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X-ray diffraction study of middlebackite [CuII2C2O4(OH)2, di-copper oxalate dihydroxide], using a mineral specimen from Mooloo Downs Station, Western Australia and chemically synthesized material

Published online by Cambridge University Press:  12 September 2019

B. H. O'Connor Open the ORCID record for B. H. O'Connor [Opens in a new window] ,
R. M. Clarke ,
J. A. Kimpton  and
D. G. Allen
B. H. O'Connor*
Affiliation:
Department of Physics and Astronomy, Curtin University, Kent St, Bentley, Perth, WA 6102, Australia
R. M. Clarke
Affiliation:
ChemCentre, PO Box 1250, Bentley, WA 6983, Australia
J. A. Kimpton
Affiliation:
Australian Synchrotron, 800 Blackburn Road, Clayton, Vic 3168, Australia
D. G. Allen
Affiliation:
MBS Environmental, 4 Cook St, West Perth, WA 6005, Australia
*
a)Author to whom correspondence should be addressed. Electronic mail: brian_oconnor@iprimus.com.au
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Abstract

Additional crystallographic data are given for the recently reported mineral middlebackite, which has been described for discoveries at Iron Knob in South Australia and Passo di San Lugano near Trento, Italy. The material examined in the present study was from a third finding of the mineral, viz. from a quartz outcrop at Mooloo Downs Station in Western Australia within which it was co-located with the chemically- and structurally-related mineral moolooite, CuIIC2O4·nH2O, reported by Clarke and Williams (1986). In this study, the crystal structure was elucidated independently of the other studies using a combination of the a priori charge flipping and simulated annealing methods with synchrotron radiation diffraction (SRD) powder data. The principal crystal data for the Mooloo Downs material are: space group P21/c with lattice parameters a = 7.2659(18) Å, b = 5.7460(11) Å, c = 5.6806(11) Å, β = 104.588(3)°; Vc = 229.46(18) Å3; empirical formula CuII2C2O4(OH)2 with 2 formula units per unit cell; and calculated density = 3.605 g cm−3. The lattice parameters agree approximately with values given for the other studies, but not within the reported error estimates. The atom coordinates, interatomic distances, and angles for the Mooloo Downs material are compared with those from the other studies using single crystal data, with the values from all three studies agreeing approximately, but again not within the reported uncertainties. The crystal chemistry found for middlebackite received strong confirmation through the synthesis for the first time of di-copper oxalate di-hydroxide. Laboratory X-ray diffraction powder data for the synthetic form of the mineral from this study agree closely with the SRD data for the natural mineral.

Keywords

middlebackitehydroxy-bridged copper oxalate mineralsynchrotron radiation diffractioncrystal structure solutionmiddlebackite–moolooite structure comparison
Type
Technical Article
Information
Powder Diffraction , Volume 34 , Issue 4 , December 2019 , pp. 311 - 324
Copyright
Copyright © International Centre for Diffraction Data 2019 

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References

Chisholm, J. E., Jones, G. C., and Purvis, G. W. (1987). “Hydrated copper oxalate, moolooite, in lichens,” Mineral. Mag. 51, 715–718.Google Scholar
Christensen, A. N., Lebech, B., Andersen, N. H., and Grivel, J-C. (2014). “The crystal structure of paramagnetic copper (II) oxalate (CuC2O4): formation and thermal decomposition of randomly-stacked anisotropic nano-sized crystallites,” Dalton Trans. 43, 16754–16768.Google Scholar
Clarke, R. M. and O'Connor, B. H. (2019). “New mineralogical data for the mineral middlebackite [Cu2C2O4(OH)2], discovered at Moolooo Downs, Western Australia,” Austral. J. Mineral.Google Scholar
Clarke, R. M. and Williams, I. R. (1986). “Moolooite, a naturally occurring hydrated copper oxalate from Western Australia,” Mineral. Mag. 50, 295–298.Google Scholar
Coelho, A. A. (2000). “Whole-profile structure solution from powder diffraction data using simulated annealing,” J. Appl. Crystallogr. 33, 899–908.Google Scholar
Demartin, F., Campostrini, I, Ferretti, P., and Rocchetti, I. (2017). “Second global occurrence of middlebackite near the Passo di San Lugano (Carano, Trento, Italy),” Geol. Alp. 14, 35–38.Google Scholar
Demartin, F., Campostrini, I, Ferretti, P., and Rocchetti, I. (2018). “Fiemmeite Cu2(C2O4)(OH)2·2H2O, a new mineral from Val di Fiemme, Trentino, Italy,” Minerals 8, 248.Google Scholar
Elliott, P. (2016). “‘Middlebackite, IMA 2015-115’, CNMNC Newsletter No 30, April 2016, page 411,” Mineral. Mag. 80, 407–413.Google Scholar
Elliott, P. (2018). “Middlebackite, a new Cu oxalate mineral from Iron Monarch, South Australia: description and crystal structure,” Pre-published accepted article, Mineral. Mag., doi: 10.1180/mgm.2018.136.Google Scholar
Fichtner-Schmittler, H. (1979). “On some features of X-ray powder patterns of OD structures,” Crystallogr. Res. Technol 14, 1079–1088.Google Scholar
Fomina, M., Hillier, S., Charnock, J. M., Melville, K, Alexander, I.J., and Gadd, G. M. (2005). “Role of oxalic acid overexcretion in transformations of toxic metal minerals by Beauveria caledonica,” Appl. Environ. Microbiol. 71, 371–381.Google Scholar
Frost, R. L., Jing, Y., and Ding, Z. (2003). “Raman and FTIR spectroscopy of natural oxalates: implications for evidence of life on Mars,” Chin. Sci. Bull. 48, 1844–1852.Google Scholar
Grice, J. D. and Gasparrini, E. (1981). “Spertiniite, a new mineral from the Jeffrey Mine, Quebec,” Can. Mineral. 19, 337–340.Google Scholar
Hill, R. J. and Flack, H. D. (1987). “The use of the Durbin-Watson d statistic in Rietveld analysis,” J. Appl. Crystallogr. 20, 356–361.Google Scholar
O'Connor, B. H., Clarke, R. M. and Kimpton, J. R. (2019). “Synchrotron radiation diffraction study of the mineral moolooite, CuC2O4.0.44H2O, and synthetic Cu oxalates,” Powder Diffr., 34, 21–34.Google Scholar
Oswald, H. R., Reller, A, Schmalle, H. W., and Dubler, E. (1990). “Structure of copper (II) hydroxide, Cu(OH)2,” Acta Crystallogr., Sect. C, 46, 2279–2284.Google Scholar
Palatinus, L. and Chapuis, G. (2007). “SUPERFLIP - a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions,” J. Appl. Crystallogr. 40, 786–790.Google Scholar
Purvis, G. W. (1984). “The occurrence of copper oxalate in lichens growing on copper-sulphide-bearing rocks in Scandinavia,” Lichenologist 16, 197–204.Google Scholar
Schmitt, B., Bronnimann, C, Eikenberry, E. F., Gozzo, F., Horrmann, C., Horisberger, R., and Patterson, B. (2003). “Mythen detector system,” Nucl. Instrum. Methods Phys. Res., Sect. A 501, 267–272.Google Scholar
Schmittler, H. (1968). “Structural principle of disordered copper(II) oxalate (CuC2O4.nH2O),” Monatsber. Dtsch. Akad. Wiss. Berlin 10, 581–604.Google Scholar
Wilson, A. J. C. (ed.) (1995). International Tables for Crystallography. Volume C: Mathematical, Physical and Chemical Tables (Kluwer Academic Publishers, Dordrecht), p. 751.Google Scholar
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