Redetermination of olivenite from an untwinned single-crystal.

The crystal structure of olivenite, ideally Cu(2)(AsO(4))(OH) [dicopper(II) arsenate(V) hydroxide], was redetermined from an untwinned and phosphate-containing natural sample, composition Cu(2)(As(0.92)P(0.08)O(4)), from Majuba Hill (Nevada, USA). Olivenite is structurally analogous with the important rock-forming mineral andalusite, Al(2)OSiO(4). Its structure consists of chains of edge-sharing, distorted [CuO(4)(OH)(2)] octa-hedra extending parallel to [001]. These chains are cross-linked by isolated AsO(4) tetra-hedra through corner-sharing, forming channels in which dimers of edge-sharing [CuO(4)(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[(As0.92·P0.08)O4]OH

M = 278.61

Monoclinic,

a = 8.5844 (3) Å

b = 8.2084 (3) Å

c = 5.9258 (2) Å

α = 90.130 (2)°

V = 417.56 (3) Å3

Z = 4

Mo Kα radiation

μ = 17.32 mm−1

T = 293 (2) K

0.06 × 0.05 × 0.05 mm

Data collection

Bruker APEX2 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2005 ▶) T min = 0.425, T max = 0.480 (expected range = 0.372–0.421)

7604 measured reflections

1580 independent reflections

1372 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.045

S = 1.10

1580 reflections

80 parameters

All H-atom parameters refined

Δρmax = 0.55 e Å−3

Δρmin = −0.84 e Å−3

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 ▶).

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808026676/wm2187sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808026676/wm2187Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Cu2[(As0.92·P0.08)O4]OH	F000 = 521
Mr = 278.61	Dx = 4.444 Mg m−3
Monoclinic, P21/n11	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2xn	Cell parameters from 1588 reflections
a = 8.5844 (3) Å	θ = 3.9–30.1º
b = 8.2084 (3) Å	µ = 17.32 mm−1
c = 5.9258 (2) Å	T = 293 (2) K
β = 90º	Euhedral, equant, green
V = 417.56 (3) Å3	0.06 × 0.05 × 0.05 mm
Z = 4

Bruker APEX2 CCD area-detector diffractometer	1580 independent reflections
Radiation source: fine-focus sealed tube	1372 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.029
T = 293(2) K	θmax = 33.1º
φ and ω–scans	θmin = 3.4º
Absorption correction: multi-scan(SADABS; Sheldrick, 2005)	h = −12→13
Tmin = 0.425, Tmax = 0.480	k = −12→12
7604 measured reflections	l = −9→9

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0158P)2 + 0.4808P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.020	(Δ/σ)max = 0.001
wR(F2) = 0.046	Δρmax = 0.55 e Å−3
S = 1.10	Δρmin = −0.84 e Å−3
1580 reflections	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
80 parameters	Extinction coefficient: 0.0009 (4)
Primary atom site location: structure-invariant direct methods

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
As1	0.24984 (3)	0.26286 (3)	0.01069 (4)	0.00764 (8)	0.916 (3)
P1	0.24984 (3)	0.26286 (3)	0.01069 (4)	0.00764 (8)	0.084 (3)
Cu1	0.38101 (3)	0.13699 (3)	0.52383 (5)	0.01125 (8)
Cu2	0.49966 (4)	0.50071 (3)	0.24933 (5)	0.01022 (8)
O1	0.1070 (2)	0.4010 (2)	0.0500 (4)	0.0148 (4)
O2	0.41871 (19)	0.3677 (2)	0.0022 (3)	0.0103 (3)
O3H	0.4028 (2)	0.3734 (2)	0.5002 (3)	0.0095 (3)
O4	0.2470 (2)	0.1303 (2)	0.2191 (3)	0.0144 (4)
O5	0.2226 (2)	0.1661 (2)	−0.2333 (3)	0.0144 (4)
H1	0.329 (4)	0.400 (5)	0.510 (7)	0.023 (10)*

	U11	U22	U33	U12	U13	U23
As1	0.00795 (12)	0.00743 (12)	0.00753 (12)	−0.00088 (8)	−0.00011 (8)	−0.00007 (8)
P1	0.00795 (12)	0.00743 (12)	0.00753 (12)	−0.00088 (8)	−0.00011 (8)	−0.00007 (8)
Cu1	0.01148 (14)	0.00725 (13)	0.01503 (15)	−0.00026 (10)	0.00225 (11)	−0.00003 (10)
Cu2	0.01370 (14)	0.01085 (14)	0.00612 (13)	−0.00421 (10)	−0.00003 (10)	−0.00002 (10)
O1	0.0108 (8)	0.0081 (7)	0.0255 (10)	0.0001 (6)	−0.0006 (7)	−0.0003 (7)
O2	0.0114 (7)	0.0118 (8)	0.0077 (8)	−0.0054 (6)	−0.0002 (6)	0.0010 (6)
O3H	0.0101 (8)	0.0084 (7)	0.0100 (8)	0.0000 (6)	0.0002 (6)	0.0005 (6)
O4	0.0164 (8)	0.0154 (8)	0.0114 (8)	−0.0059 (7)	−0.0036 (6)	0.0032 (7)
O5	0.0142 (8)	0.0178 (9)	0.0112 (8)	−0.0047 (6)	0.0022 (6)	−0.0035 (7)

As1—O4	1.6479 (18)	Cu2—O2	1.9526 (18)
As1—O5	1.6644 (19)	Cu2—O2v	1.9715 (17)
As1—O1	1.6855 (17)	Cu2—O3Hvi	1.9913 (18)
As1—O2	1.6866 (16)	Cu2—O3H	2.0001 (17)
Cu1—O1i	1.9466 (18)	Cu2—O5vii	2.3439 (17)
Cu1—O3H	1.9546 (18)	Cu2—O4iii	2.3874 (18)
Cu1—O5ii	1.9940 (18)	Cu2—Cu2v	2.9549 (6)
Cu1—O1iii	2.0132 (17)	Cu2—Cu2vi	2.9710 (6)
Cu1—O4	2.1418 (18)	O3H—H1	0.67 (4)
Cu1—Cu1iv	3.0509 (6)
O4—As1—O5	109.53 (9)	O3H—Cu2—O5vii	86.14 (7)
O4—As1—O1	109.30 (10)	O2—Cu2—O4iii	97.12 (7)
O5—As1—O1	109.72 (9)	O2v—Cu2—O4iii	89.48 (7)
O4—As1—O2	111.90 (8)	O3Hvi—Cu2—O4iii	78.52 (7)
O5—As1—O2	109.70 (9)	O3H—Cu2—O4iii	94.30 (7)
O1—As1—O2	106.63 (9)	O5vii—Cu2—O4iii	168.95 (7)
O1i—Cu1—O3H	171.47 (7)	As1—O1—Cu1viii	128.31 (10)
O1i—Cu1—O5ii	95.51 (8)	As1—O1—Cu1ix	124.56 (10)
O3H—Cu1—O5ii	89.99 (8)	Cu1viii—O1—Cu1ix	100.78 (8)
O1i—Cu1—O1iii	79.22 (8)	As1—O2—Cu2	124.61 (10)
O3H—Cu1—O1iii	92.59 (7)	As1—O2—Cu2v	127.49 (10)
O5ii—Cu1—O1iii	146.34 (8)	Cu2—O2—Cu2v	97.70 (7)
O1i—Cu1—O4	94.12 (8)	Cu1—O3H—Cu2vi	120.04 (9)
O3H—Cu1—O4	90.83 (7)	Cu1—O3H—Cu2	127.85 (10)
O5ii—Cu1—O4	104.18 (8)	Cu2vi—O3H—Cu2	96.20 (7)
O1iii—Cu1—O4	109.33 (8)	Cu1—O3H—H1	103 (3)
O2—Cu2—O2v	82.30 (7)	Cu2vi—O3H—H1	99 (3)
O2—Cu2—O3Hvi	175.64 (7)	Cu2—O3H—H1	107 (3)
O2v—Cu2—O3Hvi	97.45 (7)	As1—O4—Cu1	127.46 (10)
O2—Cu2—O3H	96.73 (7)	As1—O4—Cu2ix	111.74 (9)
O2v—Cu2—O3H	176.19 (7)	Cu1—O4—Cu2ix	114.99 (8)
O3Hvi—Cu2—O3H	83.80 (7)	As1—O5—Cu1x	125.98 (10)
O2—Cu2—O5vii	93.79 (7)	As1—O5—Cu2xi	115.32 (9)
O2v—Cu2—O5vii	90.25 (7)	Cu1x—O5—Cu2xi	117.06 (9)
O3Hvi—Cu2—O5vii	90.56 (7)

D—H···A	D—H	H···A	D···A	D—H···A
O3H—H1···O4vii	0.67 (4)	2.35 (4)	2.788 (3)	125 (4)
O3H—H1···O5vii	0.67 (4)	2.66 (4)	2.977 (2)	112 (4)

Table 1

Selected bond lengths (Å)

As1—O4	1.6479 (18)
As1—O5	1.6644 (19)
As1—O1	1.6855 (17)
As1—O2	1.6866 (16)
Cu1—O1i	1.9466 (18)
Cu1—O3H	1.9546 (18)
Cu1—O5ii	1.9940 (18)
Cu1—O1iii	2.0132 (17)
Cu1—O4	2.1418 (18)
Cu2—O2	1.9526 (18)
Cu2—O2iv	1.9715 (17)
Cu2—O3Hv	1.9913 (18)
Cu2—O3H	2.0001 (17)
Cu2—O5vi	2.3439 (17)
Cu2—O4iii	2.3874 (18)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3H—H1⋯O4vi	0.67 (4)	2.35 (4)	2.788 (3)	125 (4)
O3H—H1⋯O5vi	0.67 (4)	2.66 (4)	2.977 (2)	112 (4)

Symmetry code: (vi) .