Accepted Manuscript

Organic additives induced coordination complexes of cucurbit[5]uril with stron-

tium(II)

Kai Chen, Wei-Wei Ge, Jing Xu, Hao Zhang, Rui-Lian Lin, Jing-Xin Liu

PII: S0020-1693(18)31611-6
DOI: https://doi.org/10.1016/j.ica.2018.11.051
Reference: ICA 18666

To appear in: Inorganica Chimica Acta

Received Date: 10 September 2018

Revised Date: 27 November 2018
Accepted Date: 29 November 2018

Please cite this article as: K. Chen, W-W. Ge, J. Xu, H. Zhang, R-L. Lin, J-X. Liu, Organic additives induced
coordination complexes of cucurbit[5]uril with strontium(II), Inorganica Chimica Acta (2018), doi: https://doi.org/
10.1016/j.ica.2018.11.051

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Organic additives induced coordination complexes of cucurbit[5]uril with
strontium(II)
Kai Chen a*, Wei-Wei Ge a, Jing Xu a, Hao Zhang a, Rui-Lian Linb, Jing-Xin Liub*
a
Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control,
School of Environmental Science and Engineering, Nanjing University of Information Science
& Technology, Nanjing 210044, China. Email: catqchen@163.com
b
College of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan
243002, China. Email: jxliu411@163.com

Abstract
Three coordination complexes based on the macrocyclic ligand cucurbit[5]uril (Q[5]) with
formulas {[Sr(C30H30N20O10)H2O]Cl2}·11H2O (1),
{[Sr(C30H30N20O10)2(C6H5NO3)2(H2O)4]Cl4}·2H2O (2) and {[Sr(C30H30N20O10)Cl2]}·16H2O (3)
have been obtained by the self-assembly of Q[5] with strontium(II) in the absence and presence
of two different organic compounds, p-hydroxybenzoic acid and p-nitrophenol. Single crystal
X-ray diffraction analysis of these three complexes reveal that metal ions Sr2+ can be chelated
by Q[5] to form molecular bowl and molecular capsule. Complex 1 is a discrete molecular
bowl. Complex 2 induced by p-nitrophenol displays a molecular capsule, which connects with
the p-nitrophenol through “out-surface interaction”. Interestingly, complex 3 induced by p-
hydroxybenzoic acid is a fascinating coordination polymer with 2D planar layer structure. The
comparative study of these three complexes suggest that the organic molecules play important
roles in the self-assembly of coordination complexes.

Keywords: Cucurbit[5]uril; Coordination complex; Coordination polymer; Organic inducer; X-

ray Crystallography;

1
1. Introduction
The design and construction of coordination polymers has been an active research area in
the past decades.1-5 The main reason of this scientific interest is their artistically pleasing
structures and their potential applications in molecular adsorption, separation, heterogeneous
catalysis, sensing, magnetism, etc.6-14 In general, the construction of coordination polymers
involves the design and synthesis of appropriate organic ligand, which strongly affect the
spatial construction and properties of the coordination polymers, and ultimately determine their
functionalities. Recently, numerous literatures have demonstrated a basic strategy to construct
coordination polymers, of which the macrocycles act as building blocks to coordinate to metal
centers.15-19 No doubt, such strategy provides new opportunities for introducing functionality
for coordination polymers because each of macrocyclic cavitand possesses distinctive
properties.
As a type of macrocyclic cavitand, cucurbit[n]urils (n = 5–8, 10, abbreviated as Q[n]) have
attracted much interests not only in host-guest chemistry but also in coordination chemistry
because of their rigid hydrophobic cavity and carbonyl-laced portals.19-24 For the intermediary
and large sized Q[n]s such as the Q[7], Q[8] and Q[10], they usually display outstanding
inclusion properties for positively charged organic guests. In contrast, the small sized Q[n]s
especially the Q[5] exhibit particular metal–ion coordination abilities. In the past decade, Q[5]
has been widely used as polydentate ligand to coordinate with all kinds of metal ions, such as
alkali, alkaline-earth, and lanthanide metal ions.25-31 Nevertheless, the coordination complexes
of the Q[5] is usually low dimensional. How to design and synthesis of poly-dimensional
coordination polymers based on Q[5] is challenging.
Our previous research found that the addition of the third species including small organic
aromatic molecules and tetrachloride transition metal anions [MtransCl4]2- will affect the
coordination of a metal ion to the Q[n]s, and lead to unpredictable poly-dimensional
coordination geometry.19, 32-40 In the present work, we prepared three coordination complexes
of Q[5] with the strontium(II) in the absence and presence of two different aromatic molecules
(p-nitrophenol and p-hydroxybenzoic acid, Figure 1), and described their single crystal
structures. This study further confirms that the addition of the third species will produces high
dimensional coordination supramolecular assembly materials.

2. Experimental Section
2.1. Materials and Methods
All the reagents and solvents employed were commercially available and used as received

2
without further purification. Cucurbit[5]uril was synthesized by published procedures41, 42. The
C, H, and N microanalyses were carried out with a CE instruments EA 1110 elemental analyzer.

2.2. Syntheses
{[Sr(C30H30N20O10)H2O]Cl2}·11H2O (1): Q[5] (0.020 g, 0.020 mmol) and SrCl2·6H2O (0.021 g,
0.080 mmol) were dissolved in 5.0 ml 1 M HCl solution with stirring at room temperature for
two weeks. Purple crystals of 1 were collected in 52% yield. Anal. Calcd. (Found) for
{[Sr(C30H30N20O10)H2O]Cl2}·11H2O 1: C, 28.61 (28.81), N, 22.24 (22.56), H, 4.81 (4.68).
{[Sr(C30H30N20O10)2(C6H5NO3)2(H2O)4]Cl4}·2H2O (2): Q[5] (0.020 g, 0.020 mmol),
SrCl2·6H2O (0.021 g, 0.080 mmol), and p-nitrophenol (0.006 g, 0.040 mmol) were dissolved in
5.0 ml 1 M HCl solution with stirring at room temperature. X-ray quality colorless crystals of 2
separated after one week. Purple crystals of 2 were collected in 56% yield. Anal. Calcd. (Found)
for 2: C, 22.46 (22.49), N, 20.19 (20.55), H, 2.91 (3.13).
{[Sr(C30H30N20O10)Cl2]}·16H2O (3): Q[5] (0.020 g, 0.020 mmol), SrCl2·6H2O (0.021 g, 0.080
mmol), and p-hydroxybenzoic acid (0.005 g, 0.040 mmol) were dissolved in 5.0 ml 1 M HCl
solution with stirring at room temperature. X-ray quality colorless crystals of 2 separated after
one week. Purple crystals of 2 were collected in 52% yield. Anal. Calcd. (Found) for 2: C,
25.09 (25.47), N, 19.51 (19.75), H, 4.35 (4.51).

2.3. X-ray Crystallography

Single crystal X-ray data were collected on a Bruker Apex-2000 diffractometer at 123 K
using graphite monochromated Mo-Kα radiation (λ = 0.71073 Å) with ω/2θ scan mode.
Lorentz-polarization and absorption corrections were applied. Structural solution and full
matrix least-squares refinement based on F2 were performed with the SHELXS-97 and
SHELXL-97 program package43-45, respectively. All the non-hydrogen atoms were refined
anisotropically. The idealized positions of the hydrogen atoms were located by using ‘riding’
model with Uiso = 1.2Ueq of carrier atom. Analytical expressions of neutral-atom scattering
factors were employed, and anomalous dispersion corrections were incorporated. For these
three complexes, owing to the high degree of disordered water molecules, the SQUEEZE
routine of Platon was employed.46
A summary of the crystallographic data, data collection and refinement parameters for
complexes 1-3 is given in Table 1.

3
3. Results and Discussion
3.1. Description of the crystal structures
Slow evaporation of aqueous solution containing Q[5] and SrCl2 generates the crystals of
the complex 1. Crystal structure analysis reveals that complex 1 crystallize in the monoclinic
crystal system with the P21/c space group. The asymmetric unit of complex 1 consists of one
Q[5] ligand, one Sr2+ cation, two free chloride anions, and 4 coordinated and 11 uncoordinated
water molecules. The structure of 1, as shown in figure 2, may be viewed as a molecular bowl
formed by closure of one carbonyl-fringed portal of Q[5] via carbonyl-Sr(II) coordination. The
Sr(II) ion is octacoordinated by five carbonyl oxygens and three water molecules. One of the
coordinated water molecule is located inside of the molecular bowl. The bond lengths of Sr-
OQ[5] and Sr-Owater are 2.635(2)-2.742(2) and 2.585(2)-2.643(3) Å, respectively. The bond
lengths of Sr-OQ[5] and Sr-Owater are comparable to their counterparts in the previously reported,
closed molecular capsule {Sr2(H2O)3(NO3)[(NO3)Q*[5]]}2+.47 It should be noted here that the
Sr2+ is not coplanar with the mean plane of the five carbonyl oxygen atoms of the Q[5] portal.
It’s height that out of the mean plane of the five carbonyl oxygen atoms of the Q[5] portal is
0.721 Å.
The most remarkable feature of the crystal structure of complex 1 is that the molecular
bowl is discrete. The molecular bowl is surrounded by many solvent water molecules and
chloride anions, and they interact with each other via complicated hydrogen-bonding. In the
solid-state, numerous neighboring molecular bowls stack to form infinite 1D channels along
the a-axis (Figure 3). The channels are filled with chloride anions and water molecules. Views
of the channels of the complex 1 are shown in Figure 3. PLATON calculations indicated that
24.6 % of the crystal volume (1208.8 Å3 out of 4913.1 Å3) is occupied by chloride anion and
water molecules.48
The supramolecule found in the crystals of complex 2 was self-assembled from the aqueous
solution of Q[5] and SrCl2 in the presence of p-nitrophenol. The X-ray crystallography
confirms that complex 2 crystallize in the monoclinic system, space group C2/c. In the
asymmetric unit of complex 2 there exist one half of Q[5] ligand, one Sr(II) ion, two chloride
anions, one p-nitrophenol and two coordinated and two uncoordinated water molecules. The
perspective view of complex 2 is shown in Figure 4. The Sr(II) ion is coordinated by five
carbonyl oxygens of Q[5] ligand, and two water molecules from outside and one chloride anion
from inside. Obviously, complex 2 can be viewed as a completely closed molecular capsule, in
which a chloride anion is encapsulated. The bond lengths of Sr-OQ[5] and Sr-Owater are 2.520(1)-

4
2.616(2) and 2.526(4)-2.605(1) Å, respectively, which are very similar to those of their
counterparts in 1.
The most remarkable aspect of the structure of complex 2 is that the organic molecule p-
nitrophenol is observed outside of the molecular capsule. As shown in Figure 5, the p-
nitrophenol connects with the molecular capsule through “outer-surface interactions”,49 which
includes C−H••• interactions between the methylene of the Q[5] and the aromatic ring of the
p-nitrophenol, and C−H•••Cl halogen bonding between the methylene of the Q[5] and Cl atoms.
Addition of p-hydroxybenzoic acid in the aqueous solution of Q[5] and SrCl 2 results in the
formation of the complex 3. The single-crystal structural analysis reveals that complex 3
crystallises in the hexagonal system with the space group of P63/mcm, comprising only one
quarter of Q[5] ligand in the asymmetric unit. There is only one crystallographically
independent Sr(II) center in an asymmetric unit of complex 3. As can be seen in Figure 6, the
octacoordinated Sr(II) center coordinates to two triply bridging chloride anions and six
carbonyl oxygens, one of them from the neighboring Q[5] ligand. The Sr-OQ[5] bond lengths
(mean value 2.662 Å) in complex 1 are comparable to those of complexes 1 and 2. The heights
that out of the mean plane of the five carbonyl oxygen atoms of the Q[5] portal in complexes 2
and 3 are 0.377 and 0.442 Å, respectively, which are much smaller than that (0.721 Å) in
complex 1. Interestingly, three Sr(II) centers are further connected by three carbonyl oxygens
from three neighboring Q[5] ligands that act as μ2-bridging atoms to link two neighboring Sr(II)
centers, and are capped by two μ3-Cl ligands, giving rise to a [Sr3(3-Cl)2]4+ cluster. The Sr-Sr
distances (4.269 Å) indicate no metal-metal bonding between the three Sr(II) ions.
Furthermore, each Q[5] ligands is connected by two [Sr3(3-Cl)2]4+ clusters on its two
portals and each [Sr3(3-Cl)2]4+ cluster is coordinated to three Q[5] ligands. As a result,
propagation of the structure in the crystal generates a fascinating coordination polymer (Figure
7). The skeleton of the coordination polymer consists of a fundamental repeating unit
(C30H30N20O10)3[Sr3(3-Cl)2]28+. By looking at the coordination polymer, six [Sr3(3-Cl)2]4+
clusters are arranged in a circular fashion through six bridging Q[5] ligands (Figure 7). All
these [Sr3(3-Cl)2]4+ clusters and Q[5] ligands form a unique 2D planar layer, parallel to the ab-
plane of the unit cell. This coordination polymer structure is very similar to those reported
catenated frameworks in the literature.19 In the solid-state, adjacent planar layers with a
distance of 13.625 Å stack along c-axis and rotate an angle of 120 o. Such a staggered
arrangement generates a honeycomb-like structure with numerous thorough 1D channel along
the c axis (Figure 8). Each channel is surrounded by six other identical channels showing a

5
distance of 18.939 Å between any two channels (Figure 8). The channel spaces are not empty
but occupied by numerous chloride anions and many disordered water molecules. The solvent
accessible volume of these channels, calculated with the PLATON program, is 3237.3 Å3,
which is 38.2% of the total unit cell volume (8464.7 Å3).48

3.2. Roles of the third species in the self-assembly process

The comparative study of these three coordination complexes may make sense to us. As a
matter of fact, without the assistance of any organic compounds, the coordination of Q[5] with
Sr(II) produces low dimensional complex 1. Complexes 2 and 3 are formed only in the
presence of p-nitrophenol and p-hydroxybenzoic acid. No doubt, the third species act as an
inducer in the self-assembly process of these two complexes. The choice of the inducers is
critical in determining the coordination complexes. For the complex 2, it is proposed that the p-
nitrophenol contacts with the Q[5] ligand though “outer-surface interactions”, which
conversely affected the coordination of the Sr(II) to the Q[5] ligand, and finally generated a
different coordination structure. In the case of complex 3, although we added the third species
of p-hydroxybenzoic acid in the aqueous solution of Q[5] and SrCl2, no p-hydroxybenzoic acid
were found in the structure of complex 3. How the p-hydroxybenzoic acid affect the
coordination of the Sr(II) with the Q[5] ligand is still unclear and more experiments are
necessary.

4. Conclusion
In summery, we prepared three coordination complexes of Q[5] with the strontium(II) in
the absence and presence of two different organic compounds. Their single crystal structures
confirm that the direct coordination of Q[5] with Sr2+ generates low dimensional molecular
bowl, the complex 1. In the presence of p-nitrophenol, the self-assembly of Q[5] with Sr2+
results in complex 2, a molecular capsule structure, in which chloride anions were encapsulated,
while the p-nitrophenol connects with the molecular capsule through “out-surface interaction”.
Interestingly, p-hydroxybenzoic acid induces the coordination of Q[5] with Sr2+ to form
fascinating two dimensional coordination polymer, the complex 3, which represents good
examples of constructing poly-dimensional polymers by adding the third species. The
comparative study of these three coordination complexes suggest that the organic molecules p-
hydroxybenzoic acid and p-nitrophenol may act as inducer in the self-assembly of Q[n]s with
metal ions. Present study sheds light on the designing and constructing high dimensional
coordination polymer.

6
Supplementary materials
CCDC 1866165-1866167 contain the supplementary crystallographic data for this paper. The
data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif (or from The
Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44
1223 336 033; e-mail: deposit@ccdc.cam.ac.uk).

Acknowledgments
We thank the National Natural Science Foundation of China (Grant No.: 21601090 and
21371004), the Natural Science Foundation of Jiangsu Province (BK20160943), and Natural
Science Foundation of Anhui Province (1808085MB43)for financial support.

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FIGURE CAPTIONS:

Figure 1. Molecular structure of Q[5] and two orgnic inducers.

Figure 2. The asymmetric unit of complex 1 showing the coordination mode of Q[5] with the

Sr2+ ion. Solvate water molecules and anions are omitted for clarity.

Figure 3. Packing diagram of complex 1 viewed down the a axis; O = red, C = grey, N = light

blue, Cl = green, and Sr = turquiose. Solvate water molecules are omitted for clarity.

(Symmetry code: a: 2-x, y, 0.5-z)

Figure 4. Perspective view of the complex 2 showing the molecular capsule structure. Solvate

water molecules and anions are omitted for clarity.

Figure 5. “Outer-surface interactions” during the p-nitrophenol, chlorine atoms and molecular

capsule in complex 2.

Figure 6. Coordination geometry of Sr2+ in complex 3 showing the [Sr3(3-Cl)2]4+ cluster

structure. Solvate water molecules and anions are omitted for clarity. (Symmetry code: a: -x+y,

1-x, 0.5+x)

Figure 7. 2D planar structure in complex 3. viewed down the c axis.

Figure 8. Spacefilling diagram of complex 3 viewed down the c axis. O = red, C = grey, N =

light blue and Sr = turquiose water molecules and chloride anions are omitted for clarity.

Table 1. Crystal Data and Structure Refinement Details for Compounds 1–3.

10
Figure 1

Figure 2

Figure 3

11
Figure 4

Figure 5

Figure 6

Figure 7

12
Figure 8
Table 1.

Compound 1 2 3 Compound 1 2 3
Empirical C30H60N20 C42H44N22O22 C15H31N10O13S
Dcalcd, g cm-3 1.424 1.699 1.349
formula O25SrCl2 Sr2Cl4 rCl2
Formula
1259.26 1525.9 717.88 T, K 293 293 293
weight

Crystal system monoclinic monoclinic hexagonal μ, mm-1 1.284 2.108 2.140

Space group P 21/c C 2/c P63 Unique reflns 9575 5654 2700

a, Å 11.4652(7) 21.3870(13) 18.9393(9) Obsd reflns 6214 4203 1832

b, Å 14.6386(9) 15.2616(10) 18.9393(9) Params 604 411 167
c, Å 29.2842(18) 19.7995(18) 27.249(3) Rint 0.0984 0.0567 0.1109
a
α, deg 90 90 90 R[I> 2σ(I)] 0.0600 0.0410 0.1314

β, deg 91.563(2) 115.670(2) 90 wR[I> 2σ(I)]b 0.1570 0.1155 0.1684

γ, deg 90 90 120 R(all data) 0.1000 0.0648 0.2726

3
V, Å 4913.1(5) 5824.7(7) 8464.6(12) wR(all data) 0.1711 0.1227 0.2885
2
Z 4 4 12 GOF on F 0.995 1.052 1.254
CCDC 1866165 1866166 1866167

a
Conventional R on Fhkl: Σ||Fo|−|Fc||/Σ|Fo|, b Weighted R on |Fhkl|2: Σ[w(Fo2 − Fc2)2]/Σ[w(Fo2)2]1/2

13
 Synopsis

Three coordination complexes of cucurbit[5]uril (Q[5]) with Sr(II) were prepared in the
absence and presence of two different aromatic molecules. Their crystal structure suggest
organic compounds play important roles in the formation of poly-dimensional coordination
polymer.

14