The structure of two crystals of rubidium lead hexanitrocuprate(II)

Takagi, Shōzō; Joesten, Melvin D.; Lenhert, P. G.

doi:10.1107/s056774087600513x

Cited by 16 publications

(3 citation statements)

References 2 publications

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“…The novel μ-(η 1 - N :η 2 - O , O )-nitrite bonding geometry in the complex is characterized by a remarkably short Cu−N nitrite bond distance [1.780(8) Å], only slightly asymmetric O,O -chelation to the other copper center [Cu1‘−O1 = 2.047(9) Å; Cu1‘−O2 = 2.13(1) Å], and a planar Cu 2 (NO 2 ) core with a Cu···Cu separation of 4.31 Å. This nitrite binding mode is, to our knowledge, unprecedented in transition metal chemistry; the few known examples of such a topology involve Pb II or Cd II ions …”

Section: Resultsmentioning

confidence: 99%

Synthetic Modeling of Nitrite Binding and Activation by Reduced Copper Proteins. Characterization of Copper(I)−Nitrite Complexes That Evolve Nitric Oxide

et al. 1996

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In an effort to provide precedence for postulated intermediates in copper-protein-mediated nitrite reduction, a series of novel complexes containing the Cu I -NO 2 -unit, including monocopper(I), dicopper(I,I), and mixed valence dicopper(I,II) and copper(I)-zinc(II) species, were prepared, fully characterized, and subjected to reactivity studies designed to probe their ability to produce nitric oxide. Treatment of solutions of [LCu(CH 3 CN)]PF 6 (L ) L i-Pr 3 , 1,4,7-triisopropyl-1,4,7-triazacyclononane, or L Bn 3 , 1,4,7-tribenzyl-1,4,7-triazacyclononane) in MeOH with excess NaNO 2 yielded the novel dicopper(I,I) complexes [(LCu) 2 (µ-NO 2 )]PF 6 . The complex with L ) L i-Pr 3 was cleaved by PPh 3 to afford [L i-Pr 3 Cu(PPh 3 )]PF 6 and L i-Pr 3 Cu(NO 2 ), a structural model for the substrate adduct of copper nitrite reductase. Oxidation of the dicopper(I,I) compound (L ) L i-Pr 3 ) with (Cp 2 Fe)(PF 6 ) in CH 2 Cl 2 yielded the deep red, mixed valent, dicopper(I,II) species [(L i-Pr 3 Cu) 2 (µ-NO 2 )](PF 6 ) 2 , which was structurally characterized as its [B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 ] -salt (crystal data: triclinic space group P1 h, a ) 13.439(8) Å, b ) 13.777(5) Å, c ) 14.471(8) Å, R ) 108.22(4)°, β ) 92.08(5)°, γ ) 90.08(4)°, Z ) 1, T ) 177 K, R ) 0.074, and R w ) 0.070). A diamagnetic heterodinuclear Cu I Zn II analog, [L i-Pr 3 Cu(µ-NO 2 )ZnL i-Pr 3 ](O 3 SCF 3 ) 2 , was assembled by mixing L i-Pr 3 Cu(NO 2 ), Zn(O 3 -SCF 3 ) 2 , and L i-Pr 3 and was shown to adopt a structure similar to that of its Cu I Cu II relative (crystal data: monoclinic space group P2 1 /c, a ) 10.8752(1) Å, b ) 15.6121(3) Å, c ) 25.8020(5) Å, β ) 90.094(1)°, Z ) 4, R1 ) 0.0472, and wR2 ) 0.1082). Both compounds exhibit an intense electronic absorption feature that was assigned as a Cu I f NO 2 -MLCT transition on the basis of resonance Raman spectroscopic results.

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Section: Resultsmentioning

confidence: 99%

Synthetic Modeling of Nitrite Binding and Activation by Reduced Copper Proteins. Characterization of Copper(I)−Nitrite Complexes That Evolve Nitric Oxide

et al. 1996

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“…Although the fits of the susceptibilities are not very convincing (because of the presence of a small ferromagnetic component in the Pb compound, and experimental inaccuracy in the Ba compound), further support for this characterization may be obtained from crystal structure determinations at low temperatures [5][6][7][8][9][10][11]. lattice respectively.…”

Section: Discussionmentioning

confidence: 99%

Magnetically linear and quadratic hexanitrocuprates

Blöte

1979

Journal of Applied Physics

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Magnetic and caloric measurements on potassium lead hexanitrocuprate. K 2 PbCu(N0 2 )6' agree well with the theory for an antiferromagnetic Heisenberg linear S = 1/2 chain. Results for a related compound, in which lead is replaced by barium, can be analyzed in terms of an antiferromagnetic Heisenberg S = 1/2 simple quadratic lattice. These classifications are supported by existing data on the crystal structures of these compounds at low temperatures.PACS numbers: 75.40.Fa, 75.50.Ee J.

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“…However, the difference is not so dramatic as to cause strong disorder of the Pb atom, because in the structures of Rb2PbCu(NO2)6 (Takagi, Joesten & Lenhert, 1976) and Cs2PbCu(NO2)6 (Klein & Reinen, 1978) these distances are 2.843 and 2.847 A, where the Pb atoms occupy fixed positions.…”

Section: Appendix 2 Crystal-chemical Model Of Pb Atom Distributed On mentioning

confidence: 99%

The use of continuous atomic distributions in structural investigations

Чернышев¹,

Zhukov²,

Yatsenko³

et al. 1994

Acta Cryst Sect A

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YONG-SHENG LIU AND NING-HAI HU 601 distribution of ~o., is P(rk/R) = [2"rrlo(XR2)] -~ exp [XR 2 cos (25 + ~:)], (A4)where s c is defined in (2)-(5) and X in (15). Clearly, (A4) has a unique maximum at 2~pa, = --S c when XR 2 is large. AbstractA simple method of describing the scattering from an atom continuously distributed in the unit cell is proposed. Some experimental applications in structural investigations are presented.

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The structure of two crystals of rubidium lead hexanitrocuprate(II)

Cited by 16 publications

References 2 publications

Synthetic Modeling of Nitrite Binding and Activation by Reduced Copper Proteins. Characterization of Copper(I)−Nitrite Complexes That Evolve Nitric Oxide

Synthetic Modeling of Nitrite Binding and Activation by Reduced Copper Proteins. Characterization of Copper(I)−Nitrite Complexes That Evolve Nitric Oxide

Magnetically linear and quadratic hexanitrocuprates

The use of continuous atomic distributions in structural investigations

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