Z. Wei et al. / Polyhedron 69 (2014) 181–187
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2.2.2. 4,10-Bis(pyridin-2-ylmethyl)-1,7-dithia-4,10-
diazacyclododecane, L0
A mixture of L (1.5 g, 5 mmol) and 2-(chloromethyl)pyridine
(0.64 g, 5 mmol) in dry toluene (50 mL) was refluxed under an Ar
atmosphere for 48 h in the presence of K2CO3 (1.40 g, 10.14 mmol)
and KI (0.84 g, 5.05 mmol). Insoluble inorganic solids were filtered
off and the solvent was removed under reduced pressure to pro-
duce a pale yellow solid. This crude product was further purified
by chromatography using ethyl acetate as the eluant to give a pale
yellow solid (1.5 g, 79%). 1H NMR (CDCl3): 8.455 (d, J = 4.52 Hz, Py–
H), 7.604 (t, J = 15.08 Hz, Py–H), 7.475 (d, J = 7.79 Hz, Py–H), 7.097
(t, J = 12.18 Hz, Py–H), 3.739 (s, Py–CH2), 2.802 (t, J = 13.08 Hz,
NCH2CH2), 2.729 (t, J = 13.02 Hz, NCH2CH2). 13C NMR (CDCl3):
159.26, 149.06, 136.50, 123.05, 122.12, 61.35, 52.54, 26.66.
2.2.3. Complexes 1 and 2
A solution of ligand L (0.51 g, 1.7 mmol) in methanol (2 mL) was
added dropwise to a solution of Co(ClO4)2ꢂ6H2O (0.62 g, 1.7 mmol)
in methanol (2 mL). The reaction mixture was stirred at room tem-
perature for 4 h to give a pink precipitate. The solid (complex 1,
0.81 g, 80%) was collected by filtration, washed with methanol
and dried under vacuum. The product was recrystallized by diffu-
sion of diethyl ether into its acetonitrile solution to give crystals
suitable for X-ray crystallography. Anal. Calc. for complex 1 (C14-
H22Cl2CoN3O8S2ꢂ2H2O, FW = 590.3): C, 28.48; H, 4.44; N, 7.12.
Found: C, 27.94; H, 4.09; N, 6.60%.
Complex 2 was prepared similarly using NiCl2ꢂ6H2O (0.40 g,
1.7 mmol). The reaction was stirred at room temperature for 4 h
to give a clear solution before being concentrated. Any insoluble
solids were filtered and the filtrate was left in a refrigerator for a
few days to produce green crystals (0.75 g, 83%). Anal. Calc. for
complex 2 (C14H25N3OS2Cl2Niꢂ5H2O, FW = 535.1): C, 31.40; H,
6.54; N, 7.85. Found: C, 31.93; H, 6.51; N, 7.99%.
2.2.4. Complexes 4–6
A solution of ligand L0 (63 mg, 0.17 mmol) in methanol (2 mL)
was added dropwise to a solution of Co(ClO4)2ꢂ6H2O (0.62 g,
0.17 mol) in methanol (2 mL). The reaction was stirred at room
temperature for 4 h to give a precipitate which was collected by fil-
tration, washed with methanol and dried under vacuum. Recrystal-
lisation by diffusion of diethyl ether into an acetonitrile solution
produced crystals of complex 4 suitable for X-ray crystallography
Fig. 1. Molecular structures of the cations of complex 1 (top) and complex 2
(bottom). In all the crystallographic diagrams, hydrogen atoms have been omitted
for clarity and thermal ellipsoids are drawn at the 30% probability level.
before being dried with MgSO4. Removal of the solvent yielded a
colourless liquid (3.1 g, 89%). The product was used for the next
reaction without further purification.
(0.82 g, 75%). Anal. Calc. for complex
4 (C20H28N4O8S2Cl2Co,
Table 2
Selected bond lengths (Å) and angles (°) for complexes 1–3.
1
2
3 [23]
Co(1)–N(2) = 2.142(4)
Ni(1)–N(2) = 2.117(4)
Cu(1)–N(2) = 2.260(3)
Co(1)–N(1) = 2.057(4)
Ni(1)–N(1) = 2.063(4)
Cu(1)–N(1) = 1.992(3)
Co(1)–N(3) = 2.081(4)
Ni(1)–N(3) = 2.098(4)
Cu(1)–N(3) = 2.007(3)
Co(1)–S(1) = 2.479(2)
Ni(1)–S(1) = 2.4293(15)
Cu(1)–S(1) = 2.421(1)
Co(1)–S(2) = 2.481(2)
Ni(1)–O(1) = 2.088(4)
Cu(1)–S(2) = 2.447(1)
Co(1)–N(4) = 2.031(4)
N(1)–Ni(1)–O(1) = 90.68(17)
N(1)–Ni(1)–N(3) = 178.59(16)
O(1)–Ni(1)–N(3) = 90.73(17)
N(1)–Ni(1)–N(2) = 81.54(16)
O(1)–Ni(1)–N(2) = 172.22(16)
N(3)–Ni(1)–N(2) = 97.06(17)
N(1)–Ni(1)–S(1) = 95.78(3)
O(1)–Ni(1)–S(1) = 93.35(3)
N(3)–Ni(1)–S(1) = 84.14(3)
N(2)–Ni(1)–S(1) = 87.47(3)
S(1)a–Ni(1)–S(1) = 166.57(5)
Cu(1)–N(4) = 2.369(4)
N(4)–Co(1)–N(1) = 92.17(17)
N(1)–Co(1)–N(2) = 82.15(15)
N(3)–Co(1)–N(2) = 96.19(16)
N(4)–Co(1)–S(2) = 94.48(19)
N(1)–Co(1)–S(2) = 92.82(16)
N(3)–Co(1)–S(2) = 83.97(15)
N(2)–Co(1)–S(2) = 86.45(17)
N(4)–Co(1)–S(1) = 94.50(19)
N(1)–Co(1)–S(1) = 99.59(16)
N(3)–Co(1)–S(1) = 83.34(14)
N(2)–Co(1)–S(1) = 85.89(17)
N(4)–Co(1)–N(3) = 89.52(17)
N(1)–Cu(1)–N(4) = 93.9(1)
N(1)–Cu(1)–N(2) = 80.5(1)
N(3)–Cu(1)–N(2) = 98.3(1)
N(4)–Cu(1)–S(2) = 93.7(1)
N(1)–Cu(1)–S(2) = 96.88(8)
N(3)–Cu(1)–S(2) = 85.18(8)
N(2)–Cu(1)–S(2) = 85.24(8)
N(4)–Cu(1)–S(1) = 95.5(1)
N(1)–Cu(1)–S(1) = 92.59(8)
N(3)–Cu(1)–S(1) = 85.15(8)
N(2)–Cu(1)–S(1) = 86.52(8)
N(3)–Cu(1)–N(4) = 87.3(1)
a
Symmetry code: x, 1 – y, z.