Structure and biological properties of first row d-transition metal complexes with N-substituted sulfonamides

Figures & data

Scheme 1 Preparation of Ligands

Table I.  Physical measurements and analytical data of the metal (II) complexes.

No.			M.P (dec.) (°C)	Yield (%)	Calc. (Found) %
					C	H	N
1.	[Co(L1-H)2(H2O)2] C46H42N8O8S2 Co	[957.95]	270–275	80	57.68(57.12)	4.42(4.33)	11.70(11.42)
2.	[Cu(L1-H)2(H2O)2] C46H42N8O8S2 Cu	[962.56]	255–260	79	57.40(57.47)	4.40(4.87)	11.64(11.84)
3.	[Ni(L1-H)2(H2O)2] C46H42N8O8S2 Ni	[957.71]	268–273	81	57.69(57.66)	4.42(4.21)	11.70(11.32)
4.	[Zn(L1-H)2(H2O)2] C46H42N8O8S2 Zn	[964.41]	262–264	75	57.29(57.69)	4.39(4.46)	11.62(11.73)
5.	[Co(L2-H)2(H2O)2] C42H34N8O8S2 Co	[901.84]	299–304	82	55.94(55.41)	3.80(4.18)	12.42(12.65)
6.	[Cu(L2-H)2(H2O)2] C42H34N8O8S2 Cu	[906.46]	277–283	84	55.65(55.63)	3.78(3.81)	12.36(12.43)
7.	[Ni(L2-H)2(H2O)2] C42H34N8O8S2 Ni	[901.60]	283–288	81	55.95(55.85)	3.80(4.01)	12.43(12.36)
8.	[Zn(L2-H)2(H2O)2] C42H34N8O8S2 Zn	[908.30]	268–273	80	55.54(55.81)	3.77(3.87)	12.34(12.08)
9.	[Co(L3-H)2(H2O)2] C44H40N6O10S2 Co	[935.90]	295–298	77	56.47(56.66)	4.31(4.38)	8.98(8.84)
10.	[Cu(L3-H)2(H2O)2] C44H40N6O10S2 Cu	[940.51]	280–284	81	56.19(56.42)	4.29(4.37)	8.94(8.98)
11.	[Ni(L3-H)2(H2O)2] C44H40N6O10S2 Ni	[935.66]	290–295	82	56.48(56.67)	4.31(4.52)	8.98(8.78)
12.	[Zn(L3-H)2(H2O)2] C44H40N6O10S2 Zn	[942.36]	297–299	79	56.08(56.16)	4.28(4.32)	8.92(8.82)
13.	[Co(L4-H)2(H2O)2] C42H36N6O10S2 Co	[907.84]	245–250	83	55.57(55.46)	4.00(4.08)	9.26(9.24)
14.	[Cu(L4-H)2(H2O)2] C42H36N6O10S2 Cu	[912.46]	265–270	81	55.29(55.42)	3.98(4.07)	9.21(9.28)
15.	[Ni(L4-H)2(H2O)2] C42H36N6O10S2 Ni	[907.60]	256–261	82	55.58(55.67)	4.00 (4.12)	9.26 (9.28)
16.	[Zn(L4-H)2(H2O)2] C42H36N6O10S2 Zn	[914.30]	277–280	75	55.17(55.36)	3.97(4.12)	9.19(9.22)
17.	[Co(L5-H)2(H2O)2] C40H32N6O8S4 Co	[911.92]	288–294	83	52.68(52.56)	3.54(3.58)	9.22(9.24)
18.	[Cu(L5-H)2(H2O)2] C40H32N6O8S4 Cu	[916.54]	272–276	81	52.42(52.48)	3.52(3.67)	9.17(9.28)
19.	[Ni(L5-H)2(H2O)2] C40H32N6O8S4 Ni	[911.68]	288–292	82	52.70(52.67)	3.54(3.52)	9.22(9.28)
20.	[Zn(L5-H)2(H2O)2] C40H32N6O8S4 Zn	[918.38]	267–273	73	52.31(52.46)	3.51(3.52)	9.15(9.22)
21.	[Co(L6-H)2(H2O)2] C36H34N8O8S2 Co	[829.78]	260–65	78	52.11(52.18)	4.13(4.38)	13.50(13.44)
22.	[Cu(L6-H)2(H2O)2] C36H34N8O8S2 Cu	[834.39]	250–254	79	51.82(51.62)	4.11(4.27)	13.43(13.68)
23.	[Ni(L6-H)2(H2O)2] C36H34N8O8S2 Ni	[829.53]	255–260	77	52.13(52.17)	4.13(4.32)	13.51(13.58)
24.	[Zn(L6-H)2(H2O)2] C36H34N8O8S2 Zn	[836.23]	263–268	74	51.71(51.96)	4.10(4.22)	13.40(13.22)

Table II.  Conductivity, magnetic and spectral data of the metal (II) complexes.

No.	ΩM (Ω^− 1 cm^2 mol^− 1)	B.M (μeff)	λmax (cm^− 1)	IR (cm^− 1)
1.	86.2	4.82	7290,17430, 20490,29325	1577 (C = N), 1395 (C–O), 1325, 1120 (SO2), 955 (S–N), 835 (C–S), 440 (M–N), 525 (M–O)
2.	87.5	1.77	14845,19165, 30355	1567 (C = N), 1395 (C–O), 1325, 1120 (SO2), 955 (S–N), 835 (C–S), 435 (M–N), 520 (M–O)
3.	86.8	3.31	10445,15725, 26440,29975	1570 (C = N), 1395 (C–O), 1325, 1120 (SO2), 955 (S–N), 835 (C–S), 437 (M–N), 545 (M–O)
4.	92.3	Dia	28630	1568 (C = N), 1395 (C–O), 1325, 1120 (SO2), 955 (S–N), 835 (C–S), 437 (M–N), 528 (M–O)
5.	93.7	4.86	7470,17520, 20680,29385	1569 (C = N), 1395 (C–O), 1326, 1122 (SO2), 957 (S–N), 836 (C–S), 444 (M–N), 525 (M–O)
6.	93.2	1.78	15160,19315, 30380	1577 (C = N), 1395 (C–O), 1326, 1122 (SO2), 957 (S–N), 836 (C–S), 442 (M–N), 520 (M–O)
7.	94.0	3.30	10490,15865, 26675,30225	1570 (C = N), 1395 (C–O), 1326, 1122 (SO2), 957 (S–N), 836 (C–S), 438 (M–N), 533 (M–O)
8.	86.3	Dia	29145	1568 (C = N), 1395 (C–O), 1326, 1122 (SO2), 957 (S–N), 836 (C–S), 436 (M–N), 545 (M–O)
9.	84.8	4.78	7275,17355, 20445,29280	1570 (C = N), 1395 (C–O), 1320, 1118 (SO2), 957 (S–N), 838 (C–S), 435 (M–N), 530 (M–O)
10.	84.0	1.85	14720,19140, 30335	1567 (C = N), 1395 (C–O), 1320, 1118 (SO2), 957 (S–N), 838 (C–S), 443 (M–N), 535 (M–O)
11.	85.2	3.31	10490,15610, 26325,29850	1570 (C = N), 1395 (C–O), 1320, 1118 (SO2), 957 (S–N), 838 (C–S), 440 (M–N), 545 (M–O)
12.	86.4	Dia	28530	1568 (C = N), 1395 (C–O), 1320, 1118 (SO2), 957 (S–N), 838 (C–S), 439 (M–N), 523 (M–O)
13.	87.7	4.79	7285,17360, 20495,29395	1573 (C = N), 1395 (C–O), 1323, 1118 (SO2), 956 (S–N), 836 (C–S), 435 (M–N), 536 (M–O)
14.	89.2	1.81	14765,19140, 30335	1575 (C = N), 1395 (C–O), 1323, 1118 (SO2), 956 (S–N), 836 (C–S), 439 (M–N), 540 (M–O)
15.	88.3	3.33	10350,15610, 26325,29850	1570 (C = N), 1395 (C–O), 1323, 1118 (SO2), 956 (S–N), 836 (C–S), 435 (M–N), 535 (M–O)
16.	87.6	Dia	28780	1568 (C = N), 1395 (C–O), 1323, 1118 (SO2), 956 (S–N), 836 (C–S), 445 (M–N), 523 (M–O)
17.	90.5	4.84	7485,17360,20555,29285	1575 (C = N), 1395 (C–O), 1324, 1122 (SO2), 953 (S–N), 837 (C–S), 439 (M–N), 538 (M–O)
18.	92.3	1.83	14775,19140,30335	1577 (C = N), 1395 (C–O), 1324, 1122 (SO2), 953 (S–N), 837 (C–S), 437 (M–N), 527 (M–O)
19.	93.4	3.29	10355,15610,26325,29850	1570 (C = N), 1395 (C–O), 1324, 1122 (SO2), 953 (S–N), 837 (C–S), 440 (M–N), 535 (M–O)
20.	88.4	Dia	28990	1568 (C = N), 1395 (C–O), 1324, 1122 (SO2), 953 (S–N), 837, (C–S), 439 (M–N), 523 (M–O)
21.	93.9	4.80	7285,17360,20475,29360	1569 (C = N), 1395 (C–O), 1325, 1120 (SO2), 951 (S–N), 833 (C–S), 445 (M–N), 530 (M–O)
22.	91.0	1.85	15160,19140,30335	1571 (C = N), 1395 (C–O), 1325, 1120 (SO2), 951 (S–N), 833 (C–S), 435 (M–N), 520 (M–O)
23.	86.3	3.28	10355,15610,26325,29850	1570 (C = N), 1395 (C–O), 1325, 1120 (SO2), 951 (S–N), 833 (C–S), 440 (M–N), 535 (M–O)
24.	87.4	Dia	28755	1568 (C = N), 1395 (C–O), 1325, 1120 (SO2), 951 (S–N), 833 (C–S), 439 (M–N), 523 (M–O)

Scheme 2 Proposed Structure of the Metal (II) Complexes

Table III.  Antibacterial Bioassay of Ligands and Metal (II) Complexes*.

Bacteria	Compound [zone of inhibition (mm)]
	L1	L2	L3	L4	L5	L6	1	2	3	4	5	6	7	8	9	10	11	12	13	14	15	16	17	18	19	20	21	22	23	24	SD
Gram- negative
(a)	16	15	17	12	14	13	19	12	20	24	19	21	22	21	19	20	19	23	15	16	15	20	17	15	21	24	19	20	19	25	30
(b)	08	08	06	07	09	08	08	06	10	10	11	08	09	10	12	10	11	12	11	12	13	13	11	11	10	12	11	11	10	14	27
(c)	14	13	15	13	15	15	18	19	18	21	17	16	20	20	18	19	20	24	17	18	16	21	18	19	20	22	18	19	20	23	26
(d)	12	13	13	14	15	14	20	17	18	22	18	18	19	20	20	19	20	21	18	18	18	20	20	20	19	23	20	17	18	24	27
Gram- positive
(e)	17	17	16	16	17	16	17	16	17	23	20	21	19	21	19	20	20	22	17	18	17	24	19	19	19	24	19	20	18	26	30
(f)	15	16	19	15	14	15	20	18	15	18	17	21	17	22	20	19	22	24	18	17	18	22	19	19	18	23	20	19	22	24	28

(a) = E. coli, (b) = S. flexenari, (c) = P. aeruginosa, (d) = S. typhi, (e) = S. aureus, (f) = B. subtilis

< 10: weak; >10: moderate; > 16: Significant. SD = Standard Drug (Imipenum)

*concentration used 1 mg/mL of DMSO

Figure 1 Comparison of antibacterial activity.

Figure 2 Average antibacterial activity of ligands versus metal (II) complexes.

Table IV.  Antifungal Bioassay of Ligands and Metal (II) Complexes*.

Organism	Compound (% inhibition)
	L1	L2	L3	L4	L5	L6	1	2	3	4	5	6	7	8	9	10	11	12	13	14	15	16	17	18	19	20	21	22	23	24	SD
(a)	70	58	40	80	00	80	35	50	00	00	50	60	40	00	80	40	00	80	55	35	40	20	45	65	00	00	78	30	45	25	A
(b)	55	00	00	00	65	00	40	00	35	70	50	00	60	00	00	30	70	55	75	45	35	60	40	00	00	75	65	60	65	60	B
(c)	80	00	70	80	00	20	10	30	00	00	60	80	00	40	00	00	00	40	65	00	55	55	35	40	40	40	45	45	60	50	C
(d)	60	75	75	80	00	80	00	00	70	50	55	55	00	70	35	35	20	80	00	60	00	00	90	35	85	85	00	00	35	55	D
(e)	00	52	90	20	20	65	00	40	80	00	40	45	70	90	45	60	20	00	00	90	00	70	00	50	30	00	00	20	80	85	E
(f)	50	30	00	00	40	00	20	00	80	70	00	60	50	00	55	00	75	00	80	35	00	80	60	00	00	00	70	00	40	40	F

(a) = T. longifucus, (b) = C. Albicans, (c) = A. flavus, (d) = M. canis, (e) = F. Solani, (f) = C. glaberata

*(concentration used 200 μg/mL)

SD = Standard Drugs MIC μg/mL; A = Miconazole (70 μg/mL: 1.6822 × 10^{− 4} M),B = Miconazole (110.8 μg/mL:2.6626 × 10^{− 4} M), C = Amphotericin B (20 μg/mL: 2.1642 × 10^{− 5} M), D = Miconazole (98.4 μg/mL: 2.3647 × 10^{− 4} M), E = Miconazole (73.25 μg/mL: 1.7603 × 10^{− 4} M), F = Miconazole (110.8 μg/mL: 2.66266 × 10^{− 4} M).

Figure 3 Comparison of antifungal activity.

Figure 4 Average antifungal activity of ligands versus metal (II) complexes.

Table V.  Minimum Inhibitory Concentration (M) of the Selected Compounds (4), (12), (16), (20 and (24) against Selected Bacteria.

No.	4	12	16	20	24
Gram-negative
E. coli	5.185 × 10^− 5	–	–	5.444 × 10^− 5	5.979 × 10^− 5
P. aeruginosa	1.037 × 10^− 4	2.653 × 10^− 5	1.094 × 10^− 4	1.089 × 10^− 5	2.990 × 10^− 5
S. typhi	2.592 × 10^− 5	–	−	2.722 × 10^− 5	1.196 × 10^− 5
Gram − positive
S. aureus	–	–	5.469 × 10^− 5	1.089 × 10^− 4	1.196 × 10^− 4
B. subtilis	–	5.306 × 10^− 5	–	5.444 × 10^− 5	5.979 × 10^− 5

Table VI.  Brine Shrimp Bioassay Data of the Ligands (L₁)-(L₆) and their Metal (II) Complexes (1)-(24).

Compound	LD50 (M)
L1	> 2.312
L2	> 2.472
L3	> 2.373
L4	> 2.454
L5	> 2.442
L6	> 2.714
1	> 1.044
2	> 1.039
3	> 1.044
4	> 1.037
5	> 1.109
6	0.601
7	> 1.109
8	> 1.101
9	> 1.068
10	0.484
11	> 1.069
12	> 1.061
13	> 1.102
14	> 1.096
15	> 1.102
16	> 1.094
17	> 1.096
18	0.606
19	> 1.097
20	> 1.089
21	> 1.205
22	0.627
23	> 1.206
24	> 1.196