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Volume 68 
Part 1 
Pages i9-i10  
January 2012  

Received 5 December 2011
Accepted 16 December 2011
Online 23 December 2011

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Key indicators
Single-crystal X-ray study
T = 293 K
Mean [sigma](As-O) = 0.002 Å
Disorder in main residue
R = 0.019
wR = 0.045
Data-to-parameter ratio = 15.1
Details
Open access

Lotharmeyerite, Ca(Zn,Mn)2(AsO4)2(H2O,OH)2

Yongbo W. Yang,a* Stanley H. Evans,b Robert T. Downsb and Hexiong Yangb

aDepartment of Chemsitry and Biochemistry, University of Arizona, 1306 E. University Blvd., Tucson, Arizona 85721-0041, USA, and bDepartment of Geosciences, University of Arizona, 1040 E. 4th Street, Tucson, Arizona 85721-0077, USA
Correspondence e-mail: ywyang@email.arizona.edu

Lotharmeyerite, calcium bis(zinc/manganese) bis(arsenate) bis(hydroxide/hydrate), Ca(Zn,Mn3+)2(AsO4)2(H2O,OH)2, is a member of the natrochalcite group of minerals, which are characterized by the general formula AM2(XO4)2(H2O,OH)2, where A may be occupied by Pb2+, Ca2+, Na+, and Bi3+, M by Fe3+, Mn3+, Cu2+, Zn2+, Co2+, Ni2+, Al3+, and Mg2+, and X by PV, AsV, VV, and SVI. The minerals in the group display either monoclinic or triclinic symmetry, depending on the ordering of chemical components in the M site. Based on single-crystal X-ray diffraction data of a sample from the type locality, Mapimi, Durango, Mexico, this study presents the first structure determination of lotharmeyerite. Lotharmeyerite is isostructural with natrochalcite and tsumcorite. The structure is composed of rutile-type chains of edge-shared MO6 octahedra (site symmetry [\overline1]) extending along [010], which are interconnected by XO4 tetrahedra (site symmetry 2) and hydrogen bonds to form [M2(XO4)2(OH,H2O)2] sheets parallel to (001). These sheets are linked by the larger A cations (site symmetry 2/m), as well as by hydrogen bonds. Bond-valence sums for the M cation, calculated with the parameters for Mn3+ and Mn2+ are 2.72 and 2.94 v.u., respectively, consistent with the occupation of the M site by Mn3+. Two distinct hydrogen bonds are present, one with O...O = 2.610 (4) Å and the other O...O = 2.595 (3) Å. One of the H-atom positions is disordered over two sites with 50% occupancy, in agreement with observations for other natrochalcite-type minerals, such as natrochalcite and tsumcorite.

Related literature

For lotharmeyerite, see: Dunn (1983[Dunn, P. J. (1983). Mineral. Rec, 14, 35-36.]); Kampf et al. (1984[Kampf, A. R., Shigley, J. E. & Rossman, G. R. (1984). Mineral. Rec, 15, 223-226.]); Brugger et al. (2002[Brugger, J., Krivovichev, S. V., Kolitsch, U., Meisser, N., Andrut, M., Ansermet, S. & Burns, P. C. (2002). Can. Mineral. 40, 1597-1608.]). For related minerals in the natrochalcite group, see: Tillmanns & Gebert (1973[Tillmanns, E. & Gebert, W. (1973). Acta Cryst. B29, 2789-2794.]); Chevrier et al. (1993[Chevrier, G., Giester, G. & Zemann, J. (1993). Z. Kristallogr. 206, 7-14.]); Ansell et al. (1992[Ansell, G. H., Roberts, A. C., Dunn, P. J., Birch, W. D., Ansell, V. E. & Grice, J. D. (1992). Can. Mineral. 30, 225-227.]); Krause et al. (1998[Krause, W., Belendorff, K., Bernhardt, H. J., McCammon, C. A., Effenberger, H. & Mikenda, W. (1998). Eur. J. Mineral. 10, 179-206.], 1999[Krause, W., Effenberger, H., Bernhardt, H. J. & Martin, M. (1999). Neues Jahr. Mineral. Monatsh. 1999, 505-517.], 2001[Krause, W., Bernhardt, H. J., Effenberger, H. & Martin, M. (2001). Neues Jahr. Mineral. Monatsh. 2001, 558-576.]); Brugger et al. (2000[Brugger, J., Meisser, N., Schenk, K., Berlepsch, P., Bonin, M., Armbruster, T., Nyfeler, D. & Schmidt, S. (2000). Am. Mineral. 85, 1307-1314.], 2002[Brugger, J., Krivovichev, S. V., Kolitsch, U., Meisser, N., Andrut, M., Ansermet, S. & Burns, P. C. (2002). Can. Mineral. 40, 1597-1608.]). Parameters for bond-valence calculations were taken from Brese & O'Keeffe (1991[Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.]). For additional information on related minerals, see: Ferraris & Ivaldi (1984[Ferraris, G. & Ivaldi, G. (1984). Acta Cryst. B40, 1-6.]); Krickl & Wildner (2007[Krickl, R. & Wildner, M. (2007). Eur. J. Mineral. 19, 805-816.]).

Experimental

Crystal data

  • Ca(Zn·Mn)2(AsO4)2(H2O·OH)2

  • Mr = 474.14

  • Monoclinic, C 2/m

  • a = 9.0727 (6) Å

  • b = 6.2530 (4) Å

  • c = 7.4150 (5) Å

  • [beta] = 116.739 (4)°

  • V = 375.68 (4) Å3

  • Z = 2

  • Mo K[alpha] radiation

  • [mu] = 14.38 mm-1

  • T = 293 K

  • 0.06 × 0.05 × 0.05 mm
Data collection

  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan [SADABS (Sheldrick, 2005[Sheldrick, G. M. (2005). SADABS. University of Göttingen, Germany.]) and XABS2 (Parkin et al., 1995[Parkin, S., Moezzi, B. & Hope, H. (1995). J. Appl. Cryst. 28, 53-56.])] Tmin = 0.477, Tmax = 0.532

  • 2512 measured reflections

  • 739 independent reflections

  • 659 reflections with I > 2[sigma](I)

  • Rint = 0.022
Refinement

  • R[F2 > 2[sigma](F2)] = 0.019

  • wR(F2) = 0.045

  • S = 0.91

  • 739 reflections

  • 49 parameters

  • All H-atom parameters refined

  • [Delta][rho]max = 0.81 e Å-3

  • [Delta][rho]min = -0.77 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
O1-H1...O1i 0.82 (7) 1.79 (8) 2.610 (4) 177 (11)
O1-H2...O4ii 0.66 (5) 1.95 (5) 2.595 (3) 163 (6)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) [-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z].

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XtalDraw (Downs & Hall-Wallace, 2003[Downs, R. T. & Hall-Wallace, M. (2003). Am. Mineral. 88, 247-250.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2375 ).

Acknowledgements

The authors gratefully acknowledge support of this study by the Arizona Science Foundation.

References

Ansell, G. H., Roberts, A. C., Dunn, P. J., Birch, W. D., Ansell, V. E. & Grice, J. D. (1992). Can. Mineral. 30, 225-227.  [ChemPort]
Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.  [CrossRef] [ISI] [details]
Brugger, J., Krivovichev, S. V., Kolitsch, U., Meisser, N., Andrut, M., Ansermet, S. & Burns, P. C. (2002). Can. Mineral. 40, 1597-1608.  [CrossRef] [ChemPort]
Brugger, J., Meisser, N., Schenk, K., Berlepsch, P., Bonin, M., Armbruster, T., Nyfeler, D. & Schmidt, S. (2000). Am. Mineral. 85, 1307-1314.  [ChemPort]
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Chevrier, G., Giester, G. & Zemann, J. (1993). Z. Kristallogr. 206, 7-14.  [CrossRef] [ChemPort]
Downs, R. T. & Hall-Wallace, M. (2003). Am. Mineral. 88, 247-250.  [ChemPort]
Dunn, P. J. (1983). Mineral. Rec, 14, 35-36.  [ChemPort]
Ferraris, G. & Ivaldi, G. (1984). Acta Cryst. B40, 1-6.  [CrossRef] [ISI] [details]
Kampf, A. R., Shigley, J. E. & Rossman, G. R. (1984). Mineral. Rec, 15, 223-226.  [ChemPort]
Krause, W., Belendorff, K., Bernhardt, H. J., McCammon, C. A., Effenberger, H. & Mikenda, W. (1998). Eur. J. Mineral. 10, 179-206.  [ChemPort]
Krause, W., Bernhardt, H. J., Effenberger, H. & Martin, M. (2001). Neues Jahr. Mineral. Monatsh. 2001, 558-576.
Krause, W., Effenberger, H., Bernhardt, H. J. & Martin, M. (1999). Neues Jahr. Mineral. Monatsh. 1999, 505-517.
Krickl, R. & Wildner, M. (2007). Eur. J. Mineral. 19, 805-816.  [ChemPort]
Parkin, S., Moezzi, B. & Hope, H. (1995). J. Appl. Cryst. 28, 53-56.  [CrossRef] [ChemPort] [ISI] [details]
Sheldrick, G. M. (2005). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Tillmanns, E. & Gebert, W. (1973). Acta Cryst. B29, 2789-2794.  [CrossRef] [ChemPort] [details] [ISI]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [ISI] [CrossRef] [ChemPort] [details]

Acta Cryst (2012). E68, i9-i10   [ doi:10.1107/S1600536811054286 ]

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