Impact of binding positions of 1,3-alternate calix[4]arene tetrabenzoic acids on geometry of coordination polymers

Article abstract of DOI:10.1007/s10847-021-01091-5

In this work, calix[4]arene was used as a building block for the preparation of 1,3-alternate calix[4]arene tetrabenzoic acids. Two structural isomers, 3A and 3B were obtained which have the carboxylate groups on the para and meta positions, respectively. The reaction conditions were optimized to obtain, four coordination polymers with linkers of 3A and 3B with Zn²⁺ and Cd²⁺ in different forms. Structural analysis of the product (CU-SCRU1) from 3A with Zn²⁺ showed that it was a 1D polymeric chain. In the case of 3B with Zn²⁺ it was a 1D polymeric chain in a zig-zag shape (CU-SCRU2). The free rotation of the methylene bridge allowed the carboxylate group at the meta position of 3B to coordinate with the Zn²⁺ ion. In both cases, the carboxylate groups at each side of the organic linkers, 3A and 3B, chelated to the same metal center (Zn²⁺) which resulted in the formation of 1D coordination polymers. However, each polymeric chain extended to a 3D framework by nonclassical hydrogen bonding and intermolecular interactions for CU-SCRU1 and CU-SCRU2, respectively. The reaction of 3B and Cd²⁺ provided coordination polymers that were suitable for structural characterization. Interestingly, two products were formed in the same reaction, CU-SCRU3 and CU-SCRU4, that had different coordination structures. The structural features of these two products suggested that they exist as a 3D framework, however, the nitrogen adsorption–desorption analysis revealed that they were nonporous materials. Graphic abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10847-021-01091-5

Journal of Inclusion Phenomena and Macrocyclic Chemistry
https://doi.org/10.1007/s10847-021-01091-5
ORIGINAL ARTICLE
Impact of binding positions of 1,3‑alternate calix[4]arene tetrabenzoic
acids on geometry of coordination polymers
Suppachai Krajangsri1 · Nongnuj Muangsin2 · Buncha Pulpoka1
Received: 31 March 2021 / Accepted: 17 June 2021
© The Author(s), under exclusive licence to Springer Nature B.V. 2021
Abstract
In this work, calix[4]arene was used as a building block for the preparation of 1,3-alternate calix[4]arene tetrabenzoic
acids. Two structural isomers, 3A and 3B were obtained which have the carboxylate groups on the para and meta positions,
respectively. The reaction conditions were optimized to obtain, four coordination polymers with linkers of 3A and 3B with
Zn2+ and Cd2+ in diferent forms. Structural analysis of the product (CU-SCRU1) from 3A with Zn2+ showed that it was
a 1D polymeric chain. In the case of 3B with Zn2+ it was a 1D polymeric chain in a zig-zag shape (CU-SCRU2). The free
rotation of the methylene bridge allowed the carboxylate group at the meta position of 3B to coordinate with the Zn2+ ion. In
both cases, the carboxylate groups at each side of the organic linkers, 3A and 3B, chelated to the same metal center (Zn2+)
which resulted in the formation of 1D coordination polymers. However, each polymeric chain extended to a 3D framework by
nonclassical hydrogen bonding and intermolecular interactions for CU-SCRU1 and CU-SCRU2, respectively. The reaction
of 3B and Cd2+ provided coordination polymers that were suitable for structural characterization. Interestingly, two products
were formed in the same reaction, CU-SCRU3 and CU-SCRU4, that had diferent coordination structures. The structural
features of these two products suggested that they exist as a 3D framework, however, the nitrogen adsorption–desorption
analysis revealed that they were nonporous materials.
“Dedicated to Dr. Jacques Vicens”
* Buncha Pulpoka
buncha.p@chula.ac.th
1
Supramolecular Chemistry Research Unit and Organic
Synthesis Research Unit, Department of Chemistry, Faculty
of Science, Chulalongkorn University, Phayathai Road,
Patumwan, Bangkok 10330, Thailand
2
Department of Chemistry, Faculty of Science, Chulalongkorn
University, Phayathai Road, Patumwan, Bangkok 10330,
Thailand
Vol.:(0123456789)
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Journal of Inclusion Phenomena and Macrocyclic Chemistry
Graphic abstract
Keywords Coordination polymer · Complexation · Calix[4]arene · Crystal structure · Advanced material
are the most commonly used chelating groups because of
Introduction
their strong coordination bonds. Over four decades, various
types of organic building blocks have been successfully used
as ligands in the synthesis of coordination polymers. Most of
them are rigid core structure aromatic compounds which are
easier to tune and to form predictions for the structure and
properties of the resulting coordination polymers [15, 16].
There are fewer examples of aliphatic organic linkers due
to their fexibility increasing the complexity of the obtained
coordination polymers [17]. The choice of metal ion is also
often investigated during optimization as it plays an impor-
tant role in the formation of the products [18]. However,
the chelation between metal ions and organic linkers has
been well described and this can help to predict and design
the coordination polymers without the need to optimize the
metal ion.
Coordination polymers are materials composed of metal
ions/clusters and organic ligands bonded through coordina-
tion bonds [1]. Coordination polymers have structural fea-
tures in diferent dimensions where 1D forms a chain [2], 2D
a sheet [3], and 3D a framework [4]. The most well-known
example of a 3D framework of coordination polymers is
MOFs (metal–organic frameworks [5]. These MOF materi-
als possess interesting properties such as large surface area,
high pore volume, and relatively high thermal stability [6].
They are applicable in various areas [7], for example, gas
storage [8], gas separation [9], and heterogeneous catalyst
[10]. Recently, several new MOFs have been designed and
synthesized that provide outstanding characteristics [11].
In general, the structure and property of coordination poly-
mers depend on the organic linker and the metal ion [12].
Additionally, the reaction condition plays an important role
and diferent conditions can result in unique product forma-
tion [13]. The organic linker is the most important factor on
the polymer’s structure and properties [14]. Many organic
compounds have been designed, modifed and applied to
the synthesis of coordination polymers. The organic linker
should have at least two functional groups for the formation
of coordination bonds with the metal ion/cluster. Carboxy-
late and N-heteroaromatic compounds (pyridine derivatives)
Our research group used modifed calix[4]arene as the
building block for the development of a coordination poly-
mer based sensor [19]. Herein, we designed and synthesized
new organic linkers using calix[4]arene as a building block.
Calix[4]arene is one of the most popular building blocks in
supramolecular chemistry due to its cyclic cavity shape and
π-electron rich structure which may provide desired proper-
ties in the new coordination polymers. Two organic linkers
(3A and 3B) were designed and functionalized in a 1,3-alter-
nate conformation. 3A and 3B are structural isomers of each
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Journal of Inclusion Phenomena and Macrocyclic Chemistry
other and have the carboxylate group as the chelating group
which can form strong bonds with metal ions. Herein, the
synthesis of coordination polymers composing of d10 transi-
tion metal ions is reported.
Experimental section
Reagents
All reagents were analytical grade and used as received with-
out further purifcation. Commercial grade solvents were puri-
fed by distillation. Anhydrous solvents were dried over CaH2
and freshly distilled under nitrogen atmosphere. Calix[4]arene
was prepared following literature procedures [20].
Characterization
1H NMR spectra were obtained in CDCl3 or DMSO-d6 at
400 MHz (Varian, USA). 13C NMR spectra were obtained
in CDCl3 or DMSO-d6 at 100 MHz (Bruker, UK). Chemi-
cal shifts (δ) were reported in parts per million (ppm) and
coupling constants (J) are reported in Hertz (Hz). Mass
spectra were obtained using matrix-assisted laser desorp-
tion ionization mass spectrometry (MALDI-MS) by using
α-hydroxycyano cinnamic acid (CCA) as a matrix. XRD
patterns were obtained by X-Ray Difractometry, Rigaku
DMAX 2200 Ultima+/Cu lamp. IR spectra were obtained
by Fourier Transform Infrared Spectroscopy, Nicolet
Impact 412. Nitrogen adsorption analyses were obtained by
a Surface area analyzer, BELSORP-mini instrument. The
morphologies of coordination polymers were obtained by
Scanning Electron Microscopy, Philips XL30CP and their
thermal stabilities were measured by Thermo-gravimetric
Analysis, TG–DTA Perkin-Elmer Pyris diamond.
Scheme 1 Synthetic pathways of 1,3-alternate calix[4]arene tetraben-
zoic acids (3A and 3B)
Procedures
Scheme 1.
dried acetonitrile (10 mL) was added and the reaction mix-
ture was allowed to refux overnight. The reaction was cooled
to room temperature. Potassium carbonate was separated by
fltration, and the fltrate was dried under vacuum. The crude
product was dissolved in dichloromethane (30 mL) and then
washed with aqueous 3 M HCl (10 mL), water and brine,
respectively. The organic phase was dried over anhydrous
Na2SO4 and concentrated to one -third of the volume under
vacuum. The product was precipitated by methanol. The
resulting white solid was fltered and washed with metha-
Synthesis of organic linkers, 1,3‑alternate calix[4]arene
tetrabenzolic acids, 3A and 3B
The organic linkers 3A and 3B were synthesized following
the procedure in scheme 1.
Synthesis of 1,3‑calix[4]arene di(methyl‑p‑benzoate)
(1A) Calix[4]arene (0.53 g, 1.25 mmol) and potassium
carbonate (K2CO3) (0.69 g, 6.25 mmol) were placed into
a 100 mL two-necked round-bottom fask containing dried
acetonitrile (30 mL). The resulting mixture was refuxed
under nitrogen atmosphere for 1 h. Then, a solution of
methyl-4-(bromomethyl) benzoate (0.57 g, 2.50 mmol) in
1
nol to obtain the desired product (1A) (0.66 g, 73%). H
NMR (400 MHz, CDCl3) δ: 7.98 (4H, d, J=8.0 Hz), 7.81
(4H, d, J=6.4 Hz), 7.06 (4H, d, J=7.6 Hz), 6.91 (4H, d,
J=7.2 Hz), 6.78 (2H, t, J=7.6 Hz), 6.66 (2H, t, J=7.6 Hz),
5.13 (4H, s), 5.28 (4H, d, J=13.2 Hz), 3.92 (6H, s), 3.36
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Journal of Inclusion Phenomena and Macrocyclic Chemistry
1
(4H, d, J=13.2 Hz); 13C NMR (100 MHz, CDCl3) δ: 166.8,
153.2, 151.7, 141.8, 133.0, 130.1, 129.8, 129.2, 128.6,
127.8, 126.9, 125.7, 119.2, 77.6, 52.1, 31.4; IR (Nujol): νmax
3373, 2924, 1722, 1463, 1279, 1197,1108, 1018, 756.
(0.58 g, 56%). H NMR (400 MHz, CDCl3): δ 8.05 (4H,
d, J=7.6 Hz), 7.95 (4H, s), 7.50 (4H, d, J=8.0 Hz), 7.33
(4H, d, J=7.2 Hz), 6.68 (8H, d, J=7.2 Hz), 6.46 (4H, t,
J=7.6 Hz), 4.86 (8H, s), 3.97 (12H, s), 3.57(8H, s); 13C
NMR (100 MHz, CDCl3) δ: 167.2, 155.7, 138.4, 133.8,
132.2, 131.1, 129.9, 128.4, 128.2, 127.7, 122.4, 71.9, 52.1,
37.1; IR (Nujol): νmax 2949, 1721, 1588, 1454, 1367, 1286,
1200, 1092, 747. MALDI-TOF mass (m/z): Anal. caled for
[C64H58O12 +Na+]: 1041.382, found 1039.787.
Synthesis of 1,3‑calix[4]‑arene di(methyl‑m‑benzoate)
(1B) 1B was synthesized following the synthetic method
as described for 1A but methyl-3-(bromomethyl) benzoate
(0.57 g, 2.50 mmol) was used as a reagent instead of methyl-
4-(bromomethyl)benzoate. 1,3-Calix[4]-arene di(methyl-
m-benzoate) (1B) was obtained as a white solid. (0.62 g,
Synthesis of 1,3‑alternate calix[4]arene tetra‑p‑benzoic acid
(3A): A solution of 1,3-alternate calix[4]arene tetra(methyl-
p-benzoate) (2A) (1.02 g, 1.00 mmol) in ethanol (30 mL)
in a 100 mL two-necked round-bottom fask was gently
heated until 2A was completely soluble. Then, a solution
of potassium hydroxide (5.60 g, 100.00 mmol) in water
(10 mL) was added. The resulting mixture was refuxed
until completion (TLC analysis). The reaction mixture was
concentrated under reduced pressure and then acidifed by
aqueous 3 M HCl (30 mL). The precipitate was fltered and
washed with water to yield the desired product 3A (0.87 g,
90%). 1H NMR (400 MHz, DMSO-d6) δ: 12.93 (4H, s), 8.00
(8H, d, J=7.6 Hz), 7.23 (8H, d, J=7.6 Hz), 6.59 (8H, d,
J=7.6 Hz), 6.28 (4H, d, J=7.0 Hz), 4.86 (4H, s); 3.59 (4H,
s); 13C NMR (100 MHz, DMSO-d6) δ: 167.3, 155.6, 143.1,
133.7, 130.4, 129.5, 128.6, 126.9, 121.7, 71.0, 36.5; FT-IR
(KBr pellet) ν/cm−1: 3466, 2915, 1682, 1453, 1418, 1279,
1195, 1092, 1034, 757. MALDI-TOF mass (m/z): Anal.
caled for [C60H50O12 +Na+]: 985.320, found 983.657.
1
69%). H NMR (400 MHz, CDCl3) δ: 8.16 (2H, s), 8.02
(4H, t, J=7.2 Hz), 7.73 (2H, s), 7.32 (2H, t, J=7.6 Hz),
7.04 (4H, d, J=7.6 Hz), 6.88 (4H, d, J=7.6 Hz), 6.76 (2H,
t, J=7.4 Hz), 6.66 (2H, t, J=7.4 Hz), 5.11 (8H, s), 4.50 (4H,
d, J=12.8 Hz), 3.87 (12H, s), 3.33 (4H, d, J=13.2 Hz); 13
C
NMR (100 MHz, CDCl3) δ: 166.8, 153.3, 151.7, 137.2,
133.1, 132.2, 130.4, 129.3, 129.2, 129.1, 128.6, 128.5,
127.9, 125.6, 119.1, 77.8, 52.2, 31.4; IR (Nujol): νmax 3394,
2949, 1721, 1590, 1465, 1287, 1202, 1087, 747.
Synthesis of 1,3‑alternate calix[4]arene tetra(methyl‑p‑ben‑
zoate) (2A): A solution of 1,3-calix[4]arene di(methyl-
p-benzoate) (1A) (0.43 g, 0.60 mmol) and potassium car-
bonate (K2CO3) (1.38 g, 10.00 mmol) in dried acetonitrile
(30 mL) was placed into a 100 mL two-necked round-bot-
tom fask. The mixture was refuxed under a nitrogen atmos-
phere for 1 h. Then, a solution of methyl-4-(bromomethyl)
benzoate (0.30 g, 1.32 mmol) in dried acetonitrile (10 mL)
was added. The reaction mixture was refuxed for 2 days.
The potassium carbonate was then fltered of and the fltrate
was placed into the rotary evaporator to remove the solvent.
The crude extract was then dissolved with dichlorometh-
ane (30 mL) and washed with 3 M HCl (10 mL), water and
brine, respectively. The organic layer was dried over anhy-
drous Na2SO4, fltered and the solvent removed under vac-
uum to one-third of the volume. The desired product (2A)
was obtained as a white solid (0.35 g, 57%) by precipita-
tion with methanol. 1H NMR (400 MHz, DMSO-d6) δ: 8.15
(8H, d, J=7.6 Hz), 7.20 (8H, d, J=7.6 Hz), 6.66 (8H, d,
J=7.6 Hz), 6.45 (4H, t, J=7.4 Hz), 4.92 (8H, s), 4.05 (12H,
s), 3.63 (8H, s); 13C NMR (100 MHz, CDCl3) δ: 167.2,
155.5, 143.0, 133.9, 131.1, 129.2, 129.1, 126.5, 122.7, 71.2,
52.2, 37.4; IR (Nujol): νmax 2949, 1718, 1613, 1452, 1287,
1196, 1107, 1020, 754. MALDI-TOF mass(m/z): Anal.
caled for [C64H58O12+Na+]: 1041.382, found 1039.513.
Synthesis of 1,3‑alternate calix[4]arene tetra‑m‑benzoic acid
(3B): 1,3-Alternate calix[4]arene tetra-m-benzoic acid (3B)
was obtained by the same procedure used for the synthesis
of 3A but 2B (0.31 g, 0.30 mmol) was used as a starting
material instead of 2A. The desired product was obtained as
a white precipitate (0.26 g, 90% yield). 1H NMR (400 MHz,
DMSO-d6) δ: 12.88 (4H, s), 7.89 (4H, d, J=9.2 Hz), 7.42
(4H, d, J=7.4 Hz), 7.22 (4H, d, J=7.6 Hz), 6.60 (8H, d,
J=7.6 Hz), 6.26 (4H, t, J=7.2 Hz), 4.74 (8H, s), 3.52 (8H,
s); 13C NMR (100 MHz, DMSO-d6) δ: 167.4, 155.5, 138.4,
133.6, 132.2, 130.4, 130.2, 127.9, 127.8, 121.6, 71.4, 36.4;
FT-IR (KBr pellet) ν/cm−1: 3432, 2917, 1691, 1588, 1456,
1409, 1303, 1250, 1200, 1090, 748. MALDI-TOF mass
(m/z): Anal. caled for [C60H50O12 +Na+]: 985.320, found
983.616.
Synthesis of coordination polymers
Synthesis of 1,3‑alternate calix[4]arene tetra(methyl‑m‑ben‑
zoate) (2B): Following the synthetic method as described
for 2A, 2B was achieved by using 1B (0.70 g, 1.00 mmol)
and methyl-3-(bromomethyl) benzoate (0.50 g, 2.20 mmol)
as starting materials. 1,3-Alternate calix[4]arene
tetra(methyl-m-benzoate) (2B) was obtained as a white solid
Synthesis of coordination polymers from 3Aand Zn(II) ion A
solvothermal reaction was carried out with the organic
linker 3A and Zn(NO3)2.6H2O in a mixed solvent of DMF
and DEF (diethylfomamide) (1:1, v/v) that was placed in a
10 mL vial and sealed. It was kept at 90 °C in an oven for
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Journal of Inclusion Phenomena and Macrocyclic Chemistry
48 h, then cooled to room temperature over 12 h. and color-
less needle-like crystals were obtained (CU-SCRU1).
Synthesis of coordination polymers from 3B and Zn(II)ion A
solvothermal reaction was carried out with the organic linker
3B and Zn(NO3)2.6H2O in 100 mL of a Tefon-lined stain-
less steel vessel containing a mixture of DMF:DEF (1:1,
v/v, 30 mL) as solvents. The mixture was heated to 150 °C
in 6 h and kept at this temperature for 48 h. After cooling
to room temperature for 24 h, cubic colorless crystals were
obtained (SCRU-CU2).
Synthesis of coordination polymers from 3B and Cd(II)
ion The organic linker 3B with Cd(NO3)2.4H2O was dis-
solved in a mixture of DMF and DEF (1:1, v/v) in a 10 mL
vial and sealed. The reaction vessel was kept at 90 °C in the
oven for 48 h, then cooled to room temperature over 12 h
which yielded colorless polyhedral crystals (CU-SCRU3
and CU-SCRU4).
Fig. 1 Crystal structures of compound 2B and 3A (ORTEP draws of
2B and 3A displacement ellipsoids are scaled to the 25% probability
level)
Synthesis of coordination polymers.
Synthesis of coordination polymers by organic linkers, 3A
and 3B, were successfully carried out under optimized con-
ditions to provide four single crystals from three reactions
which meant that there were two types of coordination poly-
mers formed in the same reaction.
Results and discussion
Synthesis of 1,3‑alternate calix[4]arene
tetra‑benzoic acids, 3A and 3B.
Coordination polymers, CU‑SCRU1 and CU‑SCRU2.
The synthesis of 1,3-alternate calix[4]arene tetrabenzoic
acids, 3A, and 3B involved three reaction steps. In the frst
step, calix[4]arene reacted with methyl-4-(bromomethyl)
benzoate or methyl-3-(bromomethyl) benzoate in dry
CH3CN by using K2CO3 as base to selectively provided
1,3-calix[4]arene di(methyl-p-benzoate) (1A) or 1,3-calix[4]
arene di(methyl-m-benzoate) (1B) in good yields of 73%
and 69%, respectively. In the second step, the reaction of
1A or 1B with methyl-4-(bromomethyl) benzoate or methyl-
3-(bromomethyl) benzoate in the presence of K2CO3 pro-
vided the desired conformation of the products, 1,3-alternate
calix[4]arene tetra(methyl-p-benzoate) (2A) or 1,3-alternate
calix[4]arene tetra(methyl-m-benzoate) (2B) in moderate
yields, 57% and 56% respectively. The 1,3-alternate confor-
mations of 2A and 2B were confrmed by singlet signals of
methylene bridge protons at 3.63 and 3.57 ppm, respectively.
The products obtained in each step were easily precipitated
in CH2Cl2/MeOH. In the fnal step, compound 2A or 2B
was hydrolyzed under refuxing condition in the presence of
excess KOH and then acidifed by HCl to provide 1,3-alter-
nate calix[4]arene tetra-p-benzoic acid (3A), 92% yield, or
1,3-alternate calix[4]arene tetra-m-benzoic acid (3B), 90%
yield. The single crystals of 2B and 3A were obtained as
shown in Fig. 1.
The optimal reaction conditions of the reaction between
1,3-alternate calix[4]arene tetra-p-benzoic acid (3A) or
1,3-alternate calix[4]arene tetra-m-benzoic acid (3B) and
Zn(II) ion provided the 1D coordination polymers, named
CU-SCRU1 (3A-Zn) and CU-SCRU2 (3B-Zn), respectively.
Single-crystal X-ray difraction analysis showed that CU-
SCRU1 was composed of two kinds of crystallographically
independent Zn(II) ions. The Zn1(II) ion which exhibits
octahedral coordination geometry with four monodentate
carboxylate oxygen atoms in the equatorial positions and
two oxygen atoms from DMF molecules in the axial posi-
tions (Fig. 2). The Zn1-O bond lengths were in the range of
2.047–2.128 Å.
The coordination environment of the Zn2(II) ion is the
same as the Zn1(II) ion with the Zn2-O bond lengths being
in the range of 2.040–2.134 Å.
The coordination geometry of Zn1(II) and Zn2(II) ions
are perpendicular to each other. The structure of CU-SCRU1
extends in a 1D linear chain by coordination bonds as dis-
played in Fig. 3. The 2D and 3D structures of CU-SCRU1
were formed by 1D-polymeric chains with weak intermo-
lecular interaction (nonclassical H-bonding).
The CU-SCRU2 was composed of two kinds of crystal-
lographically independent Zn(II) ions. Both the Zn1(II) ion
and the Zn2(II) ion were in a tetrahedral geometry com-
posed of three oxygen atoms from three carboxylic groups
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Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 4 (a) Coordination environment of CU-SCRU2; the asymmetric
unit and the related coordination atoms are labeled as follows with
the hydrogen atoms omitted for clarity: green, Zn1 and Zn2; red,
O; blue, N; black, C. (b) The tetrahedral coordination modes of the
Zn(II) ion in the complex CU-SCRU2
Fig. 2 Coordination environment of CU-SCRU1; (a) the asymmetric
unit and the related coordination atoms are labeled as follows with
the hydrogen atoms omitted for clarity: green, Zn1 and Zn2; red, O;
blue, N; black, C. (b) Zn(II) ion located in an octahedral geometry,
image generated by Mercury
Table 1 Selected bond lengths (Å) and bond angles (deg) for CU-
SCRU11 and CU-SCRU22
CU-SCRU1
CU-SCRU2
O(10)-Zn(1) 2.128(7)
Zn(1)-Zn(2) 2.936(2)
O(11)-Zn(1) 2.047(8)
O(6)-Zn(1) 1.970(10)
O(13)-Zn(1) 2.068(9)
Zn(1)-O(9)#2 1.938(9)
O(6)-Zn(2) 2.134(6)
Zn(1)-O(11)#2 1.992(9)
O(13)-Zn(1) 1.957(10)
O(7)-Zn(2) 2.062(7)
O(14)-Zn(2) 2.040(9)
O(5)-Zn(2) 2.007(9)
O(11)#1-Zn(1)-O(11) 180.0(7)
O(11)#1-Zn(1)-O(13)#1 92.9(4)
O(11)-Zn(1)-O(13)#1 87.1(4)
O(13)#1-Zn(1)-O(13) 180.0(4)
O(11)#1-Zn(1)-O(10) 95.6(3)
O(11)-Zn(1)-O(10) 84.4(3)
O(13)#1-Zn(1)-O(10) 91.5(3)
O(13)-Zn(1)-O(10) 88.5(3)
O(10)-Zn(1)-O(10)#1 180.0(2)
O(14)#2-Zn(2)-O(14) 180.0(3)
O(14)-Zn(2)-O(7)#2 90.5(4)
O(14)-Zn(2)-O(7) 89.5(4)
O(7)#2-Zn(2)-O(7) 180.0(1)
O(14)#2-Zn(2)-O(6)#2 89.9(4)
O(14)-Zn(2)-O(6)#2 90.1(4)
O(7)-Zn(2)-O(6)#2 94.6(3)
O(14)-Zn(2)-O(6) 89.9(4)
O(7)-Zn(2)-O(6) 85.4(3)
O(6)#2-Zn(2)-O(6) 180.0(2)
O(7)-Zn(2) 1.907(8)
Zn(2)-O(12)#2 1.999(10)
O(13)-Zn(2) 1.927(10)
Zn(2)-O(13)-Zn(1) 98.2(5)
O(9)#2-Zn(1)-O(13) 123.2(4)
O(9)#2-Zn(1)-O(6) 111.8(4)
O(13)-Zn(1)-O(6) 110.8(4)
O(9)#2-Zn(1)-O(11)#2 107.8(4)
O(13)-Zn(1)-O(11)#2 100.8(4)
O(6)-Zn(1)-O(11)#2 98.9(4)
O(7)-Zn(2)-O(13) 123.8(4)
O(7)-Zn(2)-O(12)#2 115.4(4)
O(13)-Zn(2)-O(12)#2 105.8(4)
O(7)-Zn(2)-O(5) 103.9(4)
O(13)-Zn(2)-O(5) 106.6(4)
O(12)#2-Zn(2)-O(5) 97.9(4)
Fig. 3 (a) Overall 1D polymeric chain of CU-SCRU1. (b) Side view
2D structure of CU-SCRU1 (c) Top view of the 3D structure of CU-
SCRU1. (d) Non-classical H-bonding between 1D-polymeric chains
of CU-SCRU1 (Images are generated by Mercury)
in chelating monodentate mode and one oxygen atom in
a bridging mode between the Zn1(II) ion and the Zn2(II)
ion (see Fig. 4). For the Zn1(II) ion, the bond lengths of
Zn1-O were in the range of 1.938–1.992 Å and the bond
angle of the tetrahedral geometry was 98.9–123.2°. In the
case of the Zn2(II) ion, the Zn2-O bond lengths were in the
range 1.907–2.007 Å and their bond angles lied between
1Symmetry transformations used to generate
equivalent atoms: #1 -x+1,-y,-z
#2 -x, y+2,z+1
2Symmetry transformations used to
generate equivalent atoms: #1 -x+1,-y,-
z #2 -x,-y+2,-z+1
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Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 6 Coordination environment of CU-SCRU3. (Images are gener-
ated by Mercury)
Fig. 5 (a) Overall 1D polymeric chain of CU-SCRU2. (b) Side view
2D structure of CU-SCRU2 (c) Top view of the 3D structure of CU-
SCRU2. (Images are generated by Mercury)
three diferent 3B anions. Selected bond lengths and bond
angles of CU-SCRU3 and CU-SCRU4 are listed in Table 2.
The structure of CU-SCRU3 featured a 3D framework
as displayed in Fig. 7
103.9° and 115.4°. Selected bond lengths and bond angles
are listed in Table 1.
The crystal structure of CU-SCRU4 is shown in Fig. 8
which was also composed of two kinds of crystallographi-
cally independent Cd(II) ions. The Cd1(II) ion was in a dis-
torted octahedral geometry completed by six oxygen atoms
from four carboxylic groups in chelating/bridging monoden-
tate, bidentate and bis-bidentate modes. The coordination
environment of Cd2(II) forms an octahedral geometry built
from two oxygen atoms from water molecules and four oxy-
gen atoms from four carboxylic groups in chelating/bridging
monodentate, bidentate and bis-bidentate fashions.
The structure of CU-SCRU4 also features in a 3D frame-
work as illustrate in Fig. 9.
The structure of CU-SCRU2 was a 1D zig-zag polymeric
chain which was extended by coordination bonds as shown
in Fig. 5. The 2D and 3D structures of the CU-SCRU2 were
extended by weak intermolecular interactions.
Comparing the coordination geometries of the Zn(II)
ions in the complex of CU-SCRU1 and CU-SCRU2, they
possess octahedral and tetrahedral coordination geometry,
respectively which might result from the diferent positions
of the carboxylic acid groups on the organic linkers 3A and
3B and their diferent synthesis conditions as mentioned
previously.
In comparison to CU-SCRU2, two carboxylate groups
on each side of the 3B ligand chelated to Zn(II) ion which
made its structure a 1D polymeric chain. However, in CU-
SCRU3 and CU-SCRU4, the carboxylate groups had dif-
ferent chelating manners. The Cd(II) ions shared a coordi-
nation bond with a carboxylate from other organic linkers
which made them form a 3D structure. It should be noted
that the organic linkers contain a free rotation of -CH2 that
can increase the complexity of the formation of coordina-
tion polymers. However, the nitrogen adsorption–desorption
study showed that they were nonporous material as demon-
strated in Figs. 10 and 11.
Coordination polymers, CU‑SCRU3 and CU‑SCRU4.
With suitable reaction conditions, the coordination between
the organic linker 3B and the Cd(II) ion provided colorless
polyhedral crystals which were characterized by single-crys-
tal X-ray difraction analysis. Interestingly, there were two
crystal structures (CU-SCRU3 and CU-SCRU4) formed in
the same reaction. This phenomenon might be explained
by the free rotation of the methylene bridge in organic link-
ers 3A and 3B resulting in diferent coordination polymer
structures [21]. From the crystal structure of CU-SCRU3,
as shown in Fig. 6, two Cd(II) ions showed diferent coor-
dination environments. The Cd1(II) ion was at the center of
an octahedral geometry, formed from four carboxylate oxy-
gen atoms and two oxygen atoms from the solvent (DMF).
However, the Cd2(II) ion formed a six-coordinated twisted
octahedral geometry, surrounded by six oxygen atoms from
In summary, new organic linkers, 1,3-alternate calix[4]
arene tetrabenzoic acids, 3A and 3B were synthesized
using simple synthetic pathways. The optimized reac-
tion condition in the synthesis of the coordination poly-
mer between 3A/3B with Zn(II) and Cd(II) provided four
single-crystals. The coordination polymer structure from
3A and Zn(II) resulted in a 1D straight polymeric chain
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Table 2 Selected Bond Lengths (Å) and Bond Angles (deg) for CU-
SCRU31 and CU-SCRU42
CU-SCRU3
CU-SCRU4
O(4)-Cd(1) 2.20(2)
Cd1-O(5) 2.489(14)
O(6)-Cd(1) 2.290(15)
Cd1-O(6) 2.307(10)
O(7)-Cd(1) 2.09(4)
Cd1-O(14)#6 2.128(17)
Cd1-O(10)#7 2.136(17)
Cd1-O(8)#8 2.291(11)
Cd1-O(7)#8 2.521(14)
Cd2-O(9)#6 2.244(15)
Cd2-O(8)#9 2.263(13)
Cd2-O(11)#5 2.276(16)
Cd2-O(6) 2.300(14)
Cd(1)-O(7)#3 2.09(4)
Cd(1)-O(4)#3 2.20(2)
Cd(1)-O(6)#3 2.290(15)
Cd(2)-O(3)#3 2.29(2)
Cd(2)-O(3)#4 2.29(2)
Cd(2)-O(5)#5 2.505(16)
O(5)-Cd(2) 2.505(16)
O(6)-Cd(2) 2.299(12)
Cd2-O(12) 2.48(2)
Cd(2)-O(6)#5 2.299(12)
Cd(1)-O(6)-Cd(2) 112.2(7)
O(7)#3-Cd(1)-O(7) 85(3)
O(7)-Cd(1)-O(4)#3 86.3(16)
O(7)-Cd(1)-O(4) 88.3(13)
O(4)#3-Cd(1)-O(4) 173(2)
O(7)#3-Cd(1)-O(6) 96.5(14)
O(7)-Cd(1)-O(6) 170.4(11)
O(4)#3-Cd(1)-O(6) 84.2(12)
O(4)-Cd(1)-O(6) 101.2(7)
O(6)-Cd(1)-O(6)#3 84.1(6)
Cd2- O(13) 2.44(3)
O(5)-Cd1-O(7)#8 172.3(4)
O(6)-Cd1-O(5) 53.0(4)
O(8)#8-Cd1-O(6) 93.7(4)
O(8)#8-Cd1-O(7)#8 55.0(4)
O(10)#7-Cd1-O(5) 88.9(6)
O(10)#7-Cd1-O(6) 133.9(8)
O(10)#7-Cd1-O(7)#8 86.8(6)
O(14)#6-Cd1-O(5) 88.4(7)
O(14)#6-Cd1-O(8)#8 133.4(9)
O(14)#6-Cd1-O(10)#7 108.8(11)
O(3)#3-Cd(2)-O(3)#4 118.1(19) O(9)#6-Cd2-O(11)#5 177.2(8)
O(3)#3-Cd(2)-O(6) 93.8(7)
O(3)#4-Cd(2)-O(6) 129.6(9)
O(6)-Cd(2)-O(6)#5 93.8(6)
O(3)#3-Cd(2)-O(5) 89.5(6)
O(3)#4-Cd(2)-O(5) 85.4(6)
O(6)-Cd(2)-O(5) 55.0(5)
O(8)#9-Cd2-O(6) 83.8 (4)
O(8)#9-Cd2-O(13) 171.4(6)
O(11)#5-Cd2-O(13) 92.5 (8)
O(6)-Cd2-O(13) 90.3(7)
O(9)#6-Cd2-O(12) 93.5(8)
O(8)#9-Cd2-O(12) 89.6(6)
O(6)-Cd2-O(12) 171.5(5)
O(13)-Cd2-O(12) 96.8(9)
Fig. 7 Overall 3D framework of CU-SCRU3 generated by Mercury.
(a) View along the a-axis, (b) View along the c-axis
O(6)#5-Cd(2)-O(5) 133.7(5)
O(5)-Cd(2)-O(5)#5 170.1(5)
1Symmetry transformations used to generate equivalent atoms:
#1 -x+7/4,-y+3/4,z #2 -x+2,-y+1,-z #3 x,-y+5/4,-z+1/4 #4
-x+5/4,y,-z+1/4
#5 -x+5/4,-y+5/4,z
2Symmetry transformations used to generate equivalent atoms:
#1 x+1/2,y+1/2,z #2 -x+1/2,y+1/2,-z+1/2 #3 x,-y+2,z+1/2 #4
x+1,-y+2,z+1/2
#5 -x+1,-y+2,-z+1 #6 x,-y+2,z-1/2 #7 x-1,-y+2,z-1/2 #8 x-1/2,y-
1/2,z
#9 -x+1/2,y-1/2,-z+1/2
Fig. 8 Coordination environment of CU-SCRU4 (Images are gener-
ated by Mercury)
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 11 SEM images of coordination polymers, (a) CU-SCRU1, (b)
CU-SCRU2, (c) CU-SCRU3 and CU-SCRU4)
while 3B with Zn(II) yielded a 1D coordination polymer
in a zig-zag shape. It is important to note that organic
linkers which contain moieties that are not preorganized to
coordinate with the metal ion might result in the formation
of various structures such as the case of organic linker 3B
with Cd(II). In this case, two diferent non-porous single
crystals in the same reaction were produced, CU-SCRU3,
and CU-SCRU4.
Supplementary Information The online version contains supplemen-
tary material available at https://doi.org/10.1007/s10847-021-01091-5.
Acknowledgements This research is fund by Graduate School of Chu-
lalongkorn University, TSRI Fund (CU_FRB640001_01_33_1) and
The National Research Council of Thailand. The authors thank Dr.
Andrew William King for language editing.
Fig. 9 Overall 3D framework of CU-SCRU4 generated by Mercury.
(a) View along the a-axis, (b) View along the c-axis
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