**6. Appendix**

Bond lengths (Å) of [(*n*-C4H9)4N]4[α-PW11{Al(OH2)}O39]: W(1)-O(1) 1.883(4); W(1)-O(1)1 1.883(4); W(1)-O(1)2 1.883(4); W(1)-O(1)3 1.883(4); W(1)-O(2) 2.465(5); W(1)-O(2)4 2.465(5); W(1)-O(3) 1.667(4); P(1)-O(2) 1.522(5); P(1)-O(2)5 1.522(5); P(1)-O(2)6 1.522(5); P(1)-O(2)7 1.522(5); P(1)-O(2)4 1.522(5); P(1)-O(2)8 1.522(5); P(1)-O(2)9 1.522(5); P(1)-O(2)10 1.522(5); Al(1)-O(1) 1.883(4); Al(1)-O(1)1 1.883(4); Al(1)-O(1)2 1.883(4); Al(1)-O(1)3 1.883(4); Al(1)-O(3) 1.667(4). Symmetry operators: (1) X,Z,Y (2) Z,Y,-X+1 (3) Z,-X+1,Y (4) Y,Z,-X+1 (5) Y,Z,X (6) Z,X,Y (7) X,Y,-Z+1 (8) Z,X,-Y+1 (9) -Z+1,X,-Y+1 (10) -Y+1,-Z+1,-X+1.

Bond angles (º) of [(*n*-C4H9)4N]4[α-PW11{Al(OH2)}O39]: O(1)-W(1)-O(1)1 87.5(2); O(1)-W(1)- O(1)2 87.08(18); O(1)-W(1)-O(1)3 154.8(2); O(1)-W(1)-O(2) 63.32(19); O(1)-W(1)-O(2)4 92.40(18); O(1)-W(1)-O(3) 102.58(17); O(1)1-W(1)-O(1)2 154.8(2) O(1)1-W(1)-O(1)3 87.08(18); O(1)1-W(1)-O(2) 63.32(19); O(1)1-W(1)-O(2)4 92.40(18); O(1)1-W(1)-O(3) 102.58(17); O(1)2- W(1)-O(1)3 87.5(2); O(1)2-W(1)-O(2) 92.40(18); O(1)2-W(1)-O(2)4 63.32(19); O(1)2-W(1)-O(3) 102.58(17); O(1)3-W(1)-O(2) 92.40(18); O(1)3-W(1)-O(2)4 63.32(19); O(1)3-W(1)-O(3) 102.58(17); O(2)-W(1)-O(2)4 41.76(15); O(2)-W(1)-O(3) 159.12(11); O(2)4-W(1)-O(3) 159.12(11); O(2)-P(1)- O(2)5 109.5(3); O(2)-P(1)-O(2)6 109.5(3); O(2)-P(1)-O(2)7 70.5(3); O(2)-P(1)-O(2)4 70.5(3); O(2)- P(1)-O(2)8 180.0(4); O(2)-P(1)-O(2)9 109.5(3); O(2)-P(1)-O(2)10 70.5(3); O(2)5-P(1)-O(2)6 109.5(3); O(2)5-P(1)-O(2)7 70.5(3); O(2)5-P(1)- O(2)4 70.5(3); O(2)5-P(1)-O(2)8 70.5(3); O(2)5-P(1)- O(2)9 109.5(3); O(2)5-P(1)-O(2)10 180.0(4); O(2)6-P(1)-O(2)7 180.0(4); O(2)6-P(1)-O(2)4 70.5(3); O(2)6-P(1)-O(2)8 70.5(3); O(2)6-P(1)-O(2)9 109.5(3); O(2)6-P(1)-O(2)10 70.5(3); O(2)7-P(1)-O(2)4 109.5(3); O(2)7-P(1)-O(2)8 109.5(3); O(2)7-P(1)-O(2)9 70.5(3); O(2)7-P(1)-O(2)10 109.5(3); O(2)4- P(1)-O(2)8 109.5(3); O(2)4-P(1)-O(2)9 180.0(4); O(2)4-P(1)-O(2)10 109.5(3); O(2)8-P(1)-O(2)9 70.5(3); O(2)8-P(1)-O(2)10 109.5(3); O(2)9-P(1)-O(2)10 70.5(3); O(1)-Al(1)-O(1)1 87.5(2); O(1)-

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Al(1)-O(1)2 87.08(18); O(1)-Al(1)–O(1)3 154.8(2); O(1)-Al(1)-O(3) 102.58(17); O(1)1-Al(1)-O(1)2 154.8(2); O(1)1-Al(1)-O(1)3 87.08(18); O(1)1-Al(1)-O(3) 102.58(17); O(1)2-Al(1)-O(1)3 87.5(2); O(1)2-Al(1)-O(3) 102.58(17); O(1)3-Al(1)-O(3) 102.58(17); W(1)-O(1)-W(1)11 140.7(3); W(1)- O(1)-Al(1)11 140.7(3); W(1)11-O(1)-Al(1) 140.7(3); Al(1)-O(1)-Al(1)11 140.7(3); W(1)-O(2)-W(1)11 91.97(16); W(1)-O(2)-W(1)12 91.97(16); W(1)-O(2)-P(1) 123.9(3); W(1)-O(2)-O(2)7 131.4(3); W(1)-O(2)-O(2)4 69.1(3); W(1)-O(2)-O(2)10 131.4(3); W(1)11-O(2)-W(1)12 91.97(16); W(1)11-O(2)- P(1) 123.9(3); W(1)11-O(2)-O(2)7 69.1(3) W(1)11-O(2)-O(2)4 131.4(3); W(1)11-O(2)- O(2)10 131.4(3); W(1)12-O(2)-P(1) 123.9(3); W(1)12-O(2)-O(2)7 131.4(3); W(1)12-O(2)-O(2)4 131.4(3); W(1)12-O(2)-O(2)10 69.1(3); P(1)-O(2)-O(2)7 54.7(3); P(1)-O(2)-O(2)4 54.7(3); P(1)-O(2)-O(2)10 54.7(3); O(2)7-O(2)-O(2)4 90.0(3); O(2)7-O(2)-O(2)10 90.0(3); O(2)4-O(2)-O(2)10 90.0(3). Symmetry operators: (1) X,Z,Y (2) Z,Y,-X+1 (3) Z,-X+1,Y (4) Y,Z,-X+1 (5) Y,Z,X (6) Z,X,Y (7) X,Y,-Z+1 (8) Z,X,-Y+1 (9) -Z+1,X,-Y+1 (10) -Y+1,-Z+1,-X+1 (11) -Y+1,Z,-X+1 (12) -Z+1,-X+1,Y.
