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Acta Crystallographica Section E
Structure Reports
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ISSN 1600-5368
Editors: W. Clegg and D. G. Watson
Redetermination of olivenite from an untwinned single-crystal
Chen Li, Hexiong Yang and Robert T. Downs
Acta Cryst. (2008). E64, i60–i61
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ISSN 1600-5368
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Acta Crystallographica Section E
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Acta Cryst. (2008). E64, i60–i61
Li et al. · Cu2 [(As0.92 ·P0.08 )O4 ]OH
inorganic compounds
Acta Crystallographica Section E
Data collection
Structure Reports
Online
ISSN 1600-5368
Redetermination of olivenite from an
untwinned single-crystal
Chen Li, Hexiong Yang* and Robert T. Downs
Department of Geosciences, University of Arizona, 1040 E. 4th Street, Tucson, AZ
85721-0077, USA
Correspondence e-mail: hyang@u.arizona.edu
Bruker APEX2 CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2005)
Tmin = 0.425, Tmax = 0.480
(expected range = 0.372–0.421)
7604 measured reflections
1580 independent reflections
1372 reflections with I > 2(I)
Rint = 0.029
Refinement
R[F 2 > 2(F 2)] = 0.020
wR(F 2) = 0.045
S = 1.10
1580 reflections
80 parameters
All H-atom parameters refined
max = 0.55 e Å3
min = 0.84 e Å3
Table 1
Selected bond lengths (Å).
Received 29 July 2008; accepted 18 August 2008
Key indicators: single-crystal X-ray study; T = 293 K; mean (Cu–O) = 0.002 Å;
disorder in main residue; R factor = 0.021; wR factor = 0.046; data-to-parameter
ratio = 19.8.
The crystal structure of olivenite, ideally Cu2(AsO4)(OH)
(dicopper(II) arsenate(V) hydroxide), was redetermined from
an untwinned and phosphate-containing natural sample,
composition Cu2(As0.92P0.08O4), from Majuba Hill (Nevada,
USA). Olivenite is structurally analogous with the important
rock-forming mineral andalusite, Al2OSiO4. Its structure
consists of chains of edge-sharing, distorted [CuO4(OH)2]
octahedra extending parallel to [001]. These chains are crosslinked by isolated AsO4 tetrahedra through corner-sharing,
forming channels in which dimers of edge-sharing
[CuO4(OH)] trigonal bipyramids are located. The structure
is stabilized by medium to weak O—H O hydrogen bonds.
In contrast to the previous refinements from powder and
single crystal X-ray data, all non-H atoms were refined with
anisotropic displacement parameters and the H atom was
located.
Related literature
For olivenite, see: Heritsch (1938); Richmond (1940); Berry
(1951); Walitzi (1963); Toman (1977); Burns & Hawthorne
(1995). For other minerals of the olivenite group, see: Hill
(1976); Cordsen (1978); Frost et al. (2002). For correlations
between O—H stretching frequencies and O—H O donor–
acceptor distances, see: Libowitzky (1999). For general background, see: Robinson et al. (1971).
Experimental
Crystal data
Cu2[(As0.92P0.08)O4]OH
Mr = 278.61
Monoclinic, P21 =n11
a = 8.5844 (3) Å
b = 8.2084 (3) Å
c = 5.9258 (2) Å
= 90.130 (2)
i60
Li et al.
V = 417.56 (3) Å3
Z=4
Mo K radiation
= 17.32 mm1
T = 293 (2) K
0.06 0.05 0.05 mm
As1—O4
As1—O5
As1—O1
As1—O2
Cu1—O1i
Cu1—O3H
Cu1—O5ii
Cu1—O1iii
1.6479
1.6644
1.6855
1.6866
1.9466
1.9546
1.9940
2.0132
(18)
(19)
(17)
(16)
(18)
(18)
(18)
(17)
Cu1—O4
Cu2—O2
Cu2—O2iv
Cu2—O3Hv
Cu2—O3H
Cu2—O5vi
Cu2—O4iii
2.1418
1.9526
1.9715
1.9913
2.0001
2.3439
2.3874
(18)
(18)
(17)
(18)
(17)
(17)
(18)
Symmetry codes: (i) x þ 12; y 12; z þ 12; (ii) x; y; z þ 1; (iii) x þ 12; y þ 12; z þ 12; (iv)
x þ 1; y þ 1; z; (v) x þ 1; y þ 1; z þ 1; (vi) x þ 12; y þ 12; z þ 12.
Table 2
Hydrogen-bond geometry (Å, ).
D—H A
O3H—H1 O4
O3H—H1 O5vi
vi
D—H
H A
D A
D—H A
0.67 (4)
0.67 (4)
2.35 (4)
2.66 (4)
2.788 (3)
2.977 (2)
125 (4)
112 (4)
Symmetry code: (vi) x þ 12; y þ 12; z þ 12.
Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT
(Bruker, 2005); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XtalDraw (Downs & Hall-Wallace, 2003); software used to prepare
material for publication: SHELXTL (Sheldrick, 2008).
The authors gratefully acknowledge the support of this
study from the RRUFF project.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: WM2187).
References
Berry, L. G. (1951). Am. Mineral., 36, 484-503.
Bruker (2003). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2005). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Burns, P. C. & Hawthorne, F. C. (1995). Can. Mineral. 33, 885–888.
Cordsen, A. (1978). Can. Mineral. 16, 153–157.
Downs, R. T. & Hall-Wallace, M. (2003). Am. Mineral. 88, 247–250.
Frost, R. L., Martens, W. N. & Williams, P. A. (2002). J. Raman Spectrosc. 33,
475–484.
Heritsch, H. (1938). Z. Kristallogr. 99, 466–479.
Hill, R. J. (1976). Am. Mineral. 61, 979–986.
Libowitzky, E. (1999). Monatsh. Chem. 130, 1047–1059.
Richmond, W. E. (1940). Am. Mineral. 25, 441–479.
Robinson, K., Gibbs, G. V. & Ribbe, P. H. (1971). Science, 172, 567–570.
doi:10.1107/S1600536808026676
electronic reprint
Acta Cryst. (2008). E64, i60–i61
inorganic compounds
Sheldrick, G. M. (2005). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Acta Cryst. (2008). E64, i60–i61
Toman, K. (1977). Acta Cryst. B33, 2628–2631.
Walitzi, E. M. (1963). Tschermaks Mineral. Petrol. Mitt. 8, 275–280.
electronic reprint
Li et al.
Cu2[(As0.92P0.08)O4]OH
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