K(MoO2)4O3(AsO4).

A new compound with a non-centrosymmetric structure, potassium tetra-kis-[dioxomolybdenum(IV)] arsenate trioxide, K(MoO2)4O3(AsO4), has been synthesized by a solid-state reaction. The [(MoO2)4O3(AsO4)](+) three-dimensional framework consists of single arsenate AsO4 tetra-hedra, MoO6 octa-hedra, MoO5 bipyramids and bi-octa-hedral units of edge-sharing Mo2O10 octa-hedra. The [Mo2O8]∞ octa-hedral chains running along the a-axis direction are connected through their corners to the AsO4 tetra-hedra, MoO6 octa-hedra and MoO5 bipyramids, so as to form large tunnels propagating along the a axis in which the K(+) cations are located. This structure is compared with compounds containing M 2O10 (M = Mo, V, Fe) dimers and with those containing M 2O8 (M = V) chains.

Related literature

For background to the physico-chemical properties of related compounds, see: Piffard et al. (1985 ▶); Centi et al. (1988 ▶); Stucky et al. (1989 ▶); Northrup et al. (1994 ▶); Ouerfelli et al. (2007 ▶). For details of structurally related compounds, see: Amoros & LeBail (1992 ▶), Boudin et al. (1994 ▶); Guesdon et al. (1994 ▶, 1995 ▶); Borel et al. (1994 ▶, 2000 ▶); LeBail et al. (1995 ▶); Berrah et al. (1999 ▶); Hajji et al. (2009 ▶). For the preparation, see: Jouini et al. (2012 ▶). For bond-valence sums, see: Brown & Altermatt (1985 ▶).

Experimental

Crystal data

K(MoO2)4O3(AsO4)

M = 737.78

Orthorhombic,

a = 8.0442 (8) Å

b = 11.9167 (9) Å

c = 12.6799 (10) Å

V = 1215.50 (18) Å3

Z = 4

Mo Kα radiation

μ = 7.16 mm−1

T = 298 K

0.42 × 0.33 × 0.22 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.077, T max = 0.212

8046 measured reflections

2647 independent reflections

2611 reflections with I > 2σ(I)

R int = 0.030

2 standard reflections every 120 min intensity decay: 1.2%

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.045

S = 1.10

2647 reflections

191 parameters

Δρmax = 0.52 e Å−3

Δρmin = −0.69 e Å−3

Absolute structure: Flack (1983 ▶), 2399 Friedel pairs

Flack parameter: 0.089 (10)

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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813013664/vn2070sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813013664/vn2070Isup2.hkl

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

K(MoO2)4O3(AsO4)	F(000) = 1360
Mr = 737.78	Dx = 4.032 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 8.0442 (8) Å	θ = 10–15°
b = 11.9167 (9) Å	µ = 7.16 mm−1
c = 12.6799 (10) Å	T = 298 K
V = 1215.50 (18) Å3	Prism, yellow
Z = 4	0.42 × 0.33 × 0.22 mm

Enraf–Nonius CAD-4 diffractometer	2611 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 27.0°, θmin = 2.4°
ω/2θ scans	h = −10→4
Absorption correction: ψ scan (North et al., 1968)	k = −15→15
Tmin = 0.077, Tmax = 0.212	l = −16→16
8046 measured reflections	2 standard reflections every 120 min
2647 independent reflections	intensity decay: 1.2%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0195P)2 + 2.5252P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.018	(Δ/σ)max = 0.001
wR(F2) = 0.045	Δρmax = 0.52 e Å−3
S = 1.10	Δρmin = −0.69 e Å−3
2647 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
191 parameters	Extinction coefficient: 0.00488 (17)
0 restraints	Absolute structure: Flack (1983), 2399 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.089 (10)

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
Mo1	0.99047 (5)	0.41688 (3)	0.61974 (3)	0.01100 (9)
Mo2	0.78403 (5)	0.64073 (3)	0.90494 (3)	0.00936 (9)
Mo3	0.19469 (5)	0.63578 (3)	0.92886 (3)	0.00829 (9)
Mo4	0.46142 (5)	0.71544 (3)	0.68083 (3)	0.01289 (10)
As1	0.56223 (6)	0.43948 (3)	0.65276 (3)	0.00879 (10)
K1	0.9351 (2)	0.75546 (14)	0.60338 (12)	0.0474 (4)
O1	0.7659 (5)	0.5009 (3)	0.9106 (3)	0.0236 (8)
O2	0.4420 (4)	0.5521 (2)	0.6643 (3)	0.0155 (7)
O3	0.3320 (4)	0.6807 (3)	0.8313 (2)	0.0146 (7)
O4	0.6627 (4)	0.6759 (3)	0.7968 (3)	0.0187 (8)
O5	0.4982 (6)	0.8616 (3)	0.7455 (3)	0.0273 (9)
O6	0.7604 (5)	0.4761 (3)	0.6609 (3)	0.0313 (10)
O7	0.2779 (6)	0.7443 (3)	0.6214 (3)	0.0305 (10)
O8	0.6055 (6)	0.7332 (3)	0.5839 (3)	0.0330 (10)
O9	0.2086 (5)	0.4954 (3)	0.9257 (3)	0.0200 (8)
O10	0.9963 (4)	0.6679 (2)	0.8464 (2)	0.0136 (6)
O11	0.8536 (4)	0.3194 (2)	0.5245 (2)	0.0099 (6)
O12	0.1790 (4)	0.3351 (2)	0.5557 (2)	0.0100 (6)
O13	0.5239 (4)	0.3741 (2)	0.5374 (2)	0.0103 (6)
O14	0.0441 (5)	0.3976 (4)	0.7460 (3)	0.0309 (10)
O15	0.0494 (5)	0.5469 (3)	0.5840 (4)	0.0347 (10)

	U11	U22	U33	U12	U13	U23
Mo1	0.00734 (18)	0.01387 (16)	0.01180 (17)	−0.00106 (15)	0.00059 (14)	−0.00650 (13)
Mo2	0.00731 (17)	0.01417 (17)	0.00660 (17)	−0.00085 (15)	−0.00026 (14)	−0.00219 (13)
Mo3	0.00694 (17)	0.01092 (16)	0.00703 (16)	0.00121 (14)	0.00010 (13)	−0.00095 (13)
Mo4	0.0238 (2)	0.00954 (16)	0.00534 (16)	0.00046 (15)	−0.00095 (16)	−0.00032 (12)
As1	0.0092 (2)	0.01012 (18)	0.00711 (19)	0.00226 (17)	−0.00031 (17)	−0.00295 (15)
K1	0.0510 (9)	0.0557 (8)	0.0355 (7)	0.0067 (8)	0.0015 (8)	−0.0129 (7)
O1	0.032 (2)	0.0155 (16)	0.0235 (19)	−0.0039 (15)	0.0019 (17)	−0.0053 (13)
O2	0.0163 (16)	0.0096 (13)	0.0206 (16)	0.0036 (13)	0.0004 (15)	−0.0043 (12)
O3	0.0107 (16)	0.0233 (15)	0.0098 (14)	−0.0029 (13)	0.0028 (13)	−0.0026 (12)
O4	0.0123 (18)	0.0337 (19)	0.0100 (15)	0.0033 (15)	−0.0020 (13)	−0.0028 (13)
O5	0.054 (3)	0.0143 (14)	0.0135 (15)	−0.006 (2)	0.0064 (17)	−0.0017 (12)
O6	0.0116 (18)	0.044 (2)	0.038 (2)	0.0011 (17)	0.0001 (17)	−0.0319 (18)
O7	0.039 (3)	0.0190 (16)	0.033 (2)	0.0086 (17)	−0.020 (2)	0.0029 (16)
O8	0.050 (3)	0.029 (2)	0.0200 (18)	−0.0101 (19)	0.015 (2)	0.0005 (15)
O9	0.0235 (19)	0.0150 (15)	0.0214 (18)	0.0024 (15)	−0.0081 (17)	−0.0046 (13)
O10	0.0103 (15)	0.0262 (15)	0.0042 (13)	0.0015 (14)	−0.0028 (13)	−0.0014 (11)
O11	0.0085 (15)	0.0130 (14)	0.0082 (14)	−0.0021 (12)	−0.0028 (12)	−0.0010 (11)
O12	0.0074 (15)	0.0102 (13)	0.0123 (14)	0.0006 (11)	0.0012 (12)	−0.0019 (11)
O13	0.0084 (15)	0.0158 (13)	0.0066 (13)	−0.0002 (12)	−0.0003 (12)	−0.0050 (11)
O14	0.024 (2)	0.053 (2)	0.0156 (16)	0.0141 (19)	−0.0036 (16)	−0.0148 (16)
O15	0.028 (2)	0.0197 (17)	0.057 (3)	−0.0052 (17)	0.021 (2)	−0.0103 (17)

Mo1—O14i	1.674 (4)	Mo4—O8	1.703 (4)
Mo1—O15i	1.682 (4)	Mo4—O5	1.947 (3)
Mo1—O12i	1.977 (3)	Mo4—O2	1.964 (3)
Mo1—O11	2.005 (3)	Mo4—O3	2.213 (3)
Mo1—O6	2.048 (4)	Mo4—O4	2.237 (3)
Mo2—O1	1.675 (4)	As1—O6	1.656 (4)
Mo2—O4	1.735 (3)	As1—O2	1.661 (3)
Mo2—O10	1.890 (4)	As1—O5vi	1.662 (3)
Mo2—O11ii	1.936 (3)	As1—O13	1.685 (3)
Mo2—O13ii	2.289 (3)	K1—O14iii	2.558 (4)
Mo2—O12iii	2.388 (3)	K1—O15i	2.662 (4)
Mo3—O9	1.677 (3)	K1—O8	2.676 (5)
Mo3—O3	1.742 (3)	K1—O8vii	2.745 (5)
Mo3—O12iv	1.934 (3)	K1—O7i	2.771 (5)
Mo3—O10v	1.946 (3)	K1—O9iii	3.106 (4)
Mo3—O13iv	2.237 (3)	K1—O7vii	3.118 (5)
Mo3—O11iii	2.300 (3)	K1—O10	3.290 (3)
Mo4—O7	1.693 (4)	K1—O4	3.423 (4)
O14i—Mo1—O15i	108.2 (2)	O9—Mo3—O13iv	90.84 (15)
O14i—Mo1—O12i	97.31 (16)	O3—Mo3—O13iv	162.09 (13)
O15i—Mo1—O12i	97.29 (16)	O12iv—Mo3—O13iv	84.88 (12)
O14i—Mo1—O11	129.64 (18)	O10v—Mo3—O13iv	72.32 (12)
O15i—Mo1—O11	121.71 (18)	O9—Mo3—O11iii	165.14 (15)
O12i—Mo1—O11	83.60 (13)	O3—Mo3—O11iii	89.84 (13)
O14i—Mo1—O6	92.10 (18)	O12iv—Mo3—O11iii	72.79 (11)
O15i—Mo1—O6	90.35 (19)	O10v—Mo3—O11iii	79.19 (12)
O12i—Mo1—O6	165.36 (13)	O13iv—Mo3—O11iii	76.06 (11)
O11—Mo1—O6	81.76 (14)	O7—Mo4—O8	104.3 (2)
O1—Mo2—O4	103.02 (19)	O7—Mo4—O5	97.95 (19)
O1—Mo2—O10	105.44 (17)	O8—Mo4—O5	95.13 (18)
O4—Mo2—O10	99.00 (15)	O7—Mo4—O2	94.84 (16)
O1—Mo2—O11ii	99.25 (16)	O8—Mo4—O2	95.74 (17)
O4—Mo2—O11ii	103.76 (14)	O5—Mo4—O2	160.62 (14)
O10—Mo2—O11ii	141.44 (13)	O7—Mo4—O3	90.67 (18)
O1—Mo2—O13ii	87.18 (16)	O8—Mo4—O3	165.03 (19)
O4—Mo2—O13ii	168.11 (14)	O5—Mo4—O3	82.88 (13)
O10—Mo2—O13ii	72.05 (12)	O2—Mo4—O3	82.47 (13)
O11ii—Mo2—O13ii	80.21 (12)	O7—Mo4—O4	165.11 (18)
O1—Mo2—O12iii	165.31 (15)	O8—Mo4—O4	90.47 (19)
O4—Mo2—O12iii	90.04 (14)	O5—Mo4—O4	78.55 (16)
O10—Mo2—O12iii	78.65 (12)	O2—Mo4—O4	85.37 (14)
O11ii—Mo2—O12iii	70.72 (12)	O3—Mo4—O4	74.58 (12)
O13ii—Mo2—O12iii	80.64 (10)	O6—As1—O2	110.01 (18)
O9—Mo3—O3	104.30 (17)	O6—As1—O5vi	112.4 (2)
O9—Mo3—O12iv	99.44 (15)	O2—As1—O5vi	102.26 (18)
O3—Mo3—O12iv	101.66 (14)	O6—As1—O13	110.60 (17)
O9—Mo3—O10v	103.77 (16)	O2—As1—O13	110.10 (15)
O3—Mo3—O10v	94.47 (15)	O5vi—As1—O13	111.22 (16)
O12iv—Mo3—O10v	147.40 (12)