X-ray diffraction study of middlebackite [Cu II 2 C 2 O 4 (OH) 2 , di-copper oxalate dihydroxide], using a mineral specimen from Mooloo Downs Station, Western Australia and chemically synthesized material

• Published in: Powder diffraction 2019-12, Vol.34 (4), p.311-324
• Main Authors: O'Connor, B. H., Clarke, R. M., Kimpton, J. A., Allen, D. G.
• Format: Article
• Language: English
• Subjects: Carbon; Charge simulation; Chemical synthesis; Copper; Crystal structure; Crystallography; Lattice parameters; Mathematical analysis; Mineralogy; Minerals; Organic chemistry; Outcrops; Simulated annealing; Single crystals; Synchrotron radiation; Unit cell; X-ray diffraction
• ISSN: 0885-7156; 1945-7413
• DOI: 10.1017/S0885715619000630

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, Cu II C 2 O 4 · n H 2 O, 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 P 2 1 / c with lattice parameters a = 7.2659(18) Å, b = 5.7460(11) Å, c = 5.6806(11) Å, β = 104.588(3)°; V c = 229.46(18) Å 3 ; empirical formula Cu II 2 C 2 O 4 (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.