Nickel crystal structure

H. Bode, K. Behmelt, and]. Witte, Crystal Structures of Nickel Hydroxides, ClTCE Meeting, Strashourg, France, 1965. 

Stainless and heat-resisting steels containing at least 18% by weight chromium and 8% nickel are in widespread use in industry. The structure of these steels is changed from magnetic body centered cubic or ferritic crystal structure to a nonmagnetic, face-centered cubic or austenitic crystal structure. 

Vanadium also promotes dehydrogenation reactions, but less than nickel. Vanadium s contribution to hydrogen yield is 20% to 50% of nickel s contribution, but vanadium is a more severe poison. Unlike nickel, vanadium does not stay on the surface of the catalyst. Instead, it migrates to the inner (zeolite) part of the catalyst and destroys the zeolite crystal structure. Catalyst surface area and activity are permanently lost. 

However, just as two liquids may be completely miscible and form a complete range of solutions from one pure liquid to the other, so certain metals, for example copper and nickel, exhibit complete solid solubility over the whole range of compositions from pure copper to pure nickel. Clearly for two metals to be soluble in each other over the whole compositional range, they must have the same crystal structure, i.e. they must be isomorphous. 

A crystal-structure determination on [Ni(PhCH2CS2)2] showed evidence of a Ni-Ni bond (Ni—Ni distance, 256 pm) in a bridging, acetate-cage, binuclear complex (363). Each nickel atom is 5-coordinate and is in a tetragonally distorted, square-pyramid spectroscopic evidence for a Ni-Ni bond has been obtained (364). The polarized crystal spectra showed more bands than predicted for a mononuclear, diamagnetic, square-planar nickel(Il), and the spectra are indicative of substantial overlap of the d-orbitals between the two nickel atoms. The bis(dithiobenzation)nickeKII) complex was found to exhibit unusual spectrochemical behavior (365). 

An X-ray crystal-structure determination (370) revealed that mixed, nickel coordination exists in the trimeric complex, [Ni(S2CPh)2]3. The trimeric structure is similar to that found (371) in [Pd(PhCS2>]. The structure contains one molecule of type A linked centrosymmetrically through short Ni-S bridges to two molecules of type B, the three molecules being closely parallel (XXVII). Bonamico and co-workers (372)... 

Fig. 8.13 Tetragonal crystal structures ofCaNi(BN) or LaNi(BN) (a) and La3Ni2(BN)2N (b), and MO scheme of [BN] (c). Nickel atoms (dark grey) are arranged in plane layers.

Wuerges J, J-W Lee, Y-I Yim, H-S Yrm, S-O Kang, KD Carugo (2004) Crystal structure of nickel-containing superoxide dismutase reveals another type of active site. Proc Natl Acad Sci USA 101 8569-8574. 

One of the few crystal structures solved for a metal complex of a heterocyclic thiosemicarbazone is bis(l-formylisoquinoline thiosemicarbazone) nickel(II) monohydrate, [Ni(21-H)2] (Fig. 5) [208]. The nickel(II) center was found to be NNS coordinated by two approximately planar thiosemicarbazone ligands. 

Nickel is found in thiolate/sulflde environment in the [NiFe]-hydrogenases and in CODH/ACS.33 In addition, either a mononuclear Ni-thiolate site or a dinuclear cysteine-S bridged structure are assumed plausible for the new class of Ni-containing superoxide dismutases, NiSOD (A).34 [NiFe]-hydrogenase catalyzes the two-electron redox chemistry of dihydrogen. Several crystal structures of [NiFe]-hydrogenases have demonstrated that the active site of the enzyme consists of a heterodinuclear Ni—Fe unit bound to thiolate sulfurs of cysteine residues with a Ni—Fe distance below 3 A (4) 35-39 This heterodinuclear active site has been the target of extensive model studies, which are summarized in Section 6.3.4.12.5. 

Ni3(2,2,2-tet)3(/u-N3)3](PF6)3 and its perchlorate analogue have been suggested as trinuclear complexes with an irregular triangle structure.2117 While a crystal structure is lacking, EXAFS and XANES spectra support the occurrence of azido-bridged trinuclear nickel(II) compounds with Ni- -Ni separations of 5.16 A and 5.12 A, respectively. Two J parameters had to be... 

Reduction of both nickel porphyrins and thiaporphyrins to Ni1 species has been studied by EPR and 2H NMR spectroscopy.179, 2 58 The Ni1 complex of 5,10,15,20-tetraphenyl-21-thiaporphyrin has been isolated and characterized. Reaction of this complex with sulfur dioxide produced a paramagnetic five-coordinated Ni1 S02 adduct, while reaction with nitrogenous base ligands (amines, pyridines, imidazoles) yielded five- and six-coordinate complexes. In addition, the crystal structure of Ni1 diphenyldi-p-tolyl-21-thiaporphyrin has been determined. The coordination geometry about the nickel center is essentially square planar with extremely short Ni—N and Ni—S bonds (Ni—N = 2.015(2) A, 2.014(12) A, and 1.910(14) A and Ni—S = 2.143(6) A).2359... 

The crystal structures of two nickel-complexes which contain cis.ds-cyclooctadiene as chelate ligands are known (89). For complex formation the 2v -symmetric boat-form is most favourable. The energetical compromise in the complexes is therefore such that the... 

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