Crystal Structure of Cu(I)Cu(II)4O(SeO3)Cl5, a New Heterovalent Copper Compound

Krivovichev, Sergey V.; Филатов, С. К.; Armbruster, Thomas; Pankratova, O. Yu.

doi:10.1023/b:doch.0000048084.41568.46

Cited by 18 publications

(12 citation statements)

References 10 publications

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“…It is the unique feature of Cu 2+ to form anion-centered units of different dimensionalities reviewed recently by Krivovichev et al (2013b). These minerals form as a result of volcanic exhalative processes that can be modeled using gas transport reactions as was originally suggested by Filatov et al (1992) and confirmed by a number of successful syntheses of mineral analogues under laboratory conditions by chemical vapor transport (CVT) reactions method (Millet et al 2001;Krivovichev et al 2004;Berdonosov et al 2009;Zhang et al 2010;Kovrugin et al 2015).…”

Section: Introductionmentioning

confidence: 95%

Emulating exhalative chemistry: synthesis and structural characterization of ilinskite, Na[Cu5O2](SeO3)2Cl3, and its K-analogue

et al. 2015

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The K-and Na-synthetic analogues of the fumarolic mineral ilinskite have been synthesized by the chemical vapor transport (CVT) reactions method. The A-[Cu 5 O 2 ](SeO 3 ) 2 Cl 3 (A + = K + , Na + ) compounds crystallize in the orthorhombic space group Pnma: a = 18.1691(6) Å, b = 6.4483(2) Å, c = 10.5684(4) Å, V = 1238.19(7) Å 3 , R 1 = 0.018 for 1957 unique reflections with F > 4σ F for K[Cu 5 O 2 ](SeO 3 ) 2 Cl 3 (KI), and a = 17.7489(18) Å, b = 6.4412(6) Å, c = 10.4880(12) Å, V = 1199.0(2) Å 3 , R 1 = 0.049 for 1300 unique reflections with F > 4σ F for Na[Cu 5 O 2 ](SeO 3 ) 2 Cl 3 (NaI). The crystal structures of KI and NaI are based upon the [O 2 Cu 5 ] 6+ sheets consisting of corner-sharing (OCu 4 ) 6+ tetrahedra. The Na-for-K substitution results in the significant expansion of the interlayer space and changes in local coordination of some of the Cu 2+ cations. The A + cation coordination changes from fivefold (for Na + ) to ninefold (for K + ). The CVT reactions method provides a unique opportunity to model physicochemical conditions existing in fumarolic environments and may be used not only to model exhalative processes, but also to predict possible mineral phases that may form in fumaroles. In particular, the K analogue of ilinskite is not known in nature, whereas it may well form from volcanic gases in a K-rich local geochemical environment.

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Section: Introductionmentioning

confidence: 95%

Emulating exhalative chemistry: synthesis and structural characterization of ilinskite, Na[Cu5O2](SeO3)2Cl3, and its K-analogue

et al. 2015

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“…Earlier, we suggested that such a variable role of selenate and selenite groups in inorganic complexes follows a peculiar empirical rule: in mixed complexes, the dentation of selenite groups is lower than that of selenate groups (Krivovichev et al, 2006). (3) 0.0250 (8) 0.0186 (7) 0.0259 (8) 0.0050 (6) 0.0030 (6) -0.0020 (6) Se2 0.87818(16) -0.13040(13) -0.41031(14) 0.0175 (3) 0.0218 (7) 0.0123 (7) 0.0200 (7) -0.013 (6) 0.0091 (6) -0.0004 (6) O1 0.0036(13) 0.1291(10) -0.1839(11) 0.026 (2) 0.026 (6) 0.027 (6) 0.028 (6) -0.007 (5) 0.009 (5) 0.002 (5) O2 0.6744(12) 0.0843(11) -0.2334(11) 0.027 (3) 0.025 (6) 0.032 (6) 0.026 (6) -0.003 (5) 0.013 (5) -0.013 (5) O3 0.01110(14) -0.1512(10) -0.2815(11) 0.029 (3) 0.039 (7) 0.020 (6) 0.025 (6) 0.001 (5) 0.002 (5) 0.001 (5) O4 0.8489 (12) 0.0179(10) -0.4526 (10) 0.022 (2) 0.028 (6) 0.020 (5) 0.020 (5) 0.000 (4) 0.012 (4) 0.002 (5) O5 0.7073(12) -0.1839(10) -0.3792 (10) 0.024 (2) 0.036 (6) 0.017 (6) 0.022 (5)…”

Section: Resultsmentioning

confidence: 99%

Crystal chemistry of selenates with mineral-like structures: VII. The structure of (H3O)[(UO2)(SeO4)(SeO2OH)] and some structural features of selenite-selenates

Krivovichev

2009

Geol. Ore Deposits

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The crystal structure of a new compound, (H 3 O)[(UO 2 )(SeO 4 )(SeO 2 OH)] (monoclinic, P 2 1 / n , a = 8.6682(19), b = 10.6545(16), c = 9.846(2) Å, β = 97.881(17) ° , V = 900.7(3) Å 3 ), was solved by direct methods and refined to R 1 = 0.050. The structure contains two symmetrically different Se atoms. The Se1 site is coordinated by three O atoms as is characteristic of Se 4+ cations. The Se2 site is coordinated by four O atoms and forms selenate anion The structure is based on selenite-selenate sheets [(UO 2 )(SeO 4 )(SeO 2 OH)] -linked by the interlayer H 3 O -ions. The sheets are parallel to (101). The structure is compared to that of schmiederite, Pb 2 Cu 2 (SeO 3 )(SeO 4 )(OH) 4 .

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“…In addition to the listed compounds, some other selenite halide 3d-metals have been described in the literature and structurally characterized. These are Cu 3 (SeO 3 ) 2 Cl 2 [15,66] [74], Co 4 (SeO 3 ) 3 Cl 2 [75], and the diselenite cobalt compound Co 3 (Se 2 O 5 ) 2 Cl 2 [75]. Symmetries and cell constants for these compounds are listed in Table 3.…”

Section: Discussionmentioning

confidence: 99%

“…From the crystallographic point of view, the most attractive compounds are layered monoclinic C2/m modifications of Cu 3 (SeO 3 ) 2 Cl 2 [66] and cobalt diselenite chloride Co 3 (Se 2 O 5 ) 2 Cl 2 [75], where chains of [CoO 4 Cl 2 ] octahedra are divided by diselenite Se 2 O 5 2groups in the crystal structure Figure 24. The compound Cu I Cu II 4 O(SeO 3 )Cl 5 [74] is a good example of a structure where Cu 2+ ions form complex chains in the crystal structure separated by chains constructed by [Cu I Cl 3 ] 2triangles, as shown in Figure 25. As a 3d transition metal, zinc forms a selenite chloride known as mineral Sophiite with the composition Zn 2 (SeO 3 )Cl 2 [89] and its synthetic polymorph [90] but due to its 3d 10 electron configuration it cannot possess magnetic properties.…”

Section: Discussionmentioning

confidence: 99%

“…The nature of the Se-Cl interactions deserves special attention. The analysis of the bond-critical points of the Laplacian of the electron-density distribution indicates that, at least in selenite chlorides under consideration, it is different from that of the halogen or chalcogen bonds [74][75][76], i.e., it is not of the electron donor/electron acceptor type. The regions with concentrated and depleted regions of electron density around Se 4+ and Cl − ions do not correlate with each other and are not aligned with the Se-Cl bonding paths.…”

Section: Burnsite Kcdcu 7 O 2 (Seo 3 ) 2 CLmentioning

confidence: 99%

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Crystal Structures of Compounds Containing Ions Selenite

2019

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The chemistry of materials containing Se oxyanions in the +4 oxidation state, such as selenite, hydrogenselenite, and oxoselenate, are of increasing interest in the research community for several reasons. First, the lone pair on the selenium atom can behave as structure-directing agent towards the formation of materials characterized by the presence of hollows or channels in their intimate structures, moreover, the weakly coordinative capability of the Se(IV) electron lone pairs could give rise to interesting supramolecular interactions, and finally, it is known that the incorporation of selenite anions can lead to non-centrosymmetric structures and, consequently, to materials displaying remarkable physicochemical properties. The most important feature is that the full comprehension of the properties of this type of materials cannot be exhaustively understood unless the complete solid state crystal structure is available. In this Special Issue, entitled "Crystal Structures of Compounds Containing Ions Selenite", a series of new selenite-containing compounds synthesized by different methodologies and fully caracterized in the solid state is reported. Moreover the fundamental role of detailed structural analysis in understanding the interactions in the solid state that are responsible for the peculiar chemical-physical properties of such materials is discussed.

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Crystal Structure of Cu(I)Cu(II)₄O(SeO₃)Cl₅, a New Heterovalent Copper Compound

Cited by 18 publications

References 10 publications

Emulating exhalative chemistry: synthesis and structural characterization of ilinskite, Na[Cu5O2](SeO3)2Cl3, and its K-analogue

Emulating exhalative chemistry: synthesis and structural characterization of ilinskite, Na[Cu5O2](SeO3)2Cl3, and its K-analogue

Crystal chemistry of selenates with mineral-like structures: VII. The structure of (H3O)[(UO2)(SeO4)(SeO2OH)] and some structural features of selenite-selenates

Crystal Structures of Compounds Containing Ions Selenite

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