electronic reprint Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 Editors: W. Clegg and D. G. Watson Redetermination of conichalcite, CaCu(AsO4)(OH) Rachel R. Henderson, Hexiong Yang, Robert T. Downs and Robert A. Jenkins Acta Cryst. (2008). E64, i53–i54 This open-access article is distributed under the terms of the Creative Commons Attribution Licence http://creativecommons.org/licenses/by/2.0/uk/legalcode, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited. ISSN 1600-5368 Acta Crystallographica Section E Volume 61 Structure Reports Part 11 Online November 2005 Editors: W. Clegg and D. G. Watson Acta Crystallographica Section E: Structure Reports Online is the IUCr’s highly popu- lar open-access structural journal. It provides a simple and easily accessible publication mechanism for the growing number of inorganic, metal-organic and organic crystal struc- Inorganic compounds ture determinations. The electronic submission, validation, refereeing and publication Metal-organic compounds Organic compounds facilities of the journal ensure very rapid and high-quality publication, whilst key indica- tors and validation reports provide measures of structural reliability. In 2007, the journal published over 5000 structures. The average publication time is less than one month. journals.iucr.org International Union of Crystallography * Chester Crystallography Journals Online is available from journals.iucr.org Acta Cryst. (2008). E64, i53–i54 Henderson et al. · CaCu(AsO4)(OH) inorganic compounds Acta Crystallographica Section E Experimental Structure Reports Crystal data Online ˚ 3 CaCu(AsO4)(OH) V = 395.49 (2) A ISSN 1600-5368 Mr = 259.57 Z =4 Orthorhombic, P212121 Mo K radiation a = 7.3822 (2) A˚ = 15.03 mmÀ1 Redetermination of conichalcite, b = 5.8146 (2) A˚ T = 293 (2) K c = 9.2136 (3) A˚ 0.06 Â 0.05 Â 0.04 mm CaCu(AsO4)(OH) Data collection Rachel R. Henderson, Hexiong Yang,* Robert T. Downs Bruker APEXII CCD 7088 measured reflections diffractometer 1602 independent reflections and Robert A. Jenkins Absorption correction: multi-scan 1487 reflections with I >2(I) (TWINABS; Sheldrick, 2008) Rint = 0.023 Department of Geosciences, University of Arizona, 1040 E. 4th Street, Tucson, AZ Tmin = 0.492, Tmax = 0.585 85721-0077, USA (expected range = 0.461–0.548) Correspondence e-mail: [email protected] Refinement Received 2 July 2008; accepted 29 July 2008 2 2 ˚ À3 R[F >2(F )] = 0.018 Ámax = 0.63 e A wR(F 2) = 0.038 Á = À0.49 e A˚ À3 T ˚ min Key indicators: single-crystal X-ray study; = 293 K; mean (As–O) = 0.002 A; S = 1.03 Absolute structure: Flack (1983), R factor = 0.018; wR factor = 0.038; data-to-parameter ratio = 20.3. 1602 reflections 644 Friedel pairs 79 parameters Flack parameter: 0.00 (2) All H-atom parameters refined The crystal structure of conichalcite [calcium copper(II) arsenate(V) hydroxide], with ideal formula CaCu(AsO4)- (OH), was redetermined from a natural twinned specimen Table 1 ˚ found in the Maria Catalina mine (Chile). In contrast to the Selected bond lengths (A). previous refinement from photographic data [Qurashi & Ca—O5i 2.3626 (13) Cu—O5vi 1.8855 (16) 7 Ca—O3ii 2.3995 (17) Cu—O1vi 2.0666 (16) Barnes (1963). Can. Mineral. , 561–577], all atoms were Ca—O4iii 2.4818 (16) Cu—O1 2.0688 (15) refined with anisotropic displacement parameters and with the Ca—O2iv 2.5178 (17) Cu—O3vii 2.2976 (15) H atom located. Conichalcite belongs to the adelite mineral Ca—O4v 2.5281 (16) Cu—O4viii 2.3882 (14) Ca—O1iv 2.5462 (14) As—O4 1.6749 (16) group. The Jahn–Teller-distorted [CuO6] octahedra share Ca—O3 2.5786 (17) As—O3 1.6779 (16) edges, forming chains running parallel to [010]. These chains Ca—O2 2.6264 (17) As—O2 1.6796 (16) are cross-linked by eight-coordinate Ca atoms and by sharing Cu—O5 1.8850 (15) As—O1 1.7099 (13) À þ 1; À þ ; À 1 þ 1; À þ 3; À ; þ ; Symmetry codes: (i) x 2 y 1 z 2; (ii) x 2 y 2 z; (iii) x y 1 z; (iv) vertices with isolated AsO4 tetrahedra. Of five calcium À þ ; þ 1; À þ 1 þ 1; À þ 1; À À ; À 1; À þ 1 x 1 y 2 z 2; (v) x 2 y 2 z; (vi) x y 2 z 2; (vii) À 1; À þ 1; À À þ 1; À ; þ 1 arsenate minerals in the adelite group, the [MO6](M = Cu, x 2 y 2 z; (viii) x 2 y z 2. Zn, Co, Ni and Mg) octahedron in conichalcite is the most distorted, and the donor–acceptor O—HÁÁÁO distance is the shortest. Table 2 Hydrogen-bond geometry (A˚ , ). Related literature D—HÁÁÁAD—H HÁÁÁADÁÁÁAD—HÁÁÁA For background on the adelite mineral family, see: Qurashi & O5—H1ÁÁÁO2ix 0.86 (4) 1.91 (4) 2.678 (2) 149 (3) Barnes (1963, 1964); Qurashi et al. (1953). For structure À ; ; refinements in the adelite group, see: Effenberger et al. (2002) Symmetry code: (ix) x 1 y z. for adelite, CaMgAsO (OH); Clark et al. (1997) and Giusep- 4 Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT petti & Tadini (1988) for austinite, CaZnAsO (OH); Yang et 4 (Bruker, 2005); data reduction: SAINT; program(s) used to solve al. (2007) for cobaltaustinite, CaCoAsO4(OH); Cesbron et al. structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine (1987) for nickelaustinite, CaNiAsO4(OH). Correlations structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Xtal- between O—H streching frequencies and O—HÁÁÁO donor– Draw (Downs & Hall-Wallace, 2003); software used to prepare acceptor distances are given by Libowitzky (1999). Raman material for publication: SHELXTL (Sheldrick, 2008). spectroscopic data on some minerals of the adelite group have been reported by Martens et al. (2003); for general back- The authors gratefully acknowledge support of this study by ground, see: Robinson et al. (1971). the RRUFF project. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2185). Acta Cryst. (2008). E64, i53–i54 doi:10.1107/S1600536808024173 Henderson et al. i53 electronic reprint inorganic compounds References Giuseppetti, G. & Tadini, C. (1988). Neues Jahrb. Mineral. Monatsh. 1988, 159– 166. Bruker (2003). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Libowitzky, E. (1999). Monatsh. Chem. 130, 1047–1059. Bruker (2005). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Martens, W., Frost, R. L. & Williams, P. A. (2003). J. Raman Spectrosc. 34, 104– Cesbron, F., Ginderow, D., Giraud, R., Pelisson, P. & Pillard, F. (1987). Can. 111. 25 Mineral. , 401–407. Qurashi, M. M. & Barnes, W. H. (1963). Can. Mineral. 7, 561–577. Clark, L. A., Pluth, J. J., Steele, I., Smith, J. V. & Sutton, S. R. (1997). Mineral. Qurashi, M. M. & Barnes, W. H. (1964). Can. Mineral. 8, 23–39. 61 Mag. , 677–683. Qurashi, M. M., Barnes, W. H. & Berry, L. G. (1953). Am. Mineral. 38, 557–559. 88 Downs, R. T. & Hall-Wallace, M. (2003). Am. Mineral. , 247–250. Robinson, K., Gibbs, G. V. & Ribbe, P. H. (1971). Science, 172, 567–570. Effenberger, H., Krause, W. & Bernhardt, H. J. (2002). Exp. Miner. Petrol. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. 9 Geochem. Abstr. , 30. Yang, H., Costin, G., Keogh, J., Lu, R. & Downs, R. T. (2007). Acta Cryst. E63, 39 Flack, H. D. (1983). Acta Cryst. A , 876–881. i53–i55. i54 Henderson et al. CaCu(AsO4)(OH) Acta Cryst. (2008). E64, i53–i54 electronic reprint electronic reprint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