Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2
Crystallization of Cd[S2CN(iPr)CH2CH2OH]2 from ethanol yields the coordination polymer [{Cd[S2CN(iPr) CH2CH2OH]2}·EtOH]∞ (1) within 3 h. When the solution is allowed to stand for another hour, the needles begin to dissolve and prisms emerge of the supramolecular isomer (SI), binuclear {Cd[S2CN(...
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De Gruyter
2016
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| Online Access: | http://eprints.sunway.edu.my/617/ http://eprints.sunway.edu.my/617/1/ZKrist.%20231%202016%20113_Deposited.pdf |
| _version_ | 1848801861492015104 |
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| author | Tan, Yee Seng * Siti Nadiah Abdul Halim, Tiekink, Edward R. T. * |
| author_facet | Tan, Yee Seng * Siti Nadiah Abdul Halim, Tiekink, Edward R. T. * |
| author_sort | Tan, Yee Seng * |
| building | SU Institutional Repository |
| collection | Online Access |
| description | Crystallization of Cd[S2CN(iPr)CH2CH2OH]2 from
ethanol yields the coordination polymer [{Cd[S2CN(iPr)
CH2CH2OH]2}·EtOH]∞ (1) within 3 h. When the solution is
allowed to stand for another hour, the needles begin to
dissolve and prisms emerge of the supramolecular isomer
(SI), binuclear {Cd[S2CN(iPr)CH2CH2OH]2}2·2EtOH (2).
These have been fully characterized spectroscopically
and by X-ray crystallography. Polymeric 1 has 2-fold symmetry
and features dithiocarbamate ligands coordinating
two octahedral Cd atoms in a μ2κ2-tridentate mode.
Binuclear 2 is centrosymmetric with two ligands being
μ2κ2-tridentate as for 1 but the other two being κ2-chelating
leading to square pyramidal geometries. The conversion
of the kinetic crystallization product, 1, to thermodynamic
2 is irreversible but transformations mediated by recrystallization
(ethanol and acetonitrile) to related literature
SI species, namely coordination polymer [{Cd[S2CN(iPr)
CH2CH2OH]2}3·MeCN]∞ and binuclear {Cd[S2CN(iPr)CH2CH
2
OH]2}2·2H2O·2MeCN, are demonstrated, some of which
are reversible. Three other crystallization outcomes are
described whereby crystal structures were obtained for
the 1:2 co-crystal {Cd[S2CN(iPr)CH2CH2OH]2}2:2[3-(propan-
2-yl)-1,3-oxazolidine-2-thione] (3), the salt co-crystal [iPr
NH2(CH2CH2OH)]4[SO4]2{Cd[S2CN(iPr)CH2CH2OH]2}2 (4) and
the salt [iPrNH2(CH2CH2OH)]{Cd[S2CN(iPr)CH2CH2OH]3} (5).
These arise as a result of decomposition/oxidation of the
dithiocarbamate ligands. In each of 3 and 4 the binuclear
{Cd[S2CN(iPr)CH2CH2OH]2}2 SI, as in 2, is observed strongly
suggesting a thermodynamic preference for this form. |
| first_indexed | 2025-11-14T21:14:11Z |
| format | Article |
| id | sunway-617 |
| institution | Sunway University |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T21:14:11Z |
| publishDate | 2016 |
| publisher | De Gruyter |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | sunway-6172020-10-07T09:59:35Z http://eprints.sunway.edu.my/617/ Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2 Tan, Yee Seng * Siti Nadiah Abdul Halim, Tiekink, Edward R. T. * QD Chemistry Crystallization of Cd[S2CN(iPr)CH2CH2OH]2 from ethanol yields the coordination polymer [{Cd[S2CN(iPr) CH2CH2OH]2}·EtOH]∞ (1) within 3 h. When the solution is allowed to stand for another hour, the needles begin to dissolve and prisms emerge of the supramolecular isomer (SI), binuclear {Cd[S2CN(iPr)CH2CH2OH]2}2·2EtOH (2). These have been fully characterized spectroscopically and by X-ray crystallography. Polymeric 1 has 2-fold symmetry and features dithiocarbamate ligands coordinating two octahedral Cd atoms in a μ2κ2-tridentate mode. Binuclear 2 is centrosymmetric with two ligands being μ2κ2-tridentate as for 1 but the other two being κ2-chelating leading to square pyramidal geometries. The conversion of the kinetic crystallization product, 1, to thermodynamic 2 is irreversible but transformations mediated by recrystallization (ethanol and acetonitrile) to related literature SI species, namely coordination polymer [{Cd[S2CN(iPr) CH2CH2OH]2}3·MeCN]∞ and binuclear {Cd[S2CN(iPr)CH2CH 2 OH]2}2·2H2O·2MeCN, are demonstrated, some of which are reversible. Three other crystallization outcomes are described whereby crystal structures were obtained for the 1:2 co-crystal {Cd[S2CN(iPr)CH2CH2OH]2}2:2[3-(propan- 2-yl)-1,3-oxazolidine-2-thione] (3), the salt co-crystal [iPr NH2(CH2CH2OH)]4[SO4]2{Cd[S2CN(iPr)CH2CH2OH]2}2 (4) and the salt [iPrNH2(CH2CH2OH)]{Cd[S2CN(iPr)CH2CH2OH]3} (5). These arise as a result of decomposition/oxidation of the dithiocarbamate ligands. In each of 3 and 4 the binuclear {Cd[S2CN(iPr)CH2CH2OH]2}2 SI, as in 2, is observed strongly suggesting a thermodynamic preference for this form. De Gruyter 2016 Article PeerReviewed text en http://eprints.sunway.edu.my/617/1/ZKrist.%20231%202016%20113_Deposited.pdf Tan, Yee Seng * and Siti Nadiah Abdul Halim, and Tiekink, Edward R. T. * (2016) Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2. Zeitschrift für Kristallographie - Crystalline Materials, 231 (2). pp. 113-126. ISSN 2194-4946 http://dx.doi.org/10.1515/zkri-2015-1889 doi:10.1515/zkri-2015-1889 |
| spellingShingle | QD Chemistry Tan, Yee Seng * Siti Nadiah Abdul Halim, Tiekink, Edward R. T. * Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2 |
| title | Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2 |
| title_full | Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2 |
| title_fullStr | Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2 |
| title_full_unstemmed | Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2 |
| title_short | Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2 |
| title_sort | exploring the crystallization landscape of cadmium bis(n-hydroxyethyl, n-isopropyldithiocarbamate), cd[s2cn(ipr)ch2ch2oh]2 |
| topic | QD Chemistry |
| url | http://eprints.sunway.edu.my/617/ http://eprints.sunway.edu.my/617/ http://eprints.sunway.edu.my/617/ http://eprints.sunway.edu.my/617/1/ZKrist.%20231%202016%20113_Deposited.pdf |