms of J?rgensen’s principle of symbiosis. X-ray structure and Hirshfeld surface analyses have shown that the crystal structure of 1 is determined by two perpendicular 1-D chains formed by weak hydrogen bonds along the a- and c-axes, whereas the supramolecular architecture of 2 exhibits 2-D sheets parallel to the ab-plane interconnected by C–H?πinteractions along the c-axis. A vibrational analysis of both products has been conducted at the DFT B3LYP-D3/LACV3P** level of calculation.
Calorimetric and Raman Spectroscopic Studies of Cadmium(II) Thiocyanato Complexes in N,N-Dimethylformamide
Ishiguro, Shin-ichi,Takamuku, Toshiyuki,Ohtaki, Hitoshi
, p. 3901 - 3906 (1988)
Formation of thiocyanato complexes of cadmium(II) ion has been calorimetrically studied in N,N-dimethylformamide (DMF) at 25 deg C.Calorimetric data obtained were well explained in terms of the formation of a series of four mononuclear n>(2-n)+ (n=1-4, X=SCN) complexes, and their formation constants, enthalpies, and entropies were determined.Raman band shifts for the C-S stretching vibration of SCN- ion indicated that SCN- ion binds to cadmium(II) ion only with the N end within the mono- or dithiocyanato complex, + or .Within the tri- and tetracyanato complexes, thiocyanate ions bind with both the N and S ends, and the coordination modes, - and 2-, were suggested.The coordination modes for the di- and tetrathiocyanato complexes in DMF, and 2-, are different from those in water, and >Cd(NCS)2(SCN)>2-.It is thus shown that the N-bonding becomes more favorable in DMF than in water.Such a result may mainly be ascribed to relatively weakened solvation of the SCN- ion in DMF, especially at the N atom site which is hydrogen-bonded with water molecules but not with DMF.
New coordination compounds based on Cd(NCS)2(4-ethylpyridine) x (x = 4, 2, 1)
Woehlert, Susanne,Jess, Inke,Naether, Christian
, p. 385 - 391 (2013)
The reactions of different ratios of cadmium(II) thiocyanate and 4-ethylpyridine as neutral co-ligand in water at room temperature leads to the formation of the three new coordination compounds of different topology. In the crystal structure of the 1:4 compound (1:4 = ratio between metal and neutral co-ligand) Cd(NCS)2(4-ethylpyridine)4 (1) discrete complexes are found, in which the cadmium ions are coordinated by two terminal N-bonded anionic ligands and four 4-ethylpyridine co-ligands. In the crystal structure of the 1:2 compound [Cd(NCS)2(4-ethylpyridine) 2]n (2) the cadmium cations are coordinated by two S-bonded, two N-bonded thiocyanato anions and two 4-ethylpyridine ligands, all of them are trans-oriented. The Cd2+ cations are connected by μ-1, 3 bridging thiocyanato anions into chains, which elongate in the direction of the crystallographic a axis. In the crystal structure of the 1:1 compound [Cd(NCS)2(4-ethylpyridine)]n (3) a more condensed coordination network is observed, in which each Cd2+ cation is coordinated by two N-bonded and three S-bonded as well as one 4-ethylpyridine ligand within slightly distorted octahedra. The cadmium cations are linked into chains by μ-1, 3- and μ-1, 1, 3-bridging thiocyanato anions. On heating the 1:4 compound 1 two mass steps are observed in the TG curve, of which the first one is well resolved. The residue obtained after the first TG step is investigated by XRPD, elemental analysis, and IR spectroscopy, it is proven that the 1:2 compound Cd(NCS)2(4-ethylpyridine)2 is obtained as a phase pure material. Based on the results of IR spectroscopic investigations the coordination mode of the thiocyanato anions was additionally investigated. Copyright
Syntheses, structures, and thermal reactivity of new ZnII and CdII thio- and selenocyanato coordination compounds
Boeckmann, Jan,Reinert, Thorben,Jess, Inke,Naether, Christian
, p. 1137 - 1144 (2011)
Reaction of ZnII and CdII thiocyanate or selenocyanate with pyrazine leads to the formation of new ZnII and CdII coordination compounds. The structures of [Zn(NCSe) 2(pyrazine)2]n (1A), [Cd(NCS) 2(pyrazine)2]n (2A) and [Cd(NCSe) 2(pyrazine)2]n (3A) consist of octahedrally coordinated metal cations which are surrounded by two terminal N-bonded anions and two μ2-bridging pyrazine molecules. The metal cations are connected via the pyrazine ligands into layers, which are further linked by weak intermolecular S...S respectively Se...Se interactions. Investigations on the thermal degradation behavior of 1A, 2A, and 3A using simultaneous differential thermoanalysis and thermogravimetry as well as X-ray powder diffraction, IR- and Raman spectroscopy prove that on heating, the pyrazine-rich compound 1A decomposes in one step into zinc selenocyanate without the formation of a pyrazine-deficient intermediate. In contrast, for compounds 2A and 3A a stepwise decomposition is observed, leading to the formation of the pyrazine-deficient compounds [Cd(NCS)2(pyrazine)]n (2B-I and 2B-II) and [Cd(NCSe)2(pyrazine)]n (3B) as intermediates. The structures and the thermal reactivity are discussed and compared with that of related transition metal thiocyanates and selenocyanates with pyridine as N-donor ligand. Copyright
Cesium-133 NMR study of CsCd(SCN)3: Relative orientation of the chemical shift and electric field gradient tensors
Kroeker, Scott,Eichele, Klaus,Wasylishen, Roderick E.,Britten, James F.
, p. 3727 - 3733 (1997)
Single-crystal NMR was used to characterize the cesium-133 chemical shift and electric field gradient (EFG) tensors in CsCd(SCN)3. The principal axes of the two interaction tensors are not coincident, a reflection of the general positioning of cesium nuclei within the unit cell. Relative orientations of the chemical shift and EFG tensors have been determined, but assignment of the two magnetically distinct sites remains elusive. The span of the chemical shift, 94.4 ppm, is moderate in comparison with other cesium salts, and the magnitude of the nuclear quadrupole coupling constant, 148 kHz, is in the midrange of those reported for cesium compounds. Excellent agreement is observed between experimental 133Cs NMR spectra of a stationary powder sample and spectra calculated using NMR parameters from the single-crystal analysis. Moreover, simulations indicate that the static line shape is very sensitive to the relative orientation of the chemical shift and EFG tensors. Experimental 133Cs NMR spectra obtained with magic-angle and variable-angle spinning are well reproduced by calculations utilizing single-crystal NMR data.
Synthesis, Structures and Propertiesm of a Fourth Modification of [Cd(NCS)2(pyridine)2]n
Neumann, Tristan,Jess, Inke,N?ther, Christian
, p. 622 - 626 (2015)
Reaction of Cd(NCS)2 with pyridine in water accidently lead to the formation of crystals of a fourth modification of [Cd(NCS)2(pyridine)2]n, which most likely corresponds to form I reported by Taniguchi et al. but which was not structurally characterized by these authors. This modification crystallizes in the monoclinic space group C2/c with a = 10.6032(3) ?, b = 15.8676(5) ?, c = 26.2795(8), b = 96.001(2)°and V = 4397.2(2) ?3. The structure of this compound is very similar to that of form III reported recently, in which the Cd cations are octahedrally coordinated by two pyridine ligands and four thiocyanato anions. The cations are linked by pairs of anionic ligands into chains, in which the thiocyanato anions are always trans-coordinated. Further investigations show that larger amounts of pure form I cannot be prepared because it is always contaminated with form II, in which the thiocyanato anions are cis-coordinated. Solvent mediated conversion experiments using mixtures of the trans-modifications I and III as well as the cis-modification II prove that form III disappears first and therefore, is less stable than the second trans-modification I. IR and Raman spectroscopic investigations show, that all forms cannot be distinguished from each other using these methods.
Cd(II) and Zn(II) thiocyanate coordination compounds with 3-ethylpyridine: Synthesis, crystal structures and properties
Neumann, Tristan,Jess, Inke,Dos Santos Cunha, Cesar,Terraschke, Huayna,N?ther, Christian
, p. 115 - 123 (2018/02/06)
Reaction of Cd(NCS)2 and Zn(NCS)2 with 3-ethylpyridine leads to the formation of compounds of compositions M(NCS)2(3-ethylpyridine)4 (M=Cd, 1-Cd; Zn, 1-Zn) and M(NCS)2(3-ethylpyridine)2 (M=Cd, 2-Cd; Zn, 2-Zn). 1-Cd and 1-Zn are isotypic and form discrete complexes in which the metal cations are octahedrally coordinated by two trans-coordinating N-bonded thiocyanate anions and four 3-ethylpyridine co-ligands. In 2-Cd the cations are also octahedrally coordinated but linked into chains by pairs of μ-1,3-bridging anionic ligands. 2-Zn is built up of discrete complexes, in which the Zn cation is tetrahedrally coordinated by two N-bonded thiocyanate anions and two 3-ethylpyridine co-ligands. Compounds 1-Cd, 2-Cd and 2-Zn can be prepared in a pure state, whereas 1-Zn is unstable and transforms on storage into 2-Zn. If 1-Cd and 1-Zn are heated, a transformation into 2-Cd, respectively 2-Zn is observed. Luminescence measurements reveal that 1-Cd, 2-Cd and 2-Zn emit light in the blue spectral range with maxima at, respectively, 21724, 21654 and 22055 cm-1, assigned to ligand-based luminescence.
Synthesis, Crystal Structures, and Properties of M(NCS)2-3-aminomethylpyridine Coordination Compounds (M = Cd, Zn)
Neumann, Tristan,Germann, Luzia S.,Moudrakovski, Igor,Dinnebier, Robert E.,dos Santos Cunha, Cesar,Terraschke, Huayna,N?ther, Christian
, p. 1904 - 1912 (2017/10/07)
Reaction of Cd(NCS)2 or Zn(NCS)2 with 3-aminomethylpyridine (3-AMPy) leads to the formation of five compounds with the compositions [Cd(NCS)2(3-AMPy)2·(3-AMPy)]n (1-Cd), [M(NCS)2(3-AMPy)2]n [M = Cd (2-Cd), Zn (2-Zn)] [Cd(NCS)2(3-AMPy)]n (3-Cd), and [Zn(NCS)2(3-AMPy)]2 (3-Zn). In 1-Cd the Cd cations are linked by the 3-AMPy ligands into layers that consist of rings, built up of four Cd cations and four 3-AMPy ligands. These layers are stacked to form channels, in which the 3-AMPy solvate molecules are located. In the isotypic compounds 2-Cd and 2-Zn the metal cations are also linked into layers by the 3-AMPy ligands with an identical layer topology as that in 1-Cd, but a completely different conformation of the 3-AMPy ligand. In the most 3-AMPy deficient compound 3-Cd, the Cd cations are linked by μ-1,3-bridging thiocyanate anions and 3-AMPy ligands into chains, that are further connected into layers by additional anionic ligands. In 3-Zn two Zn cations are linked by pairs of 3-AMPy ligands into discrete dimers. Thermoanalysis and X-ray powder diffraction (XRPD) investigations show that upon heating 1-Cd transforms into 2-Cd and 2-Zn into 3-Zn. The compounds 2-Cd, 3-Cd, 2-Zn, and 3-Zn present ligand-based luminescence in the blue-green spectral range with maxima between 21276 and 21795 cm–1.
