Scheelite-type NaDy(WO4)2

Zhao, D.; Li, F.; Cheng, W.; Zhang, H.

doi:10.1107/S1600536809052271

Scheelite-type NaDy(WO₄)₂

The title compound sodium dysprosium(III) bis[tungstate(VI)], NaDy(WO₄)₂, has been synthesized under high temperature solution growth (HTSG) conditions in air. The compound crystallizes with the scheelite structure and is composed of isolated WO₄ tetrahedra ( $\overline{4}$ symmetry) with one set of bond lengths and distorted [(Na/Dy)O₈] dodecahedra ( $\overline{4}$ symmetry; occupancy ratio Na:Dy = 1:1) with two sets of bond lengths.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809052271/wm2287sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809052271/wm2287Isup2.hkl Contains datablock I

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (W-O) = 0.007 Å
Disorder in main residue
R factor = 0.024
wR factor = 0.056
Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........      NA/DY
                    (NA/DY)O1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........      NA/DY
                    (NA/DY)O1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........      NA/DY
                    (NA/DY)O1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........      NA/DY
                    (NA/DY)O1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........      NA/DY
                    (NA/DY)O1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........      NA/DY
                    (NA/DY)O1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........      NA/DY
                    (NA/DY)O1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........      NA/DY
                    (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    O1     (NA/DY)O1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    W1     O1     (NA/DY)
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    W1     O1     (NA/DY)
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    DY1    O1     (NA/DY)
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........      NA/DY
                    (NA/DY)O1     (NA/DY)

Alert level G
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................      14.00 Perc.
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  40 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

  40 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

In the past years an increasing interest in the synthesis and characterization of rare-earth double tungstate(VI) crystals with general formula ARE(WO₄)₂ (A = alkali metal, RE = rare-earth metal) has been observed due to their interesting magnetic, electric and optical properties (Perets et al., 2007; Huang et al., 2006; Li et al., 1990; Han et al., 2002). These compounds are attractive solid-state laser host materials because of their large rare-earth ion admittance. Most of these crystals have tetragonal symmetry and crystallize with the scheelite structure (CaWO₄) in space group I4₁/a (Sillen & Nylander, 1943). In the title structure, the Ca²⁺ position of the original CaWO₄ structure is statistically occupied by Na⁺ and Dy³⁺ ions in an 1:1 ratio. The crystal structure of NaDy(WO₄)₂ is composed of a two-direction packing of isolated WO₄ tetrahedra interconnected by distorted [(Na/Dy)O₈] dodecahedra, as shown in Fig. 2.

Related literature top

For the structures, properties and applications of alkali rare-earth bis-tungstates with general formula ARE(WO₄)₂ (A = alkali metal, RE = rare-earth metal), see: Perets et al. (2007); Han et al. (2002); Huang et al. (2006); Li et al. (1990). For the scheelite (CaWO₄) structure, see: Sillen & Nylander (1943).

Experimental top

Single crystal of NaDy(WO₄)₂ were prepared by a high temperature solution reaction, using analytical reagents of Dy₂O₃, Na₂CO₃ and WO₃ in the molar ratio of Na: Dy: W = 8:1:10. The starting mixture was finely ground in an agate mortar to ensure the best homogeneity and reactivity, and then transferred to a platinum crucible to be heated at a temperature of 773 K for 8 h. The sintered product was reground and continuously heated at 1273 K for 20 h, cooled to 673 K at a rate of 4 K/h, and then quenched to room temperature. A few light yellow and prismatically shaped crystals of the title compound were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Part of the structure of NaDy(WO₄)₂ showing the labelling of the atoms (displacement ellipsoids are drawn at the 50% probability level).
	Fig. 2. View of the crystal structure of NaDy(WO₄)₂ (WO₄ tetrahedra are shaded in sea-green; Na/Dy atoms are drawn as yellow balls).

Sodium dysprosium(III) bis[tungstate(VI)] top

Crystal data top

NaDy(WO₄)₂	D_x = 7.186 Mg m⁻³
M_r = 681.19	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 405 reflections
Hall symbol: -I 4ad	θ = 3.6–27.5°
a = 5.2545 (5) Å	µ = 48.27 mm⁻¹
c = 11.4029 (15) Å	T = 298 K
V = 314.83 (6) Å³	Prism, light yellow
Z = 2	0.10 × 0.10 × 0.08 mm
F(000) = 578

Data collection top

Rigaku Mercury70 diffractometer	181 independent reflections
Radiation source: fine-focus sealed tube	143 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 14.6306 pixels mm^-1	θ_max = 27.5°, θ_min = 4.3°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −6→6
T_min = 0.263, T_max = 1.000	l = −14→13
1128 measured reflections

Refinement top

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)] = 0.024	w = 1/[σ²(F_o²) + (0.0045P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.056	(Δ/σ)_max < 0.001
S = 0.87	Δρ_max = 1.55 e Å⁻³
181 reflections	Δρ_min = −1.40 e Å⁻³
15 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0295 (17)

Crystal data top

NaDy(WO₄)₂	Z = 2
M_r = 681.19	Mo Kα radiation
Tetragonal, I4₁/a	µ = 48.27 mm⁻¹
a = 5.2545 (5) Å	T = 298 K
c = 11.4029 (15) Å	0.10 × 0.10 × 0.08 mm
V = 314.83 (6) Å³

Data collection top

Rigaku Mercury70 diffractometer	181 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	143 reflections with I > 2σ(I)
T_min = 0.263, T_max = 1.000	R_int = 0.053
1128 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	15 parameters
wR(F²) = 0.056	0 restraints
S = 0.87	Δρ_max = 1.55 e Å⁻³
181 reflections	Δρ_min = −1.40 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Na1	0.5000	−0.2500	0.1250	0.0068 (4)	0.50
Dy1	0.5000	−0.2500	0.1250	0.0068 (4)	0.50
W1	0.0000	0.2500	0.1250	0.0091 (4)
O1	0.2419 (14)	0.0977 (13)	0.0404 (6)	0.0187 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na1	0.0090 (6)	0.0090 (6)	0.0024 (8)	0.000	0.000	0.000
Dy1	0.0090 (6)	0.0090 (6)	0.0024 (8)	0.000	0.000	0.000
W1	0.0098 (4)	0.0098 (4)	0.0076 (6)	0.000	0.000	0.000
O1	0.024 (5)	0.017 (4)	0.015 (3)	0.001 (3)	0.003 (3)	0.001 (3)

Geometric parameters (Å, º) top

(Na/Dy)1—O1ⁱ	2.457 (7)	(Na/Dy)1—O1^vii	2.471 (7)
(Na/Dy)1—O1ⁱⁱ	2.457 (7)	(Na/Dy)1—O1	2.471 (7)
(Na/Dy)1—O1ⁱⁱⁱ	2.457 (7)	W1—O1^viii	1.785 (7)
(Na/Dy)1—O1^iv	2.457 (7)	W1—O1^ix	1.785 (7)
(Na/Dy)1—O1^v	2.471 (7)	W1—O1	1.785 (7)
(Na/Dy)1—O1^vi	2.471 (7)	W1—O1^x	1.785 (7)

O1ⁱ—(Na/Dy)1—O1ⁱⁱ	79.7 (3)	O1^vi—(Na/Dy)1—O1^vii	98.76 (12)
O1ⁱ—(Na/Dy)1—O1ⁱⁱⁱ	126.1 (2)	O1ⁱ—(Na/Dy)1—O1	68.80 (16)
O1ⁱⁱ—(Na/Dy)1—O1ⁱⁱⁱ	126.1 (2)	O1ⁱⁱ—(Na/Dy)1—O1	76.3 (3)
O1ⁱ—(Na/Dy)1—O1^iv	126.1 (2)	O1ⁱⁱⁱ—(Na/Dy)1—O1	73.31 (14)
O1ⁱⁱ—(Na/Dy)1—O1^iv	126.1 (2)	O1^iv—(Na/Dy)1—O1	152.4 (3)
O1ⁱⁱⁱ—(Na/Dy)1—O1^iv	79.7 (3)	O1^v—(Na/Dy)1—O1	98.76 (12)
O1ⁱ—(Na/Dy)1—O1^v	152.4 (3)	O1^vi—(Na/Dy)1—O1	98.76 (12)
O1ⁱⁱ—(Na/Dy)1—O1^v	73.31 (14)	O1^vii—(Na/Dy)1—O1	134.1 (3)
O1ⁱⁱⁱ—(Na/Dy)1—O1^v	68.80 (16)	O1^viii—W1—O1^ix	107.0 (2)
O1^iv—(Na/Dy)1—O1^v	76.3 (3)	O1^viii—W1—O1	114.6 (4)
O1ⁱ—(Na/Dy)1—O1^vi	73.31 (14)	O1^ix—W1—O1	107.0 (2)
O1ⁱⁱ—(Na/Dy)1—O1^vi	152.4 (3)	O1^viii—W1—O1^x	107.0 (2)
O1ⁱⁱⁱ—(Na/Dy)1—O1^vi	76.3 (3)	O1^ix—W1—O1^x	114.6 (4)
O1^iv—(Na/Dy)1—O1^vi	68.80 (16)	O1—W1—O1^x	107.0 (2)
O1^v—(Na/Dy)1—O1^vi	134.1 (3)	W1—O1—Dy1ⁱⁱ	131.4 (3)
O1ⁱ—(Na/Dy)1—O1^vii	76.3 (3)	W1—O1—(Na/Dy)1ⁱⁱ	131.4 (3)
O1ⁱⁱ—(Na/Dy)1—O1^vii	68.80 (16)	W1—O1—(Na/Dy)1	120.8 (3)
O1ⁱⁱⁱ—(Na/Dy)1—O1^vii	152.4 (3)	Dy1ⁱⁱ—O1—(Na/Dy)1	103.7 (3)
O1^iv—(Na/Dy)1—O1^vii	73.31 (14)	(Na/Dy)1ⁱⁱ—O1—(Na/Dy)1	103.7 (3)
O1^v—(Na/Dy)1—O1^vii	98.76 (12)

Symmetry codes: (i) x, y−1/2, −z; (ii) −x+1, −y, −z; (iii) y+1/4, −x+1/4, z+1/4; (iv) −y+3/4, x−3/4, z+1/4; (v) y+3/4, −x+1/4, −z+1/4; (vi) −y+1/4, x−3/4, −z+1/4; (vii) −x+1, −y−1/2, z; (viii) −x, −y+1/2, z; (ix) −y+1/4, x+1/4, −z+1/4; (x) y−1/4, −x+1/4, −z+1/4.

Experimental details

Crystal data
Chemical formula	NaDy(WO₄)₂
M_r	681.19
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	298
a, c (Å)	5.2545 (5), 11.4029 (15)
V (Å³)	314.83 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	48.27
Crystal size (mm)	0.10 × 0.10 × 0.08

Data collection
Diffractometer	Rigaku Mercury70 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.263, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	1128, 181, 143
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.056, 0.87
No. of reflections	181
No. of parameters	15
Δρ_max, Δρ_min (e Å⁻³)	1.55, −1.40

Computer programs: CrystalClear (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2004), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

(Na/Dy)1—O1ⁱ	2.457 (7)	W1—O1	1.785 (7)
(Na/Dy)1—O1	2.471 (7)

Symmetry code: (i) y+1/4, −x+1/4, z+1/4.

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