Supplementary Information

Reactivity of thiazolidine-2-thione towards CuI/CuII: Synthesis and structures of [3-(2-thiazolin-2-yl)thiazolidine-2-thione]copper(I) bromide and [bis(2,2’-bipyridine)nitratocopper(II)] nitrate

TARLOK S LOBANA, a,* ANU RANI, a AMANPREET K JASSAL a and JERRY P JASINSKI b

a Department of Chemistry,Guru Nanak Dev University,Amritsar 143 005, India

b Department of Chemistry, Keene State College, Keene NH 03435–2001 USA

Email.

Table S1 shows various copper(II) nitrate complexes with bipyridines in which nitrates are variably coordinated and adopt broadly two types of crystal modifications, though there is no simple rationale to predict or group together modifications.

Table S1. Compounds reported with cell parameters (Å/o)

S.No. / Compound / Space group,
(T, K; R%) / a b c
α β γ / [Ref]
2 / [Cu(bipy)2(ONO2)](NO3) / P21/n(14)
(173(2) K, 3.99) 2a / 11.318(1), 12.160(1) 14.967(1)
90, 98.01(1), 90 / This work
P21/n(14)
(296(2) K, 4.09 )2b / 11.340(5), 12.249(5), 15.065(6)
90, 98.04(2) 90 / This work
3 / [Cu(bipy)2(ONO2)](NO3) / P21/n(14)
(293 K, 4.86) / 11.331(1), 12.271(1), 15.088(1)
90.00, 98.28(0), 90.00 / [12]
4 / Cu(bipy)2(ONO2)](NO3)MeOH / P-1(2)
(100 K, 3.62) / 7.686(0), 11.890(0), 13.364(1)
109.49(0), 92.90(0) , 101.35(0) / [13]
5 / [Cu(bipy4,4-OMe)2(ONO2)](NO3) MeOH / P-1(2)
(100 K, 5.53) / 7.631(1,) 11.598(1), 16.577(2)
104.14(0), 99.43(0), 102.36(0) / [14]
6 / [Cu(bipy)2(ONO2)](NO3)4,5-dicyanoim- idazole hydrate / P-1(2)
(295 K, 5.10) / 12.398(2) , 13.679(3), 8.837(2)
100.77(2), 100.39(1), 103.40(2) / [15]
7 / [Cu(bipy5,5-Me)2(ONO2)](NO3) / P-1(2)
(293 K, 4.89) / 8.135(1), 10.572(2), 15.740(2)
96.69(2), 104.47(2) , 105.88(2) / [16]
8 / [Cu(bipy)2(O2NO)](NO3)0.5H2O / P-1(2)
(100 K, 5.78) / 7.249(1) 14.831(2) 20.070(3)
108.62(0) 91.95(0) 93.05(0) / [17]
9 / [Cu(bipy)2(O2NO)](NO3)H2O / P-1(2)
(295 K, 5.46) / 7.488(2) 10.017(2) 15.061(2)
106.18(0) 91.34(0) 89.66(0) / [18]
10 / [Cu(bipy)2(O2NO)](NO3)H2O / P-1(2)
(188 K, 3.33) / 12.045(1) 14.630(2) 15.070(25)
61.79(1) 86.35(1) 67.60(1) / [19]
11 / [Cu(bipy)2(O2NO)](NO3)H2O / P-1(2)
(295 K, 5.30) / 7.464(3) 10.002(5) 15.503(6)
111.50(5) 91.43(5) 90.47(4) / [20]
12 / trans-[Cu(bipy)2(ONO2)2] CH3CN / P21/n(14)
(150 K, 5.06) / 13.652(0) 7.725(0) 22.190(0)
90.00 93.21(0) 90.00 / [21 ]
13 / [Cu(bipy4,4-OH)2](NO3)2H2O / P-1(2)
(150 K, 5.75) / 7.060(0) 11.194(1) 15.516(1)
100.74(0) 93.52(0) 108.30(0) / [22]

Table S2. Bond lengths (Å) and angles (o) of compound 2{2a, 173(2) K; 2b, 296(2) K}

2a / 2b / 2a / 2b
Cu1- O1 / 2.0828(18) / 2.115(3) / N1 - Cu1- N4 / 108.36(7) / 109.37(10)
Cu1- N1 / 2.1215(18) / 1.983(2) / N2 - Cu1- N3 / 176.46(7) / 176.43(10)
Cu1 - N2 / 1.9875(17) / 2.111(3) / N2 - Cu1- O1 / 87.61(7) / 87.59(9) .
Cu1 – N3 / 1.9776(18) / 2.018(3) / N2 - Cu1- N4 / 99.05(7) / 99.41(10)
Cu1 – N4 / 2.0228(17) / 1.973(2) / N3 - Cu1- O1 / 90.31(7) / 90.04(10)
O1- N5 / 1.280(3) / 1.270(3) / N3 - Cu1- N4 / 81.40(7) / 81.35(10)
O2-N5 / 1.199(3) / 1.206(4) / N4 - Cu1- O1 / 150.49(7) / 149.96(10)
O3-N5 / 1.241(3) . / 1.238(3) / O1- N5- O3 / 117.14(19) / 117.0(3)
N1- Cu1- N2 / 79.93(7) / 80.00(10) / O1- N5- O2 / 120.5(2) / 121.3(3)
N1 - Cu1- O1 / 101.10(7) / 100.59(10) / O2- N5- O3 / 122.3(2) / 121.7(4)
N1 - Cu1- N3 / 103.30(7) / 103.07(10)

Bonding trends of nitrate in presence of 2,2’-bipyridines

In literature, coordination of 2, 2’-bipyridine and its substituted derivatives to CuII with nitrate as the counter anion has been reported (Scheme 1S).12–22 It is observed that the nitrate has shown four types of bonding modes: nonionic, CuII-ONO2, CuII-O2NO, CuII-(ONO2)2 and ionic, [CuII](NO3)2 in its bipy complexes, namely, (i) [CuL2(ONO2)](NO3) (L= bipy, bipy4,4-OMe, bipy5,5-Me)12–16 (ii), [CuL2(O2NO)](NO3) (L= bipy)17-20 (iii) trans-[Cu(bipy)2(ONO2)2],21and (iv) [Cu(bipy4,4-OH)2](NO3)2H2O22respectively.

References 12–22 given in main paper