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Self-assembled Transition Metal Coordination Frameworks of ...

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Zinc(II) & C admium(ll) complexes<br />

Table 6.4. Relevant bond lengths (A ) <strong>of</strong> molecular square grid complex 29<br />

26(1)-N(2)<br />

Zn(l)—N(23)<br />

Zfl( 1 )-0( 1)<br />

Zfl(1)—0(4)<br />

Zn(l)—N(l)<br />

26(1)-N(24)<br />

26(2)-N(8)<br />

Zn(2)-—N(5)<br />

26(2)-0(2)<br />

26(2)-N(7)<br />

26(2)-N(6)<br />

Zfl(2)-0( 1)<br />

Zn(3)—N(14)<br />

26(3)-N(1 1)<br />

Zfl(3)—0(3)<br />

Zfl(3)-0(2)<br />

26(3)-N(12)<br />

Zn(3)—N(l3)<br />

26(4)-N(20)<br />

Zn(4)—N(l7)<br />

211(4)-1\1(18)<br />

211(4)-N(19)<br />

2.084(3)<br />

2.093(3)<br />

2.128(3)<br />

2.139(3)<br />

2.167(3)<br />

2.191(3)<br />

2.063(3)<br />

2.094(3)<br />

2.147(3)<br />

2.151(3)<br />

2.164(4)<br />

2.186(3)<br />

2.080(3)<br />

2.107(3)<br />

2.125(3)<br />

2.141(3)<br />

2.153(3)<br />

2.178(4)<br />

2.044(3)<br />

2.078(3)<br />

2.141(4)<br />

2.141(3)<br />

Zr1(4)-0(4)<br />

ZI1(4)-0(3)<br />

0(1)-C(13)<br />

0(2)—€(33)<br />

O(3)—C(63)<br />

0(4)—C(33)<br />

N(2)—N(3)<br />

N(4)—N(5)<br />

N(4)—C(l3)<br />

N(3)—C(l3)<br />

N(3)—N(9)<br />

N(lO)—N(l 1)<br />

C(38)—N(9)<br />

C(38)—N(l0)<br />

N(l4)—N(15)<br />

N(l6)—N(l7)<br />

C(63)—N(l5)<br />

C(63)—N(l6)<br />

N(20)—N(2l)<br />

N(22)—N(23)<br />

C(88)—N(2l)<br />

C(88)—N(22)<br />

2.163(3)<br />

2.164(3)<br />

1.288(5)<br />

1.286(5)<br />

1.271(4)<br />

1.287(5)<br />

1.376(5)<br />

1.360(5)<br />

1.364(5)<br />

1.338(5)<br />

1.377(5)<br />

1.349(5)<br />

1.314(5)<br />

1.386(5)<br />

1.383(5)<br />

1.354(5)<br />

1.337(5)<br />

1.382(5)<br />

1.370(5)<br />

1.343(5)<br />

1.328(5)<br />

1.375(5)<br />

III the tetranuclear cation [Zn(I-IL5)]44+, the ligands are coordinated in the<br />

monoanionic form by deprotonation afier enolization. The hydrogen atoms on N(3),<br />

N(9), N(l5) and N(2l) are deprotonated on coordination, while their counterparts<br />

retained. This is confirmed by the C(13)—O( 1) bond distance <strong>of</strong> 2.288(5) A, and a<br />

decrease <strong>of</strong> 0.026(7) A for C(13)—N(3) bond compared to C(l3)—N(4) bond, for<br />

example. Two (HL5)' ligands bind to a Zn(II) in the mer configuration (with pairs <strong>of</strong> O<br />

atoms and pyridyl N atoms each bearing a cis relationship, whereas the azomethine N<br />

atoms are trans to each other) to form distorted octahedral metal centers, similar to<br />

sulfur coordinated Zn(II) tetramer <strong>of</strong> bis(2-acetylpyridine) thiocarbohydrazone [13]<br />

but different from the cis-mer configuration seen in mononuclear Zn(II)<br />

semicarbazone complex [8]. The Zn—Npy bond lengths are greater compared to that <strong>of</strong><br />

Zn—N,z0m¢mim indicating the strength <strong>of</strong> latter bonds. The Zn—O distances are<br />

259

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