Supplementary Materials

Synthesis and structures of silver(I) complexes of 4-amino-3,5-dipropyl-4H-1,2,4-triazole and 4-amino-3,5-dibutyl-4H-1,2,4-triazole:

A possible mechanism of formation of Ag4tz6 cluster

Guo-Sheng Han, Wen-Bo Li, Yang Li, Peng-Cheng Duan, Guang Yang *

College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450001, China

Fig. S1 The IR spectrum of the complex [Ag2(4-NH2-3,5-Bu2-tz)2(NO3)2].

Fig. S2 The 1H-NMR spectrum of [Ag2(4-NH2-3,5-Bu2-tz)2(NO3)2].

Fig. S3 The IR spectrum of complex [Ag4(4-NH2-3,5-Pr2-tz)6(NO3)2](NO3)2

Fig S4 The IR spectrum of complex [Ag4(4-NH2-3,5-Pr2-tz)6](ClO4)4

Fig. S5 The 1H-NMR spectrum of [Ag4(4-NH2-3,5-Pr2-tz)6](ClO4)4 in acetone-d6.

Fig. S6 The IR spectrum of the complex [Ag4(4-NH2-3,5-Pr2-tz)6](CF3SO3)4.

Fig. S7 The IR spectrum of the complex [Ag4(4-NH2-3,5-Bu2-tz)6](BF4)4.

Fig. S8 The ellipsoid diagram of the asymmetric unit of [Ag2(4-NH2-3,5-Bu2-tz)2](NO3)2. The H atoms have been omitted for charity.

Fig. S9 The ellipsoid diagram of the asymmetric unit of [Ag4(4-NH2-3,5-Pr2-tz)6(NO3)2](NO3)2. The H atoms have been omitted for charity.

Fig. S10 The ellipsoid diagram of the asymmetric unit of [Ag4(4-NH2-3,5-Pr2-tz)6](ClO4)4. The H atoms have been omitted for charity.

Fig. S11 The ellipsoid diagram of the asymmetric unit of [Ag4(4-NH2-3,5-Pr2-tz)6](CF3SO3)4. The H atoms have been omitted for charity.

Fig. S12 The ellipsoid diagram of the asymmetric unit of [Ag4(4-NH2-3,5-Bu2-tz)6](BF4)4. The H atoms have been omitted for charity.

Table S1 Selected bond lengths (Å) and bond angles (°) for 1–5.

1
Ag(1)-O(1) 2.437(6)
Ag(2)-O(4) 2.313(4)
Ag(1)-N(6) 2.261(3)
Ag(1)-N(1) 2.278(3)
Ag(2)-N(2) 2.198(3)
Ag(2)-N(5) 2.241(3)
N(2)-Ag(2)-Ag(1a) 114.8(10)
N(5)-Ag(2)-Ag(1a) 56.58(9) / N(6)-Ag(1)-O(1) 27.48(12)
N(1)-Ag(1)-O(1) 109.89(12)
N(10)-O(1)-Ag(1) 102.4(2)
N(1)-N(2)-Ag(2) 118.5(2)
N(2)-Ag(2)-N(5) 122.78(12)
Ag(1)-Ag(2a) 3.3407(5)
N(6)-Ag(1)-Ag(2a) 74.57(9)
N(1)-Ag(1)-Ag(2a) 128.00(9)
2
Ag(1)-O(1) 2.599(6)
Ag(1)-Ag(2) 3.2295(8)
Ag(1)-N(10) 2.257(4)
Ag(1)-N(1) 2.448(4) / N(10)-Ag(1)-O(1) 103.87(14)
N(10)-Ag(1)-N(1) 99.70(13)
N(5)-Ag(2)-Ag(1) 129.74(10)
N(5)-Ag(2)-N(9) 133.50(14)
3
Ag(1)-N(8) 2.147(3)
Ag(1)-N(1) 2.157(3)
Ag(1)-N(9) 2.586(3)
Ag(2)-N(5) 2.165(3)
Ag(2)-N(2) 2.180(3)
Ag(2)-N(12) 2.513(3)
Ag(2)-N(9) 2.592(3)
N(12)-Ag(2)-N(9) 87.34(10) / N(8)-Ag(1)-N(1) 154.22(10)
N(8)-Ag(1)-N(9) 96.98(10)
N(1)-Ag(1)-N(9) 104.44(10)
N(5)-Ag(2)-N(2) 150.91(12)
N(5)-Ag(2)-N(12) 105.97(10)
N(2)-Ag(2)-N(12) 96.47(10)
N(5)-Ag(2)-N(9) 94.61(10)
N(2)-Ag(2)-N(9) 104.85(10)
4
Ag(1)-N(11) 2.165(3)
Ag(1)-N(1) 2.184(3)
Ag(1)-N(13) 2.586(3)
Ag(2)-N(2) 2.175(3)
Ag(2)-N(4) 2.190(3)
Ag(2)-N(17) 2.530(4)
Ag(2)-N(14) 2.620(3)
Ag(3)-N(7) 2.155(3)
Ag(3)-N(5) 2.161(3)
Ag(4)-N(10) 2.167(3)
Ag(4)-N(8) 2.181(3)
Ag(4)-N(13) 2.557(3)
Ag(4)-N(16) 2.600(3)
N(8)-Ag(4)-N(16) 108.54(12)
N(13)-Ag(4)-N(16) 85.90(11) / N(11)-Ag(1)-N(1) 157.11(12)
N(11)-Ag(1)-N(13) 102.12(12)
N(1)-Ag(1)-N(13) 94.25(12)
N(2)-Ag(2)-N(4) 150.19(12)
N(2)-Ag(2)-N(17) 107.69(11)
N(4)-Ag(2)-N(17) 95.16(11)
N(2)-Ag(2)-N(14) 94.52(11)
N(4)-Ag(2)-N(14) 106.08(11)
N(17)-Ag(2)-N(14) 86.26(10)
N(7)-Ag(3)-N(5) 156.51(13)
N(10)-Ag(4)-N(8) 152.63(13)
N(10)-Ag(4)-N(13) 102.80(12)
N(8)-Ag(4)-N(13) 93.48(13)
N(10)-Ag(4)-N(16) 94.59(12)
5
Ag(1)-N(5) 2.143(7)
Ag(1)-N(5a) 2.198(7)
Ag(1)-N(1) 2.513(6)
Ag(1)-Ag(3) 3.355(3)
Ag(2)-N(9) 2.177(6)
Ag(2)-N(9a) 2.177(6)
Ag(2)-N(2) 2.451(7)
Ag(2)-N(2a) 2.451(6)
Ag(2)-Ag(3) 3.3670(10)
Ag(2)-Ag(3a) 3.3670(10)
Ag(3)-N(10) 2.193(7)
Ag(3)-N(6) 2.207(6)
Ag(3)-N(1) 2.552(7)
Ag(3)-N(2a) 2.629(6) / N(5)-Ag(1)-N(5a) 154.5(3)
N(5)-Ag(1)-N(1) 112.3(3)
N(5a)-Ag(1)-N(1) 93.0(3)
N(9)-Ag(2)-N(9a) 149.3(3)
N(9)-Ag(2)-N(2) 96.8(2)
N(9a)-Ag(2)-N(2) 106.1(2)
N(9)-Ag(2)-N(2a) 106.1(2)
N(9a)-Ag(2)-N(2a) 96.8(2)
N(2)-Ag(2)-N(2a) 83.6(3)
N(10)-Ag(3)-N(6) 154.3(3)
N(10)-Ag(3)-N(1) 97.1(2)
N(6)-Ag(3)-N(1) 107.5(2)
N(10)-Ag(3)-N(2a) 103.9(2)
N(6)-Ag(3)-N(2a) 86.8(2)
N(1)-Ag(3)-N(2a) 82.6(2)

Symmetry codes: For 1: a) 1-x, 1-y, 2-z. For 5: a) 1-x, 1-y, z.