1 : 1 complexes of silver(I) thiocyanate with (substituted) thiourea ligands

G.A. Bowmaker, C. Pakawatchai, S. Saithong, Brian Skelton, Allan White

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Syntheses and single crystal X-ray structural characterizations, together with infrared spectroscopic studies, are recorded for 1:1 adducts of silver(I) thiocyanate with thiourea (‘tu’) and N,N′-diethylthiourea (‘detu’≡ (EtNH)2CS). The two complexes display novel and different polymeric forms. That formed with tu is a double-stranded form, comprising a pair of Ag(μ-S-tu)Ag(μ-… strands linked by pairs of μ-SCN anions, the whole array having quasi-2 symmetry about the polymer axis. The detu adduct takes the ionic form [Ag(detu)2](∞|∞)[Ag(SCN)2](∞|∞), both cation and anion being one-dimensional polymers lying in parallel, and both of the form …Ag(μ-S-L)2Ag(μ-… (L = SCN or detu), disposed about crystallographic axes. Redeterminations of the structures of AgSCN:tu, etu (1:2) (‘etu’ = ethylenethiourea, (CH2NH)2CS)) with quasi-trigonal silver atom environments (the etu adduct the more closely so), are also recorded as a basis for an IR spectroscopic characterization of the [(NCS)Ag(S-xtu)2] array. A mechanochemical/infrared study of the AgSCN:etu (1:1) system showed that no 1:1 complex exists in this case, the product being a mixture of the 1:2 complex and a novel 1:0.5 complex. The latter complex was prepared both mechanochemically and from solution, and characterized by infrared spectroscopy. Diagnostic ligand and metal–ligand bands in the IR and far-IR spectra are assigned for all of the complexes studied and for AgSCN and are discussed in relation to the structures of the complexes. The double degeneracy of the δ(SCN) mode of the coordinated thiocyanate is lifted and the first overtone of this band at gains intensity in the IR in the 1:1 complexes, behaviour that is not observed for the terminal bonding mode that is present in the 1:2 complexes.
Original languageEnglish
Pages (from-to)2588-2598
JournalDalton Transactions
Volume2009
Issue number14
DOIs
Publication statusPublished - 2009

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Thiourea
Silver
Ligands
Anions
Polymers
Ethylenethiourea
Infrared radiation
Cations
Infrared spectroscopy
Single crystals
X rays
Atoms
thiocyanate

Cite this

Bowmaker, G.A. ; Pakawatchai, C. ; Saithong, S. ; Skelton, Brian ; White, Allan. / 1 : 1 complexes of silver(I) thiocyanate with (substituted) thiourea ligands. In: Dalton Transactions. 2009 ; Vol. 2009, No. 14. pp. 2588-2598.
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title = "1 : 1 complexes of silver(I) thiocyanate with (substituted) thiourea ligands",
abstract = "Syntheses and single crystal X-ray structural characterizations, together with infrared spectroscopic studies, are recorded for 1:1 adducts of silver(I) thiocyanate with thiourea (‘tu’) and N,N′-diethylthiourea (‘detu’≡ (EtNH)2CS). The two complexes display novel and different polymeric forms. That formed with tu is a double-stranded form, comprising a pair of Ag(μ-S-tu)Ag(μ-… strands linked by pairs of μ-SCN anions, the whole array having quasi-2 symmetry about the polymer axis. The detu adduct takes the ionic form [Ag(detu)2](∞|∞)[Ag(SCN)2](∞|∞), both cation and anion being one-dimensional polymers lying in parallel, and both of the form …Ag(μ-S-L)2Ag(μ-… (L = SCN or detu), disposed about crystallographic axes. Redeterminations of the structures of AgSCN:tu, etu (1:2) (‘etu’ = ethylenethiourea, (CH2NH)2CS)) with quasi-trigonal silver atom environments (the etu adduct the more closely so), are also recorded as a basis for an IR spectroscopic characterization of the [(NCS)Ag(S-xtu)2] array. A mechanochemical/infrared study of the AgSCN:etu (1:1) system showed that no 1:1 complex exists in this case, the product being a mixture of the 1:2 complex and a novel 1:0.5 complex. The latter complex was prepared both mechanochemically and from solution, and characterized by infrared spectroscopy. Diagnostic ligand and metal–ligand bands in the IR and far-IR spectra are assigned for all of the complexes studied and for AgSCN and are discussed in relation to the structures of the complexes. The double degeneracy of the δ(SCN) mode of the coordinated thiocyanate is lifted and the first overtone of this band at gains intensity in the IR in the 1:1 complexes, behaviour that is not observed for the terminal bonding mode that is present in the 1:2 complexes.",
author = "G.A. Bowmaker and C. Pakawatchai and S. Saithong and Brian Skelton and Allan White",
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Bowmaker, GA, Pakawatchai, C, Saithong, S, Skelton, B & White, A 2009, '1 : 1 complexes of silver(I) thiocyanate with (substituted) thiourea ligands' Dalton Transactions, vol. 2009, no. 14, pp. 2588-2598. https://doi.org/10.1039/b819096h

1 : 1 complexes of silver(I) thiocyanate with (substituted) thiourea ligands. / Bowmaker, G.A.; Pakawatchai, C.; Saithong, S.; Skelton, Brian; White, Allan.

In: Dalton Transactions, Vol. 2009, No. 14, 2009, p. 2588-2598.

Research output: Contribution to journalArticle

TY - JOUR

T1 - 1 : 1 complexes of silver(I) thiocyanate with (substituted) thiourea ligands

AU - Bowmaker, G.A.

AU - Pakawatchai, C.

AU - Saithong, S.

AU - Skelton, Brian

AU - White, Allan

PY - 2009

Y1 - 2009

N2 - Syntheses and single crystal X-ray structural characterizations, together with infrared spectroscopic studies, are recorded for 1:1 adducts of silver(I) thiocyanate with thiourea (‘tu’) and N,N′-diethylthiourea (‘detu’≡ (EtNH)2CS). The two complexes display novel and different polymeric forms. That formed with tu is a double-stranded form, comprising a pair of Ag(μ-S-tu)Ag(μ-… strands linked by pairs of μ-SCN anions, the whole array having quasi-2 symmetry about the polymer axis. The detu adduct takes the ionic form [Ag(detu)2](∞|∞)[Ag(SCN)2](∞|∞), both cation and anion being one-dimensional polymers lying in parallel, and both of the form …Ag(μ-S-L)2Ag(μ-… (L = SCN or detu), disposed about crystallographic axes. Redeterminations of the structures of AgSCN:tu, etu (1:2) (‘etu’ = ethylenethiourea, (CH2NH)2CS)) with quasi-trigonal silver atom environments (the etu adduct the more closely so), are also recorded as a basis for an IR spectroscopic characterization of the [(NCS)Ag(S-xtu)2] array. A mechanochemical/infrared study of the AgSCN:etu (1:1) system showed that no 1:1 complex exists in this case, the product being a mixture of the 1:2 complex and a novel 1:0.5 complex. The latter complex was prepared both mechanochemically and from solution, and characterized by infrared spectroscopy. Diagnostic ligand and metal–ligand bands in the IR and far-IR spectra are assigned for all of the complexes studied and for AgSCN and are discussed in relation to the structures of the complexes. The double degeneracy of the δ(SCN) mode of the coordinated thiocyanate is lifted and the first overtone of this band at gains intensity in the IR in the 1:1 complexes, behaviour that is not observed for the terminal bonding mode that is present in the 1:2 complexes.

AB - Syntheses and single crystal X-ray structural characterizations, together with infrared spectroscopic studies, are recorded for 1:1 adducts of silver(I) thiocyanate with thiourea (‘tu’) and N,N′-diethylthiourea (‘detu’≡ (EtNH)2CS). The two complexes display novel and different polymeric forms. That formed with tu is a double-stranded form, comprising a pair of Ag(μ-S-tu)Ag(μ-… strands linked by pairs of μ-SCN anions, the whole array having quasi-2 symmetry about the polymer axis. The detu adduct takes the ionic form [Ag(detu)2](∞|∞)[Ag(SCN)2](∞|∞), both cation and anion being one-dimensional polymers lying in parallel, and both of the form …Ag(μ-S-L)2Ag(μ-… (L = SCN or detu), disposed about crystallographic axes. Redeterminations of the structures of AgSCN:tu, etu (1:2) (‘etu’ = ethylenethiourea, (CH2NH)2CS)) with quasi-trigonal silver atom environments (the etu adduct the more closely so), are also recorded as a basis for an IR spectroscopic characterization of the [(NCS)Ag(S-xtu)2] array. A mechanochemical/infrared study of the AgSCN:etu (1:1) system showed that no 1:1 complex exists in this case, the product being a mixture of the 1:2 complex and a novel 1:0.5 complex. The latter complex was prepared both mechanochemically and from solution, and characterized by infrared spectroscopy. Diagnostic ligand and metal–ligand bands in the IR and far-IR spectra are assigned for all of the complexes studied and for AgSCN and are discussed in relation to the structures of the complexes. The double degeneracy of the δ(SCN) mode of the coordinated thiocyanate is lifted and the first overtone of this band at gains intensity in the IR in the 1:1 complexes, behaviour that is not observed for the terminal bonding mode that is present in the 1:2 complexes.

U2 - 10.1039/b819096h

DO - 10.1039/b819096h

M3 - Article

VL - 2009

SP - 2588

EP - 2598

JO - Dalton Transactions: the international journal for inorganic, organometallic and bioinorganic chemistry

JF - Dalton Transactions: the international journal for inorganic, organometallic and bioinorganic chemistry

SN - 1477-9226

IS - 14

ER -