Calcium coordination compounds based on phenoxyacetic acids: Microwave synthesis, thermostability and influences on the crystal structures of chlorine substituent group on ligands

Article abstract of DOI:10.1080/00958972.2015.1126259

Three calcium coordination compounds, [Ca(CPA)(H₂O)₄]·(CPA), 1, [Ca(MCPA)₂(H₂O)₂]·H₂O, 2, and [Ca(TCPA)₂(H₂O)₃]·2H₂O, 3 [HCPA = 3-chlorophenoxyacetic acid, HMCPA = 2-methyl-4-chlorophenoxyacetic acid, and HTCPA = 2,4,6-trichlorophenoxyacetic acid], have been synthesized by the microwave method with advantages that include shorter reaction times, lower energy consumption, and higher product yield. The structures have been characterized by IR, elemental analysis, and single-crystal X-ray diffraction. Influences on the crystal structures by changing the number and position of chlorine substituent group in phenoxyacetic acid are discussed. Steric hindrance effects involving the Cl and an ability to form the O-HCl hydrogen bonds enrich the structure diversity. TG analysis reveals that the thermostability for the three compounds is 3 > 1 > 2, which could be influenced by the existence of hydrogen bonds (O-HCl and O-HO).

Full text of DOI:10.1080/00958972.2015.1126259

Journal of Coordination Chemistry
ISSN: 0095-8972 (Print) 1029-0389 (Online) Journal homepage: http://www.tandfonline.com/loi/gcoo20
Calcium coordination compounds based on
phenoxyacetic acids: Microwave synthesis,
thermostability and influences on the crystal
structures of chlorine substituent group on ligands
Xiuling Xu, Saisai Yan, Fan Hu, Wei Zhao & Qi Shuai
To cite this article: Xiuling Xu, Saisai Yan, Fan Hu, Wei Zhao & Qi Shuai (2015): Calcium
coordination compounds based on phenoxyacetic acids: Microwave synthesis, thermostability
and influences on the crystal structures of chlorine substituent group on ligands, Journal of
Coordination Chemistry, DOI: 10.1080/00958972.2015.1126259
To link to this article: http://dx.doi.org/10.1080/00958972.2015.1126259
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Dec 2015.
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Date: 03 January 2016, At: 22:23

Publisher: Taylor & Francis
Journal: Journal of Coordination Chemistry
DOI: http://dx.doi.org/10.1080/00958972.2015.1126259
Calcium coordination compounds based on phenoxyacetic acids: Microwave
synthesis, thermostability and influences on the crystal structures of chlorine
substituent group on ligands
XIULING XU, SAISAI YAN, FAN HU, WEI ZHAO and QI SHUAI*
College of Science, Northwest A&F University, Yangling 712100, Shaanxi Province, P. R. China
Three calcium coordination compounds, [Ca(CPA)(H
2
O)
4
2 2 2 2
]·(CPA), 1, [Ca(MCPA) (H O) ]·H O,
2
, and [Ca(TCPA) (H O) ]·2H O, 3 [HCPA = 3-chlorophenoxyacetic acid, HMCPA =
2
2
3
2
2-methyl-4-chlorophenoxyacetic acid and HTCPA = 2,4,6-trichlorophenoxyacetic acid], have
been synthesized by the microwave method with advantages that include shorter reaction times,
lower-energy consumption, and higher product yield. The structures have been characterized by
IR, elemental analysis, and single-crystal X-ray diffraction. Influences on the crystal structures
by changing the number and position of chlorine substituent group in phenoxyacetic acid are
discussed. Steric hindrance effects involving the Cl and an ability to form the O-H···Cl hydrogen
bonds enrich the structure diversity. TG analysis reveals that the thermostability for the three
compounds is 3>1>2, which could be influenced by the existence of hydrogen-bonds (O-H···Cl
and O-H···O).
Keywords: Calcium coordination compounds; Microwave method; Crystal structure;
Thermostability
*
Corresponding author. Email: shuaiqi@nwsuaf.edu.cn
1

1
. Introduction
Calcium coordination compounds have drawn much more attention owing to valuable
applications in tunable fluorescent indicators [1-3], ion sensing [4], homogeneous catalysts [5, 6]
and metal-organic frameworks (MOFs) for selective adsorption of CO and N [7-9]. Ligands
2
2
used to construct these coordination compounds are mainly focused on Schiff bases, protein,
heterocyclic compounds and aromatic carboxylic acids [10-13]. Chlorophenoxyacetic acids are
one of the most widely used aromatic carboxylic acid ligands with their own unique advantages.
First, the carboxyl group can bond with metal through a variety of coordination modes [14].
Second, chlorophenoxyacetic acids possess flexibility owing to the presence of a -OCH - spacer
2
between the phenyl ring and carboxylate [15]. Third, the chlorine substituent on benzene ring is
beneficial to the formation of O-H···Cl hydrogen-bonds. The three points above assist the
self-assembly process, giving more chances for structure diversity. A number of coordination
compounds based on chlorophenoxyacetic acids have been studied involving Li [16], Ag [17],
Co [18], Zn [19], Mn [20], Cd [21], Fe [22], Gd [23], La and Nd [24]. In these works,
phenoxyalkanoic acids form coordination compounds with metal ions, however, only one case of
calcium based on 2,4-dichlorophenoxyacetate has been reported [25]. Prompted by the above
cases, three different chlorophenoxyacetic acids, HCPA, HMCPA and HTCPA, have been
selected to construct calcium coordination compounds in this work. The synthesis used
microwave synthesis, which has proven to be an effective method to obtain crystals [26]. Effect
on the crystal structures by changing the number and position of chlorine substituents on ligands
are also discussed. Although chlorine substituents do not coordinate to the metal, a steric
hindrance effect and ability to form the O-H···Cl hydrogen-bond enriches the diversities of the
structures. The relationship between thermostability and structure has also been studied. The
order of thermostability is 3>1>2, which may be influenced by hydrogen-bonds.
2

2
2
3
. Experimental
.1. Materials and physical measurements
-Chlorophenol, 4-chloro-2-methylphenol, 2,4,6-trichlorophenol and ethyl chloroacetate were
purchased commercially from Aladdin Reagent Co. Ltd. (Shanghai, China). Microwave
synthesis was performed using a CEM Discover SP single-mode microwave reactor. Elemental
analyses (C and H) were performed on a Vario MACRO cube elemental analyzer. IR spectra
-1
were recorded on a BRUKER TENSOR 27 spectrophotometer from 400-4000 cm using the
samples prepared as pellets with KBr. TG analyses were performed on a SHIMADZU TA-60ws
-1
from 25 to 1000 °C at a heating rate of 10 °C·min in N .
2
2
2
.2. Synthesis of the ligands and coordination compounds
.2.1. Synthesis of HCPA, HMCPA and HTCPA. The three ligands were prepared by
microwave synthesis in the following route (scheme 1). A mixture of 3-chlorophenol (5 mmol)
for 1, 4-chloro-2-methylphenol (5 mmol) for 2 or 2,4,6-trichlorophenol (5 mmol) for 3, ethyl
chloroacetate (5 mmol), K CO (5 mmol), KI (1 mmol), PEG-600 (0.5 mmol) and DMF (2 mL)
2
3
was irradiated in a microwave oven under 200 W for 4 min, then 5 mL of NaOH (2 M) was
added and irradiated 5 min at 500 W. After cooling to room temperature, the resulting aqueous
solution was acidified (pH = 6) by the addition of a 1 M HCl solution under vigorous stirring.
1
Column chromatography provided three white solids. H NMR (DMSO/TMS, 500 MHz, ppm):
HCPA (Yield: 88%) δ 13.17 (s, 1H), 7.40 (t, J = 8.3 Hz, 1H), 7.14-7.07 (m, 2H), 7.02-6.97 (m,
1
H), 4.83 (s, 2H). HMCPA (Yield: 86%) δ 13.04 (s, 1H), 7.22 (d, J = 2.2 Hz, 1H), 7.15 (dt, J =
0.3, 5.1 Hz, 1H), 6.83 (d, J = 8.8 Hz, 1H), 4.70 (d, J = 12.1 Hz, 2H), 2.18 (s, 3H). HTCPA
1
(
Yield: 83%) δ 13.25 (s, 1H), 7.81 (s, 2H), 4.68 (s, 2H).
3

Scheme 1. Syntheses of HCPA: X
2
=Cl, HMCPA: X
1
=CH
3
3 1
, X =Cl, HTCP AA : X =Cl,
X
3
=Cl, X =Cl.
4
2
.2.2. Syntheses of 1-3
.2.2.1. [Ca(CPA)(H O) ] ·( CPA), 1. A mixture of HCPA (0.2 mmol), CaCl ·2H2O (0.1 mmol),
2
2
4
2
NaOH (0.2 mmol) and deionized water (8 mL) was placed in a microwave reaction tube. The
mixed solution was sealed and heated at 100 °C at 120 W in a microwave reacto rr for 1 h. Upon
-1
cooling to room temperature at 10 °C·h , colorless, block crystals suitable for X- rr ay diffraction
were obtained (yield 82% based on Ca). Anal. calc. for C H CaCl O : C, 39.73; H, 4.14 %.
1
6
20
2
10
-1
Found: C, 39.71; H, 4.15 %. IR data (cm ): v(O-H): 3409b; v(Ar-O-C): 1233m, 11 098s, 1050s;
-
-
v
asym(COO ): 1625s, 1569s; vsym(COO ): 1476s, 1422s; v(-CH
2
-): 683m.
2
.2.2.2. [Ca(MCPA) (H O) ] ·H O, 2. The procedure was similar to that of 1 exc ee pt using
2
2
2
2
HMCPA instead of HCPA. Colorless, hexagon bulk crystals for 2 were obtaine dd with yield of
7
4
2% based on Ca. Anal. calc. for C H CaCl O : C, 43.78; H, 4.46 %. Found: C, 43.77; H,
18 22 2 9
-1
-
.45 %. IR data (cm ): v(O-H): 3415b; v(Ar-O-C): 1229m, 1179s, 1071s; vasym(COO ): 1623s;
-
vsym(COO ): 1487s, 1448s, 1422s; v(-CH -): 722m.
2
2
.2.2.3. [Ca(TCPA) (H O) ] ·2 H O, 3. The procedure was similar to that of 1 exc ee pt using
2
2
3
2
HTCPA instead of HCPA. Colorless, rod-like crystals for 3 were obtained with yy ield of 86%
based on Ca. Anal. calc. for C16
H18CaCl
6
O11: C, 30.04; H, 2.82 %. Found: C, 30. 00 5; H, 2.81 %.
-
1
-
IR data (cm ): v(O-H): 3412b; v(Ar-O-C): 1257m, 1191s, 1081s, 1033; v (CO OO ): 1630s,
asym
-
1
575s; vsym(COO ): 1466s, 1422s; v(-CH -): 724m.
2
4

2
.3. Single-crystal X-ray structure determinations
All crystallographic data were collected on a Bruker SMART CCD area-detector diffractometer
at 298(2) K with graphite monochromated Mo-Kα radiation (λ = 0.71073 Å) in ω scan mode, and
the data reduction was performed using Bruker SAINT. The crystal structures were resolved by
2
direct methods and refined with full-matrix least-squares refinement on F with anisotropic
displacement parameters for non-H atoms using SHELXTL [27]. All non-hydrogen atoms and
hydrogens were refined geometrically. Structural plots were generated with Diamond. A
summary of crystallographic data for 1-3 is presented in table 1. Selected bond lengths and
angles for 1-3 are given in table 2. Hydrogen bonding distances and angles for 1-3 are listed in
table 3.
3
3
3
. Results and discussion
.1. Structural descriptions for 1-3
.1.1. Crystal structure of [Ca(CPA)(H O) ]·(CPA), 1. Single-crystal X-ray diffraction
2
4
analysis reveals that the crystal system and space group for 1 are triclinic and P-1, respectively.
The asymmetric unit contains one Ca(II) centre, one coordinated CPA, four coordinated water
molecules, and one lattice CPA. Each Ca(II) is coordinated by eight oxygens, of which three
(O1A, O1 and O2WB) belong to CPA and the other five (O1W, O1WB, O2W, O3W and O4W)
come from coordination water molecules. The coordination environment around Ca(II) is
presented in figure 1(a) with atom numbering scheme. The eight-coordinate Ca(II) is in a
distorted bicapped trigonal prism, where O1A, O2W and O3W form the top plane of the trigonal
prism and the bottom plane is completed by O1, O1W and O1WB, while O4W and O2WB cap
two quadrilateral faces formed by O1WB-O1-O1A-O3W and O1W-O2W-O3W-O1WB,
2
1
respectively. The coordination mode of CPA in 1 is μ -η : η , which means one oxygen links two
3
metal ions and the other oxygen connects one metal ion, so the carboxyl group coordinates to
three ions. The carboxyl group of the CPA and coordination water connect neighboring Ca(II)
5

2 2 2 2 n
ions to form a 1D linear chain with {Ca (CPA) (H O) } dimeric repeat units, which shows
drum-like and tetragon configurations appearing alternately along the b-axis (figure 2(a)). An
interesting structural feature for 1 is the formation of the 2D layer by hydrogen-bond interactions
involving the lattice CPA molecules and coordinated water. Specifically, in the
{
Ca (CPA) (H O) } dimeric repeat units, hydrogen-bonds are formed between coordinated
2 2 2 2 n
water and uncoordinated CPA, in which O1W, O2W, O3W and O4W donate hydrogens to
oxygen of uncoordinated CPA. The uncoordinated CPA serves as a bidentate bridge to link
coordinated water of neighboring chains. In this manner, parallel 1D chains (figure 2(b)) are
involved in hydrogen-bond interactions to form a 2D layer (figure 2(c)) in the ac plane.
3
.1.2. Crystal structure of [Ca(MCPA)
2
(H
2
O)
2
]·H O, 2. Coordination compound 2 crystallizes
2
in the monoclinic crystal system and P2(1)/c space group. The asymmetric unit consists of one
Ca(II), two MCPA anions, two coordinated waters and one lattice water (figure 3(a)). Each Ca(II)
is also eight coordinate by six carboxylate oxygens (O1, O1B, O2A, O2B, O4, O5) from MCPA
ligands and two water molecules (O7, O8). Similar to 1, the Ca(II) is also in a distorted bicapped
trigonal prism, where O1B, O2B and O7 form the top plane of the trigonal prism and the bottom
plane is completed by O8, O4 and O5, while O1 and O2A cap two quadrilateral faces formed by
O2B-O4-O8-O7 and O1B-O5-O8-O7. Different from 1, the MCPA ligands in 2 show two
2
2
1
1
coordination modes: μ -η : η (figure 3(b)) and μ -η : η (figure 3(c)), respectively.
3
1
In 2, the infinite 1D zigzag chain is formed through connection of the metal centers by
carboxyl group oxygens of MCPA ligands, alternately arranged on both sides of the zigzag chain
(
figure 4(a)). The 2D layer (figure 4(b)) was formed by two kinds of hydrogen-bond interactions:
) the hydrogen-bond between carboxyl group oxygen and lattice water and 2) the
hydrogen-bond between oxygens of lattice water and hydrogens of coordinated water molecules.
1
3
.1.3. Crystal structure of [Ca(TCPA)
2
(H
2
O)
3
]·2H O, 3. Single crystal X-ray diffraction
2
analysis reveals that 3 crystallizes in the triclinic crystal system and P-1 space group. As shown
6

in figure 5(a), the asymmetric unit contains one crystallographically unique Ca(II), two TCPA
anions, three coordinated waters and two lattice waters. The eight-coordinate Ca(II) exhibits a
bicapped trigonal prism with top plane completed by O1W, O2B, O3, bottom plane completed
by O6B, O5A, O3W, and two caps of O2W and O5 corresponding to the quadrilateral faces of
O3-O3W-O6B-O1W and O2B-O5A-O3W-O3. From figure 6(a), the 1D metal-node-based chain
with the unique feature of an eight-membered ring and chair-like configuration alternately along
the b-axis is formed through the calcium connections linked by the ligands through coordination
2
1
1
1
modes of μ -η : η in figure 5(b) and μ -η : η in figure 5(c).
2
2
As shown in figure 6, the 2D layer for 2 was formed by the hydrogen-bond (O-H···Cl and
O-H···O) interactions involving TCPA ligands and coordinated water as well as lattice water.
The lattice water can form hydrogen-bonds with the coordinated water (such as
O2W-H2WA···O6W) and also hydrogen-bonds with the carboxylic oxygen (O5W-H5WA···O6),
which is similar to 1 and 2. Lattice water molecules (O5W, O6W) can also donate two free
hydrogens (H5WB, H6WB) to chlorine of TCPA (the two o-position chlorines), then form
O5W-H5WB···Cl5 and O6W-H6WB···Cl3 hydrogen-bonds, which are not found in 1 and 2. The
construction of 1D phenoxyacetic acid coordination compounds which are further extended into
2D layer assisted by O-H···Cl hydrogen-bond interactions remains scarce.
3
.1.4. Influences on crystal structures by changing number and position of chlorine
substituent. The number and position of the chlorine substituent in aromatic rings of 1-3 affect
formation of O-H···Cl hydrogen-bonds. All three coordination compounds have intermolecular
O-H···O hydrogen-bonds, however, only 3 has O-H···Cl hydrogen-bonds. As shown in figure 7,
the distances between chlorine and the nearest oxygen are 6.93 Å for m-position substituted
chlorine in 1 (figure 7(a)) and 5.62 Å for p-position substituted chlorine in 2 (figure 7(b)); both
are too far to form the O-H···Cl hydrogen-bond. There are two o-position substituted chlorines in
3
, one has a distance of 2.59 Å with oxygen of lattice water (figure 7(c)).
7

3
.2. Thermogravimetric analysis of 1-3
Coordination compounds 1-3 have three general mass-loss steps (figure 8). The first mass-loss is
for release of water molecules including all coordinated as well as lattice waters from
9
5.89-202.97 °C for 1, 64.64-141.40 °C for 2, and 89.97 -185.57 °C for 3. The experimental
mass-losses (calculated mass loss) for 1-3 were 14.678% (14.898%), 10.47% (10.945%) and
4.563% (14.083%). The next two mass-losses correspond to continuous collapse of the
frameworks, from 202.97 °C to 726.18 °C for 1, 141.40 °C to 571.83 °C for 2, and 185.57 °C to
89.12 °C for 3. The final residue could be assigned to CaO, with the experimental residue
calculated residue) of 11.771% (11.602%) for 1, 11.015% (11.367%) for 2, and 9.28% (8.775%)
for 3. The final decomposition temperature is in the order 3>1>2
789.12 °C>726.18 °C>571.83 °C), which reveals the thermostability for the three compounds is
1
7
(
(
also in the order 3>1>2. The results of TG coincide quite well with the structures. From the
structural analysis above, we can clearly see that O-H···O hydrogen-bonds exist in all three title
compounds, but O-H···O hydrogen-bonds in 2 are more complex than 1, so the thermostability of
1
is higher than 2. For 3, O-H···Cl hydrogen-bonds coexist with O-H···O hydrogen-bonds,
resulting in the most stable structure among the three coordination compounds.
4
. Conclusion
Three new calcium coordination compounds based on phenoxyacetic acids were microwave
synthesized and characterized (FI-IR, elemental analysis, single-crystal X-ray diffraction). All
Ca(II) ions are coordinated by eight oxygens in distorted bicapped trigonal prism arrangements.
The three compounds were very different in the extension of the 1D chain into the 2D layer. For
1
, the 2D layered network was formed by the O-H···O hydrogen-bond interactions between the
uncoordinated CPA and coordinated water. For 2, the 2D layered network was formed by the
O-H···O hydrogen-bond interactions between carboxyl group oxygen and lattice water, or
between oxygen of lattice water and hydrogen of coordinated water. For 3, the 2D layered
network was formed by O-H···O and O-H···Cl hydrogen-bonds together. Results of thermal
8

analysis proved the thermostability of the three compounds follows the order 3>1>2, which
coincide well with the structures.
Supplementary material
Crystallographic data for the structures reported in this article have been deposited with the
Cambridge Crystallographic Data Center as supplementary publication Nos. CCDC-1401086,
CCDC-1401090 and CCDC-1401091. Copies of the data can be obtained free of charge via
www.ccdc.cam.ac.uk (or from the Cambridge Crystallographic Center, 12 Union Road,
Cambridge CB2 1EZ, UK; Fax: +44 1223 336033; E-mail:deposit@ccdc.cam.ac.uk).
Acknowledgements
The authors gratefully acknowledge the financial supports from the National Natural Science
Foundation of China (Grant No. 21473136, Grant No. 21103140), the Ph.D. Programs
Foundation of Ministry of Education of China (Grant No. 20110204120037), and the
Fundamental Research Funds of the Northwest A&F University (Grant No. QN2011120, Grant
No. 2452015431).
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11

Table 1. Crystallographic data and refinement details for 1-3.
Coordination compounds
1
2
3
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
a, Å
C
16
H
20CaCl
2
O
10
C H CaCl O
9
C
16 6 11
H18CaCl O
18
22
2
483.30
493.34
639.08
298(2)
298(2)
298(2)
Triclinic
P-1
Monoclinic
P2(1)/c
18.1509(15)
6.7852(6)
18.6971(17)
90.00
Triclinic
P-1
6.6460(10)
7.3050(10)
7.3050(10)
95.576(2)
95.608(2)
90.674(2)
1003.1(2)
2
7.5532(11)
8.4537(13)
19.890(3)
79.211(2)
83.767(2)
87.403(2)
1239.8(3)
2
b, Å
c, Å
α (°)
β (°)
102.382(2)
90.00
γ (°)
3
Volume (Å )
2249.1(3)
4
Z
-3
Calculated density (mg·m )
1.600
1.457
1.712
-
1
Absorption coefficient (mm )
0.632
5.006
0.953
F (000)
Crystal size (mm)
Index range
500
1024
648
0.20×0.20×0.18
0.42×0.13×0.08
0.40×0.40×0.28
-8
h
k
8
6
-16
-5
h
21
-9
h 9
-9
k
8
-11
-19
k
11
26
-27
l
26
-21
l
22
l
Reflections collected / unique
R (int)
7200 / 4959
0.0212
6812 / 3860
0.1163
8450 / 5663
0.0248
Completeness (%)
98.0
98.8
97.5
Data / restraints / parameters
4959 / 0 / 262
1.138
3860 / 0 / 273
0.952
5663 / 0 / 307
1.025
2
Goodness-of-fit on F
Final R indices [I>2sigma(I)]
R1=0.0403
R1=0.0846
R1 =0.0580
wR
2
=0.1348
wR
2
=0.1031
wR =0.1672
2
-3
Largest diff. peak and hole (eÅ )
0.441 and -0.695
0.391 and -0.297
0.935 and -0.589
12

Table 2. Selected bond lengths (Å) and angles (°) for 1-3.
1
Ca(1)-O(2W)
2.3984(14)
2.4448(13)
2.4990(14)
2.5371(13)
139.55(5)
118.06(5)
77.22(5)
Ca(1)-O(4W)
2.4110(15)
2.4718(13)
2.5346(13)
2.5794(14)
73.36(5)
Ca(1)-O(1)
Ca(1)-O(1)A
Ca(1)-O(3W)
Ca(1)-O(1W)
Ca(1)-O(2)B
Ca(1)-O(1W)B
O(2W)-Ca(1)-O(4W)
O(2W)-Ca(1)-O(1)
O(4W)-Ca(1)-O(1)
O(2W)-Ca(1)-O(3W)
O(1)-Ca(1)-O(1W)
O(4W)-Ca(1)-O(3W)
O(1)-Ca(1)-O(3W)
O(2W)-Ca(1)-O(1W)
O(4W)-Ca(1)-O(1W)
149.96(5)
77.03(5)
82.22(5)
142.48(5)
75.89(4)
2
Ca(1)-O(1)
2.366(6)
2.412(6)
2.501(6)
2.530(6)
82.42(8)
98.46(10)
78.84(10)
69.97(11)
81.42(9)
Ca(1)-O(2)A
2.391(6)
Ca(1)-O(7)
Ca(1)-O(8)
2.419(6)
Ca(1)-O(4)
Ca(1)-O(5)
2.529(6)
Ca(1)-O(2)B
Ca(1)-O(1)B
2.550(6)
O(3)-Ca(1)-O(5)
O(3)-Ca(1)-O(3W)
O(5)-Ca(1)-O(3W)
O(3W)-Ca(1)-O(2W)
O(3)-Ca(1)-O(1W)
O(3W)-Ca(1)-O(1W)
O(3)-Ca(1)-O(2W)
O(5)-Ca(1)-O(2W)
O(1W)-Ca(1)-O(2W)
O(5)-Ca(1)-O(1W)
139.83(10)
83.16(11)
143.11(10)
70.16(11)
139.90(10)
3
Ca(1)-O(3)
2.385(2)
2.427(3)
2.437(2)
2.550(3)
82.42(8)
98.46(10)
78.84(10)
143.11(10)
69.97(11)
Ca(1)-O(5)
2.408(2)
2.429(2)
2.492(3)
2.680(3)
70.16(11)
83.16(11)
81.42(9)
139.90(10)
139.83(10)
Ca(1)-O(3W)
Ca(1)-O(6)A
Ca(1)-O(2)B
Ca(1)-O(1W)
Ca(1)-O(2W)
Ca(1)-O(5)A
O(3)-Ca(1)-O(5)
O(3)-Ca(1)-O(3W)
O(5)-Ca(1)-O(3W)
O(5)-Ca(1)-O(2W)
O(3W)-Ca(1)-O(2W)
O(1W)-Ca(1)-O(2W)
O(3)-Ca(1)-O(2W)
O(3)-Ca(1)-O(1W)
O(5)-Ca(1)-O(1W)
O(3W)-Ca(1)-O(1W)
Symmetry transformations used to generate equivalent atoms for 1: A -x+2, -y+1, -z,
B -x+1, -y+1, -z; for 2: A x, y+1, z, B -x+1, y+1/2, -z+3/2, C -x+1, y-1/2, -z+3/2, D x, y-1,
z; for 3: A -x+1, -y+2, -z+1, B -x+2, -y+2, -z+1
13

Table 3. Bond lengths (Å) and angles (°) of hydrogen-bond for 1-3.
D–H···A
d(D–H) d(H ···A )
d(D ···A ) ∠DHA
1
O1W-H1WA···O5
0.97
0.97
0.96
0.96
0.96
0.96
0.96
2.01
2.03
1.85
2.40
2.19
2.09
1.94
2.980(2) 174
2.784(2) 133
2.720(2) 150
3.208(2) 142
2.985(2) 139
2.912(2) 143
2.815(2) 150
O1W-H1WB···O5
O2W-H2WA···O4
O2W-H2WA···O5
O3W-H3WB···O6
O4W-H4WA···O4
O4W-H4WB···O4
2
O8-H8C···O9
0.85
0.85
0.85
1.907
1.989
2.168
2.724
161
O9-H9F···O4
O9-H9G···O5
2.838(3) 176
3.017(2) 176
3
O1W-H1WB···O6W
0.95
0.96
0.96
0.96
0.85
0.85
0.85
0.85
2.29
1.95
2.52
2.12
2.10
2.43
2.59
2.54
3.109(8) 144
2.882(10) 163
3.020(5) 113
2.778(5) 125
2.697(4) 127
2.974(7) 122
3.270(8) 138
3.289(4) 148
O2W-H2WA···O6W
O2W-H2WB···O3W
O3W-H3WA···O5W
O5W-H5WA···O6
O6W-H6WA···O3
O6W-H6WB···Cl3
O5W-H5WB···Cl5
14

Figure 1. Coordination environment and polyhedron of Ca(II) and coordination
modes in 1. Hydrogens are omitted for clarity.
1
5

Figure 2. Fragment of the 1D chain and 2D layer. Hydrogens are omitted for clarity.
1
6

Figure 3. Coordination environment, polyhedron of Ca(II) and coordination modes
in 2. Hydrogens omitted for clarity.
1
7

Figure 4. Fragment of the 1D chain and 2D layer.
1
8

Figure 5. Coordination environment and polyhedron of Ca(II) and coordination
modes in 3. Hydrogens omitted for clarity.
1
9

Figure 6. Fragment of the 1D chain and 2D layer.
2
0

Figure 7. The bond length between chlorine and nearest oxygen in 1-3.
2
1

Figure 8. TG curves of 1-3.
2
2

Graphical abstract
2
3