Structure of cis-diaquabis(hexafluoroacetylacetonato)nickel(II)

Romero, R.; Cervantes‐Lee, Francisco; Porter, L. C.

doi:10.1107/s0108270191012416

Cited by 6 publications

(7 citation statements)

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“…Two isomorphous cis -M(hfac) 2 (H 2 O) 2 structures (M = Zn, Ni) have also been reported. The unit-cell parameters for these compounds are similar to those reported by Kidd et al for “Cu(hfac) 2 ·2H 2 O” .…”

Section: Resultsmentioning

confidence: 96%

Structures of Anhydrous and Hydrated Copper(II) Hexafluoroacetylacetonate

et al. 2002

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Crystal structure analyses are reported for anhydrous copper(II) hexafluoroacetylacetonate (Cu(hfac)(2)) and for two of its hydrates. The anhydrous compound (Cu(hfac)(2), 1: P1; at 100 K, a = 5.428(1), b = 5.849(1), c = 11.516(3) A; alpha = 81.47(2), beta = 74.57(2), gamma = 86.96(2) degrees; Z = 1) contains centrosymmetric square-planar complexes with close intermolecular Cu.F contacts. The geometry of the complex is similar to that previously reported for Cu(hfac)(2).toluene. The monoaquo compound (Cu(hfac)(2)(H(2)O), 2: P2(1)/c; at 100 K, a = 10.8300(8), b = 6.5400(6), c = 21.551(3) A; beta = 90.282(8) degrees; Z = 4) consists of square-pyramidal molecules with apical H(2)O ligands, and close-lying F atoms in the sixth coordination sites. The major difference between this structure and the two other polymorphs previously reported is the nature and direction of hydrogen bonds. The yellow-green solid formed from Cu(hfac)(2) with excess H(2)O is identified as the trihydrate. In crystalline form it is the previously unreported [trans-Cu(hfac)(2)(H(2)O)(2)].H(2)O (3: P1; at 150 K, a = 8.3899(3), b = 9.6011(3), c = 11.4852(4) A; alpha = 72.397(2), beta = 79.161(2), gamma = 87.843(2) degrees; Z = 2). There is no conclusive evidence in favor of any solid with the composition Cu(hfac)(2).2H(2)O.

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Section: Resultsmentioning

confidence: 96%

Structures of Anhydrous and Hydrated Copper(II) Hexafluoroacetylacetonate

et al. 2002

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“…Both the 2 H quadrupole coupling and the paramagnetic dipole interaction caused by the unpaired electrons on Ni(II) contribute to the spectrum resulting in a highly asymmetric pattern. The reduced quadrupole coupling constant, C Q , of 117(10) kHz and η Q = 0.65(10) implies that the water molecule is rotating rapidly around the Ni−O bond axis thereby making the two crystallographically inequivalent deuterons 38 magnetically equivalent on the time scale of 2 H MAS NMR, a common observation for non-hydrogen bound coordinated water molecules in 2 H SSNMR at room temperature. 39 This high mobility is in agreement with the crystal structure, which only shows weak hydrogen bonding possibilities.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Solid State ¹³C and ²H NMR Investigations of Paramagnetic [Ni(II)(acac)₂L₂] Complexes

et al. 2013

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Nine structurally related paramagnetic acetylacetonato nickel(II) complexes: [Ni(acac)2] and trans-[Ni(acac)2(X)2]nH/D2O, X = H2O, D2O, NH3, MeOH, PMePh2, PMe2Ph, or [dppe]1/2, n = 0 or 1, dppe = 1,2-bis(diphenylphosphino)ethane, as well as cis-[Ni(F6-acac)2(D2O)2], F6-acac = hexafluoroacetylonato, have been characterized by solid state (13)C MAS NMR spectroscopy. (2)H MAS NMR was used to probe the local hydrogen bonding network in [Ni(acac)2(D2O)2]D2O and cis-[Ni(F6-acac)2(D2O)2]. The complexes serve to benchmark the paramagnetic shift, which can be associated with the resonances of atoms of the coordinated ligands. The methine (CH) and methyl (CH3) have characteristic combinations of the isotropic shift (δ) and anisotropy parameters (d, η). The size of the anisotropy (d), which is the sum of the chemical shift anisotropy (CSA) and the paramagnetic electron-nuclei dipolar coupling, is much more descriptive than the isotropic shift. Moreover, the CSA is found to constitute up to one-third of the total anisotropy and should be taken into consideration when (13)C anisotropies are used for structure determination of paramagnetic materials. The (13)C MAS NMR spectra of trans-[Ni(acac)2(PMe2Ph)2], trans-[Ni(acac)2(PMePh2)2], and the noncrystallographically characterized trans-[Ni(acac)2(dppe)]n were assigned using these correlations. The complexes with L = H2O, D2O, NH3, and MeOH can be prepared by a series of solid state desorption and sorption reactions. Crystal structures for trans-[Ni(acac)2(NH3)2] and trans-[Ni(acac)2(PMePh2)2] are reported.

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“…The E-C distances are averaged to 1.835 Å in 1 and to 1.978(3) Å in 2, while the average C-C distances are very close in 1 and 2 (Table 3). The C-E-C angles at the donor atoms are acute, averaged to 76.65 (6)°in 1 versus 72.03 (11)°in 2. The differences in geometrical parameters of molecules 1 and 2 are in accord with the increased atomic radii of selenium compared with that of sulfur.…”

Section: Resultsmentioning

confidence: 99%

“…The anhydrous Cu(hfac) 2 complex was prepared according to the recent report . Syntheses of the aqua adducts, cis -Co(hfac) 2 (H 2 O) 2 and cis -Ni(hfac) 2 (H 2 O) 2 , were based on the known literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Spirocyclic Sulfur and Selenium Ligands as Molecular Rigid Rods in Coordination of Transition Metal Centers

Petrukhina

Henck

et al. 2004

Inorg. Chem.

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A set of analogous chalcogen-containing spirocycles, 2,6-dithiaspiro[3.3]heptane, 2,6-diselenaspiro[3.3]heptane, and 2-thia-6-selenaspiro[3.3]heptane [E(2)C(5)H(8), E = S (1), Se (2), and S/Se (3)], has been prepared and fully characterized by spectroscopic methods and by X-ray diffraction. The structural characterization of 2 was presented by us earlier, while the crystal structures of 1 and 3 are reported here for the first time. Molecules 1-3 are built around the central tetrahedral carbon atom and therefore are nonplanar. The E...E separation ranges from 4.690(1) A in 1 to 4.906(1) A in 2. Molecule 3 has statistically mixed positions of sulfur and selenium atoms in the solid state with all geometric characteristics being intermediate between those of 1 and 2. Compounds 2 and 3 have been tested as molecular rigid rod ligands in coordination reactions with transition metal complexes such as Cu(hfac)(2) (4), cis-Co(hfac)(2).2H(2)O (5), and cis-Ni(hfac)(2).2H(2)O (6) (hfac = hexafluoroacetylacetonate). Several coordination products built of two building blocks, M(hfac)(2) (M = Cu, Co, and Ni) and Se(2)C(5)H(8) (2), have been prepared in crystalline form and structurally characterized. The copper-based product (7) is comprised of the oligomeric units {[Cu(hfac)(2)](3).2mu(2)-Se(2)C(5)H(8)-Se,Se'} built on the axial Cu...Se interactions averaged at 2.909 A. These units are further assembled into 1D polymeric chains via intermolecular Cu...F contacts at 2.829 A. The SSeC(5)H(8) (3) ligand was also used in the reaction with Cu(hfac)(2) to afford an analogue of 7, namely {[Cu(hfac)(2)](3).2mu(2)-SSeC(5)H(8)-S,Se} (8). Complex 8 exhibits statistically mixed positions of the donor sulfur and selenium atoms to give an average axial Cu...S/Se contact at 2.892 A. In contrast to the copper complexes of composition 3:2, the stoichiometries of the isolated cobalt and nickel products are 1:1, [M(hfac)(2).Se(2)C(5)H(8)] (M = Co (9) and Ni (10)). Complexes 9 and 10 exhibit 1D polymer structures having alternating metal units cis-M(hfac)(2) and ligands 2 with intermolecuar M...Se separations of 2.6046(8) and 2.5523(16) A, respectively. In all products 7-10 the initial cis or trans geometry of M(hfac)(2) complexes is preserved and the spiro[3.3]heptane ligands act as bidentate linkers bridging transition metal centers via both donor ends. The magnetic properties of this series of new Cu(II), Co(II), and Ni(II) complexes have been tested by variable-temperature magnetic susceptibility measurements.

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Structure of cis-diaquabis(hexafluoroacetylacetonato)nickel(II)

Cited by 6 publications

References 5 publications

Structures of Anhydrous and Hydrated Copper(II) Hexafluoroacetylacetonate

Structures of Anhydrous and Hydrated Copper(II) Hexafluoroacetylacetonate

Solid State ¹³C and ²H NMR Investigations of Paramagnetic [Ni(II)(acac)₂L₂] Complexes

Spirocyclic Sulfur and Selenium Ligands as Molecular Rigid Rods in Coordination of Transition Metal Centers

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Structure of cis-diaquabis(hexafluoroacetylacetonato)nickel(II)

Cited by 6 publications

References 5 publications

Structures of Anhydrous and Hydrated Copper(II) Hexafluoroacetylacetonate

Structures of Anhydrous and Hydrated Copper(II) Hexafluoroacetylacetonate

Solid State 13C and 2H NMR Investigations of Paramagnetic [Ni(II)(acac)2L2] Complexes

Spirocyclic Sulfur and Selenium Ligands as Molecular Rigid Rods in Coordination of Transition Metal Centers

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Solid State ¹³C and ²H NMR Investigations of Paramagnetic [Ni(II)(acac)₂L₂] Complexes