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Journal ArticleDOI

2D polymeric cadmium(II) complexes containing 1,3-imidazolidine-2-thione (Imt) ligand, [Cd(Imt)(H2O)2(SO4)]n and [Cd(Imt)2(N3)2]n

15 Mar 2018-Journal of Molecular Structure (Elsevier)-Vol. 1156, pp 235-242

AbstractThe present study aims at preparing and carrying out the structural investigation of two polymeric cadmium(II) complexes of imidazolidine-2-thione (Imt) based on sulfate or azide ions, [Cd(Imt)(H2O)2(SO4)]n (1) and [Cd(Imt)2(N3)2]n (2). The structures of the complexes were determined by single crystal X-ray analysis. Both compounds, 1 and 2 crystallize in the form of 2D coordination polymers and the cadmium(II) ion is six-coordinate having a distorted octahedral geometry in each compound. In 1, the metal ion is bonded to one sulfur atom of Imt and five oxygen atoms with two from water and three of bridging sulfate ions. In 2, the cadmium coordination sphere is completed by two Imt molecules binding through the sulfur atoms and four nitrogen atoms of bridging azide ions. The crystal structures are stabilized by intra and intermolecular hydrogen bonding interactions. The complexes were also characterized by IR and NMR spectroscopy and the spectroscopic data is consistent with the binding of the ligands.

Topics: Octahedral molecular geometry (54%), Coordination sphere (52%), Ligand (51%), Molecule (51%), Azide (51%)

Summary (1 min read)

1. Introduction

  • Cadmium(II) is known to form a wide variety of 1:1 to 1:4 complexes with thiones (L), with the structural arrangements generally based on tetrahedl and octahedral coordination environments.
  • (MeImt = N-methylimidazolidine-2-thione) usually exist in the polymeric form.

2. Experimental

  • 1. Materials M AN US CR IP T AC CE PT ED 4 Cadmium sulfate (CdSO4 .8/3H2O) and NaN3 were obtained from Merck Chemical Company, Germany.
  • Imidazolidine-2-thione was prepared according to the method reported in the literature [36].
  • As a result, a white crystalline product was obtained, that was washed with methanol and dried.
  • Crystal data and details of the data collection are summarized in Table 1.

3. Results and Discussion

  • 1. X-ray Structure Studies Selected bond angles and distances are given in Table 1.
  • The azide anion forms an end-to-end bridge between two cadmium ions resulting into a 2D network based on a 16-membered ring motif [CdN3]4 .

4. Conclusion

  • The X-ray structures of the complexes show that both of them exist in the form of two dimensional polymers with each cadmium atom being octahedrally coordinated.
  • The polymers are assembled through triplybridging sulfate and doubly-bridging, µ(1,3) azide ions in case of 1 and 2 respectively.
  • Acknowledgement M AN US CR IP T AC CE PT ED 14 The Deanship of Scientific Research, Prince Sattam bin Abdulaziz University, Al-Kharj, Saudi Arabia is gratefully acknowledged for supporting this work through Project No. 2016/01/6822.
  • Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, e-mail: deposit@ccdc.cam.ac.uk or www.ccdc.cam.ac.uk.

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2D polymeric cadmium(II) complexes containing
1,3-imidazolidine-2-thione (Imt) ligand,
[Cd(Imt)(H2O)2(SO4)]n and [Cd(Imt)2(N3)2]n
R. Mahmood, S. Ahmad, M. Fettouhi, T. Roisnel, M.A. Gilani, K. Mehmood,
G. Murtaza, A.A. Isab
To cite this version:
R. Mahmood, S. Ahmad, M. Fettouhi, T. Roisnel, M.A. Gilani, et al.. 2D polymeric cad-
mium(II) complexes containing 1,3-imidazolidine-2-thione (Imt) ligand, [Cd(Imt)(H2O)2(SO4)]n
and [Cd(Imt)2(N3)2]n. Journal of Molecular Structure, Elsevier, 2018, 1156, pp.235-242.
�10.1016/j.molstruc.2017.11.067�. �hal-01671609�

MANUS CRIP T
ACCEP TED
ACCEPTED MANUSCRIPT
1
2D Polymeric cadmium(II) complexes containing 1,3-imidazolidine-2-thione
(Imt) ligand, [Cd(Imt)(H
2
O)
2
(SO
4
)]
n
and [Cd(Imt)
2
(N
3
)
2
]
n
Rashid Mahmood
a*
, Saeed Ahmad
b*
, Mohammed Fettouhi
c
, Thierry Roisnel
d
,
Mazhar Amjad Gilani
e
, Kashif Mehmood
f
, Ghulam Murtaza
f
, Anvarhusein A. Isab
c
a
Department of Chemistry, University of Azad Jammu and Kashmir, Chela Campus,
Muzaffarabad, Pakistan
b
Department of Chemistry, College of Sciences and Humanities, Prince Sattam bin Abdulaziz
University, Al-Kharj 11942, Saudi Arabia
c
Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261,
Saudi Arabia
d
Centre de Diffractométrie X (CDIFX), Institut des Sciences Chimiques de Rennes UMR6226
CNRS - Université de Rennes 1 35042 Rennes Cedex, France
e
Department of Chemistry, COMSATS Institute of Information Technology, Lahore, Pakistan
f
Department of Chemistry, University of Engineering and Technology, Lahore 54890, Pakistan
*Corresponding authors (E-mail: rashid_meh786@yahoo.com, saeed_a786@hotmail.com)

MANUS CRIP T
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ACCEPTED MANUSCRIPT
2
Abstract
The present study aims at preparing and carrying out the structural investigation of two
polymeric cadmium(II) complexes of imidazolidine-2-thione (Imt) based on sulfate or azide ions,
[Cd(Imt)(H
2
O)
2
(SO
4
)]
n
(1) and [Cd(Imt)
2
(N
3
)
2
]
n
(2). The structures of the complexes were
determined by single crystal X-ray analysis. Both compounds, 1 and 2 crystallize in the form of
2D coordination polymers and the cadmium(II) ion is six-coordinate having a distorted
octahedral geometry in each compound. In 1, the metal ion is bonded to one sulfur atom of Imt
and five oxygen atoms with two from water and three of bridging sulfate ions. In 2, the cadmium
coordination sphere is completed by two Imt molecules binding through the sulfur atoms and
four nitrogen atoms of bridging azide ions. The crystal structures are stabilized by intra and
intermolecular hydrogen bonding interactions. The complexes were also characterized by IR and
NMR spectroscopy and the spectroscopic data is consistent with the binding of the ligands.
Keywords: Cadmium; Imidazolidine-2-thione; Sulfate; Azide; Crystal structure

MANUS CRIP T
ACCEP TED
ACCEPTED MANUSCRIPT

MANUS CRIP T
ACCEP TED
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3
1. Introduction
Cadmium(II) is known to form a wide variety of 1:1 to 1:4 complexes with thiones (L), with the
structural arrangements generally based on tetrahedral and octahedral coordination
environments. The 1:1 complexes [1-4] for example, [Cd(Tu)(H
2
O)
2
(SO
4
)]
n
[2] and
[Cd(MeImt)(SeCN)
2
]
n
[4] (MeImt = N-methylimidazolidine-2-thione) usually exist in the
polymeric form. The structures of the 1:2 complexes such as, [Cd(Tu)
2
X
2
] [5], [Cd(Dmtu)
2
X
2
]
[6,7], [Cd(Tmtu)
2
X
2
] [8-10] or [Cd(Imt)
2
X
2
] [11,12] (X = Cl, Br, I) are the most common and
often consist of discrete monomeric molecules with a tetrahedrally [5-21] (or octahedrally
[22,23]) coordinated Cd(II) ion. In some cases, polymeric species are formed through bridging
sulfur or nitrogen atoms [21, 24-29], e.g., [Cd(Metu)
2
(SCN)
2
]
n
[24] and [Cd(Imt)
2
(SCN)
2
]
n
[25].
The 1:3 compounds are rare. The crystal structure of [Cd(Tu)
3
(SO
4
)] shows that the molecule is a
dimer, and the coordination around the metal atom is intermediate between square pyramidal and
trigonal bipyramidal [30]. Another such compound is known in the form of a co-crystal of
[Cd(Tu)
2
(H
2
O)
4
]SO
4
and [Cd(Tu)
3
(H
2
O)
3
]SO
4
[31]. The complexes with a Cd:thione ratio of 1:4
may be ionic or nonionic. In the ionic complexes like [Cd(2-mercaptopyridine)
4
](NO
3
)
2
[32] or
[Cd(Diaz)
4
]SO
4
(Diaz = 1,3-diazinane-2-thione) [33], the Cd(II) ion possesses a tetrahedral
environment. The molecular species for instance, [Cd(Diaz)
4
Cl
2
] [34] display a distorted
octahedral geometry around the metal ion [29,34,35]. These structural studies show that
thioureas or thiones coordinate to cadmium(II) via the sulfur atom. We have reported earlier the
crystal structures of several cadmium(II) complexes of heterocyclic thiones [4,5-10,14-
17,23,24,33-35]. To investigate further about the structural aspects of such complexes, we report
in this work the spectroscopic data and the X-ray structures of two new 2D polymeric
cadmium(II) complexes of imidazolidine-2-thione (Imt), [Cd(Imt)(H
2
O)
2
(SO
4
)]
n
(1) and
[Cd(Imt)
2
(N
3
)
2
]
n
(2). The main goal of the present study is to exploit the effect of binding
flexibility of sulfate and azide ions for the preparation of Cd-Imt polymers.
2. Experimental
2.1. Materials

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In this paper, Mahmood et al. reported the crystal structures of new 2D polymeric cadmium ( II ) complexes containing 1,3imidazolidine-2-thione ( Imt ) ligand.