142 results for Nicholson, Brian K., Journal article

  • Self-assembly of a columnar polymeric calcium phosphinate derived from camphene

    Henderson, William; Leach, Meto T.; Nicholson, Brian K.; Sabat, Michal (1995)

    Journal article
    University of Waikato

    (2,2-Dimethylbicyclo[2.2.1] hept-3-ylmethyl)phosphinic acid (RPO₂H₂), readily prepared from camphene and hypophosphorous acid, formed a polymeric calcium salt [{Ca(RPO₂H) ₂ (RPO₂H₂)(H₂O)}n], with both terminal and triply bridging phosphinate groups, and an overall columnar structure with an inorganic core and a pseudo-close-packed sheath of terpene moieties.

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  • Cluster Chemistry : XVII.Radical ion-initiated synthesis of ruthenium cluster carbonyls containing tertiary phosphines, phosphites, arsines, SbPh₃, or isocyanides

    Bruce, Michael I.; Matisons, Janis G.; Nicholson, Brian K. (1983)

    Journal article
    University of Waikato

    The syntheses of over sixty known and new derivatives of Ru₃(CO)₁₂ and H₄Ru₄(CO)₁₂ by substitution reactions initiated by sodium diphenylketyl are described. The range of ligands studied includes isocyanides, tertiary phosphines and phosphites, tertiary arsines and SbPh₃. The reactions are characterised by high degrees of specificity and conversion: under mild conditions up to four ligands can be introduced. Comparisons with the corresponding thermally induced reactions are made in several cases. The reactions provide routes to mixed ligand derivatives of the cluster carbonyls, although account of relative Lewis base strengths of the ligands may have to be taken. Possible mechanisms of these reactions are discussed briefly, as are the IR ν (CO) spectra of the Ru₃ (CO)12-nLn complexes.

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  • Anionic germanium polycobalt carbonyl clusters. Part 3. Preparation and structures of [Net₄][Ge₂Co₇(CO)₂₁] and [Net₄][Ge{Co₇(CO)₂₀}]; two large clusters incorporating tetrahedral GeCo₃ units

    Duffy, D. Neil; Mackay, Kenneth M.; Nicholson, Brian K.; Thomson, Ralph A. (1982)

    Journal article
    University of Waikato

    Reactions of the [Ge{Co₅(CO)₁₆}]⁻ cluster have given rise to two new germanium–polycobalt cluster anions, characterised as their Net₄⁺ salts by X-ray crystallography. The complex [NEt₄][Ge₂Co₇(CO)₂₁](1a) forms triclinic crystals, space group P , with a= 13.085(2), b= 19.712(7). c= 12.220(8)Å, α= 109.10(3), β= 92.60(2), γ= 129.32(3)°, and Z= 2. The structure was solved by direct methods and refined to R=R′= 0.046 for 2 076 reflections with l > 3σ(l). The anion (1) consists of two –GeCo₃(CO)₉ units bonded mutually trans about a trigonal planar Co(CO)₃ group, giving idealised C3v, symmetry. For [Net₄][Ge{Co₇(CO)₂₀}](2a). crystals are monoclinic, space group P21/c, with a= l2.761(7), b= 18.415(3), c= 17.675(4)Å, β= 102.91(3)°, and Z= 4. The structure was refined to R= 0.077, R′= 0.074, for 1 123 reflections with I > 2σ(I). The anion (2) is a derivative of the C3v structure of [Co₄(CO)₁₂] with the axial carbonyl ligand of one basal cobalt replaced by a –GeCo₃-(CO)₉⁻ fragment. The Co4 tetrahedron is disordered.

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  • Anionic germanium polycobalt carbonyl clusters. Part 2. Preparation and structure of [Net₄][Ge{Co₅(CO)₁₆}], a cluster which contains five-co-ordinate germanium

    Croft, Rex A.; Duffy, D. Neil; Nicholson, Brian K. (1982)

    Journal article
    University of Waikato

    Addition of [Co(CO)₄]⁻ to [Ge{Co₄(CO)n}](n= 16, 14, or 13) under mild conditions gives good yields of [Ge{Co₅(CO)₁₆}]⁻. This forms crystals with Net₄⁺ which are orthorhombic, space group Pn2₁ a with a= 12.014(1), b= 36.938(4), c= 15.249(2), and Z= 8. The crystal structure was solved by direct methods and refined, with some difficulty due to pseudo-symmetry, to R= 0.088, R′= 0.081, for 1 590 unique reflections with F² > 2σ(F²). The anion has a GeCo₅ metal skeleton consisting of a GeCo₂ triangle and a GeCo₃ tetrahedron sharing a common apex at Ge. The five Ge–Co bond lengths vary from 2.33 to 2.51 Å. Three of the CO ligands on the GeCo₃ unit bridge the three Co–Co bonds, with two terminal CO groups on each Co atom. On the GeCo₂ moiety there are six terminal and one bridging carbonyls.

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  • Preparation and the crystal and molecular structure of [Net₄][Ge{Co₂(CO)₇}{Co₂(CO)₆[HgCo(CO)₄]}]: an anion containing a mercury-bridged cobalt–cobalt bond

    Duffy, D. Neil; Mackay, Kenneth M.; Nicholson, Brian K.; Robinson, Ward T. (1981)

    Journal article
    University of Waikato

    The title compound has been isolated from the reaction of Gel4 with Na[Co(CO)₄] in the presence of Hg and has been characterised by X-ray analysis. Crystals are triclinic, a= 12.065(1), b= 17.334(2), c= 9.222(1)Å, α= 95.17(3), β= 82.72(3), γ= 96.95(3)°, space group P , and Z= 2. The structure has been solved by direct methods and refined to R= 0.049 for 3 136 reflections [I 5σ(I)]. The anion contains a common Ge atom bridging the Co–Co bonds both of a Co₂(CO)₇ unit and of a Co₂(CO)₆ unit which is also bridged by a HgCo(CO)₄ group.

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  • Transition-metal carbonyl derivatives of the germanes. Part 13. Preparation, spectroscopic properties, and the crystal and molecular structure of bis[µ-carbonyl-bis(tricarbonylcobaltio)(Co–Co)]germanium (4Co–Ge), [Ge{Co₂(CO)₇}₂]; a new type of group 4–tetracobalt species

    Gerlach, Robert F.; Mackay, Kenneth M.; Nicholson, Brian K.; Robinson, Ward T. (1981)

    Journal article
    University of Waikato

    Reaction between Gel₄ and [Co(CO)₄]⁻ or between GeH₄ and [Co₂(CO)₈] gives [Ge{Co₂(CO)₇}₂](1). The crystal and molecular structure of (1) has been obtained by X-ray methods. Crystals are triclinic, with a= 10.396(2), b= 16.495(3), c= 12.879(2)Å, α= 90.33(2), β= 97.68(2), γ= 95.03(2)°, space group P1, and Z= 4. The structure was solved by direct methods and refined by least-squares techniques to R= 0.056 for 2 852 reflections [I 5σ(l)]. The molecule exhibits approximate C₂ symmetry with the Ge atom bridging the Co–Co bonds of two Co₂(CO)₇ units. The Ge bridge is unsymmetric with unequal Ge–Co bond lengths (average 2.38, 2.34 Å); the corresponding µ-CO in each unit is asymmetrically disposed in the opposite sense. Infrared and mass spectral data for [Ge{Co₂(CO)₇}₂] are also discussed.

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  • Transition metal carbonyl derivatives of the germanes: XIV. Studies of mixed cobalt carbonyl/manganese carbonyl substituted germanes including [(CO)₅MnGeCo₃(CO)₉], μ₃-(pentacarbonylmanganesegermylidyne)cyclotris(tricarbonylcobalt)(3Co---Co)

    Christie, Judy A.; Duffy, D. Neil; Mackay, Kenneth M.; Nicholson, Brian K. (1982)

    Journal article
    University of Waikato

    [Mn(CO)₅GeH₃] reacts smoothly with Co₂(CO)₈ to form the [(CO)₅MnGeCo₃(CO)₉], which is also produced by the reaction of Mn(CO)₅⁻ with [(CO)₄CoGeCo₃(CO)₉]. [Mn(CO)₅GeMeH₂] similarly reacts with Co₂(CO)₈ to give [{Mn(CO)₅} {Co₂(CO)₇}GeMe]. The products were characterised spectroscopically and the ESR spectrum of the radical ion of the title compound is presented.

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  • New ruthenium carbonyl clusters containing unusual 5-sulfido-, 4-benzyne-, and thianthrene-derived ligands: Insertion of ruthenium into the thianthrene ring by C-S activation

    Hassan, Mohammad R.; Kabir, Shariff E.; Nicholson, Brian K.; Nordlander, Ebbe; Uddin, Md. Nazim (2007-07-01)

    Journal article
    University of Waikato

    Treatment of [Ru3(CO)12] with thianthrene in refluxing toluene afforded [( 4-S)Ru4( -CO)2(CO)9( 4- 2-C6H4)] (1), [( 5-S)Ru6( -CO)2(CO)15( - 3-C12H8S)] (2), and [( 5-S)Ru5( -CO)2(CO)11( - 3-C12H8S)( 4- 2-C6H4)] (3) in 18%, 8%, and 16% yields, respectively. Thermolysis of 2 in refluxing heptane gave compounds 1 and 3. A similar thermolysis of 3 in refluxing toluene gave 1 in 90% yield. Treatment of 3 with neat MeCN afforded the labile compound [( 5-S)Ru5( -CO)2(CO)10( - 3-C12H8S)( 4- 2-C6H4)(MeCN)] (4) in 73% yield. The reaction of 4 with P(OMe)3 gave the substitution product [( 5-S)Ru5( -CO)2(CO)10( - 3-C12H8S)( 4- 2-C6H4){P(OMe)3}] (5) in 52% yield. Compounds 1-4 have been structurally characterized. Compound 1 contains a 4-capping sulfido and a 4- 2-benzyne ligand, whereas 3, 4, and 5 contain 5-sulfido and 4- 2-benzyne ligands. The latter three compounds provide rare examples of 5-sulfido and metal-assisted opening of the thianthrene ligand on polynuclear centers. In compounds 1, 3, and 4 the 4- 2-benzyne ligand is perpendicular to the Ru4 face of the clusters and represents a previously uncharacterized bonding mode for benzyne.

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  • β-Cyclomanganated 1,5-diphenylpenta-1,4-dien-3-ones and their reactions with alkynes: routes to η5-pyranyl--- and η5-oxocycloheptadienyl---Mn(CO)3 complexes

    Tully, Warren; Main, Lyndsay; Nicholson, Brian K. (2001-08-01)

    Journal article
    University of Waikato

    1,5-Diphenylpenta-1,4-dien-3-ones (4) are cyclometalated with benzylpentacarbonylmanganese to form [[1-phenyl-2-((E)-3-phenylprop-2-en-1-oyl-κO)]ethenyl-κC1]tetracarbonylmanganese derivatives (5). Coupling of 5 with alkynes in some cases gives [4-phenyl-2-(2-phenylethenyl)pyranyl-η5]tricarbonylmanganese complexes (6) analogous to those previously reported for β-manganated chalcones, but in other cases an alternative cyclisation pathway subsequent to insertion of alkyne into the C---Mn bond leads to [6-oxo-4,7-diphenylcyclohepta-1,4-dienyl-1,2,3,4,5-η]tricarbonylmanganese complexes (7). The X-ray crystal structure determination is reported for one such compound, [6-oxo-2,4,7-triphenylcyclohepta-1,4-dienyl-1,2,3,4,5-η]tricarbonylmanganese (7a), derived from 1,5-diphenylpenta-1,4-dien-3-one and phenylacetylene. The 7-phenyl group is found to occupy the endo position, and a mechanism involving Mn-mediated aryl migration is suggested to explain this stereochemistry. The reaction of 7a with ammonium cerium(IV) nitrate gives a low yield of 2-nitro-3,5,7-triphenylcyclohepta-2,4,6-trien-1-one (9), whose structure was established by X-ray crystal structure analysis. The pyranyl complexes (6) provide the corresponding pyrylium triiodide salts (8) when demetalated with iodine.

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  • E/Z isomerism in monoalkylated derivatives of [Pt₂(μ-S)₂(PPh₃)₄] containing 2,4-dinitrophenylhydrazone substituents

    Ujam, Oguejiofo Theophilus; Devoy, Sarah M.; Henderson, William; Wilkins, Alistair L.; Nicholson, Brian K. (2011)

    Journal article
    University of Waikato

    Alkylation of [Pt₂(m-S)₂(PPh₃)₄] with 2,4-dinitrophenylhydrazone-functionalized alkylating agents XC6H4C{¼NNHC₆H₃(NO₂)₂}CH2Br (X¼H, Ph) gives monoalkylated cations [Pt₂(m-S){m-SCH₂C{¼NNHC₆H₃(NO₂)₂}C₆H₄X}(PPh₃)₄]⁺. An X-ray diffraction study on [Pt₂(m-S){m-SCH₂C{¼NNHC₆H₃(NO₂)₂}Ph}(PPh₃)₄]BPh₄ shows the crystal to be the Z isomer, with the phenyl ring and NHC₆H₃(NO₂)₂ groups mutually trans. ¹H- and ³¹P{¹H} NMR spectroscopic methods indicate a mixture of Z (major) and E (minor) isomers in solution, which slowly convert mainly to the E isomer. Reaction of [Pt₂(m-S)₂ (PPh₃)₄] with the dinitrophenylhydrazone of chloroacetone [ClCH₂C{¼NNH(C₆H₃(NO₂)₂}Me] and NaBPh₄ gives [Pt₂ (m-S){m-SCH₂C{¼NNHC₆H₃(NO₂)₂}Me}(PPh₃)₄]BPh₄, which exists as a single (E) isomer.

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  • Arylstibonic acids [H₈(RSb)₁₂O₂₈]; precursors to organometallic isopolyoxostibonates [Na₂H₉(RSb)₁₂O₃₀]-, (R = aryl).

    Clark, Christopher J.; Nicholson, Brian K.; Wright, Cody Elvin (2009)

    Journal article
    University of Waikato

    Electrospray ionisation mass spectrometry shows that arylstibonic acids, RSbO₃H₂, give rise to oxo-bridged clusters derived from [H₈(RSb)₁₂O₂₈] which act as inorganic crown ligands towards Na+ cations; structure determination of one derivative revealed a cage-like anion [Na₂H₉(p-O₂NC₆H₄Sb)₁₂O₃₀.4H₂O]-.

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  • Cyclorhenated compounds derived from 1,4-diaryl-1-azabutadienes: preparation, structures and reactions

    Asamizu, Toshie; Nielsen, Jaime L.; Nicholson, Brian K. (2010)

    Journal article
    University of Waikato

    PhCH₂Re(CO)₅ reacted with 1,4-diaryl-1-azabutadienes to give cyclometallated (η²-(C,N)-azabutadiene)Re(CO)₄ (4) together with the substituted derivatives (η¹-(N)-azabutadiene)(η²-(C,N)-azabutadiene)Re(CO)₃ (6 and 7) The substituted product was shown by NMR and X-ray crystal structure analysis to be an inseparable mixture of isomers differing in the conformation of the η¹-ligand about the N C bond—trans for (6) and cis for (7). Reaction of the mixture of 6 and 7 from 1,4-diphenyl-1-azabutadiene with phenyl acetylene gave η⁵-(1,2,4-triphenyl-1-aza-cyclohexadienyl)Re(CO)₃.

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  • Modification of kraft wood-pulp fibre with silica for surface functionalisation

    Love, Karen T.; Nicholson, Brian K.; Lloyd, John; Franich, Robert A.; Kibblewhite, R. Paul; Mansfield, Shawn D. (2008)

    Journal article
    University of Waikato

    A new science strategy for natural fibre modification was devised in which glass surface properties would be imparted to wood-derived fibre. The enhancements known from addition of silane reagents to glass fibre–polymer composites could therefore be realised for modified cellulose fibre–polymer composites. A process is described whereby the internal void spaces and micropores of never-dried Kraft pulp fibre walls were impregnated with silica. This was achieved by initial dehydration of never-dried fibre through azeotropic distillation to achieve substitution of fibre water with the silicon chemical solution over a range of concentrations. Kraft fibres were stiffened and made resistant to collapse from the effect of the azeotrope drying. Specific chemical reaction of azeotrope-dried fibre with the reagent ClSi(OEt)3 followed by base-catalysed hydrolysis of the ester groups formed a fibre-bound silica composite. The physico-chemical substitution of water from micropores and internal voids of never-dried fibre with property-modifying chemicals offers possibilities in the development of new fibre characteristics, including fibres which may be hardened, plasticised, and/or stabilised against moisture, biodegradation or fire. The embedded silica may also be used as sites of attachment for coupling agents to modify the hydrophilic character of the fibre or to functionalise the fibre surface.

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  • An orthomanganation route to 2-substituted derivatives of N-methyl-1,8-naphthalimide

    Nicholson, Brian K.; Crosby, Paul M.; Maunsell, Kieran R.; Wyllie, Megan J. (2012)

    Journal article
    University of Waikato

    N-methyl naphthalimide can be readily cyclomanganated at the 2-position, directed by the adjacent amide O atom. Di-cyclomanganation also occurs readily to attach Mn(CO)₄ groups at both 2, 7 positions. An X-ray structure determination of the mono-substituted example confirmed the five-membered metallocyclic ring. Cleavage of the Mn–C bond by HgCl₂ or ICl generates 2-substituted HgCl or I derivatives respectively. Reaction of the mono-cyclomanganated N-methyl naphthalimide with phenylacetylene gives an (η⁵-cyclohexadienyl)Mn(CO)₃ complex where the cyclohexadienyl ring has formed by two PhCCH adding in a formal [2 + 2 + 2] process across the C(1)–C(2) bond of the naphthalimide, breaking the aromaticity of the naphthalene ring as shown by a single crystal structure determination.

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  • Ruthenium and osmium carbonyl clusters incorporating stannylene and stannyl ligands

    Kabir, Shariff E.; Raha, Arun K.; Hassan, Mohammad R.; Nicholson, Brian K.; Rosenberg, Edward; Sharmin, Ayesha; Salassa, Luca (2008)

    Journal article
    University of Waikato

    The reaction of [Ru₃ (CO)₁₂] with Ph₃SnSPh in refluxing benzene furnished the bimetallic Ru-Sn compound [Ru₃(CO)₈(μ-SPh)₂(μ3-SnPh₂)(SnPh₃)₂] 1 which consists of a SnPh₂ stannylene bonded to three Ru atoms to give a planar tetra-metal core, with two peripheral SnPh₃ ligands. The stannylene ligand forms a very short bond to one Ru atom [Sn-Ru 2.538(1) Å] and very long bonds to the other two [Sn-Ru 3.074(1) Å]. The germanium compound [Ru₃(CO)₈(μ-SPh)₂(μ₃-GePh₂)(GePh₃)₂] 2 was obtained from the reaction of [Ru₃ (CO)₁₂] with Ph₃GeSPh and has a similar structure to that of 1 as evidenced by spectroscopic data. Treatment of [Os₃(CO)₁₀(MeCN)₂] with Ph₃SnSPh in refluxing benzene yielded the bimetallic Os-Sn compound [Os₃(CO)₉(μ-SPh)(μ₃-SnPh₂)(MeCN)(ƞ¹-C₆H₅)] 3. Cluster 3 has a superficially similar planar metal core, but with a different bonding mode with respect to that of 1. The Ph₂Sn group is bonded most closely to Os(2) and Os(3) [2.7862(3) and 2.7476(3) Å respectively] with a significantly longer bond to Os(1), 2.9981(3) Å indicating a weak back-donation to the Sn. The reaction of the bridging dppm compound [Ru₃(CO)₁₀(μ-dppm)] with Ph₃SnSPh afforded [Ru₃(CO)₆(μ-dppm)(μ₃-S)(μ₃-SPh)(SnPh₃)] 5. Compound 5 contains an open triangle of Ru atoms simultaneously capped by a sulfido and a PhS ligand on opposite sides of the cluster with a dppm ligand bridging one of the Ru-Ru edges and a Ph₃Sn group occupying an axial position on the Ru atom not bridged by the dppm ligand.

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  • A re-investigation of arsenoacetic acid, (AsCH₂COOH)n

    Nicholson, Brian K.; Wilson, Peter S.; Nancekivell, Adelle (2013)

    Journal article
    University of Waikato

    Detailed spectroscopic data have been obtained for arsonoacetic acid, As(CH₂COOH)O₃H₂, and its barium and sodium salts. The X-ray crystal structure of the free acid is isomorphous with phosphonoacetic acid. Reduction gave the As(I) compound arsenoacetic acid, (AsCH₂COOH)n which was shown by ESI-MS to contain cyclic species based on As–As bonds, with n mainly 3–6. The X-ray crystal structure of the hexamer was determined as the pyridine solvate and shown to have a hexacyclic As₆ ring in a puckered chair conformation, with –CH₂COOH groups in equatorial sites, each H-bonded to a pyridine molecule in the lattice.

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  • Novel polyoxometalates: Is antimony the new molybdenum?

    Nicholson, Brian K.; Clark, Christopher J. (2012)

    Journal article
    University of Waikato

    Polyoxometalates based on Mo, W or V have been known for a long time and present a diverse range of structures, with the [XMo₁₂O₄₀]ⁿ⁻ Keggin ions (X = P, Si ,…) perhaps the best known.¹ They are still subject to intense research with >4000 papers published in the past five years. Following on from our study² of aryl arsonic acids RAsO₃H₂, which are straightforward molecular species based on four-coordinate As(V), we became interested in the corresponding antimony compounds. Although aryl stibonic acids of nominal formula RSbO₃H₂ have been known for over 100 years,³ their composition has remained uncertain, as they form only amorphous solids, have complicated titration behaviour and only limited solubility. The presumption has been that they are polymeric, based on 5- or 6-coordinate Sb with Sb-O-Sb linkages, though direct evidence is sparse.⁴ Recently, it has been shown by Beckman that if very bulky R groups are used, then relatively simple dimers such as (2,6-Mes₂C₆H₃Sb₂O₂(OH)₄(Mes=mesityl) can be isolated, but these represent a special case.⁵

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  • Cyclometalated gold(III) iminophosphoranes which incorporate carbohydrate groups

    Jarman, Bevan P.; Nicholson, Brian K. (2012)

    Journal article
    University of Waikato

    Iminophosphoranes with organic groups derived from d-glucose, d-galactose and l-arabinose have been used to prepare gold(III) dichloride complexes via mercurated intermediates, since direct cyclometallation was unsuccessful. Structures and full spectroscopic data are reported. Replacement of one or more of the chloride ligands by PPh3, or by thiosalicylate gave new derivatives. Biological screening showed no enhanced activity relative to other alkyl or aryl analogues.

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  • 2-(1,4-Dioxo-1,4-dihydro-2-naphthyl)-2-methylpropanoic acid

    Dempster-Rivett, Kieran J.; Main, Lyndsay; Nicholson, Brian K.; Denny, William A. (2007)

    Journal article
    University of Waikato

    The sterically crowded title compound, C₁₄H₁₂O₄, crystallizes as centrosymmetric hydrogen-bonded dimers involving the carboxyl groups. The naphthoquinone ring system is folded by 11.5 (1)° about a vector joining the 1,4-C atoms, and the quinone O atoms are displaced from the ring plane, presumably because of steric interactions with the bulky substituent.

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  • cyclo-Tetra-μ-oxido-tetrakis[3-nitro-4-hydroxyphenylarsenic(III)]

    Lloyd, Nicholas C.; Nicholson, Brian K. (2007)

    Journal article
    University of Waikato

    The title compound, [As₄O₄(C₆H₄NO₃)₄], has an eight-membered As₄O₄ ring with a slightly twisted boat-chair conformation. The aryl groups complete the threefold coordination for each As atom. Each OH group forms a strong intramolecular O-H⋯O hydrogen bond to the adjacent NO₂ group, with only weak C-H⋯O, O⋯As [3.036 (6)-3.184 (6) Å] and O⋯O [2.921 (10)-2.930 (10) Å] interactions between tetramers.

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