Supplementary Information s42

Supplementary Information

A novel 12-tungstovanadate doubly-grafted by Zn-complexes:

synthesis, crystal structure and properties

Yan Yua, b, Haijun Panga, Huiyuan Ma*a, Yongbin Songa, Kun Wanga

aKey Laboratory of Green Chemical Engineering and Technology of College of

Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin

University of Science and Technology, Harbin 150040, P. R. China

bCollege of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar

161006, P. R. China Table S1 Selected bond lengths (Å) and angles (deg)

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)

Table S2 Typical hydrogen-bonding lengths and angles in 1

D-H…Aa D-H (Å) H…A (Å) D…A (Å) D-H…A (ο)

C4-H4···O17 0.929 2.565 3.483 169.84

C19-H19···O4 0.929 2.504 3.164 138.19

C9-H9···O19 0.932 2.480 3.309 148.20

C11-H11···O19 0.933 2.699 3.400 132.53 Fig. S1 IR spectrum of 1.

Fig. S2 PXRD patterns for 1.

Fig. S3 TG curve of 1.