The influence of substituents (R) at N 1 atom of thiophene-2-carbaldehyde thiosemicarbazones {(C 4H 3S)HC 2 N 3–N(H)–C 1( S)N 1HR} on bonding, nuclearity and H-bonded networks of copper(I) complexes
Role of substituents (R) at N 1 nitrogen of thiophene-2-carbaldehyde thiosemicarbazones {(C 4H 3S)HC 2 N 3–N(H)–C 1( S)N 1HR} on bonding and nuclearity of copper(I) halide complexes has been described. For R = Ph, X = I, a three coordinate monomer and its S-bridged dimer co-exist in the same unit ce...
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Published in | Inorganica Chimica Acta Vol. 362; no. 10; pp. 3547 - 3554 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
Elsevier B.V
01.08.2009
|
Subjects | |
Online Access | Get full text |
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Summary: | Role of substituents (R) at N
1 nitrogen of thiophene-2-carbaldehyde thiosemicarbazones {(C
4H
3S)HC
2
N
3–N(H)–C
1(
S)N
1HR} on bonding and nuclearity of copper(I) halide complexes has been described. For R
=
Ph, X
=
I, a three coordinate monomer and its S-bridged dimer co-exist in the same unit cell (
1).
The nuclearity, bonding and H-bonded networks of copper(I) halide complexes with thiophene-2-carbaldehyde thiosemicarbazones {(C
4H
3S)HC
2
N
3–N(H)–C
1(
S)N
1HR} are influenced by R substituents at N
1 atom. Thiophene-2-carbaldehyde-N
1-methyl thiosemicarbazone (HttscMe) or thiophene-2-carbaldehyde-N
1-ethyl thiosemicarbazone (HttscEt) have yielded halogen-bridged dinuclear complexes, [Cu
2(μ-X)
2(η
1-S-Htsc)
2(Ph
3P)
2] (Htsc, X: HttscMe, I,
1; Br,
2; Cl,
3; HttscEt, I,
4; Br,
5; Cl,
6), while thiophene-2-carbaldehyde-N
1-phenyl thiosemicarbazone (HttscPh) has yielded mononuclear complexes, [CuX(η
1-S-HttscPh)
2] (X, I,
7a; Br
8; Cl,
9) and a sulfur bridged dinuclear complex, [Cu
2(μ-S-HttscPh)
2(η
1-S-HttscPh)
2I
2]
7b co-existing with
7a in the same unit cell. These results are in contrast to S-bridged dimers [Cu
2(μ-S-Httsc)
2(η
1-Br)
2(Ph
3P)
2]
·
2H
2O and [Cu
2(μ-S-Httsc)
2(η
1-Cl)
2(Ph
3P)
2]
·
2CH
3CN obtained for R
=
H and X
=
Cl, Br (Httsc
=
thiophene-2-carbaldehyde thiosemicarbazone) as reported earlier. The intermolecular CH
Ph⋯π interaction in
1–
3 (2.797
Å,
1; 3.264
Å,
2; 3.257
Å,
3) have formed linear polymers, whereas the CH
Ph⋯X and N
3⋯HCH interactions in
4–
6 (2.791, 2.69
Å,
5; 2.776, 2.745
Å,
6, respectively) have led to the formation of H-bonded 2D polymer. The PhN
1H⋯π, interactions (2.547
Å,
8, 2.599
Å,
9) have formed H-bonded dimers only. The Cu⋯Cu separations are 3.221–3.404
Å (
1–
6). |
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ISSN: | 0020-1693 1873-3255 |
DOI: | 10.1016/j.ica.2009.03.043 |