Redetermination of eveite, Mn(2)AsO(4)(OH), based on single-crystal X-ray diffraction data.

The crystal structure of eveite, ideally Mn(2)(AsO(4))(OH) [dimanganese(II) arsenate(V) hydroxide], was refined from a single crystal selected from a co-type sample from Långban, Filipstad, Varmland, Sweden. Eveite, dimorphic with sarkinite, is structurally analogous with the important rock-forming mineral andalusite, Al(2)OSiO(4), and belongs to the libethenite group. Its structure consists of chains of edge-sharing distorted [MnO(4)(OH)(2)] octa-hedra (..2 symmetry) extending parallel to [001]. These chains are cross-linked by isolated AsO(4) tetra-hedra (..m symmetry) through corner-sharing, forming channels in which dimers of edge-sharing [MnO(4)(OH)] trigonal bipyramids (..m symmetry) are located. In contrast to the previous refinement from Weissenberg photographic data [Moore & Smyth (1968 ▶). Am. Mineral.53, 1841-1845], all non-H atoms were refined with anisotropic displacement param-eters and the H atom was located. The distance of the donor and acceptor O atoms involved in hydrogen bonding is in agreement with Raman spectroscopic data. Examination of the Raman spectra for arsenate minerals in the libethenite group reveals that the position of the peak originating from the O-H stretching vibration shifts to lower wavenumbers from eveite, to adamite, zincolivenite, and olivenite.

Related literature

For background to eveite, see: Moore (1968 ▶); Moore & Smyth (1968 ▶); Hålenius & Westlund (1998 ▶). For other minerals of the libethenite group, see: Hawthorne (1976 ▶); Cordsen (1978 ▶); Toman (1978 ▶); Li et al. (2008 ▶). Correlations between O—H streching frequencies and O—H⋯O donor–acceptor distances were given by Libowitzky (1999 ▶).

Experimental

Crystal data

Mn2AsO4(OH)

M = 265.81

Orthorhombic,

a = 8.5478 (16) Å

b = 8.7207 (16) Å

c = 6.2961 (12) Å

V = 469.33 (15) Å3

Z = 4

Mo Kα radiation

μ = 12.29 mm−1

T = 293 K

0.05 × 0.05 × 0.04 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2005 ▶) T min = 0.579, T max = 0.639

3315 measured reflections

911 independent reflections

849 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.055

S = 1.09

911 reflections

49 parameters

All H-atom parameters refined

Δρmax = 1.28 e Å−3

Δρmin = −1.15 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811044266/wm2546sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044266/wm2546Isup2.hkl

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

Mn2AsO4(OH)	F(000) = 496
Mr = 265.81	Dx = 3.762 Mg m−3
Orthorhombic, Pnnm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2 2n	Cell parameters from 2202 reflections
a = 8.5478 (16) Å	θ = 4–32°
b = 8.7207 (16) Å	µ = 12.29 mm−1
c = 6.2961 (12) Å	T = 293 K
V = 469.33 (15) Å3	Cuboid, pale gray
Z = 4	0.05 × 0.05 × 0.04 mm

Bruker APEXII CCD area-detector diffractometer	911 independent reflections
Radiation source: fine-focus sealed tube	849 reflections with I > 2σ(I)
graphite	Rint = 0.015
φ and ω scan	θmax = 32.6°, θmin = 4.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2005)	h = −12→5
Tmin = 0.579, Tmax = 0.639	k = −13→12
3315 measured reflections	l = −7→9

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021	All H-atom parameters refined
wR(F2) = 0.055	w = 1/[σ2(Fo2) + (0.0327P)2 + 0.4777P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.005
911 reflections	Δρmax = 1.28 e Å−3
49 parameters	Δρmin = −1.15 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0034 (7)

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
Mn1	0.0000	0.0000	0.24719 (6)	0.01052 (10)
Mn2	0.35839 (4)	0.13367 (4)	0.5000	0.01082 (11)
As1	0.24335 (3)	0.25667 (3)	0.0000	0.00735 (9)
O1	0.3874 (2)	0.3726 (2)	0.5000	0.0101 (3)
O2	0.4144 (2)	0.3545 (2)	0.0000	0.0115 (3)
O3	0.1033 (2)	0.3922 (2)	0.0000	0.0171 (4)
O4	0.22306 (16)	0.14338 (15)	0.2163 (2)	0.0131 (3)
H1	0.287 (7)	0.394 (6)	0.5000	0.042 (14)*

	U11	U22	U33	U12	U13	U23
Mn1	0.01271 (19)	0.01066 (19)	0.00818 (18)	0.00186 (12)	0.000	0.000
Mn2	0.01072 (18)	0.00927 (18)	0.01247 (18)	0.00027 (12)	0.000	0.000
As1	0.00733 (13)	0.00605 (14)	0.00868 (14)	−0.00111 (7)	0.000	0.000
O1	0.0105 (7)	0.0079 (8)	0.0119 (8)	−0.0004 (6)	0.000	0.000
O2	0.0097 (8)	0.0141 (9)	0.0106 (8)	−0.0056 (6)	0.000	0.000
O3	0.0099 (8)	0.0084 (8)	0.0331 (12)	0.0015 (6)	0.000	0.000
O4	0.0141 (6)	0.0143 (6)	0.0108 (6)	−0.0049 (5)	−0.0023 (5)	0.0026 (5)

Mn1—O1i	2.1406 (13)	Mn2—O4	2.1296 (14)
Mn1—O1ii	2.1406 (13)	Mn2—O4vi	2.1296 (14)
Mn1—O2iii	2.1630 (13)	Mn2—O3i	2.131 (2)
Mn1—O2i	2.1630 (13)	As1—O3	1.683 (2)
Mn1—O4iv	2.2884 (13)	As1—O4vii	1.6915 (14)
Mn1—O4	2.2884 (13)	As1—O4	1.6915 (14)
Mn2—O1	2.0984 (19)	As1—O2	1.6929 (18)
Mn2—O3v	2.106 (2)
O1i—Mn1—O1ii	86.72 (7)	O1—Mn2—O4	91.42 (5)
O1i—Mn1—O2iii	172.52 (7)	O3v—Mn2—O4	122.98 (4)
O1ii—Mn1—O2iii	94.51 (5)	O1—Mn2—O4vi	91.42 (5)
O1i—Mn1—O2i	94.51 (5)	O3v—Mn2—O4vi	122.98 (4)
O1ii—Mn1—O2i	172.52 (7)	O4—Mn2—O4vi	114.00 (8)
O2iii—Mn1—O2i	85.24 (7)	O1—Mn2—O3i	164.36 (8)
O1i—Mn1—O4iv	91.67 (6)	O3v—Mn2—O3i	75.00 (9)
O1ii—Mn1—O4iv	81.22 (6)	O4—Mn2—O3i	97.05 (5)
O2iii—Mn1—O4iv	95.81 (6)	O4vi—Mn2—O3i	97.05 (5)
O2i—Mn1—O4iv	91.36 (6)	O3—As1—O4vii	109.72 (6)
O1i—Mn1—O4	81.22 (6)	O3—As1—O4	109.72 (6)
O1ii—Mn1—O4	91.67 (6)	O4vii—As1—O4	107.26 (9)
O2iii—Mn1—O4	91.36 (6)	O3—As1—O2	105.09 (10)
O2i—Mn1—O4	95.81 (6)	O4vii—As1—O2	112.51 (6)
O4iv—Mn1—O4	170.25 (7)	O4—As1—O2	112.51 (6)
O1—Mn2—O3v	89.37 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4viii	0.88 (6)	2.57 (4)	2.885 (2)	102 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4i	0.88 (6)	2.57 (4)	2.885 (2)	102 (3)

Symmetry code: (i) .