Wyllieite-type Ag(1.09)Mn(3.46)(AsO(4))(3).

Single crystals of wyllieite-type silver(I) manganese(II) tris-orthoarsenate(V), Ag(1.09)Mn(3.46)(AsO(4))(3), were grown by a solid-state reaction. The three-dimensional framework is made up from four Mn(2+)/Mn(3+) cations surrounded octa-hedrally by O atoms. The MnO(6) octa-hedra are linked through edge- and corner-sharing. Three independent AsO(4) tetra-hedra are linked to the framework through common corners, delimiting channels along [100] in which two partly occupied Ag(+) sites reside, one on an inversion centre and with an occupancy of 0.631 (4), the other on a general site and with an occupancy of 0.774 (3), both within distorted tetra-hedral environments. One of the Mn sites is also located on an inversion centre and is partly occupied, with an occupancy of 0.916 (5). Related compounds with alluaudite-type or rosemaryite-type structures are compared and discussed.

Related literature

For background to framework structures with tetra­hedral and octa­hedral building units, see: Leclaire et al. (2002 ▶); Lii et al. (1990 ▶); Haddad et al. (1992 ▶); Hajji & Zid (2006 ▶); Borel et al. (1997 ▶); Masquelier et al. (1995 ▶). For details of structural relationships with other compounds, see: Warner et al. (1993 ▶); Korzenski et al. (1998 ▶); Chouaibi et al. (2001 ▶); Pertlik (1987 ▶); Antenucci et al. (1995 ▶); Zid et al. (2005 ▶); Ayed et al. (2004 ▶); MacKay et al. (1996 ▶); Alvarez-Vega et al. (2006 ▶); Frigui et al. (2010 ▶, 2011a ▶); Hatert (2006 ▶); Moore & Ito (1973 ▶, 1979 ▶); Yakubovich et al. (2005 ▶); Fransolet (1995 ▶); Moore & Molin-Case (1974 ▶). For preparative details, see: Frigui et al. (2010 ▶, 2011 ▶). For the bond-valence method, see: Brown & Altermatt (1985 ▶).

Experimental

Crystal data

Ag1.09Mn3.46(AsO4)3

M = 724.02

Monoclinic,

a = 6.7470 (7) Å

b = 12.9820 (9) Å

c = 11.2970 (8) Å

β = 98.85 (3)°

V = 977.72 (17) Å3

Z = 4

Mo Kα radiation

μ = 16.64 mm−1

T = 298 K

0.25 × 0.15 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.071, T max = 0.210

2522 measured reflections

2138 independent reflections

1704 reflections with I > 2σ(I)

R int = 0.038

2 standard reflections every 120 min intensity decay: 1.1%

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.098

S = 1.08

2138 reflections

188 parameters

1 restraint

Δρmax = 1.08 e Å−3

Δρmin = −1.37 e Å−3

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶; Macíček & Yordanov, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812018843/wm2611sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812018843/wm2611Isup2.hkl

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

Ag1.09Mn3.46(AsO4)3	F(000) = 1330
Mr = 724.02	Dx = 4.919 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 6.7470 (7) Å	θ = 11–15°
b = 12.9820 (9) Å	µ = 16.64 mm−1
c = 11.2970 (8) Å	T = 298 K
β = 98.85 (3)°	Prism, red
V = 977.72 (17) Å3	0.25 × 0.15 × 0.10 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	1704 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 27.0°, θmin = 2.4°
ω/2θ scans	h = −8→0
Absorption correction: ψ scan (North et al., 1968)	k = −1→16
Tmin = 0.071, Tmax = 0.210	l = −14→14
2522 measured reflections	2 standard reflections every 120 min
2138 independent reflections	intensity decay: 1.1%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032	w = 1/[σ2(Fo2) + (0.0433P)2 + 6.7709P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.098	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 1.08 e Å−3
2138 reflections	Δρmin = −1.37 e Å−3
188 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.00067 (14)

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	0.58985 (10)	0.11831 (5)	0.23334 (6)	0.00808 (18)
As2	0.87952 (9)	0.39792 (5)	0.26469 (6)	0.00878 (18)
As3	0.23349 (9)	0.28782 (5)	−0.00773 (6)	0.00740 (18)
Mn1	0.40485 (14)	0.35350 (7)	0.27517 (9)	0.0080 (2)
Mn2	0.73285 (15)	0.23422 (8)	0.49855 (8)	0.0099 (2)
Mn3	0.5000	0.0000	0.5000	0.0143 (5)	0.916 (5)
Mn4	0.07641 (16)	0.16561 (8)	0.21311 (9)	0.0144 (2)
Ag1	0.75155 (11)	−0.01201 (7)	0.00310 (6)	0.0239 (3)	0.774 (3)
Ag2	0.0000	0.5000	0.0000	0.0305 (5)	0.631 (4)
O1	0.5493 (7)	0.0060 (3)	0.1633 (4)	0.0126 (10)
O2	0.7681 (7)	0.1779 (3)	0.1698 (4)	0.0132 (9)
O3	0.6539 (7)	0.1019 (3)	0.3815 (4)	0.0130 (10)
O4	0.3803 (7)	0.1906 (3)	0.2135 (4)	0.0117 (9)
O5	0.0876 (7)	0.3269 (4)	0.2693 (4)	0.0172 (10)
O6	0.2259 (7)	−0.0884 (4)	0.3793 (4)	0.0136 (10)
O7	0.0586 (8)	0.0122 (4)	0.1655 (4)	0.0191 (11)
O8	0.7207 (6)	0.3394 (3)	0.3436 (4)	0.0104 (9)
O9	0.4128 (6)	0.2108 (3)	−0.0446 (4)	0.0092 (9)
O10	0.1085 (8)	0.1383 (4)	0.3815 (5)	0.0209 (11)
O11	0.3397 (7)	0.3798 (3)	0.0854 (4)	0.0155 (10)
O12	0.0524 (7)	0.2180 (4)	0.0434 (4)	0.0137 (10)

	U11	U22	U33	U12	U13	U23
As1	0.0147 (3)	0.0049 (3)	0.0058 (3)	−0.0002 (2)	0.0051 (2)	0.0003 (2)
As2	0.0092 (3)	0.0131 (3)	0.0046 (3)	−0.0024 (2)	0.0028 (2)	0.0001 (2)
As3	0.0097 (3)	0.0049 (3)	0.0088 (3)	0.0000 (2)	0.0049 (2)	−0.0016 (2)
Mn1	0.0108 (5)	0.0069 (4)	0.0065 (5)	−0.0005 (3)	0.0021 (4)	−0.0010 (3)
Mn2	0.0142 (5)	0.0077 (5)	0.0072 (5)	−0.0006 (4)	0.0001 (4)	−0.0010 (3)
Mn3	0.0232 (9)	0.0055 (7)	0.0182 (9)	0.0008 (6)	0.0161 (7)	0.0004 (6)
Mn4	0.0176 (5)	0.0147 (5)	0.0114 (5)	−0.0004 (4)	0.0039 (4)	−0.0010 (4)
Ag1	0.0227 (4)	0.0383 (5)	0.0117 (4)	−0.0005 (3)	0.0058 (3)	0.0009 (3)
Ag2	0.0409 (9)	0.0123 (7)	0.0465 (10)	0.0030 (6)	0.0331 (7)	−0.0008 (6)
O1	0.022 (2)	0.006 (2)	0.010 (2)	−0.0022 (18)	0.0046 (19)	−0.0020 (17)
O2	0.021 (2)	0.008 (2)	0.012 (2)	0.0001 (19)	0.0088 (19)	0.0036 (18)
O3	0.027 (3)	0.008 (2)	0.004 (2)	0.0001 (19)	0.0034 (19)	0.0011 (17)
O4	0.018 (2)	0.011 (2)	0.007 (2)	0.0017 (18)	0.0019 (18)	−0.0006 (17)
O5	0.009 (2)	0.032 (3)	0.012 (2)	−0.002 (2)	0.0069 (18)	0.003 (2)
O6	0.021 (2)	0.013 (2)	0.005 (2)	0.0040 (19)	−0.0025 (18)	−0.0011 (18)
O7	0.026 (3)	0.024 (3)	0.008 (2)	0.016 (2)	0.004 (2)	0.005 (2)
O8	0.010 (2)	0.012 (2)	0.012 (2)	0.0018 (17)	0.0083 (18)	0.0055 (18)
O9	0.010 (2)	0.013 (2)	0.006 (2)	0.0021 (17)	0.0054 (17)	−0.0005 (17)
O10	0.033 (3)	0.011 (2)	0.018 (3)	−0.014 (2)	−0.001 (2)	0.003 (2)
O11	0.023 (3)	0.009 (2)	0.015 (2)	−0.0083 (19)	0.005 (2)	−0.0061 (19)
O12	0.013 (2)	0.019 (2)	0.010 (2)	−0.0068 (19)	0.0066 (18)	−0.0042 (19)

As1—O1	1.661 (4)	Mn2—O9iv	2.256 (4)
As1—O3	1.677 (4)	Mn2—O6vi	2.333 (5)
As1—O2	1.681 (5)	Mn3—O11iv	2.204 (5)
As1—O4	1.683 (5)	Mn3—O11vii	2.204 (5)
As2—O5i	1.674 (5)	Mn3—O3	2.246 (5)
As2—O8	1.677 (4)	Mn3—O3vi	2.246 (5)
As2—O6ii	1.682 (4)	Mn3—O6vi	2.413 (5)
As2—O7ii	1.701 (5)	Mn3—O6	2.413 (5)
As3—O9	1.671 (4)	Mn4—O10	1.915 (5)
As3—O11	1.678 (4)	Mn4—O12	2.017 (5)
As3—O12	1.693 (5)	Mn4—O7	2.062 (5)
As3—O10iii	1.695 (5)	Mn4—O2viii	2.069 (5)
Mn1—O1ii	2.105 (4)	Mn4—O4	2.075 (5)
Mn1—O11	2.148 (5)	Mn4—O5	2.186 (6)
Mn1—O5	2.159 (5)	Ag1—O1	2.439 (5)
Mn1—O8	2.160 (5)	Ag1—O7ix	2.454 (5)
Mn1—O9iv	2.193 (4)	Ag1—O1ix	2.547 (5)
Mn1—O4	2.224 (4)	Ag1—O7i	2.566 (5)
Mn2—O3	2.183 (5)	Ag2—O10x	2.418 (5)
Mn2—O8	2.212 (4)	Ag2—O10iii	2.418 (5)
Mn2—O12v	2.226 (5)	Ag2—O6iii	2.478 (5)
Mn2—O2iv	2.227 (5)	Ag2—O6x	2.478 (5)
O1—As1—O3	111.2 (2)	O3—Mn2—O9iv	88.97 (17)
O1—As1—O2	106.1 (2)	O8—Mn2—O9iv	73.49 (16)
O3—As1—O2	113.2 (2)	O12v—Mn2—O9iv	145.34 (18)
O1—As1—O4	110.7 (2)	O2iv—Mn2—O9iv	89.79 (17)
O3—As1—O4	106.6 (2)	O3—Mn2—O6vi	73.47 (17)
O2—As1—O4	109.1 (2)	O8—Mn2—O6vi	162.80 (17)
O5i—As2—O8	109.6 (2)	O12v—Mn2—O6vi	93.92 (17)
O5i—As2—O6ii	108.4 (2)	O2iv—Mn2—O6vi	85.10 (17)
O8—As2—O6ii	110.6 (2)	O9iv—Mn2—O6vi	114.06 (17)
O5i—As2—O7ii	108.7 (3)	O11iv—Mn3—O11vii	180.0 (2)
O8—As2—O7ii	106.3 (2)	O11iv—Mn3—O3	98.46 (17)
O6ii—As2—O7ii	113.2 (2)	O11vii—Mn3—O3	81.54 (17)
O9—As3—O11	109.1 (2)	O11iv—Mn3—O3vi	81.54 (17)
O9—As3—O12	110.6 (2)	O11vii—Mn3—O3vi	98.46 (17)
O11—As3—O12	115.4 (2)	O3—Mn3—O3vi	180.0
O9—As3—O10iii	116.9 (2)	O11iv—Mn3—O6vi	78.51 (17)
O11—As3—O10iii	100.1 (2)	O11vii—Mn3—O6vi	101.49 (17)
O12—As3—O10iii	104.6 (3)	O3—Mn3—O6vi	70.87 (17)
O1ii—Mn1—O11	100.20 (18)	O3vi—Mn3—O6vi	109.13 (17)
O1ii—Mn1—O5	104.8 (2)	O11iv—Mn3—O6	101.49 (17)
O11—Mn1—O5	86.86 (18)	O11vii—Mn3—O6	78.51 (17)
O1ii—Mn1—O8	82.81 (18)	O3—Mn3—O6	109.13 (17)
O11—Mn1—O8	114.17 (18)	O3vi—Mn3—O6	70.87 (17)
O5—Mn1—O8	156.39 (18)	O6vi—Mn3—O6	180.00 (19)
O1ii—Mn1—O9iv	94.00 (18)	O10—Mn4—O12	170.8 (2)
O11—Mn1—O9iv	163.49 (17)	O10—Mn4—O7	94.2 (2)
O5—Mn1—O9iv	81.37 (18)	O12—Mn4—O7	94.9 (2)
O8—Mn1—O9iv	75.76 (16)	O10—Mn4—O2viii	101.8 (2)
O1ii—Mn1—O4	175.83 (18)	O12—Mn4—O2viii	79.54 (19)
O11—Mn1—O4	81.08 (17)	O7—Mn4—O2viii	89.83 (19)
O5—Mn1—O4	79.20 (19)	O10—Mn4—O4	93.8 (2)
O8—Mn1—O4	93.05 (17)	O12—Mn4—O4	83.35 (18)
O9iv—Mn1—O4	85.35 (17)	O7—Mn4—O4	99.78 (19)
O3—Mn2—O8	91.75 (17)	O2viii—Mn4—O4	161.04 (18)
O3—Mn2—O12v	119.67 (18)	O10—Mn4—O5	84.0 (2)
O8—Mn2—O12v	85.69 (17)	O12—Mn4—O5	86.98 (19)
O3—Mn2—O2iv	155.86 (18)	O7—Mn4—O5	177.62 (19)
O8—Mn2—O2iv	110.95 (18)	O2viii—Mn4—O5	89.03 (18)
O12v—Mn2—O2iv	71.89 (18)	O4—Mn4—O5	81.91 (17)