Self-assembled Transition Metal Coordination Frameworks of ...

Table 3.10. Selected bond lengths (A) and bond angles (°) of [Ni(L8)2] (6a)
Ni(l)—N(6)
Ni(l)—N(2)
Ni(l)—N(l)
Ni(l)—N(5)
Ni(l)—S(2)
Ni(1)—S(l)
s(1)-c(13)
5(2)—¢(30)
C(6)—N(2)
C(23)—N(6)
N(2)—N(3)
N(6)—N(7)
N(3)—C(l3)
N(7)—C(30)
2.030(5)
2.035(5)
2.123(5)
2.135(6)
2.4229(18)
2.4349(18)
1.729(6)
1.713(6)
1.301(8)
1.331(8)
1.353(7)
1.344(7)
1.334(8)
1.371(8)
N(6)—Ni(1)—N(2)
N(6)—Ni(1)—N(l)
N(2)—Ni(1)—N(l)
N(6)—Ni(l)—N(5)
N(2)—Ni(1)—N(5)
N(1)—Ni(l)—N(5)
N(6)—Ni(1)—S(2)
N(2)—Ni(l)—S(2)
N(l)—Ni(l)—S(2)
N(5)—Ni(1)—S(2)
N(6)—Ni(1)—S(l)
N(2)—Ni(l)—S(l)
N(l)—Ni(l)—S(l)
N(5)—Ni(l)—S(l)
S(2)—Ni(l )-s(1)
165.8(2)
92.40(19)
78.12 (10)
78.86(19)
007(2)
91.1(2)
70.96(14)
110.38(17)
90.76(15)
158.79(14)
109.03(14)
80.60(15)
158.54(14)
91.96(15)
9403(6)
Ni(II) complexes
In compound 5' 2‘/zH2O, two molecules of the neutral ligand HL7 are
coordinated in the meridional fashion [45] using pairs of cis quinolyl nitrogen, trans
azomethine nitrogen and cis thione sulfur atoms, while in compound 6a, the Ni(II)
center is coordinated in a meridional fashion using pairs of cis pyridyl nitrogen, trans
azomethine nitrogen and cis thiolate sulfur atoms [46,47] by two monoanionic
ligands. This results into two bicyclic chelate systems. The thione coordination as
found in 5- 2'/2H2Q is rare for thiosemicarbazones. In 5- 2‘/zH2O, the bicyclic chelate
systems Ni(l), S(l), C(11), N(3), N(2), C(10), C(9), N(l) and Ni(l), S(2), C(26),
N(7), N(6), C(25), C(24), N(5) are slightly deviated from planarity as evidenced by
the maximum deviation of 0.183(6) A for C(9) and -0.121(5) A for N(7) respectively
from their respective mean planes. However in 6a, the bicyclic chelate system Ni(l),
S(l), C(13), N(3), N(2), C(6), C(5), N(l) and Ni(l), S(2), C(30), N(7), N(6), C(23),
C(22), N(5) are approximately planar with a maximum mean plane deviation of
0.100(5) A for N(l) and -0.070(6) A for C(23) respectively. The dihedral angle
formed by the mean planes of the bicyclic chelate systems of each of the ligands is
83.50(10)° in 5' 2‘/zH2O and 86.98(ll)° in 6a. In compound 5- 2‘/zl-I20, the trans
109