β-Xenophyllite-type Na4Li0.62Co5.67Al0.71(AsO4)6.

The title compound, tetrasodium lithium cobalt aluminium hexa-(orthoarsenate), was synthesized by a solid state reaction route. In the crystal structure, Co(2+) ions are partially substituted by Al(3+) in an octa-hedral environment [M1 with site symmetry 2/m; occupancy ratio Co:Al = 0.286 (10):0.714 (10)]. The charge compensation is ensured by Li(+) cations sharing a tetra-hedral site with Co(2+) ions [M2 with site symmetry 2; occupancy ratio Co:Li = 0.690 (5):0.310 (5)]. The anionic unit is formed by two octa-hedra and three tetra-hedra linked only by corners. The CoM1M2As2O19 units associate to an open three-dimensional framework containing tunnels propagating along the a-axis direction. One Na(+) cation is located in the periphery of the tunnels while the other two are situated in the centres: all Na(+) cations exhibit half-occupancy. The structure of the studied material is compared with those of various related minerals reported in the literature.

Related literature

For applications of these and related phases, see: Aurivillius et al. (1964 ▶); Nagpure et al. (2010 ▶); Prabaharan et al. (1997 ▶). For details of structurally related compounds, see: Alvarez-Vega et al. (2006 ▶); Keller et al. (1981 ▶); Frigui et al. (2012 ▶); Goodenough et al. (1976 ▶); Marzouki et al. (2012 ▶); Ben Smida et al. (2013 ▶); Guesmi & Driss (2012 ▶); Moring & Kostiner (1986 ▶); Kobashi et al. (1998 ▶); Ben Smail et al. (1999 ▶); Burke et al. (2006 ▶); Redhammer et al. (2005 ▶); Hatert et al. (2005 ▶); Moore & Molin-Case (1974 ▶). For the bond-valence method, see: Brown & Altermatt, (1985 ▶).

Experimental

Crystal data

Na4Li0.62Co5.67Al0.71(AsO4)6

M = 1283.06

Monoclinic,

a = 10.7444 (9) Å

b = 14.847 (2) Å

c = 6.7223 (8) Å

β = 105.51 (2)°

V = 1033.3 (2) Å3

Z = 2

Mo Kα radiation

μ = 14.22 mm−1

T = 298 K

0.26 × 0.24 × 0.22 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.033, T max = 0.042

1615 measured reflections

1174 independent reflections

1048 reflections with I > 2σ(I)

R int = 0.027

2 standard reflections every 120 min intensity decay: 1.4%

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.068

S = 1.13

1174 reflections

117 parameters

2 restraints

Δρmax = 0.87 e Å−3

Δρmin = −0.87 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, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813025233/vn2076sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813025233/vn2076Isup2.hkl

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

Na4Li0.62Co5.67Al0.71(AsO4)6	F(000) = 1196
Mr = 1283.06	Dx = 4.124 Mg m−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 25 reflections
a = 10.7444 (9) Å	θ = 11–15°
b = 14.847 (2) Å	µ = 14.22 mm−1
c = 6.7223 (8) Å	T = 298 K
β = 105.51 (2)°	Prism, purple
V = 1033.3 (2) Å3	0.26 × 0.24 × 0.22 mm
Z = 2

Enraf–Nonius CAD-4 diffractometer	1048 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 27.0°, θmin = 2.4°
ω/2θ scans	h = −13→13
Absorption correction: ψ scan (North et al., 1968)	k = −1→18
Tmin = 0.033, Tmax = 0.042	l = −8→2
1615 measured reflections	2 standard reflections every 120 min
1174 independent reflections	intensity decay: 1.4%

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)] = 0.026	w = 1/[σ2(Fo2) + (0.0261P)2 + 8.122P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.068	(Δ/σ)max = 0.001
S = 1.13	Δρmax = 0.87 e Å−3
1174 reflections	Δρmin = −0.87 e Å−3
117 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraints	Extinction coefficient: 0.00110 (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)
As2	0.59838 (4)	0.82118 (3)	0.79004 (7)	0.00867 (15)
As1	0.81961 (6)	0.0000	0.56316 (10)	0.01067 (18)
Co3	0.67950 (6)	0.81829 (4)	0.31816 (9)	0.00996 (17)
Co2	0.0000	0.83579 (9)	0.5000	0.0144 (5)	0.690 (5)
Li2	0.0000	0.83579 (9)	0.5000	0.0144 (5)	0.310 (5)
Co1	0.5000	0.0000	0.5000	0.0076 (6)	0.286 (10)
Al1	0.5000	0.0000	0.5000	0.0076 (6)	0.714 (11)
Na1	0.9266 (5)	0.8844 (3)	0.0071 (7)	0.0323 (11)	0.50
Na2	0.1821 (6)	0.0000	0.9226 (9)	0.0199 (12)	0.50
Na3	0.4291 (12)	0.0000	−0.0240 (13)	0.066 (4)	0.50
O1	0.4915 (3)	0.7349 (2)	0.7760 (5)	0.0176 (7)
O2	0.6883 (3)	0.7907 (2)	0.6291 (5)	0.0150 (7)
O3	0.4874 (3)	−0.0941 (2)	0.7033 (5)	0.0127 (6)
O4	0.9410 (5)	0.0000	0.7772 (8)	0.0239 (12)
O5	0.6804 (5)	0.0000	0.6305 (8)	0.0195 (11)
O6	0.6918 (3)	0.8497 (3)	0.0228 (5)	0.0180 (7)
O7	0.8273 (4)	−0.0903 (3)	0.4118 (6)	0.0252 (9)

	U11	U22	U33	U12	U13	U23
As2	0.0063 (2)	0.0112 (2)	0.0081 (2)	0.00085 (16)	0.00117 (17)	−0.00121 (16)
As1	0.0072 (3)	0.0091 (3)	0.0148 (3)	0.000	0.0014 (2)	0.000
Co3	0.0079 (3)	0.0123 (3)	0.0094 (3)	0.0006 (2)	0.0019 (2)	0.0006 (2)
Co2	0.0101 (7)	0.0177 (8)	0.0154 (7)	0.000	0.0034 (5)	0.000
Li2	0.0101 (7)	0.0177 (8)	0.0154 (7)	0.000	0.0034 (5)	0.000
Co1	0.0055 (10)	0.0075 (10)	0.0097 (10)	0.000	0.0019 (7)	0.000
Al1	0.0055 (10)	0.0075 (10)	0.0097 (10)	0.000	0.0019 (7)	0.000
Na1	0.040 (3)	0.025 (2)	0.025 (2)	−0.009 (2)	−0.003 (2)	0.0085 (19)
Na2	0.023 (3)	0.020 (3)	0.018 (3)	0.000	0.007 (2)	0.000
Na3	0.171 (11)	0.013 (3)	0.025 (4)	0.000	0.044 (7)	0.000
O1	0.0134 (17)	0.0148 (17)	0.0213 (18)	−0.0011 (14)	−0.0010 (14)	0.0044 (14)
O2	0.0170 (17)	0.0176 (17)	0.0129 (16)	0.0088 (14)	0.0085 (13)	0.0025 (13)
O3	0.0100 (14)	0.0109 (15)	0.0175 (16)	0.0019 (12)	0.0043 (12)	−0.0009 (13)
O4	0.015 (2)	0.023 (3)	0.026 (3)	0.000	−0.007 (2)	0.000
O5	0.011 (2)	0.020 (3)	0.028 (3)	0.000	0.006 (2)	0.000
O6	0.0162 (17)	0.0290 (19)	0.0081 (15)	−0.0074 (15)	0.0018 (13)	−0.0028 (14)
O7	0.0240 (18)	0.026 (2)	0.030 (2)	−0.0131 (16)	0.0150 (17)	−0.0160 (17)

As2—O6i	1.672 (3)	Co1—O3iii	1.984 (3)
As2—O2	1.694 (3)	Co1—O3	1.984 (3)
As2—O1	1.706 (3)	Co1—O3x	1.984 (3)
As2—O3ii	1.724 (3)	Na1—O1iv	2.314 (6)
As1—O4	1.663 (5)	Na1—O4xi	2.342 (6)
As1—O5	1.674 (5)	Na1—O4xii	2.443 (6)
As1—O7	1.698 (4)	Na1—O1xiii	2.573 (6)
As1—O7iii	1.698 (4)	Na1—O6	2.605 (6)
Co3—O7ii	2.056 (4)	Na2—O4xiv	2.512 (8)
Co3—O6	2.078 (3)	Na2—O6xv	2.585 (5)
Co3—O2	2.107 (3)	Na2—O6xvi	2.585 (5)
Co3—O2iv	2.119 (3)	Na2—O7v	2.596 (6)
Co3—O1v	2.165 (3)	Na2—O7x	2.596 (6)
Co3—O3vi	2.188 (3)	Na2—O4xvii	2.692 (8)
Co2—O7vi	2.100 (4)	Na2—O5xvii	2.972 (8)
Co2—O7vii	2.100 (4)	Na3—O3xviii	2.513 (8)
Co2—O1viii	2.155 (4)	Na3—O3xix	2.513 (8)
Co2—O1ix	2.155 (4)	Na3—O3x	2.524 (8)
Co1—O5	1.902 (5)	Na3—O3v	2.524 (8)
Co1—O5x	1.902 (5)	Na3—O6xx	2.583 (7)
Co1—O3v	1.984 (3)	Na3—O6xxi	2.583 (7)
O6i—As2—O2	111.31 (17)	O2—Co3—O3vi	89.99 (13)
O6i—As2—O1	117.96 (17)	O2iv—Co3—O3vi	164.89 (13)
O2—As2—O1	104.74 (18)	O1v—Co3—O3vi	72.81 (12)
O6i—As2—O3ii	108.63 (17)	O7vi—Co2—O7vii	117.0 (2)
O2—As2—O3ii	116.12 (16)	O7vi—Co2—O1viii	105.07 (14)
O1—As2—O3ii	97.73 (16)	O7vii—Co2—O1viii	104.44 (13)
O4—As1—O5	108.4 (3)	O7vi—Co2—O1ix	104.44 (13)
O4—As1—O7	111.45 (18)	O7vii—Co2—O1ix	105.07 (14)
O5—As1—O7	110.63 (16)	O1viii—Co2—O1ix	121.69 (19)
O4—As1—O7iii	111.45 (18)	O5—Co1—O5x	180.00 (13)
O5—As1—O7iii	110.63 (16)	O5—Co1—O3v	93.93 (15)
O7—As1—O7iii	104.2 (3)	O5x—Co1—O3v	86.07 (15)
O7ii—Co3—O6	84.43 (15)	O5—Co1—O3iii	86.07 (15)
O7ii—Co3—O2	89.93 (15)	O5x—Co1—O3iii	93.93 (15)
O6—Co3—O2	173.76 (14)	O3v—Co1—O3iii	180.0
O7ii—Co3—O2iv	91.41 (15)	O5—Co1—O3	86.07 (15)
O6—Co3—O2iv	96.91 (14)	O5x—Co1—O3	93.93 (15)
O2—Co3—O2iv	80.51 (14)	O3v—Co1—O3	90.49 (19)
O7ii—Co3—O1v	173.12 (14)	O3iii—Co1—O3	89.51 (19)
O6—Co3—O1v	96.60 (14)	O5—Co1—O3x	93.93 (15)
O2—Co3—O1v	89.32 (14)	O5x—Co1—O3x	86.07 (15)
O2iv—Co3—O1v	95.21 (13)	O3v—Co1—O3x	89.51 (19)
O7ii—Co3—O3vi	100.36 (14)	O3iii—Co1—O3x	90.49 (19)
O6—Co3—O3vi	93.66 (14)	O3—Co1—O3x	180.0