Synthesis and characterization of three new Cd(II) coordination polymers with bidentate flexible ligands: Formation of 3D and 1D structures

Article abstract of DOI:10.1016/j.molstruc.2018.05.054

Three new coordination polymers of {[Cd(bib)₃](ClO₄)₂}_n (1), [Cd(μ₂-bip)₂(N₃)₂]_n (2) and [Cd(μ-bib^Me)Cl₂]_n (3) were prepared by using the neutral N-donor ligands 1,4-bis(imidazolyl)butane (bib), 1,3-bis(imidazolyl)propane (bip) and 1,4-bis(2-methylimidazolyl)butane (bib^Me) and CdX₂ (X = ClO₄ ^?, N₃ ^? and Cl^?). The results of the X-ray measurements demonstrate that in the crystal structure of 1 and 2 the cadmium(II) ion adopts CdN₆ octahedral geometry while, in the structure of 3, the metal ion forms CdN₂Cl₂ tetrahedral geometry. In compound 1, six bib ligands are coordinated to one central cadmium(II) to form an open 3D 2-fold interpenetrating framework of the α-polonium (pcu) type topology, while in compound 2 and 3 the N₃ ^? or Cl^? groups are terminally bonded to the metal center and each linker compound (bip or bib^Me) acts as bridging ligand connecting two metal ions to form a one-dimensional zig-zag chain. The adjacent 1D chains of complex 2 and 3 are further extended into a non-covalent 2D network structure by C–H?N and C–H?Cl intermolecular hydrogen bonds, respectively. The complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction.

Full text of DOI:10.1016/j.molstruc.2018.05.054

Accepted Manuscript
Synthesis and characterization of three new Cd(II) coordination polymers with
bidentate flexible ligands: Formation of 3D and 1D structures
Mehdi Khalaj, Arash Lalegani, Jafar Akbari, Majid Ghazanfarpour-Darjani, Krzysztof
Lyczko, Janusz Lipkowski
PII:
S0022-2860(18)30620-3
10.1016/j.molstruc.2018.05.054
MOLSTR 25227
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 22 January 2018
Revised Date: 19 April 2018
Accepted Date: 15 May 2018
Please cite this article as: M. Khalaj, A. Lalegani, J. Akbari, M. Ghazanfarpour-Darjani, K. Lyczko, J.
Lipkowski, Synthesis and characterization of three new Cd(II) coordination polymers with bidentate
flexible ligands: Formation of 3D and 1D structures, Journal of Molecular Structure (2018), doi: 10.1016/
j.molstruc.2018.05.054.
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Synthesis and characterization of three new Cd(II) coordination
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polymers with bidentate flexible ligands: Formation of 3D and 1D structures
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Mehdi Khalaja *, Arash Lalegania, Jafar Akbaria,Majid Ghazanfarpour-Darjania
Krzysztof Lyczkob and Janusz Lipkowskic
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aYoung Researchers and Elite Club, Buinzahra Branch, Islamic Azad University, Buinzahra,
Iran
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bInstitute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland
cCardinal Stefan Wyszynski University in Warsaw, Woycickiego 1/3, 01-238 Warsaw, Poland
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*
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E-mail: khalaj_mehdi@yahoo.com
Tel.: +98 2834220838; Fax: +98 2834226118
Abstract
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Three new coordination polymers of {[Cd(bib)3](ClO4)2}n (1), [Cd(µ2-bip)2(N3)2]n (2) and
[Cd(ꢀ-bibMe)Cl2]n (3) were prepared by using the neutral N-donor ligands 1,4-
bis(imidazolyl)butane
(bib),
1,3-bis(imidazolyl)propane
(bip)
and
1,4-bis(2-
methylimidazolyl)butane (bibMe) and CdX2 (X=ClO4 , N3 and Cl-). The results of the X-ray
measurements demonstrate that in the crystal structure of 1 and 2 the cadmium(II) ion adopts
CdN6 octahedral geometry while, in the structure of 3, the metal ion forms CdN2Cl2
tetrahedral geometry. In compound 1, six bib ligands are coordinated to one central
cadmium(II) to form an open 3D 2-fold interpenetrating framework of the α-polonium (pcu)
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type topology, while in compound 2 and 3 the N3 or Cl- groups are terminally bonded to the
metal center and each linker compound (bip or bibMe) acts as bridging ligand connecting two
metal ions to form a one-dimensional zig-zag chain. The adjacent 1D chains of complex 2
and 3 are further extended into a non-covalent 2D network structure by C–H···N and C-
H···Cl intermolecular hydrogen bonds, respectively. The complexes were characterized by
elemental analysis, IR spectroscopy and single-crystal X-ray diffraction.
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Keywords: Metal-organic frameworks; Cadmium(II) complexes; Coordination polymers;
Crystal structure; Flexible nitrogen-donor ligands.
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1. Introduction
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During the past decade, the functional metal organic frameworks (MOF) and coordination
polymers (CPs) with transition metal cores have stimulated great interests in the field of

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crystal engineering and material chemistry for not only their fascinating structures but also
their potential applications in field such as sensing [1], luminescence [2,3], gas storage [4,5],
separations [6], drug delivery [7], magnetism [8], catalysis [9] and bioapplications [10]. The
final structures of coordination polymers are dependent upon the reaction medium
ligand ratio, nature of ligand, metal center, counter ion and auxiliary ligand [11−16] Therefore,
the important factor for constructing CPs and MOFs mainly relies on selections of metal centers
and bridging ligands A relatively wide range of data is available in the literature concerning
, metal to
.
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the preparation, characterization and application of copper, iron, mercury and zinc-containing
MOFs [17-22]. The flexible N-donor ligand, 1,4-bis(imidazolyl)butane (bib) is a good
candidate for the construction of coordination polymers [17,18,22], from which the most CPs
show two- or three-dimensional structures. This ligand forms structures which have
interpenetration and in this case, there is no free space in the solid state. To avoid
interpenetration, the use of ligands bip and bibMe is appropriate. The cadmium coordination
polymers containing flexible organic ligands those derived from N, O and S-donor have been
synthesized and structurally characterized [23-29]. Some Cd(II) coordination polymers were
shown luminescent properties [23-25]. For example multicarboxylate ligand and bis
imidazole was reacted with Cd(II) for constructing luminescent coordination polymers
(LCPs) [30]. Also some Cd(II) networks were shown to enhance or quench the fluorescence
emission of the organic ligand [31-32]. On the other hand, cadmium(II) compounds of
thiones are important as simple structural model in metallothioneins [25-29]. For compounds
of this metal, ligand-to-ligand charge transfer (LLCT) and ligand-to-metal charge transfer
(LMCT) have been reported [33]. In turn, the d-d transitions are not expected for Cd(II) due
to a d10 electronic configuration. In this paper we present the synthesis and structural
characterization of three coordination polymers of Cd(II) ions with flexible imidazole based
ligands (Scheme 1), in order to investigate the influence of the counter anion or coligand and
ligand on the framework of the compounds.

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Scheme 1. Structures of the flexible ligands; 1,4-bis(imidazolyl)butane (bib), 1,3-
bis(imidazolyl)propane (bip) and 1,4-bis(2-methylimidazolyl)butane (bibMe).
2. Experimental
2.1. Materials and general methods
All experiments were carried out in air atmosphere. Starting materials were purchased from
commercial sources and used without further purification. The ligands bib [34] and bip [35]
were prepared according to the published methods. Infrared spectra (4000-400 cm-1) were
recorded using KBr pellets with a BOMEN MB102 FT-IR spectrometer. Elemental analyses
for C, H and N were performed on a Thermo Finigan Flash EA 1120 CHN analyzer. X-ray
powder diffraction patterns were recorded on a Philips X’Pert Pro diffractometer (Cu Ka
radiation, λ = 1.54184 Å) in the 2θ range 5-50˚.
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2.2. Preparation of 1,4-bis(2-methylimidazolyl)butane (bibMe)
This ligand was prepared according to the reported method [36] with some modification.
Typically a mixture of 2-methylimidazole (4.1 g, 50 mmol) and KOH (2.8 g, 50 mmol) in
THF (50 mL) was stirred at 66 °C for 1 h, and then the 1,4-dichlorobutane (3.2 g, 25 mmol)
was added. The mixture was cooled to room temperature after being stirred at 60 °C for 24 h.
In the next step THF was removed and the residue was extracted with ethyl acetate (100 × 3
mL). The extracted solution was put in a water bath (90 °C) for 3 h, and the colorless oil
bibMe was obtained in 70% yield. Anal. Calc. for C12H18N4: C, 66.02; H, 8.31; N, 25.66;

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found: C, 66.08; H, 8.34; N, 25.71%. Selected IR (KBr, cm-1): 3162 (s), 2948 (s), 2681 (m),
2608 (m), 1672 (m), 1565 (m), 1500 (s), 1426 (s), 1362 (w), 1304 (m), 1280 (s), 1216 (s),
1146 (s), 1104 (s), 987 (s), 752 (s), 677 (s), 666 (s).
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2.3. Preparation of {[Cd(bib)3](ClO4)2}n (1)
A mixture of EtOH and water (1:1, 5 mL) was gently layered on the top of an aqueous
solution (5 mL) of CdCl2 (0.018g, 0.10 mmol) and NaClO4 (0.025g, 0.20 mmol) in a test
tube. A solution of bib (0.057g, 0.30 mmol) in EtOH (5 mL) was added carefully to the
colorless solution as a third layer. Crystals suitable for X-ray crystallography were obtained
after a few days. They were collected and washed with small amounts of water and dried in
air (0.63 g, 69% based on Cd). Anal. Calc. for C30H42CdCl2N14O8: C 39.59, H 4.65, N 21.55;
found: C 39.63, H 4.68, N 21.59%. Selected IR (KBr, cm-1): 3123 (m), 2949 (w), 2870 (m),
1630 (s), 1517 (s), 1460 (m), 1371 (s), 1283 (2), 1235 (s), 1094 (vs), 940 (s), 836 (s), 764
(m), 739 (w), 720 (s), 624 (s).
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2.4. Preparation of [Cd(µ2-bip)2(N3)2]n (2)
A mixture of EtOH and water (1:1, 5 mL) was gently layered on the top of an aqueous
solution (5 mL) of CdCl2 (0.018 g, 0.10 mmol) in a test tube. A solution of bip (0.035 g, 0.2
mmol) and NaN3 (0.013 g, 0.2 mmol) in EtOH/H2O (2:1, 6 mL) was added carefully as a
third layer. Transparent crystals were obtained after 4 days (0.44 g, 80% based on Cd). Anal.
Calc. for C18H24CdN14: C, 39.39; H, 4.41; N, 35.72; found: C, 39.43; H, 4.46; N, 35.43%.
Selected IR (KBr, cm-1): 3335 (w), 3114 (m), 2035 (vs), 1619 (w), 1516 (s), 1460 (w), 1440
(w), 1434 (w), 1395 (w), 1326 (m), 1233 (m), 1105 (s), 1085 (s), 930 (s), 828 (m), 750 (m),
660 (s).
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2.5. Preparation of [Cd(µ-bibMe)Cl2]n (3)
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This compound was obtained as an unexpected product in an attempt to synthesize
{[Cd(bibMe)3](NO3)2}n. A mixture of EtOH and water (1:1, 5 mL) was gently layered on the
top of an aqueous solution (5mL) of CdCl2 (0.018g, 0.10 mmol) and NaNO3 (0.012g, 0.20
mmol) in a test tube. A solution of bibMe (0.065g, 0.30 mmol) in EtOH (5 mL) was added
carefully to the colorless solution as a third layer. Colorless crystals suitable for X-ray
crystallography were obtained after a few days. They were collected and washed with small
amounts of water and dried in air. X-ray analysis reveals that the crystals, with the molecular
formula of [Cd(bibMe)Cl2], were the product of this reaction (0.33 g, 82% based on Cd). Anal.
Calc. for C12H18CdCl2N4: C 35.89, H 4.52, N 17.65; found: C 35.92, H 4.55, N 17.68%.

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Selected IR (KBr, cm-1): 3126 (m), 2920 (m), 1518 (s), 1454 (m), 1315 (m), 1307 (m), 1268
(m), 1035 (m), 807 (m), 683 (m), 562 (m).
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Caution: Perchlorate and Azide compounds are potentially explosive and should be handled
with care.
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2.6. X-ray crystallography
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X-ray diffraction data were measured at 100K with a Mo Kα radiation (λ = 0.7107 Å) using a
Rigaku SuperNova E (dual source) or a Bruker APEX II CCD diffractometers. For all
operations (data collection, cell refinement, data reduction and multi-scan absorption
correction) with both diffractometers CrysAlis PRO or Bruker software was used,
respectively. The structures were solved by direct methods and refined by a full-matrix least-
squares technique on F2 data using SHELXTL programs [37]. All non-hydrogen atoms were
refined anisotropically. Hydrogen atoms bonded to carbon atoms were inserted in calculated
positions and refined isotropically as a riding model. Details concerning the data collections
and refinements are given in Table 1.
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3. Results and discussion
3.1. Synthesis
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Coordination polymers were prepared in ethanol-water solutions by the reactions 1-3 shown
below.
CdCl2+ 2NaClO4 + 3bib → Cd(bib)3(ClO4)2+ 2NaCl
CdCl2+ 2NaN3 + 2bip → Cd(µ-bip)2(N3)2+ 2NaCl
CdCl2+ bibMe → Cd(bibMe)Cl2
(1)
(2)
(3)
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They are stable and can be stored in a desiccator. Polymers are insoluble in common organic
solvents such as DMF, MeCN and DMSO. The direct mixing of the reactants is not a general
method for the preparation of these polymers because it leads to the formation of a precipitate
of undefined compositions. In order to get suitable crystals of pure compound for the X-ray
crystallography and further studies a three-layer diffusion method was used. In this method a
buffer band (ethanol-water) is utilized to separate the two solutions, one of them is an
aqueous solution of the cadmium(II) salt and the second is an ethanol solution of the

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imidazole based ligand. When these two solutions diffuse into the buffer band and meet with
each other, the product slowly forms and crystallizes.
3.2. Description of Crystal Structures
3.2.1. Crystal Structure of 1
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Single-crystal X-ray structural analysis reveals that this compound crystallizes in the trigonal
space group R-3 with Z=3 (Table 1). The crystal structure of 1 consists of 3D polymeric
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[Cd(bib)3]2+ macrocations and uncoordinated ClO4 anions. As shown in Fig. 1, the
cadmium(II) ion lies on an inversion center and is coordinated by six nitrogen atoms from the
imidazole rings of the six µ2-bib ligands in an almost regular CdN6 octahedral environment
with the N-Cd-N bond angles close to 90˚ and the Cd-N distances being 2.356(11) and
2.355(11) Å (Table 2). The resemblance between the Cd-N bond lengths in 1 can be
attributed to the fact that, the bib ligands represent one type of conformations, namely anti-
anti-anti with shortest N···N and Cd···Cd distances of 10.25 and 14.35 Å and dihedral angles
of the two imidazole rings of 0˚. Six bib ligands are simultaneously coordinated to one central
cadmium atom to form an open 3D 2-fold interpenetrating framework with α-polonium (pcu)
topology [point symbol (412.63)] (Fig. 2). As is common for the 2-fold interpenetrating
frameworks the values of the crystallographic parameters for both networks are the same. The
topology of this coordination polymer was determined with the use of the ToposProprogram
[38]. Examples of this topology have been reported in the literature for some coordination
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polymers [39-41]. In the structure of 1, the ClO4 anions are located in the voids. Perchlorate
anions are involved in the formation of the C-HꢁꢁꢁO hydrogen bonds between the oxygen
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atoms of the ClO4 anion and hydrogen atoms of the imidazole rings and -(CH2)4- spacer of
the µ2-bib ligands (Fig. 3). Structural compression between 1 and {[Cd(btb)3](PF6)2}n
[btb=1,4-bis(1,2,4-triazol-1-yl)butane] shows that in the crystal structures of both
compounds the conformation of the flexible ligands is anti-anti-anti, but 1 forms 3D 2-fold
while, {[Cd(btb)3](PF6)2}n 3D 3-fold interpenetrating framework [42]. Accordingly, flexible
ligands are responsible for directing the interpenetrating of these polymers.
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3.2.2. Crystal Structure of 2
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Single crystal X-ray structural analysis reveals that this compound crystallizes in the triclinic
space group P -1 with Z=1 (Table 1). In this structure there is one molecule in the unit cell
(Table 1). This means that only half of the molecule is present in the asymmetric part of the

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unit cell. In this structure the cadmium atom is placed at the inversion center and is
surrounded by six nitrogen atoms, which resemble the axially compressed octahedral
coordination geometry. The equatorial plane is formed by four nitrogen atoms from the
imidazole rings of the four symmetry related µ2-bip ligands with the Cd-N distances being
2.356(1) and 2.329(1) Å. The axial positions are occupied by two azide nitrogen atoms with
Cd-N bond lengths 2.365(2) Å. As a co-ligand, azide moiety is almost linear [N5-N6-
N7 177.81(15)°] and bent at N5 atom [Cd1-N5-N6 122.61(10)°] (Table 2) what is common
for the linear azide ligand which adopts an end-on terminal coordination mode (Fig. 4). In the
structure 2, two neighboring cadmium ions are interconnected by two bridging µ2-bip
ligands. As a result; a 20-membered macrocyclic dimeric unit is formed. The dimeric units
are linked together and form infinite one-dimensional chains (Fig. 5). Crystal structure of 2 is
built of layers formed by such chains. Each of the linker ligands adopts an anti-gauche
conformation with the dihedral angle between the two imidazole rings of 72.3(1)° and links
two Cd(II) ions through the imine nitrogen atoms. The shortest N···N and Cd···Cd distances
are 7.64 and 10.69 Å, respectively. One H atom of the CH bond of the imidazole moiety of
the bip ligand interacts with a N atom of azide to yield intermolecular C-H···N contacts with
H···N distance of 2.52 Å. In the presence of these interactions, the neighboring chains are
further extended into a 2D framework structure (Fig. 6). It is not surprising that small
changes in the structure of flexible ligands as, for example a change of the position of the
donor atoms or different spacer lengths can cause significant changes of the structures.
Inserting the molecule of nic or 2,5-dmpyz and Quz (see Scheme 2) to the structure of 2
instead of bip leads to the formation of 3D and 2D, respectively [9, 10]. In the others, where
bipy or acyp are used instead of the bip ligand (see Scheme 2), the coordination polimers
built of the 1D chains are also formed [43,44]. Moreover, the use of bdmpzm instead of bip
leads to the formation of a monomer complex instead of a coordination polymer [45].
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3.2.3. Crystal Structure of 3
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This compound crystallizes in the orthorhombic space group P 212121 with Z=4 (Table 1). As
shown in Fig. 7, the cadmium(II) ion is coordinated by two chlorine anions with Cd-Cl
distances of 2.438(1) and 2.446(1) Å and two N nitrogen atoms of two crystallographically
equivalent ꢀ-bibMe ligands with Cd-N distance of 2.223(3) and 2.228(3) Å in a distorted
tetrahedral CdN
2
Cl coordination geometry. The cadmium(II) ion has a slightly distorted
2
tetrahedral geometry with large compression of the N6-Cd1-N7 angle [106.70(11)°] and
enlargement of the Cl1-Cd1-N6 angle [112.56(8)°] (Table 2). In the crystal structure of 3, the

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ꢀ-bibMe compound acts as a bridging bidentate ligand, linking the Cd(II) centers into a one-
dimensional zigzag chain structure running along the crystallographic b-axis (Fig. 8). Each of
the linker ligands adopts an anti- anti- anti conformation with the dihedral angle between the
two 2-methylimidazole rings of 35.51° and links two Cd(II) ions through the imine nitrogen
atoms. The shortest N···N and Cd···Cd distances are 10.12 and 13.58 Å, respectively. H
atoms of the CH groups in the 2-methylimidazole moieties of the bibMe ligand are involved
in the intermolecular C-H···Cl contacts with the H···Cl distances of 2.77 (H9···Cl1) and 2.81
(H2···Cl2) Å. In the presence of these interactions, the neighboring chains are further
extended into a 2D framework structure (Fig. 9). Inserting the molecule of bpa (see Scheme
2) to the structure of 3 instead of bibMe leads to the formation of a dinuclear complex [46]. In
the others, where L or Hpbi is used (see Scheme 2), the coordination polimers built of the 1D
chains are formed, but the coordination geometry around cadmium is octahedral. On the other
hand, Hpbi forms a 3D structure, through intermolecular X–H···Cl (X = N and C) hydrogen
bonds and π–π stacking interactions [47,48]. Also the reaction of CdCl2 and bibMe ligand with
variable ratios, in the absence of NaNO3 led to obtain structure (3) (See Supplementary
Information).
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Scheme 2. Structures of the ligands: nicotinate anion (nic); 2,5- dimethylpyrazine (2,5-
dmpyz); quinazoline (Quz); 2,2'-bipyridyl (bipy); 2-acetylpyridine (acyp); 1,4-bis(1,2,4-

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triazol-1-yl)butane (btb); bis(3,5-dimethylpyrazol-1-yl)methane (bdmpzm); 3,5-bis(3-
pyridyl-3-(3'-methylphenyl)-1,3,4-oxadiazole (L); bis(3-aminopropy1)amine (bpa) and 2-
(pyrazin-2-yl)-1H-benzimidazole (Hpbi).
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3.3. Spectroscopic characterization
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The IR spectra of the complexes showed strong bands corresponding to the stretching
vibration of the C=N bonds of the imidazole or 2-Methylimidazole rings of the bib, bip and
bibMe ligands at the range of 1516-1518 (s) cm-1. The medium bands in the range of 3114-
2870 cm-1 are mainly assigned to the C-H stretching vibrations of the CH2 (for 1-3) and CH3
(3) groups of the bridging ligands. The infrared spectrum of 1 displays two sharp bands at
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624 and 1094 cm-1 due to the vibrations of the ClO4 ion. In the case of 2 the intense
absorption band at 2035 cm-1 is attributed to the azide ligand [49]. In order to confirm the
phase purity of the synthesized polymers, X-ray powder diffraction (XRPD) experiments
were carried out in which the experimental spectra were consistent with their simulated
spectra (Fig. S1).
Conclusion
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In conclusion, we have synthesized successfully three new cadmium(II) complexes with
flexible imidazole-based ligands. These compounds display two different structures. Polymer
1 exhibits three-dimensional architecture while compounds 2 and 3 form one dimensional
infinite polymeric chains. The structure of the last two complexes is extended into a 2D
framework by means of hydrogen bonding interactions. Polymer 3 was obtained as an
unexpected product in an attempt to synthesize the {[Cd(bibMe)3](NO3)2}n compound. The
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results of this work indicate that the counter ions (such as ClO4 , N3 and Cl-) and the structure
of the flexible ligands have a significant influence on the formation and structure of these
complexes.
Acknowledgement
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We thank Young Researchers and Elite Club, Islamic Azad University Buinzahra Branch for
financial support.
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Appendix A. Supplementary data

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CCDC 1562630, 1562476 and 1562477 contains the supplementary crystallographic data for
1-3, respectively. Crystallographic data can be obtained free of charge from the Cambridge
Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/datarequest/cif. or from the
Cambridge Crystallographic Data Centre,12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk
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Table 1. Crystal data and structure refinement for compounds 1-3.
1
2
3
Chemical formula
Formula weight
Diffractometer
λ (Mo Kα) (Å)
Crystal system
Space group
a (Å)
C30H42CdCl2N12O8 C18H24CdN14
C12H18CdCl2N4
882.06
APEX II CCD
0.71073
trigonal
R -3
548.91
401.60
SuperNova E
0.71073
orthorhombic
P 212121
9.30590(10)
9.8889(2)
16.5699(3)
90
SuperNova E
0.71073
triclinic
P -1
13.543(4)
13.543(4)
18.048(5)
90
7.8163(3)
9.0013(4)
9.4913(3)
76.215(3)
75.570(3)
64.676(4)
577.91(4)
1
b (Å)
c (Å)
α (°)
β (°)
90
90
γ (°)
V (Å3)
120
90
2866.6(13)
3
1524.85(4)
4
Z
D
calcd. (g·cm-3)
1.533
1.577
1.749
ꢀ (mm-1)
0.775
0.982
1.774
F(000)
1356
278
800
Crystal size (mm)
Reflections collected
Rint
0.26 x 0.19 x 0.16 0.30 x 0.15 x 0.12 0.18 x 0.10 x 0.08
10149
26093
49032
0.0668
0.0396
0.0445
Data/restraints/parameters
Final R [I>2σ(I)] R1, wR2
GOF
668/ 0/ 85
0.0935, 0.1868
1.112
3219/ 0/ 151
0.0186, 0.0475
1.063
4054/ 0/ 174
0.0276, 0.0712
1.206
Largest diff. peak/hole (e·Å‾3)
1.065/ -2.007
1.022/ -0.528
1.609/ -0.628
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Table 2. Selected bond distances (Å) and angles (°) for compounds 1-3.
Compound 1
Cd1-N1
N1-Cd1-N1
2.356(11) Cd1-N1
2.355(11)
180.0(6)
90.0(4)
N1-Cd1-N1
Compound 2
Cd1-N1
Cd1-N3
N1-Cd1-N5
N1-Cd1-N1
N1-Cd1-N5
N1-Cd1-N3
N1-Cd1-N5
2.356(1)
2.329(1)
88.08(4)
Cd1-N5
N5-Cd1-N5
N5-Cd1-N3
2.365(1)
180.00(4)
88.93(4)
180.00(4) N5-Cd1-N3
91.07(4)
91.92(4)
93.95(4)
86.05(4)
N3-Cd1-N3
N5-N6-N7
Cd1-N5-N6
180.00(4)
177.81(15)
122.61(10)
Compound 3
Cd1-Cl1
Cd1-Cl2
2.438(1)
2.446(1)
Cd1-N6
Cd1-N7
2.228(3)
2.223(3)
Cl1-Cd1-Cl2
Cl2-Cd1-N6
Cl2-Cd1-N7
111.51(3) Cl1-Cd1-N6
108.52(8) Cl1-Cd1-N7
110.29(8) N6-Cd1-N7
112.56(8)
107.14(8)
106.70(11)
351
352
Figure Captions:
353 Fig. 1.View of the coordination environment of Cadmium(II) in 1.
-
354
355
356
Fig. 2. (a) View of the 3D α-polonium for single network of 1. Hydrogen atoms and ClO4
are omitted for clarity. (b) View of the 2-fold interpenetrating network of 1.(c) Schematic
drawing of the 2-fold interpenetrated 3D structure of 1.
357
358
359
360
361
362
363
Fig. 3. Non-classic C–H···O hydrogen bonds in the structure of 1.
Fig. 4. View of the coordination environment of Cadmium(II) in 2.
Fig. 5. Layered structures of 2 formed by 1D chain. Hydrogen atoms omitted for clarity.
Fig. 6. View of the 2D of 2 formed by non-classic C–H···N hydrogen bonds.
Fig. 7. View of the coordination environment of Cadmium(II) in 3.
Fig. 8. Layered structures of 3 formed by 1D chain. Hydrogen atoms omitted for clarity.
Fig. 9. View of the 2D of 3 formed by non-classic C–H···Cl hydrogen bonds.
364
365
Fig. S1. View of the X-ray powder diffraction (XRPD) experimental spectra and simulated
spectra 1-3.
366

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• Highlights
•
Structure of the organic ligands plays a dominant role in the structure coordination
polymers.
-
-
•
•
Also counter ions such as ClO4 , N3 and Cl- impact on the structure.
The polymers have been characterized by X-ray diffraction, elemental and infrared
spectroscopy.