Square planar platinum(II) complexes with N, S –donor ligands: Synthesis, characterization, DNA interaction and cytotoxic activity

Mohan N. Patel*, Chintan R. Patel, Hardik N. Joshi and Pankaj A. VekariyaDepartment of Chemistry, Sardar Patel University,

Vallabh Vidyanagar-388 120, Gujarat, India

Phone number: (+912692) 226856*218

Corresponding address:

Supplementary material 1 Thermal analysis data of the complexes

Complexes / TG range(˚C) / % Mass loss
experimental (calculated) / Assignment
Complex: 1 / 320–550 / 64.21 (64.68) / Removal of the ligands and leaving PtO as residue
Complex: 2 / 325–540 / 65.14 (65.60) / Removal of the ligands and leaving PtO as residue
Complex: 3 / 295–555 / 68.23 (67.94) / Removal of the ligands and leaving PtO as residue
Complex: 4 / 335–545 / 64.01 (64.44) / Removal of the ligands and leaving PtO as residue
Complex: 5 / 328–516 / 67.63 (67.95) / Removal of the ligands and leaving PtO as residue
Complex: 6 / 310–520 / 66.32 (65.63) / Removal of the ligands and leaving PtO as residue

Supplementary material 2Probable mass fragmentation pattern of complex 1


Supplementary material 31H NMR data for the complexes 1-6.

Complex: 1

1H NMR (DMSO-d6, 400 MHz) δ/ppm:8.280 (d, 2H, H3,5), 8.193–8.065 (complex, 1H, H4′′), 7.693 (d, 4H, H2′′,6′′,2′′′,6′′′), 7.560 (t, 3H, H5′), 7.495 (t, 3H, H3′,3′′′,5′′′), 7.416 (t, 2H, H3′′,5′′), 7.233 (t, 1H, H4′).

Complex: 2

1H NMR (DMSO-d6, 400 MHz) δ/ppm:8.302 (d, 3H, H3,5,5′), 8.236–8.163 (complex, 2H, H3′′,5′′), 8.108 (d, 1H, H2′′), 8.062 (d, 1H, H6′′), 7.711 (dd, 2H, H4′,4′′), 7.579–7.235 (complex, 5H, H3′,2′′′,3′′′,5′′′,6′′′).

Complex: 3

1H NMR (DMSO-d6, 400 MHz) δ/ppm:8.290 (d, 2H, H3,5), 8.270–8.008 (complex, 5H, H5′,3′′,5′′,2′′′,6′′′), 7.770 (t, 2H, H2′′,6′′), 7.697 (dd, 1H, H4′′), 7.583–7.480 (complex, 3H, H3′,3′′′,5′′′), 7.234 (dd, 1H, H4′).

Complex: 4

1H NMR (DMSO-d6, 400 MHz) δ/ppm:8.309 (d, 3H, H3,5, 5′), 8.184 (d, 1H, H2′′), 8.131 (d, 1H, H6′′), 8.064 (dd, 1H, H4′′), 7.949 (d, 2H, H3′′,5′′), 7.687 (dd, 1H, H4′), 7.608 (d, 2H, H2′′′,6′′′), 7.382 (d, 2H, H3′′′,5′′′), 7.226 (dd, 1H, H3′), 2.406 (s, 3H, –CH3).

Complex: 5

1H NMR (DMSO-d6, 400 MHz) δ/ppm:8.313 (d, 3H, H3,5,5′), 8.293 (s, 1H, H2′′′), 8.236 (d, 1H, H2′′), 8.164 (d, 1H, H6′′), 8.112–8.052 (complex, H3′), 7.711 (dd, 2H, H4′,4′′), 7.580–7.481 (complex, 4H, H3′′,5′′,4′′′,6′′′), 7.236 (dd, 1H, H5′′′).

Complex: 6

1H NMR (DMSO-d6, 400 MHz) δ/ppm:8.302 (d, 2H, H3,5), 8.242 (s, 1H, H2′′′), 8.140 (d, 2H, H2′′,6′′), 8.066 (d, 1H, H4′′′), 8.019 (d, 1H, H3′), 7.698 (d, 1H, H5′), 7.628–7.481 (complex, 5H, H4′,3′′,4′′,5′′,6′′′), 7.236 (t, 1H, H5′′′).

Supplementary material 4Effect of complexes on brine shrimp lethality bioassay

Compound / Conc. µM / Log Conc. / No. of nauplii taken / No. of nauplii live / No. of nauplii dead / % of mortality / LC50 µM
1 / 1 / 0.000 / 10 / 8 / 2 / 20
2 / 0.301 / 10 / 7 / 3 / 30
3 / 0.477 / 10 / 6 / 4 / 40 / 04.07
4 / 0.602 / 10 / 5 / 5 / 50
6 / 0.778 / 10 / 4 / 6 / 60
8 / 0.903 / 10 / 3 / 7 / 70
2 / 1 / 0.000 / 10 / 8 / 2 / 20
3 / 0.477 / 10 / 7 / 3 / 30
5 / 0.699 / 10 / 6 / 4 / 40 / 06.25
7 / 0.845 / 10 / 5 / 5 / 50
9 / 0.954 / 10 / 4 / 6 / 60
11 / 1.041 / 10 / 3 / 7 / 70
3 / 3 / 0.477 / 10 / 8 / 2 / 20
5 / 0.699 / 10 / 7 / 3 / 30
7 / 0.845 / 10 / 6 / 4 / 40 / 08.91
9 / 0.954 / 10 / 5 / 5 / 50
12 / 1.079 / 10 / 4 / 6 / 60
15 / 1.176 / 10 / 3 / 7 / 70
4 / 6 / 0.778 / 10 / 9 / 1 / 10
12 / 1.079 / 10 / 8 / 2 / 20
18 / 1.255 / 10 / 7 / 3 / 30 / 30.90
24 / 1.380 / 10 / 6 / 4 / 40
32 / 1.505 / 10 / 5 / 5 / 50
40 / 1.602 / 10 / 4 / 6 / 60
50 / 1.699 / 10 / 3 / 7 / 70
5 / 3 / 0.477 / 10 / 9 / 1 / 10
6 / 0.778 / 10 / 7 / 3 / 30
10 / 1.000 / 10 / 6 / 4 / 40 / 15.85
16 / 1.204 / 10 / 5 / 5 / 50
20 / 1.301 / 10 / 4 / 6 / 60
25 / 1.398 / 10 / 3 / 7 / 70
6 / 3 / 0.477 / 10 / 9 / 1 / 10
6 / 0.778 / 10 / 8 / 2 / 20
9 / 0.954 / 10 / 7 / 3 / 30 / 14.79
12 / 1.079 / 10 / 6 / 4 / 40
15 / 1.176 / 10 / 5 / 5 / 50
18 / 1.255 / 10 / 4 / 6 / 60
21 / 1.322 / 10 / 3 / 7 / 70

Supplementary material 5 Physicochemical parameters of ligands L1-L6

1. L1

Anal. Calc. for C21H14FNS: Calc. (Found): C, 76.11 (76.21); H, 4.26 (4.25); N, 4.23 (4.30); S, 9.68 (9.78).Yield: 55%, mp: 126-128 °C, mol. wt. 331.08;1H NMR (CDCl3, 400 MHz) δ/ppm:8.193 (dd, 2H, H3,5), 7.784 (d, 1H, H5′), 7.757–7.712 (complex, 4H, H2′′′,3′′′,5′′′,6′′′), 7.559–7.522 (complex, 2H, H3′,4′′), 7.478 (dt, 2H, H3′′,5′′), 7.281–7.221 (complex, 2H, H2′′,6′′), 7.189–7.167 (complex, 1H, H4′).13C NMR (CDCl3, 100 MHz) δ/ppm: 164.70 (C4′′′), 155.92 (C2), 154.70 (C6), 152.85 (C4), 149.14 (C2′), 129.26 (C1′′), 128.97 (C1′′′), 128.87 (C3′′,5′′), 128.76 (C3′′′,5′′′), 127.96 (C2′′,6′′), 127.80 (C4′′), 127.06 (C2′′′,6′′′), 124.72 (C5′), 116.61 (C4′), 116.25 (C3′), 116.04 (C5), 115.12 (C3).IR (KBr, 4000–400 cm–1): 3065 ν(C–H)ar; 1550, 1495 ν(C=C); 1386 ν(C=N); 1177 ν(C=S); 1101 ν(C–F); 1386, 1360 (pyridine skeleton band); 1111, 843 (p–substituted aromatic ring); 760 δ(C–H).

2. L2

Anal. Calc. for C21H14ClNS: Calc. (Found): C, 72.51 (72.65); H, 4.06 (4.15); N, 4.03 (4.20); S, 9.22 (9.30).Yield: 65%, mp: 116-118 °C, mol. wt.347.05;1H NMR (CDCl3, 400 MHz) δ/ppm:8.190 (dd, 2H, H3,5), 7.779 (d, 1H, H3′), 7.746 (dd, 2H, H3′′′,5′′′), 7.685 (dd, 2H, H5′,6′′′), 7.539 (dt, 4H, H2′′,3′′,5′′,6′′), 7.495–7.455 (complex, 2H, H4′′,2′′′), 7.189–7.164 (complex, 1H, H4′).13C NMR (CDCl3, 100 MHz) δ/ppm: 157.52 (C2), 152.93 (C6), 148.96 (C4), 145.27 (C2′), 138.88 (C1′′), 137.28 (C1′′′), 135.30 (C4′′′), 129.34 (C3′′,5′′), 129.30 (C3′′′,5′′′), 128.75 (C2′′,6′′), 128.42 (C4′′), 127.98 (C2′′′,6′′′), 127.85 (C5′), 127.05 (C4′), 124.76 (C3′), 116.49 (C5), 115.02 (C3).IR (KBr, 4000–400 cm–1): 3065, 3037 ν(C–H)ar; 1546, 1493 ν(C=C); 1416 ν(C=N); 1233 ν(C=S); 1092 ν(C–Cl); 1384, 1360 (pyridine skeleton band); 1107, 858 (p–substituted aromatic ring); 770 δ(C–H).

3. L3

Anal. Calc. for C21H14BrNS: Calc. (Found): C, 64.29 (64.10); H, 3.60 (3.43); N, 3.57 (3.60); S, 8.17 (8.27).Yield: 62%, mp: 121-123 °C, mol. wt. 391.00;1H NMR (CDCl3, 400 MHz) δ/ppm:8.239 (d, 2H, H3,5), 8.138 (d, 1H, H5′), 7.978 (t, 2H, H2′′′,6′′′), 7.889 (d, 2H, H3′′′,5′′′), 7.854–7.580 (complex, 4H, H3′,3′′,4′′,5′′), 7.417 (t, 2H, H2′′,6′′), 7.126 (t, 1H, H4′).13C NMR (CDCl3, 100 MHz) δ/ppm: 157.56 (C2), 152.97 (C6), 151.62 (C4), 150.18 (C2′), 149.01 (C1′′), 145.28 (C1′′′), 138.86 (C4′′′), 137.79 (C3′′,5′′), 129.30 (C3′′′,5′′′), 128.78 (C2′′,6′′), 128.70 (C4′′), 127.99 (C2′′′,6′′′), 127.86 (C5′), 127.04 (C4′), 123.49 (C3′), 116.45 (C5), 114.98 (C3).IR (KBr, 4000–400 cm–1): 3106, 3062 ν(C–H)ar; 1547, 1487 ν(C=C); 1384 ν(C=N); 1228 ν(C=S); 1072 ν(C–Br); 1383, 1365 (pyridine skeleton band); 1110, 857 (p–substituted aromatic ring); 768 δ(C–H).

4. L4

Anal. Calc. for C22H17NS: Calc. (Found): C, 80.70 (80.85); H, 5.23 (5.10); N, 4.28 (4.35); S, 9.79 (9.69).Yield: 57%, mp: 97-99 °C, mol. wt.327.11;1H NMR (CDCl3, 400 MHz) δ/ppm:8.204 (d, 2H, H3,5), 7.814 (d, 2H, H2′′′,6′′′), 7.753 (d, 1H, H5′), 7.665 (d, 2H, H3′′′,5′′′), 7.542 (t, 2H, H5′,4′′), 7.464 (dd, 2H, H3′′,5′′), 7.364 (d, 2H, H2′′,6′′), 7.176 (dd, 1H, H4′), 2.474 (s, 3H, CH3). 13C NMR (CDCl3, 100 MHz) δ/ppm: 157.29 (C2), 152.73 (C6), 150.07 (C4), 145.59 (C2′), 139.19 (C1′′), 139.16 (C1′′′), 135.88 (C4′′′), 129.84 (C3′′,5′′), 129.12 (C3′′′,5′′′), 128.71 (C2′′,6′′), 127.93 (C4′′), 127.60 (C2′′′,6′′′), 127.15 (C5′), 127.06 (C4′), 126.97 (C3′), 116.62 (C5), 115.12 (C3), 21.27 (–CH3).IR (KBr, 4000–400 cm–1): 3096, 3030 ν(C–H)ar; 2915 ν(C–H)al; 1547, 1494 ν(C=C); 1418 ν(C=N); 1184 ν(C=S); 1386, 1365 (pyridine skeleton band); 1128, 870 (p–substituted aromatic ring); 815 δ(C–H).

5. L5

Anal. Calc. for C21H14BrNS: Calc. (Found): C, 64.29 (64.20); H, 3.60 (3.70); N, 3.57 (3.45); S, 8.17 (8.27).Yield: 59%, mp: 106-108 °C, mol. wt. 391.00;1H NMR (CDCl3, 400 MHz) δ/ppm:8.208 (d, 2H, H3,5), 8.188 (s, 1H, H2′′′), 7.888–7.742 (complex, 3H, H3′′,5′′,5′′′), 7.655 (dt, 2H, H4′′,4′′′), 7.622 (t, 2H, H2′′,6′′), 7.566–7.459 (complex, 2H, H3′,5′), 7.420 (t, 1H, H6′′′), 7.181 (dd, 1H, H4′).13C NMR (CDCl3, 100 MHz) δ/ppm: 157.53 (C2), 152.96 (C6), 148.70 (C4), 145.21 (C2′), 140.98 (C1′′), 138.79 (C1′′′), 131.99 (C5′′′), 130.64 (C2′′′), 130.19 (C4′′′), 129.34 (C3′′,5′′), 128.76 (C2′′,6′′), 128.01 (C4′′), 127.91 (C6′′′), 127.07 (C5′), 125.81 (C4′), 124.85 (C3′), 123.26 (C3′′′), 116.59 (C5), 115.13 (C3).IR (KBr, 4000–400 cm–1): 3095, 3059 ν(C–H)ar; 1547, 1495 ν(C=C); 1385 ν(C=N); 1190 ν(C=S); 1070 ν(C–Br); 1386, 1360 (pyridine skeleton band); 924, 792, 776 (m–substituted aromatic ring); 830 δ(C–H).

6. L6

Anal. Calc. for C21H14ClNS: Calc. (Found): C, 72.51(72.40); H, 4.06 (4.14); N, 4.03 (4.22); S, 9.22(9.10).Yield: 54%, mp: 98-100 °C, mol. wt.347.05;1H NMR (CDCl3, 400 MHz) δ/ppm:8.210 (d, 2H, H3,5), 8.190 (s, 1H, H2′′′), 7.784–7.730 (complex, 3H, H4′′,5′′′,6′′′), 7.639–7.614 (complex, 1H, H4′′′), 7.546 (t, 2H, H3′′,5′′), 7.499–7.284 (complex, 4H, H3′,5′,2′′,6′′), 7.182 (dd, 1H, H4′).13C NMR (CDCl3, 100 MHz) δ/ppm: 157.54 (C2), 152.97 (C6), 148.80 (C4), 145.22 (C2′), 140.72 (C1′′), 138.81 (C1′′′), 135.13 (C3′′′), 130.39 (C4′′′), 129.33 (C5′′′), 129.06 (C2′′′), 128.76 (C3′′,5′′), 128.00 (C2′′,6′′), 127.90 (C3′), 127.30 (C4′′), 127.07 (C4′), 125.34 (C6′′′), 124.84 (C5′), 116.59 (C5), 115.13 (C3).IR (KBr, 4000–400 cm–1): 3087 ν(C–H)ar; 1547, 1494 ν(C=C); 1385 ν(C=N); 1178 ν(C=S); 1074 ν(C–Cl); 1385, 1360 (pyridine skeleton band); 867, 794, 740 (m–substituted aromatic ring); 829 δ(C–H).