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Chapter 3 Unpublished Results Table 3.5. Crystal Data and Structure Refinement for Na-15 and Na-16. Code Na-15 Na-16 Emp. formula Na 10[Yb(H 2O) 3Sb 2W 21O 72(OH)]·41H 2O Na 10[Lu(H 2O) 3Sb 2W 21O 72(OH)]·42H 2O M r 6469.0 6489.0 Crystal system triclinic triclinic Space group (no.) P1̅ (2) P1̅ (2) a / Å 13.3196(8) 13.3368(18) b / Å 18.1807(13) 18.198(2) c/Å 23.8781(17) 23.895(3) α / deg 107.974(3) 108.071(5) ß/ deg 90.071(3) 90.048(5) γ/ deg 108.460(3) 108.357(4) V / Å 3 5185.6(6) 5201.5(12) Z 2 2 T / ºC -100 -100 λ / Å 0.71073 0.71073 D / g cm -3 4.14 4.14 μ / mm -1 24.8 24.7 R [I ≥ 2σ(I)] a 0.0436 0.0510 R w (all data) b 0.1545 0.1518 __________________________ a R = ∑|F o| – |F c| |∑| |F o|; b R w = {∑[w(F o 2 – F c 2 ) 2 ] / ∑[w(F o 2 ) 2 ]} 1/2 . Table 3.6. Crystal Data and Structure Refinement for Na-18 – Na-20. Code Na-18 Na-19 Na-20 Emp. formula Na 8[Yb 2(H 2O) 6Sb 2W 20O 70]·37H 2O Na 8[Lu 2(H 2O) 6Sb 2W 20O 70]·37H 2O Na 8[Yb 2(H 2O) 6Sb 2W 20O 70]·37H 2O M r 6344.9 6367.1 6176.9 Crystal system triclinic triclinic triclinic Space group (no.) P1̅ (2) P1̅ (2) P1̅ (2) a / Å 13.510(3) 13.5753(7) 13.6116(7) b / Å 13.516(3) 13.6389(8) 13.6742(8) c/Å 14.290(2) 14.2889(7) 14.3433(7) α / deg 106.174(11) 93.268(3) 93.180(3) ß/ deg 93.469(12) 106.357(2) 106.647(3) γ/ deg 106.313(13) 106.282(3) 106.078(4) V / Å 3 2377.6(7) 2410.0(2) 2431.3(2) Z 1 1 1 T / ºC -100 -100 -100 λ / Å 0.71073 0.71073 0.71073 D / g cm -3 4.16 4.39 4.22 μ / mm -1 26.7 26.5 25.4 R [I ≥ 2σ(I)] a 0.066 0.056 0.059 R w (all data) b 0.1874 0.1782 0.1781 __________________________ a R = ∑|F o| – |F c| |∑| |F o|; b R w = {∑[w(F o 2 – F c 2 ) 2 ] / ∑[w(F o 2 ) 2 ]} 1/2 . 121
Chapter 3 Unpublished Results 3.B.2.4. Results and Discussion We have synthesized and structurally characterized the mono- and di-lanthanide containing polyanions [Ln(H 2 O) 3 Sb 2 W 21 O 72 (OH))] 10− (15–17) and [Ln 2 (H 2 O) 6 Sb 2 W 20 O 70 )] 8− (18 – 20). The sodium salts of polyanions 15–20 Na 10 [Yb(H 2 O) 3 Sb 2 W 21 O 72 (OH)]·41H 2 O (Na-15), Na 10 [Lu(H 2 O) 3 Sb 2 W 21 O 72 (OH)]·42H 2 O (Na-16), Na 10 [Y(H 2 O) 3 Sb 2 W 21 O 72 (OH)]·40H 2 O (Na-17), Na 8 [Yb 2 (H 2 O) 6 Sb 2 W 20 O 70 )]·37H 2 O (Na-18), Na 8 [Lu 2 (H 2 O) 6 Sb 2 W 20 O 70 )]·38H 2 O (Na-19), and Na 8 [Y 2 (H 2 O) 6 Sb 2 W 20 O 70 )]·37H 2 O (Na-20) have been characterized in the solid state by FTIR spectroscopy, single-crystal XRD, TGA and elemental analyses. All polyanions 15–20 are based on the Sb 2 W 20 skeleton with one (15–17) or two (18–20) incorporated lanthanide ions. The mono-lanthanide(III)-containing polyanions [Ln(H 2 O) 3 Sb 2 W 21 O 72 (OH))] 10− (Ln = Yb (15), Lu(16), Y(17)) were synthesized using simple and conventional open beaker conditions by interaction of the sodium salt of the trilacunary precursor SbW 9 with Ln 3+ ions in aqueous acidic (pH = 3) medium. A high concentration of NaCl (1.0 M) was needed in order to obtain the desired crystalline products. The same reaction performed in water did not result in any crystalline product. The presence of sodium ions in the synthesis medium is therefore crucial for the successful synthesis and isolation of polyanions 15–17. Interaction of the SbW 9 precursor with transition metal ions at an appropriate pH is known to result in products based on two SbW 9 subunits sandwiching either 3 ({M 3 (α- SbW9)2}, “Hervé dimer”) or 4 ({M 4 (β-SbW9)2}, “Krebs dimer”) transition metal ions. 3,4 For example, our group has reported the “Hervé dimer” for M = copper(II), zinc(II), manganese(II) and cobalt(II), 4c palladium(II), 4g and the “Krebs dimer” for M = iron(III), 4d and indium(III). 4h We have also isolated a dimethyltin-containing tungstoantimonate(III). 4m 122
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