<p> Supplementary Information</p><p>A novel 12-tungstovanadate doubly-grafted by Zn-complexes:</p><p> synthesis, crystal structure and properties</p><p>Yan Yua, b, Haijun Panga, Huiyuan Ma*a, Yongbin Songa, Kun Wanga</p><p> aKey Laboratory of Green Chemical Engineering and Technology of College of</p><p>Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin</p><p>University of Science and Technology, Harbin 150040, P. R. China</p><p> bCollege of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar</p><p>161006, P. R. China Table S1 Selected bond lengths (Å) and angles (deg)</p><p>Atoms Dist.(Å) Atoms Dist.(Å) Atoms Angle(°) W(1)-O(22) 1.658(13) W(5)-O(13) 1.665(14) N(6)-Zn(1)-N(1) 105.3(6) W(1)-O(14) 1.865(15) W(5)-O(8) 1.880(15) N(6)-Zn(1)-N(2) 79.1(6) W(1)-O(8) 1.937(15) W(5)-O(6) 1.892(15) N(1)-Zn(1)-N(2) 171.1(6) W(1)-O(1) 2.43(2) W(5)-O(16) 1.905(15) N(6)-Zn(1)-N(4) 97.6(6) W(2)-O(19) 1.657(14) W(5)-O(7) 1.911(15) N(1)-Zn(1)-N(4) 78.6(6) W(2)-O(9) 1.874(15) W(5)-O(1) 2.36(2) N(2)-Zn(1)-N(4) 93.1(6) W(2)-O(7) 1.936(15) W(5)-O(3) 2.38(2) N(6)-Zn(1)-O(20) 167.5(6) W(2)-O(3) 2.41(2) W(6)-O(20) 1.680(12) N(1)-Zn(1)-O(20) 87.2(6) W(3)-O(17) 1.677(13) W(6)-O(10) 1.884(17) N(2)-Zn(1)-O(20) 88.4(5) W(3)-O(5) 1.889(16) W(6)-O(33) 1.895(16) N(4)-Zn(1)-O(20) 84.3(5) W(3)-O(27) 1.899(18) W(6)-O(16) 1.908(16) O(3)-V(1)-O(1) 67.8(10) W(3)-O(10) 1.906(18) W(6)-O(9) 1.914(16) O(3)-V(1)-O(40) 110.1(10) W(3)-O(35) 1.918(17) W(6)-O(11) 2.32(2) O(1)-V(1)-O(40) 71.4(10) W(3)-O(11) 2.37(2) W(6)-O(3) 2.38(2) O(3)-V(1)-O(11) 70.1(11) W(3)-O(40) 2.40(2) Zn(1)-O(3W) 2.103(13) O(1)-V(1)-O(11) 107.3(10) W(4)-O(4) 1.657(13) Zn(1)-N(6) 2.105(15) O(40)-V(1)-O(11) 71.3(10) W(4)-O(35) 1.894(15) Zn(1)-N(1) 2.120(15) O(3)-V(1)-O(1) 67.8(10) W(4)-O(31) 1.891(18) Zn(1)-N(2) 2.158(15) O(3)-V(1)-O(40) 110.1(10) W(4)-O(14) 1.897(14) Zn(1)-N(4) 2.181(16) O(1)-V(1)-O(40) 71.4(10) W(4)-O(6) 1.897(15) Zn(1)-O(20) 2.208(13) O(3)-V(1)-O(11) 70.1(11) W(4)-O(1) 2.39(2) V(1)-O(1) 1.67(2) O(1)-V(1)-O(11) 107.3(10) W(4)-O(40) 2.39(2) V(1)-O(40) 1.68(2) O(40)-V(1)-O(11) 71.3(10) V(1)-O(3) 1.67(2) V(1)-O(11) 1.72(2) O(3)-V(1)-O(1) 67.8(10)</p><p>Table S2 Typical hydrogen-bonding lengths and angles in 1</p><p>D-H…Aa D-H (Å) H…A (Å) D…A (Å) D-H…A (ο)</p><p>C4-H4···O17 0.929 2.565 3.483 169.84</p><p>C19-H19···O4 0.929 2.504 3.164 138.19</p><p>C9-H9···O19 0.932 2.480 3.309 148.20</p><p>C11-H11···O19 0.933 2.699 3.400 132.53 Fig. S1 IR spectrum of 1.</p><p>Fig. S2 PXRD patterns for 1.</p><p>Fig. S3 TG curve of 1.</p>