13689-92-4Relevant articles and documents
Thiocyanato Coordination Polymers with Isomeric Coordination Networks - Synthesis, Structures, and Magnetic Properties
Werner, Julia,Run?evski, Tom?e,Dinnebier, Robert,Ebbinghaus, Stefan G.,Suckert, Stefan,N?ther, Christian
, p. 3236 - 3245 (2015)
The reactions of M(NCS)2 (M = Mn, Fe, and Ni) with 4-acetylpyridine (4-Acpy) in water lead to the formation of discrete complexes of composition M(NCS)2(4-Acpy)2(H2O)2, in which the metal cations are coordinated only N-terminally to the thiocyanato anions. When heated, these precursors dehydrate, and some of them transform into compounds of composition [M(NCS)2(4-Acpy)2]n, in which the metal cations are linked by pairs of μ-1,3-bridging anionic ligands into chains (1D isomer). In contrast, the thermal decomposition of Ni(NCS)2(4-Acpy)4 or crystallization from solution leads to the formation of an isomeric 2D network of the same composition, which is thermodynamically more stable than the 1D isomer. Temperature-dependent magnetic measurements of the 1D isomer [Fe(NCS)2(4-Acpy)2]n at 200 Oe reveal antiferromagnetic ordering at TN = 4.5 K. Field-dependent measurements show a metamagnetic transition into a saturated paramagnetic phase at a critical field of ca. 700 Oe. In contrast, magnetic measurements of the 2D isomer [Ni(NCS)2(4-Acpy)2]n at 1000 Oe show a ferromagnetic transition at TC = 8.6 K, whereas only paramagnetic behavior is observed for the Ni 1D isomer.
Transition metal complexes with pyrazole based ligands, part 15. Cobalt(iii)-, nickel(ii)- and copper(ii)-complexes with 3,5-dimethyl-1-thiocarboxamidepyrazole
Meszaros Szecsenyi,Leovac,Ja?imovi?,Pokol
, p. 943 - 952 (2003)
The complex formation of cobalt(II)-, nickel(II) and copper(II) sulphate hydrates with 3,5-dimethyl-1-thiocarboxamidepyrazole (HL) was studied. The influence of the anions on the course of the reaction was also examined, using nickel(II) salts with various anions. Beside the NiSO4.7H 2O the reaction has been carried out with Ni(OAc)2, Ni(CF3COO)2 and Ni(SCN)2, Compounds with the following composition were obtained: Co(L)3, Ni(L)2 and [Cu(SCN)L]2. The structure of the ligand and the Co(L)3 complex was determined by single crystal X-ray analysis, while that of the Ni(L)2 was solved by analysis of powder diffraction X-ray data, The most probable structure of the copper(II) complex is proposed on the basis of the elemental analyses data, FT-IR spectrometry and magnetic measurement. The thermal decomposition of the complexes was investigated by thermogravimetry, DSC and coupled TG-MS measurements. In the case of the nickel(II) compound, a relatively stable intermediate was detected in the 550-650 K temperature range. The composition of the intermediate, Ni(SCN)(NCS), was determined by FT-IR-spectrometry.
Large-ring chain and sheet polymeric metal complexes of extended-reach siloxypyridine ligands of type O[iPr2SiO(CH2)npy]2
Goodgame, David M.L.,Lickiss, Paul D.,Rooke, Stephanie J.,White, Andrew J.P.,Williams, David J.
, p. 61 - 73 (2003)
The preparations are reported of a range of metal complexes of Mn(II), Co(II), Ni(II) and Zn(II) with the 'extended reach' ligands O[iPr2SiO(CH2)npy]2 (n=0, 1 or 3, I-III) and with Cu(II), Cd(II) and Ag(I) for II; six of them have been shown by X-ray studies to have polymeric structures. The compounds M[O(iPr2SiOpy)2]2Cl2 (M=Co, Cu) form chains of 24-membered macrocycles, as does Co[O(iPr2SiOCH2py)2] 2I2(H2O)2. A similar structure is formed by Mn[O(iPr2SiOCH2py)2] 2Cl2 but in this case the rings are 28-membered. The complex Cu[O(iPr2SiOpy)2]Cl2 forms sheets of 52-membered macrocycles with chloride bridged Cu2Cl4 units at the node points. The structure of Cu2[O(iPr2SiOpy)2]4Cl 3 comprises sheets of 48-membered rings which are linked into pairs of sheets by linear, but weak, Cu-Cl-Cu bridges. X- and Q-band EPR spectra of the manganese compounds are also reported, as are relevant spectroscopic results for the other complexes.
Tuning of the Critical Temperature in Magnetic 2D Coordination Polymers by Mixed Crystal Formation
Wellm, Carsten,Rams, Micha?,Neumann, Tristan,Ceglarska, Magdalena,N?ther, Christian
, p. 3117 - 3123 (2018)
Reaction of Co(NCS)2 and Ni(NCS)2 with 4-acetylpyridine under different conditions leads to the formation of mixed crystals of the layered compound with the composition [CoxNi1-x(NCS)2(4-acetylpyridine)2]n (x = 0.15 0.3, 0.5, and 0.7). Mixed crystal formation was investigated by a combination of X-ray powder diffraction (XRPD), atomic absorption spectroscopy (AAS), simultaneous scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX), differential scanning calorimetry (DSC), and magnetic and heat capacity measurements. Dependent on the synthetic method, homo- or heterogeneous mixed crystals were obtained as already indicated by XRPD, where significant differences to the pattern of physical mixtures of the homometallic counterparts [M(NCS)2(4-acetylpyridine)2]n with M = Co or Ni) with the same Co/Ni ratio are observed. Mixed crystals can also be obtained from physical mixtures under thermodynamic control, indicating that they are more stable than the homometallic compounds. This is further supported by AAS, which indicates that the solubility of the mixed crystals is lower than that of the homometallic compounds. Magnetic and heat capacity measurements show a linear increase of the critical temperature of magnetic ordering with increasing Ni content and also confirm that homogeneous samples were obtained.
Synthesis and electrical properties of some new heterobimetallic coordination polymers MPb(SCN)4 (M = Co, Ni) and their reaction products with Lewis bases
Singh, Nanhai,Singh, Vinay Kumar
, p. 1743 - 1757 (2001)
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Holt, Stephen D.,Piggott, Brian,Hursthouse, Michael B.,Short, Richard L.
, p. 1457 - 1462 (1987)
Isoquinoline-based Werner clathrates with xylene isomers: Aromatic interactions vs. molecular flexibility
Wicht, Merrill M.,Báthori, Nikoletta B.,Nassimbeni, Luigi R.
, p. 6863 - 6870 (2015)
The crystal structures of the Werner clathrates Ni(NCS)2(isoquinoline)4 (H) with para-xylene (px), meta-xylene (mx) and ortho-xylene (ox) have been elucidated. The kinetics of thermal decomposition of the three inclusion compounds were performed using the isothermal technique of Flynn and Wall. Selectivity of H for the xylene isomers was determined for both the liquid and vapour phase binary mixtures of the xylenes. The chosen ligand has a larger aromatic system to improve the possible π interactions between H and the selected guests. The planarity of the isoquinoline ligand causes H rigidity and its selectivity was compared to a related Werner complex containing the more flexible 4-phenylpyridine. This journal is
Structural Diversity in Ni Chain Coordination Polymers: Synthesis, Structures, Isomerism and Magnetism
Jochim, Aleksej,Rams, Micha?,Neumann, Tristan,Wellm, Carsten,Reinsch, Helge,Wójtowicz, Gabriela M.,N?ther, Christian
, p. 4779 - 4789 (2018)
Reaction of Ni(NCS)2 with different co-ligands based on pyridine derivatives substituted in 4-position leads to the formation of 1D coordination polymers with the composition [Ni(NCS)2(co-ligand)2]n, in which the metal cations are coordinated octahedrally by two S- and two N-bonding thiocyanate anions as well as two neutral co-ligands and are linked into chains by μ-1,3-bridging thiocyanate anions. Dependent on the nature of the co-ligand, novel isomers with linear and corrugated chains are observed, in which the Ni cations are trans- or cis-cis-trans coordinated. This also includes a dimer and two isomeric chain compounds with 4-chloropyridine as ligand, of which one is metastable at room-temperature. For all these compounds, together with several additional Ni(NCS)2 chain compounds, the values of the intrachain exchange interaction J are extracted based on magnetic measurements. The values of J for 13 different Ni(NCS)2 compounds are compared with the structural results to investigate if there are some simple relations between the magnetic exchange, the metal coordination and the chain geometry. The low temperature magnetic properties of the Ni(NCS)2 dimer and the chain compounds are also discussed based on magnetic and specific heat measurements.
Synthesis, Crystal Structures and Properties of Ni(NCS)2-3-Cyanopyridine Coordination Compounds including a Ferromagnetic Layered Compound
Krebs, Christoph,Thiele, Solveig,Ceglarska, Magdalena,N?ther, Christian
, p. 2122 - 2129 (2021)
Reactions of Ni(NCS)2 and 3-cyanopyridine in different solvents lead to the formation of Ni(NCS)2(3-cyanopyridine)4 (1) already reported in the literature, Ni(NCS)2(3-cyanopyridine)2(H2O)2 (2), Ni(NCS)2(3-cyanopyridine)2(CH3OH)2 (3), Ni(NCS)2(3-cyanopyridine)2(CH3CN)2 (4) and Ni(NCS)2(3-cyanopyridine)2 (5). The crystal structures of 1–4 consist of discrete octahedral complexes, in which the thiocyanate anions, as well as the 3-cyanopyridine coligands, are only terminally N-bonded. In compound 5 the Ni cations are octahedrally coordinated and linked by pairs of thiocyanate anions into dinuclear units that are further connected into layers by single μ-1,3-bridging anionic ligands. TG-DTA measurements of the discrete complex 1 reveal that in the first step half of the coligands are emitted leading to the formation of compound 5. In contrast, compounds 2 and 3 transform into a new crystalline phase of the same composition (6) upon heating that should also contain μ-1,3-bridging anionic ligands, but the outcome of this reaction strongly depends on the reaction conditions. The acetonitrile complex 4 is unstable at room temperature and decomposes into a mixture of different phases including the aqua complex 2. Magnetic measurements of compound 5 prove a ferromagnetic transition at Tc=6.0 K. This result is compared to those obtained for other thiocyanate compounds exhibiting a similar layer topology.
Synthesis, structures, magnetic, and theoretical investigations of layered Co and Ni thiocyanate coordination polymers
Suckert, Stefan,Rams, Micha?,B?hme, Michael,Germann, Luzia S.,Dinnebier, Robert E.,Plass, Winfried,Werner, Julia,N?ther, Christian
, p. 18190 - 18201 (2016)
Reaction of cobalt(ii) and nickel(ii) thiocyanate with ethylisonicotinate leads to the formation of [M(NCS)2(ethylisonicotinate)2]n with M = Co (2-Co) and M = Ni (2-Ni), which can also be obtained by thermal decomposition
Structures, Thermodynamic Relations, and Magnetism of Stable and Metastable Ni(NCS)2 Coordination Polymers
Neumann, Tristan,Ceglarska, Magdalena,Germann, Luzia S.,Rams, Micha?,Dinnebier, Robert E.,Suckert, Stefan,Jess, Inke,N?ther, Christian
, p. 3305 - 3314 (2018)
Reaction of Ni(NCS)2 with 4-aminopyridine in different solvents leads to the formation of compounds with the compositions Ni(NCS)2(4-aminopyridine)4 (1), Ni(NCS)2(4-aminopyridine)2(H2O)2 (2), [Ni(NCS)2(4-aminopyridine)3(MeCN)]·MeCN (3), and [Ni(NCS)2(4-aminopyridine)2]n (5-LT). Compounds 1, 2, and 3 form discrete complexes, with octahedral metal coordination. In 5-LT the Ni cations are linked by single thiocyanate anions into chains, which are further connected into layers by half of the 4-aminopyridine coligands. Upon heating, 1 transforms into an isomer of 5-LT with a 1D structure (5-HT), that on further heating forms a more condensed chain compound [Ni(NCS)2(4-aminopyridine)]n (6) that shows a very unusual chain topology. If 3 is heated, a further compound with the composition Ni(NCS)2(4-aminopyridine)3 (4) is formed, which presumably is a dimer and which on further heating transforms into 6 via 5-HT as intermediate. Further investigations reveal that 5-LT and 5-HT are related by enantiotropism, with 5-LT being the thermodynamic stable form at room-temperature. Magnetic and specific heat measurements reveal ferromagnetic exchange through thiocyanate bridges and magnetic ordering due to antiferromagnetic interchain interactions at 5.30(5) K and 8.2(2) K for 5-LT and 6, respectively. Consecutive metamagnetic transitions in the spin ladder compound 6 are due to dipolar interchain interactions. A convenient formula for susceptibility of the ferromagnetic Heisenberg chain of isotropic spins S = 1 is proposed, based on numerical DMRG calculations, and used to determine exchange constants.
Szlyk, Edward
, p. 249 - 254 (1993)
Synthesis and crystal structure of complexes of manganese(II), cobalt(II), and nickel(II) isothiocyanates with ε-caprolactam
Kochnev,Peresypkina,Virovets,Cherkasova
, p. 1067 - 1072 (2012)
The possibility of ε-caprolactam (CPL) to coordinate to manganese(II), cobalt(II), and nickel(II) rhodanides has been investigated. New complexes trans-[M(CPL)4(NCS)2], where M = Mn (I), Co (II), and Ni (III), have been synthesized. The complexes have been studied by chemical analysis and IR spectroscopy. According to X-ray diffraction, complexes are isostructural to each other and crystallize in monoclinic space group P2 1/c3 Z = 2. For I: a = 6.9457(2) A?, b = 17.7751(6) A?, c = 12.8999(4) A?, β = 104.2670(10)°, V = 1543.51(8) A?3, Pcalc = 1.342 g/cm3, R1 = 0.0426. For II: a = 6.8925(2) A?, b = 17.8189(8) A?, c = 12.7278(6) A?, β = 104.421(2)°, V = 1513.93(11) A?3, Pcalc = 1.377 g/cm3, R1 = 0.0280. For III: a = 6.7804(2), b = 18.4631(4), c = 12.4841(3), β = 105.2950(10)°, V = 1507.49(7) 3, Pcalc = 1.382 g/cm3, R1 = 0.0273. Structures I-III are molecular; the metal atom in each of them coordinates four CPL molecules and two NCS groups via oxygen and nitrogen atoms, respectively. Pleiades Publishing, Ltd., 2012.
Synthesis, structures, and magnetic properties of new thiocyanato coordination polymers with 4-(3-phenylpropyl)pyridine as ligand
Werner, Julia,Jess, Inke,N?ther, Christian
, p. 2161 - 2168 (2014)
The reaction of different metal salts with 4-(3-phenylpropyl) pyridine (ppp) lead to the formation of compounds of composition M(NCS)2(ppp)4 [M = Mn (Mn-1); Fe (Fe-1), Ni (Ni-1); Cd (Cd-1)], M(NCS)2(ppp)2(H2O)2 [M = Mn (Mn-2); Ni (Ni-2)] and [M(NCS)2(ppp)2]n [M = Mn (Mn-3); Ni (Ni-3); Cd (Cd-3)]. On heating compounds M-1 decompose without the formation of any ppp deficient intermediate. In contrast, on heating, Ni-2 transforms into a compound of composition M(NCS)2(ppp)2 that does not correspond to Ni-3. Unfortunately, this compound is of low crystallinity and therefore, its structure cannot be determined. The crystal structures of compounds M-1 and M-2 consist of discrete complexes, in which the metal cations are octahedrally coordinated. In compounds M-3 the metal cations are linked by pairs of μ-1,3-bridging anions into chains. IR spectroscopic investigations show, that the value of the asymmetric CN stretching vibration depend on the coordination mode of the anionic ligand as well as on the nature of the metal cation. Magnetic measurements reveal that Ni-3 shows only Curie-Weiss behavior without any magnetic anomaly. A similar behavior is also found for Ni-3. Comparison of the magnetic properties of Ni-3 with those of similar compounds indicates that the magnetic properties are only minor influenced by the Co-ligand.
