Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809052271/wm2287sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536809052271/wm2287Isup2.hkl |
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
Single crystal of NaDy(WO_{4})_{2} were prepared by a high temperature solution reaction, using analytical reagents of Dy_{2}O_{3}, Na_{2}CO_{3} and WO_{3} 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.
The Na1 and Dy1 atoms are in a substitutional-type disorder in the structure. Therefore the atomic position and anisotropic displacement parameters of Na1 and Dy1 atoms were constrained to be identical. In the initial least-squares refinement, the occupancy factors of Na1 and Dy1 atoms were set to be free. The results show that the occupancy factors were close to 1:1, viz Na1: Dy1 = 0.50273: 0.49727, and were eventually fixed in a 1:1 ratio. The highest peak in the final difference electron density map is 1.55 e/Å^{3} from the W1 site, and the deepest hole is -1.40 e/Å^{3} from the Na1/Dy1 site.
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).
NaDy(WO_{4})_{2} | D_{x} = 7.186 Mg m^{−}^{3} |
M_{r} = 681.19 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4_{1}/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) Å^{3} | Prism, light yellow |
Z = 2 | 0.10 × 0.10 × 0.08 mm |
F(000) = 578 |
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 on F^{2} | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F^{2} > 2σ(F^{2})] = 0.024 | w = 1/[σ^{2}(F_{o}^{2}) + (0.0045P)^{2}] where P = (F_{o}^{2} + 2F_{c}^{2})/3 |
wR(F^{2}) = 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+0.001xFc^{2}λ^{3}/sin(2θ)]^{-1/4} |
0 restraints | Extinction coefficient: 0.0295 (17) |
NaDy(WO_{4})_{2} | Z = 2 |
M_{r} = 681.19 | Mo Kα radiation |
Tetragonal, I4_{1}/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) Å^{3} |
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 |
R[F^{2} > 2σ(F^{2})] = 0.024 | 15 parameters |
wR(F^{2}) = 0.056 | 0 restraints |
S = 0.87 | Δρ_{max} = 1.55 e Å^{−}^{3} |
181 reflections | Δρ_{min} = −1.40 e Å^{−}^{3} |
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 F^{2} against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^{2}, conventional R-factors R are based on F, with F set to zero for negative F^{2}. The threshold expression of F^{2} > σ(F^{2}) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^{2} 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 | 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) |
U^{11} | U^{22} | U^{33} | U^{12} | U^{13} | U^{23} | |
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) |
(Na/Dy)1—O1^{i} | 2.457 (7) | (Na/Dy)1—O1^{vii} | 2.471 (7) |
(Na/Dy)1—O1^{ii} | 2.457 (7) | (Na/Dy)1—O1 | 2.471 (7) |
(Na/Dy)1—O1^{iii} | 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) |
O1^{i}—(Na/Dy)1—O1^{ii} | 79.7 (3) | O1^{vi}—(Na/Dy)1—O1^{vii} | 98.76 (12) |
O1^{i}—(Na/Dy)1—O1^{iii} | 126.1 (2) | O1^{i}—(Na/Dy)1—O1 | 68.80 (16) |
O1^{ii}—(Na/Dy)1—O1^{iii} | 126.1 (2) | O1^{ii}—(Na/Dy)1—O1 | 76.3 (3) |
O1^{i}—(Na/Dy)1—O1^{iv} | 126.1 (2) | O1^{iii}—(Na/Dy)1—O1 | 73.31 (14) |
O1^{ii}—(Na/Dy)1—O1^{iv} | 126.1 (2) | O1^{iv}—(Na/Dy)1—O1 | 152.4 (3) |
O1^{iii}—(Na/Dy)1—O1^{iv} | 79.7 (3) | O1^{v}—(Na/Dy)1—O1 | 98.76 (12) |
O1^{i}—(Na/Dy)1—O1^{v} | 152.4 (3) | O1^{vi}—(Na/Dy)1—O1 | 98.76 (12) |
O1^{ii}—(Na/Dy)1—O1^{v} | 73.31 (14) | O1^{vii}—(Na/Dy)1—O1 | 134.1 (3) |
O1^{iii}—(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) |
O1^{i}—(Na/Dy)1—O1^{vi} | 73.31 (14) | O1^{ix}—W1—O1 | 107.0 (2) |
O1^{ii}—(Na/Dy)1—O1^{vi} | 152.4 (3) | O1^{viii}—W1—O1^{x} | 107.0 (2) |
O1^{iii}—(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—Dy1^{ii} | 131.4 (3) |
O1^{i}—(Na/Dy)1—O1^{vii} | 76.3 (3) | W1—O1—(Na/Dy)1^{ii} | 131.4 (3) |
O1^{ii}—(Na/Dy)1—O1^{vii} | 68.80 (16) | W1—O1—(Na/Dy)1 | 120.8 (3) |
O1^{iii}—(Na/Dy)1—O1^{vii} | 152.4 (3) | Dy1^{ii}—O1—(Na/Dy)1 | 103.7 (3) |
O1^{iv}—(Na/Dy)1—O1^{vii} | 73.31 (14) | (Na/Dy)1^{ii}—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(WO_{4})_{2} |
M_{r} | 681.19 |
Crystal system, space group | Tetragonal, I4_{1}/a |
Temperature (K) | 298 |
a, c (Å) | 5.2545 (5), 11.4029 (15) |
V (Å^{3}) | 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[F^{2} > 2σ(F^{2})], wR(F^{2}), 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).
(Na/Dy)1—O1^{i} | 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. |
In the past years an increasing interest in the synthesis and characterization of rare-earth double tungstate(VI) crystals with general formula ARE(WO_{4})_{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 (CaWO_{4}) in space group I4_{1}/a (Sillen & Nylander, 1943). In the title structure, the Ca^{2+} position of the original CaWO_{4} structure is statistically occupied by Na^{+} and Dy^{3+} ions in an 1:1 ratio. The crystal structure of NaDy(WO_{4})_{2} is composed of a two-direction packing of isolated WO_{4} tetrahedra interconnected by distorted [(Na/Dy)O_{8}] dodecahedra, as shown in Fig. 2.