Three cobalt(ii) coordination polymers based on V-shaped aromatic polycarboxylates and rigid bis(imidazole) ligand: Syntheses, crystal structures, physical properties and theoretical studies

Article abstract of DOI:10.1039/c2ce26606g

To investigate the effect of organic anions on the coordination frameworks, we synthesized three new complexes, namely, Co(SDBA)(BIMB) (1), Co ₂(SA)(BIMB)_1.5(H₂O) (2) and Co(FBA)(BIMB) _0.5·H₂O (3) (H₂SDBA = 4,4′-dicarboxybiphenylsulfone, H₄SA = 3,3′,4,4′- diphenylsulfonetetracarboxylate acid and H₂FBA = 4,4′- (hexafluoroisopropylidene)bis(benzoic acid)), which were obtained by the reactions of 4,4′-bis(1-imidazolyl)biphenyl (BIMB), and three V-shaped aromatic polycarboxylates as organic anions with Co(NO₃) ₂·6H₂O. Single crystal structure analysis shows that complex 1 features a 3-fold interpenetrating three-dimensional (3D) framework with CdSO₄-type topology. Complex 2 has a previously unknown 3D trinodal (4,4,6)-connected framework with a Schlaefli symbol of (4·6⁴·8)₂(4³·6 ³)₂(4⁴·6¹⁰·8). Complex 3 exhibits a three-dimensional 2-fold interpenetrating pillared helical-layer open framework of α-Po topology based upon binuclear paddlewheel units. The results reveal that the carboxylic building blocks with different conformations play a significant role in promoting the diversity of the observed structural motifs. The magnetic properties of the three complexes as well as the SHG and ferroelectric properties for 1 have also been investigated. Finally, theoretical calculations were carried out on the conformation of the BIMB ligand in the three complexes.

Full text of DOI:10.1039/c2ce26606g

View Article Online / Journal Homepage
CrystEngComm
Accepted Manuscript
This is an Accepted Manuscript, which has been through the RSC Publishing peer
review process and has been accepted for publication.
CrystEngComm
Accepted Manuscripts are published online shortly after acceptance, which is prior
to technical editing, formatting and proof reading. This free service from RSC
Publishing allows authors to make their results available to the community, in
citable form, before publication of the edited article. This Accepted Manuscript will
be replaced by the edited and formatted Advance Article as soon as this is available.
www.rsc.org/crystengcomm
Volume 12 | Number 5 | May 2010 | Pages 1317–1658
To cite this manuscript please use its permanent Digital Object Identifier (DOI®),
which is identical for all formats of publication.
More information about Accepted Manuscripts can be found in the
Information for Authors.
Please note that technical editing may introduce minor changes to the text and/or
graphics contained in the manuscript submitted by the author(s) which may alter
content, and that the standard Terms & Conditions and the ethical guidelines
that apply to the journal are still applicable. In no event shall the RSC be held
responsible for any errors or omissions in these Accepted Manuscript manuscripts or
any consequences arising from the use of any information contained in them.
HOT ARTICLE
COMMUNICATION
Hall et al.
HIGHLIGHT
Wang, Su et al.
Alginate-mediated routes to the
selective synthesis of complex metal
oxide nanostructures
Long
Ionothermal synthesis of a new
open-framework zinc phosphate
NIS-3 with low framework density
pH effect on the assembly of
metal–organic architectures
www.rsc.org/crystengcomm
Registered Charity Number 207890

Page 1 of 44
CrystEngComm
View Article Online
1
2
3
Three cobalt(II) coordination polymers based on
V-shaped aromatic polycarboxylates and rigid
bis(imidazole) ligand: Syntheses, crystal structures,
physical properties and theoretical studies
4
5
6
7
Hong Zhoua, Guang-Xiang Liu,a,* Xiao-Feng Wanga and Yan Wangb,*
a
8
School of Biochemical and Environmental Engineering, Nanjing Xiaozhuang
9
University, Nanjing 211171, P. R. China
b
10
11
12
13
School of Chemistry and Chemical Engineering, Anqing Normal University, Anqing
246003, P. R. China
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Corresponding Author:
Dr. GuangꢀXiang Liu
Mailing Address: School of Biochemical and Environmental Engineering
Nanjing Xiaozhuang University, Nanjing 211171, P. R. China
Telephone:
Eꢀmail:
+86ꢀ25ꢀ86178260
njuliugx@gmail.com (G. X. Liu)
Dr. Yan Wang
Mailing Address: School of Chemistry and Chemical Engineering
Anqing Normal University, Anqing 246003, P. R. China
Telephone:
Eꢀmail:
+86ꢀ556ꢀ5500090
wangyan@aqtc.edu.cn (Y. Wang)

CrystEngComm
Page 2 of 44
View Article Online
28
29
Abstract
To investigate the effect of organic anions on the coordination frameworks, we
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
synthesized
three
new
complexes,
namely,
Co(SDBA)(BIMB)
(1),
Co2(SA)(BIMB)1.5(H2O) (2) and Co(FBA)(BIMB)0.5·H2O (3) (H2SDBA
=
4,4’ꢀdicarboxybiphenylsulfone, H4SA = 3,3’,4,4’ꢀdiphenylsulfonetetracarboxylate
acid and H2FBA = 4,4’ꢀ(hexafluoroisopropylidene)bis(benzoic acid)), which were
obtained by the reactions of 4,4′ꢀbis(1ꢀimidazolyl)biphenyl (BIMB), and three
Vꢀshaped aromatic polycarboxylates as organic anions with Co(NO3)2ꢁ6H2O. Single
crystal structure analysis shows that complex 1 features a 3ꢀfold interpenetrating
threeꢀdimensional (3D) framework with CdSO4ꢀtype topology. Complex 2 has an
previously unknown 3D trinodal (4,4,6)ꢀconnected framework with Schläli symbol of
(4.64.8)2(43.63)2(44.610.8). Complex
3
exhibits
a
threeꢀdimensional 2ꢀfold
interpenetrating pillared helicalꢀlayer open framework of αꢀPo topology based upon
binuclear paddlewheel units. The results reveal that the carboxylic building blocks
with different conformations play a significant role in promoting the diversity of the
observed structural motifs. The magnetic properties of three complexes as well as
SHG and ferroelectric properties for 1 have also been investigated. Finally, theoretical
calculations were carried about the conformation of the BIMB ligand in three
complexes.
Keywords: cobalt(II) coordination polymer; magnetic property; nonlinear optical
property; ferroelectric property; theoretical calculation

Page 3 of 44
CrystEngComm
View Article Online
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
Introduction
Crystal engineering to synthesis rationally coordination polymers attract much interest
because of their potential applications as functional materials in the field of
heterogeneous catalysis porosity, luminescence, conductivity, molecular magnetism,
nonlinear optics and chirality.1ꢀ4 Their fascinating architectures and topological
networks also account for their wide interest.5ꢀ8 In order to build novel molecular
architectures, much effort has been devoted to modify the building blocks and to
control the assembled motifs for required products via selecting different organic
ligands.9,10 Besides that, several factors also influence the construction of molecular
architecture, such as pH value, template, reaction temperature, the solvent system,
metal ions and counterions.11ꢀ13 Among these factors, the selection of organic ligands
is one of the most important aspects.14 The configuration, rigidity, substituent and
coordination modes of organic ligands have an important effect on the final structures.
Generally, polycarboxylate ligands feature prominently in the construction of
coordination polymers, and the reported coordination polymers are mostly constructed
by rigid polycarboxylate ligands.15 Recently, more and more attention has been paid
to the flexible polycarboxylate ligands,16 but studies of semirigid Vꢀshaped
polycarboxylate ligands are relatively few.17
Up to now, a number of pyridylꢀcontaining ligands have been widely employed
as the second ligands for meeting the requirement of coordination geometries of metal
ions or tuning the fine structure.18 Compared with rigid bridging pyridyl ligands,
4,4′ꢀbis(1ꢀimidazolyl)biphenyl (BIMB) possesses a similar rigid structure but a more

CrystEngComm
Page 4 of 44
View Article Online
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
flexible coordination fashion and an excellent coordination ability, and has the
potential to construct porous MOFs. BIMB has two coordination fashions (Scheme 1),
cisꢀconfiguration and transꢀconfiguration, while free rotation of the imidazolyl ring
and benzene ring makes its style more diverse.19 In the progress of linking metal ions,
terminal nitrogen atoms from the fiveꢀmembered ring units of imidazolyl ligands have
a weaker steric hindrance than those from sixꢀmembered ring units of pyridyl ligands.
Inspired by those ideas, we successfully obtained three new threeꢀdimensional (3D)
MOFs, namely, Co(SDBA)(BIMB) (1), Co2(SA)(BIMB)1.5(H2O) (2) and
Co(FBA)(BIMB)0.5·H2O (3). They are characterized by elemental analysis and Xꢀray
crystallography. The crystal structures as well as topological analysis of these
complexes will be represented and discussed in detail. In addition, their physical
properties are also studied.
Experimental section
Materials and general methods
All the reagents and solvents for syntheses and analyses were purchased from Sigma
or TCI and employed as received without further purification. The BIMB ligand was
prepared according to the reported method.20 Elemental analyses (C, H and N) were
performed on a Vario EL III elemental analyzer. Infrared spectra were performed on a
Nicolet AVATARꢀ360 spectrophotometer with KBr pellets in the 4000 ꢀ 400 cmꢀ1
region. The secondꢀorder nonlinear optical intensity was estimated by measuring a
powder sample relative to urea. A pulsed Qꢀswitched Nd:YAG laser at a wavelength

Page 5 of 44
CrystEngComm
View Article Online
95
96
of 1064 nm was used to generate a SHG signal from powder samples. The
backscattered SHG light was collected by a spherical concave mirror and passed
through a filter that transmits only 532 nm radiation. The ferroelectric property of the
solidꢀstate sample was measured by the Premier II ferroelectric tester at room
temperature. Variableꢀtemperature susceptibilities were measured using a MPMSꢀ7
SQUID magnetometer. Diamagnetic corrections were made with Pascal’s constants
for all constituent atoms.21
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
Preparation of Co(SDBA)(BIMB) (1). A mixture containing Co(NO3)2·6H2O
(29.6mg, 0.1 mmol), H2SDBA (30.6 mg, 0.1 mmol), BIMB (28.6 mg, 0.1 mmol) and
NaOH (8.0 mg, 0.2 mmol) in 15 ml deionized water was sealed in a 25 ml Teflon
lined stainless steel container and heated at 160 ºC for 3 days. Purple pillar crystals of
1 were collected by filtration and washed with water and ethanol several times with a
yield of 64%. Anal. calcd for C32H22N4O6SCo: C 59.17; H 3.41; N 8.63; Found: C
1
59.12; H 3.38; N 8.60%. IR(KBr pellet, cm- ): 3443(br), 3151(m), 1634(s), 1603(s),
1564(m), 1519(s), 1361(s), 1300(m), 1253(w), 1158(m), 1095(s), 958(m), 833(m),
751(s), 690(w), 626(w), 561(w).
Preparation of Co2(SA)(BIMB)1.5(H2O) (2). A mixture containing Co(NO3)2·6H2O
(59.2 mg, 0.2 mmol), H4SA (39.4 mg, 0.1 mmol), BIMB (57.2 mg, 0.2 mmol) and
LiOH·H2O (16.8 mg, 0.4 mmol) in 15 ml deionized water was sealed in a 25 ml
Teflon lined stainless steel container and heated at 140 ºC for 3 days. Purple platelet
crystals of 2 were collected by filtration and washed with water and ethanol several
times with a yield of 41%. Anal. calcd for C43H29N6O11SCo2: C 54.04; H 3.06; N 8.79;

CrystEngComm
Page 6 of 44
View Article Online
1
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
Found: C 54.02; H 3.04; N 8.76%. IR(KBr pellet, cm- ): 3447(br), 3157(m), 1620(s),
1580(s), 1520(m), 1407(s), 1366(s), 1325(m), 1244(w), 1101(m), 1067(m), 969(m),
818(m), 796(m), 745(w), 715(w), 644(w), 532(w).
Preparation of Co(FBA)(BIMB)0.5·H2O (3). A mixture containing Co(NO3)2·6H2O
(59.2mg, 0.2 mmol), H2FBA (39.2 mg, 0.1 mmol), BIMB (28.6 mg, 0.1 mmol) and
LiOH·H2O (8.4 mg, 0.2 mmol) in 15 ml deionized water was sealed in a 25 ml Teflon
lined stainless steel container and heated at 140 ºC for 3 days. Purple pillar crystals of
3 were collected by filtration and washed with water and ethanol several times with a
yield of 46%. Anal. calcd for C26H17F6N2O5Co: C 51.16; H 2.81; N 4.59; Found: C
51.13; H 2.77; N 4.55%. IR (KBr pellet, cmꢀ1): 3442(br), 3139(w), 1605(s), 1517(m),
1391(s), 1259(s), 1208(m), 1167(s), 1116(m), 1066(m), 964(w), 933(w), 832(m),
781(m), 740(m), 720(m), 648(w), 577(w).
X-Ray crystallography
Crystallographic data collections for complexes 1 - 3 were carried out on a Bruker
Smart Apex II CCD with graphiteꢀmonochromated MoꢀKα radiation (λ = 0.71073 Å)
at 293(2) K using the ωꢀscan technique. The data were integrated by using the SAINT
program,22 which was also used for the intensity corrections for the Lorentz and
polarization effects. An empirical absorption correction was applied using the
SADABS program.23 The structures were solved by direct methods using the program
SHELXSꢀ97 and all nonꢀhydrogen atoms were refined anisotropically on F2 by the
fullꢀmatrix leastꢀsquares technique using the SHELXLꢀ97 crystallographic software
package. The hydrogen atoms of the water molecules were located in a difference

Page 7 of 44
CrystEngComm
View Article Online
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
Fourier map, and the other hydrogen atoms were generated geometrically. All
calculations were performed on a personal computer with the SHELXLꢀ97
crystallographic software package.24 The details of the crystal parameters, data
collection and refinement for the complexes are summarized in Table 1, and selected
bond lengths and angles with their estimated standard deviations are listed in Table 2.
CCDCꢀ893724 (1), 893725 (2) and 893726 (3) contain the crystallographic data for
this paper.
<Table 1 and Table 2 here>
Results and discussion
IR spectra
The absence of such bands at around 1700 cmꢀ1 in the IR spectrum of three complexes
indicates the complete deprotonation of H2SDBA, H4SA and H2FBA. The
characteristic bands of carboxyl groups are shown in the range of 1540 ꢀ 1620 cmꢀ1 for
antisymmetric stretching and 1360 ꢀ 1460 cmꢀ1 for symmetric stretching. The
separations (ꢁ) between νasym (CO2) and νsym (CO2) bands indicate the presence of
different coordination modes. The bands in the region 640 ꢀ1310 cmꢀ1 are attributed to
the ꢀCHꢀ inꢀplane or outꢀofꢀplane bend, ring breathing, and ring deformation
absorptions of benzene ring, respectively. Weak absorptions observed at 3139 – 3159
cmꢀ1 can be attributed to νCꢀH of benzene ring.. The IR spectra exhibit the
characteristic peaks of imidazole groups at ca. 1520 cmꢀ1.25

CrystEngComm
Page 8 of 44
View Article Online
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
Crystal structure of Co(SDBA)(BIMB) (1)
Singleꢀcrystal Xꢀray structural analysis reveals that complex 1 crystallizes in the
acentric group Cc with Flack parameter of 0.025(10). The asymmetry unit contains
one independent cobalt ion, one SDBA dianion, and one BIMB ligand. The Co(II) ion
is coordinated by two oxygen atoms from two adjacent SDBA dianions and two
nitrogen atoms from BIMB linkers to give the CoO2N2 tetrahedral geometry (Fig. 1a).
The CoꢀO/N bond lengths are in the range of 1.9538(19) ꢀ 2.052(2) Å, which are
comparable to those reported in other relative Co(II) polymers.26 The completely
deprotonated SDBA ligand shows a bi(monodentate) coordination manner, while the
BIMB adopts a transꢀconformation. The Co(II) cations are bridged by SDBA to form
a 1D zigzag chain, as shown in Fig. 1b. These chains are further connected by
bridging BIMB linkers to give rise to a complicated 3D network with the small
solventꢀaccessible void space (equal to 4.2% of the cell volume) (Fig. 1c). Better
insight into the elegant framework of 1 can be accessed by the topology method. In
this analysis, the metal center can be viewed as 4ꢀconnect node. In this way, this net
can be simplified as CdSO4 topology (Fig. 1d).27 Moreover, the occurrence of 3ꢀfold
interpenetration and polycatenane character are also observed, as exhibited in Fig. 1e
and 1f.
<Figure 1 here>
Crystal structure of Co2(SA)(BIMB)1.5(H2O) (2)

Page 9 of 44
CrystEngComm
View Article Online
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
To investigate the influence of the carboxylate ligand on the structure of the
complexes, the reaction of BIMB and H4SA with Co(NO3)2·6H2O was carried out, and
a new complex 2 was obtained. As illustrated in Fig. 2a, although all the Co(II)
centers have octahedral geometries, the two unique metal centers exhibit different
coordination environments: Co1 lies in a distorted octahedral coordination sphere, the
equatorial plane of which comprises three carboxylate oxygen atoms (O1, O2, and
O4A) from two distinct SA4ꢀ anions and one BIMB nitrogen atom (N5); another
imidazole nitrogen atom (N1) and one coordinated water molecule (O1W) occupy the
axial coordination site. Co2 is surrounded by five carboxylate oxygen atoms from
three inequivalent SA4ꢀ ainions and one BIMB nitrogen atom in a distorted octahedron
sphere. In 2, the CoꢀO bond lengths range between 2.041(3) and 2.343(3) Å, and the
CoꢀN distances are 2.064(4) and 2.152(3) Å, both of which are in the normal range.28
Two Co2 atoms are double bridged by two carboxylate groups with Co2ꢁꢁꢁCo2
separations of 3.612 Å to from a dinuclear Co2 unit. The fully deprotonated SA4ꢀ
ligand coordinates to five Co atoms with four carboxylate groups adopting four
different
coordination
fashions:
ꢂ1ꢀη1:η0ꢀmonodentate,
ꢂ1ꢀη1:η1ꢀchelating,
ꢂ2ꢀη1:η1ꢀbridging and ꢂ2ꢀη2:η1ꢀbridging fashion.25 The SA4ꢀ ligand thus links cobalt
ions to form a 1D chain structure (Fig. 2b). In addition, it should be noted that there
are two independent sets of BIMB spacers adopting cisꢀ and transꢀconformations,
respectively, which establish a physical bridge between Co atoms with CoꢁꢁꢁCo
separations of 17.28 and 17.36 Å, and one of them resides at a crystallographic
inversion center, resulting in the formation of a complicated 3D structure (Fig. 2c).

CrystEngComm
Page 10 of 44
View Article Online
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
A better insight into the nature of this intricate framework can be acquired by
using topological analysis. In 2, each SA4ꢀ anion is fourꢀconnected by linking to two
Co atoms and two dinuclear Co2 units; the BIMB groups can be simplified to be linear
connectors. Co1 and dinuclear Co2 unit were also considered as distinct nodes;
therefore, the combination of nodes and connectors suggests an uncommon trinodal
(4,4,6)ꢀconnected network with a Schäfli symbol of (4.64.8)2(43.63)2(44.610.8) for
(Co1)2(SA)2(Co2) (Fig. 2d).29 As far as we know, this topology is completely new
within coordination polymer chemistry. The discovery of this new topology is useful
at the basic level in the crystal engineering of coordination networks.
<Figure 2 here>
Crystal structure of Co(FBA)(BIMB)0.5·H2O (3)
Singleꢀcrystal Xꢀray analysis revealed that complex 3 displays a 3D 2ꢀfold
interpenetrated polymeric structure with 1D helical channels. The asymmetric unit
contains one cobalt ion, one FBA dianion, and half of the BIMB ligand (Fig. 3a) with
the metalꢀbased building unit comprising a binuclear Co(II)ꢀtetracarboxylate
paddlewheel cluster.30 In this binuclear unit (Fig. 3b), each Co(II) ion resides in a
square pyramidal coordination geometry with the apical position occupied by one
nitrogen atom from the BIMB ligand, while the basal plane consists of four
carboxylate oxygen atoms. The intradimer CoꢁꢁꢁCo separation is 2.9177(11) Å, within
the normal range found in other reported bimetallic paddlewheel units of type

Page 11 of 44
CrystEngComm
View Article Online
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
[M2(O2CR)4].31 In 3, each paddlewheel unit connects to four neighboring paddlewheel
clusters via bridging FBA2ꢀ dianions, which adopt a bridging tetradentate mode to
form a 2D undulating (4,4) net with large rhombꢀlike windows (Fig. 3c). The
dimensions of the rhombic window are 14.24 × 14.24 Å2 as measured between the
centroids of the binuclear Co(II) subunits at the corners of the window. As depicted in
Fig. 3d, the skeleton of this 2D sheet can also be described as a unique helical layer in
which the left and right helical chains appear alternatively by sharing the paddlewheel
clusters. The pitch of helix is double the b parameter (14.393 Å).
Most strikingly, the two diagonals of the rhombic window are equal to unit cell
parameters b and c, respectively. Two closest identical helical layers shift by b so that
the paddlewheel units from one layer fall in the center of the window of the other
layer, and interpenetrate each other in a parallel 2D→2D fashion, resulting in an
interwoven bilayer with 1D double helical channels. The FBA2ꢀ ligand presents a
dihedral angle of 77.98º between the two benzene rings, and this configuration
contributes to the parallel 2D→2D interpenetration. The skeleton of these 2D layers
can also be viewed as a unique helical tubular double layer, which is similar to the
previously reported CoꢀFBA sheets in the compound [Co(FBA)(py)]n.32 These helical
interpenetrated double layers are extended to a 3D framework with the aid of the
pillar BIMB ligand (Fig. 3e). The BIMB ligand connects the two paddle wheels of
two different double layers with a separation of 17.92 Å in a regular
transꢀconformation. The connectivity pattern of linker BIMB forms 1D chains
through the crystallographic c axis connecting the double layers in the ab plane. The

CrystEngComm
Page 12 of 44
View Article Online
249
250
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
two imidazole rings in the BIMB ligand twist from the phenyl ring plane by a torsion
angle of 75.89°. If the paddleꢀwheel dimer can be topologically viewed as an
octahedral node, meanwhile the FBA2ꢀ and BIMB bridges can be viewed as linkers,
the topology of single net for 3 can be best described as an uninodal sixꢀconnected
distorted primitive cubic (αꢀPo) net (Fig. 3f).30 Two identical nets interpenetrate each
other, giving rise to a 2ꢀfold interpenetrating framework.
<Figure 3 here>
It is well known that the organic anions play an important role in determining the
final structures of the compounds. By varying the anions under similar synthetic
conditions three related Co(II) complexes with different structures were successfully
synthesized. The roles played by the carboxylate anions in complexes 1ꢀ3 can be
explained in terms of their differences in the positions and numbers of the carboxylate
groups. It is a feasible method to introduce ligands to construct coordination polymers
with different structural types.
SHG activity and ferroelectric properties of complex 1
Secondꢀorder nonꢀlinear optical (NLO) materials have attracted more and more
attention in fields such as laser frequency conversion and optical parameter oscillators.
Among them, new NLO materials made from metalꢀorganic coordination polymers
have been a major point of focus in recent years because of their advantages over pure
inorganic or organic compounds. It is wellꢀknown that only a nonꢀcentrosymmetric

Page 13 of 44
CrystEngComm
View Article Online
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
structure may have secondꢀorder NLO effects.33 Therefore, it is believed that complex
with Cc space group has NLO response, and quasiꢀKurtz
1
a
a
secondꢀharmonicꢀgeneration (SHG) measurement was carried out to evaluate their
potential application as a secondꢀorder NLO material. The preliminary experimental
results revealed that complex 1 exhibits modest powder SHG activity with a response
of 0.8 times of that for urea, which indicates that the complex 1 can be used as a
potential optical material.
Recently, a prevalent research have focused on developing ferroelectric
materials based on metalꢀorganic frameworks (MOFs) and have reported some such
materials.34 However, the reported ferroelectric materials are mostly built upon chiral
organic tectons, whereas the proper use of achiral ligands by spontaneous are scarce.35
Herein, we describe the preliminary investigation of the possible ferroelectric property
of complex 1. Complex 1 crystallizes in the acentric space group Cc, which belongs to
the polar point group Cs, which falls in one of the 10 polar point groups (C1, Cs, C2,
C2v, C4, C4v, C3, C3v, C6, C6v) required for ferroelectric materials. Therefore, the
ferroelectric behavior of 1 was examined. Fig. 4 clearly shows that there is an electric
hysteresis loop that is a typical ferroelectric feature with a remanent polarization (Pr)
of ca. 0.051 ꢂC cmꢀ2 and coercive field (Ec) of ca. 3.38 kV cmꢀ1. The saturation
spontaneous polarization (Ps) of 1 is ca. 0.238 ꢂC cmꢀ2. Furthermore, we also studied
the behavior of permittivity (ε) = ε1(ω) – iε2(ω), where ε1(ω) and iε2(ω) are the real
(dielectric constant) and imaginary (dielectric loss) parts, respectively. The results
reveal that the frequency dependence of the dielectric constant ε1 at room temperature

CrystEngComm
Page 14 of 44
View Article Online
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
312
313
314
(20 ºC) indicates that ε1 rapidly decreases with the increase of frequency, while
dielectric loss remains unchanged.
<Figure 4 here>
Magnetic properties
The variableꢀtemperature magnetic susceptibility measurements of complexes 1 ꢀ 3
were performed on the Quantum Design SQUID MPMS XLꢀ7 instruments in the
temperature range of 2ꢀ300 K under a field of 1000 Oe. Temperature dependence of
χ
MT and χM for complexes 1-3 as displayed in Fig. 5. Magnetic susceptibility data of
MT value of 2.16 cm3 K molꢀ1 at room temperature,
per Co(II) ion of 1 shows the
χ
which is much higher than the expected value of 1.875 cm3 K molꢀ1 for one
magnetismꢀisolated Co(II) ion with S = 3/2 and g = 2.0, they are common values for
highꢀspin complexes in tetrahedral Co(II) centers (4.30ꢀ5.20 ꢂB). The magnetic
4
behavior should be due to a larger orbital contribution arising from the A2g
groundꢀstate of Co(II).36 The
χMT value increases gradually with decreasing
temperature and move up to a maximum value of 3.257 cm3 K molꢀ1 at ca. 36.1 K,
which suggests ferromagnetic behavior, and then decrease sharply down to a
minimum value of 1.49 cm3 K molꢀ1 at 2 K, such behavior is possibly due to ZFS
(zeroꢀfield splitting) and/or antiferromagnetic interactions.31 From the structure of
complex 1, though the magnetic centers separated by the long BIMB and SDBA
ligands are weakly magnetic coupled (17.298 and 13.758 Å), the nearest Co…Co

Page 15 of 44
CrystEngComm
View Article Online
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
334
335
336
distance between adjacent chains is about 7.659 Å which should make a contribution
to the ferromagnetic behavior via intermolecular interactions. The plot of 1/ M versus
χ
T can be fitted by the CurieꢀWeiss law [χM = C/(Tꢀθ)] above 18 K, giving the Curie
constant value C = 2.75 cm3 K molꢀ1 and Weiss constant θ = +6.12 K. The Curie
constant value is consistent with the
value of θ further conforms the ferromagnetic behavior.
As for 2, the
MT value at room temperature is 4.44 cm3 K molꢀ1 per two Co(II)
χMT value at room temperature. The positive
χ
ions, which is much higher than the calculated spinꢀonly value (3.87 cm3 K molꢀ1) for
two uncoupled highꢀspin Co(II) ion (S = 3/2, g = 2). This is as expected for octahedral
highꢀspin cobalt(II) ions, which have a large firstꢀorder orbital contribution to the
magnetic moment.36 Upon cooling the
χMT value decreases smoothly to reach a value
of 1.125 cm3 K molꢀ1 at 26 K and slightly shifts the curve and then decreases to a
minimum value of 0.280 cm3 K molꢀ1 at 2 K. The results show that the complex
shows overall antiferromagnetic interactions and also spinꢀorbit coupling interactions
between the adjacent Co(II) ions.
Complex 3 is essentially a Coꢀdimer with four carboxyl ligands coordinating to
two Co(II) ions that form a typical paddle wheel SBU, which is further connected
through the axial site by the BIMB ligand. The χMT value at the room temperature is
2.22 cm3 K molꢀ1, which is little lager than the calculated spinꢀonly value of 1.875
cm3 K molꢀ1 for one isolated Co(II) ion (S = 3/2), with octahedral geometry, indicating
the orbital contribution of Co(II) ions. The plot of 1/χM versus T can be fitted by the
CurieꢀWeiss law above 2 K, giving the Curie constant value C = 2.93 cm3 K molꢀ1 and

CrystEngComm
Page 16 of 44
View Article Online
337
338
339
340
341
342
343
344
345
346
347
348
349
350
351
352
353
354
355
356
357
358
Weiss constant θ = ꢀ3.81 K. The negative θ value is indicative of a dominant
antiferromagnetic interaction between Co(II) centers. According to the structure of
complex 3, it could be presumed that the main magnetic interactions are between the
paddleꢀwheel unit metal center, while the superexchange interactions between Co(II)
ions through the BIMB bridge can be ignored due to the length of the BIMB ligands.
The results indicates the typical antiferromagnetic and spinꢀorbit coupling interactions
present in the complex.
<Figure 5 here>
Theoretical calculations
To compare the stability of the BIMB ligand in their different conformations in three
complexes, theoretical calculations have been performed. The molecular geometries
of only the ligands were taken from the CIF files, generated during the crystal
structure determination of the complexes, and are optimized. Single point energy
calculations have been carried out by using B3LYP with 6ꢀ311g** basis set. It is a
common practice in the field of polymeric metal complexes to compute the energies,
using a model structure that very closely resembles the particular moiety to reduce
mainly the computational time.37 In the present study, we have considered only the
BIMB ligand geometries in the complexes without considering coordination for the
computational simplification as model structures. These considerations are adopted in
these calculations only to compare the energies of the particular conformations. It has

Page 17 of 44
CrystEngComm
View Article Online
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
been shown, however, that these considerations can have a significant consequence on
the absolute values, and therefore, only a qualitative comparison could be expected.
From the literature, the energy calculations of the crystal structures have been
performed by optimizing the crystal structures through various optimization
procedures (Dreiding force field) using density functional theory (DFT) methods.38
The optimized energy of the BIMB ligand in three complexes show almost the same
energy (kcal/mol) in all its conformers, -452463.3423 (-452381.345) for 1,
-452617.4654 (-452589.452) and ꢀ452477.8070 (-452436.275) for 2 and
-452471.7657 (-452461.842) for 3. The values in the parentheses indicate single
point energies. From the optimized energy values, all the conformations of the BIMB
ligand converge to global minima in the potential energy surface (which corresponds
to energies of stable conformations). A qualitative comparison of single point energy
calculations reveals a slight difference in the energy values of the conformers. The
results indicate that the BIMB ligands can show stable cisꢀ and transꢀconformations,
and the energy difference between these conformations are very less, so that the
ligand can exist in different conformations depending upon the coordination
requirements.
Conclusions
In this work, we have successfully fabricated three novel coordination polymers
under hydrothermal condition. Complex 1 features a 3ꢀfold interpenetrating
threeꢀdimensional (3D) framework with CdSO4ꢀtype topology. Complex 2 has an

CrystEngComm
Page 18 of 44
View Article Online
381
382
383
384
385
386
387
388
389
390
391
392
393
394
395
396
397
398
399
400
401
402
previously unknown 3D trinodal (4,4,6)ꢀconnected framework with Schläli symbol of
(4.64.8)2(43.63)2(44.610.8). Complex
exhibits threeꢀdimensional 2ꢀfold
3
a
interpenetrating pillared helicalꢀlayer open framework of αꢀPo topology based upon
binuclear paddlewheel units. The results reveal that the carboxylic building blocks
with different conformations play a significant role in promoting the diversity of the
observed structural motifs. The magnetic properties of three complexes indicate the
typical antiferromagnetic interactions and spinꢀorbit coupling interactions between the
adjacent Co(II) ions. Complex 1 has modest power SHG activity and ferroelectric
properties. Moreover, theoretical calculations indicate that the BIMB ligands can
show stable cisꢀ and transꢀconformations, and the energy difference between these
conformations are very less.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Nos.
21271116, 21171097), the Key Project of Chinese Ministry of Education (No. 210102)
and the Natural Science Foundation of Anhui Province (No. 11040606M45).
References
1
(a) S. R. Halper, L. Do, J. R. Stork and S. M. Cohen, J. Am. Chem. Soc., 2006,
128, 15255; (b) S. Hasegawa, S. Horike, R. Matsuda, S. Furukawa, K. Mochizuki,
Y. Kinoshita and S. Kitagawa, J. Am. Chem. Soc., 2007, 129, 2607; (c) F. Luo, J.
M. Zheng and S. R. Batten, Chem. Commun., 2007, 3744; (d) S. Kitagawa and R.

Page 19 of 44
CrystEngComm
View Article Online
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
Matsuda, Coord. Chem. Rev., 2007, 251, 2490; (e) V. K. Rao, S. Chakrabarti and
S. Natarajan, Inorg. Chem., 2007, 46, 10781; (f) O. M. Yaghi, M. O’Keeffe, N. W.
Ockwig, H. K. Chae, M. Eddaoudi and J. Kim, Nature, 2003, 423, 705; (g) B.
Moulton and M. J. Zaworotko, Chem. Rev., 2001, 101, 1629.
2
(a) D. N. Dybtsev, H. Chun, S. H. Yoon, D. Kim and K. Kim, J. Am. Chem. Soc.,
2004, 126, 32; (b) B. Zhao, H. L. Gao, X. Y. Chen, P. Cheng, W. Shi, D. Z. Liao,
S. P. Yan and Z. H. Jiang, Chem. ꢀEur. J., 2006, 12, 149; (c) B. L. Chen, S. Q. Ma,
F. Zapata, F. R. Fronczek, E. B. Lobkovsky and H. C. Zhou, Inorg. Chem., 2007,
46, 1233; (d) M. Dinca and J. R. Long, J. Am. Chem. Soc., 2005, 127, 9376; (e) D.
Dubbeldam, C. J. Galvin, K. S. Walton, D. E. Ellis and R. Q. Snurr, J. Am. Chem.
Soc., 2008, 130, 10884; (f) J. R. Li, R. J. Kuppler and H. C. Zhou, Chem. Soc.
Rev., 2009, 38, 1477.
3
(a) R. J. Kuppler, D. J. Timmons, Q. R. Fang, J. R. Li, T. A. Makal, M. D. Young,
D. Q. Yuan, D. Zhao, W. J. Zhuang and H. C. Zhou, Coord. Chem. Rev., 2009,
253, 3042; (b) C. Janiak and J. K. Vieth, New J. Chem., 2010, 34, 2366; (c) S. K.
Henninger, H. A. Habib and C. Janiak, J. Am. Chem. Soc., 2009, 131, 2776; (d) S.
Q. Ma and H. C. Zhou, Chem. Commun., 2010, 46, 44.
4
(a) B. Zhao, X. Y. Chen, P. Cheng, D. Z. Liao, S. P. Yan and Z. H. Jiang, J. Am.
Chem. Soc., 2004, 126, 15394; (b) Y. C. Qiu, H. Deng, J. X. Mou, S. H. Yang, M.
Zeller, S. R. Batten, H. H. Wu and J. Li, Chem. Commun., 2009, 5415; (c) A. J.
Lan, K. H. Li, H. H. Wu, D. H. Olson, T. J. Emge, W. Ki, M. C. Hong and J. Li,
Angew. Chem., Int. Ed., 2009, 48, 2334; (d) S. A. Sapchenko, D. G. Samsonenko,

CrystEngComm
Page 20 of 44
View Article Online
425
426
427
428
429
430
431
432
433
434
435
436
437
438
439
440
441
442
443
444
445
446
D. N. Dybtsev, M. S. Melgunov and V. P. Fedin, Dalton Trans., 2011, 40, 2196.
5
6
7
(a) M. Higuchi, D. Tanaka, S. Horike, H. Sakamoto, K. Nakamura, Y. Takashima,
Y. Hijikata, N. Yanai, J. Kim, K. Kato, Y. Kubota, M. Takata and S. Kitagawa, J.
Am. Chem. Soc., 2009, 131, 10336; (b) K. H. Li, D. H. Olson, J. Seidel, T. J.
Emge, H.W. Gong, H. P. Zeng and J. Li, J. Am. Chem. Soc., 2009, 131, 10368; (c)
X. D. Chen, X. H. Zhao, M. Chen and M. Du, Chem. ꢀEur. J., 2009, 15, 12974; (d)
M. H. Zeng, Q. X. Wang, Y. X. Tan, S. Hu, H. X. Zhao, L. S. Long and M.
Kurmoo, J. Am. Chem. Soc., 2010, 132, 2561.
(a) H. He, D. Yuan, H. Ma, D. Sun, G. Zhang and H. C. Zhou, Inorg. Chem., 2010,
49, 7605; (b) X. Zhao, H. He, T. Hu, F. Dai and D. Sun, Inorg. Chem., 2009, 48,
8057; (c) Y. L. Zhou, M. H. Zeng, L. Q. Wei, B. W. Li and M. Kurmoo, Chem.
Mater., 2010, 22, 4295; (d) B. GilꢀHernandez, P. Gili, J. K. Vieth, C. Janiak and J.
Sanchiz, Inorg. Chem., 2010, 49, 7478; (e) Y. Z. Zheng, W. Xue, M. L. Tong, X.
M. Chen and S. L. Zheng, Inorg. Chem., 2008, 47, 11202; (f) X. Bao, P. H. Guo, J.
L. Liu, J. D. Leng and M. L. Tong, Chem. ꢀEur. J., 2011, 17, 2335.
(a) O. Shekhah, H. Wang, M. Paradinas, C. Ocal, B. Schupbach, A. Terfort, D.
Zacher, R. A. Fischer and C. Woll, Nat. Mater., 2009, 8, 481; (b) J. Xu, W. Su and
M. Hong, Cryst. Growth Des., 2011, 11, 337; (c) Q. Y. Yang, K. Li, J. Luo, M.
Pan and C. Y. Su, Chem. Commun., 2011, 47, 4234; (d) A. S. Degtyarenko, P. V.
Solntsev, H. Krautscheid, E. B. Rusanov, A. N. Chernega and K. V. Domasevitch,
New J. Chem., 2008, 32, 1910; (e) Q. Pan, J. Li, Q. Chen, Y. Han, Z. Chang, W. C.
Song and X. H. Bu, Microporous Mesoporous Mater., 2010, 132, 453; (f) C. M.

Page 21 of 44
CrystEngComm
View Article Online
447
448
449
450
451
452
453
454
455
456
457
458
459
460
461
462
463
464
465
466
467
468
Gandolfo and R. L. LaDuca, Cryst. Growth Des., 2011, 11, 1328; (g) B. Zheng, J.
Bai, J. Duan, L. Wojtas and M. J. Zaworotko, J. Am. Chem. Soc., 2011, 133, 748.
(a) R. L. LaDuca, Coord. Chem. Rev., 2009, 253, 1759; (b) X. F. Kuang, X. Y. Wu,
R. M. Yu, J. P. Donahue, J. S. Huang and C. Z. Lu, Nat. Chem., 2010, 2, 461; (c)
V. Niel, A. L. Thompson, M. C. Muñoz, A. Galet, A. E. Goeta and J. A. Real,
Angew. Chem., Int. Ed., 2003, 42, 3760; (d) L. Q. Ma and W. B. Lin, Angew.
Chem. Int. Ed., 2009, 48, 3637; (e) Y. Gong, Y. C. Zhou, T. F. Liu, J. Lu, D. M.
Proserpio and R. Cao, Chem Commun, 2011, 47, 5982; (f) K. M. Park, D. Whang,
E. Lee, J. Heo and K. Kim, Chem. ꢀEur. J., 2002, 8, 498; (g) J. A. Aitken and M.
G. Kanatzidis, J. Am. Chem. Soc., 2004, 126, 11780.
8
9
(a) J. Gopalakrishnan, Chem. Mater., 1995, 7, 1265; (b) A. Stein, S. W. Keller
and T. E. Mallouk, Science, 1993, 259, 1558; (c) J. Zubieta, Comp. Coord. Chem.,
2004, 1, 697; (d) E. Burkholder and J. Zubieta, Solid State Sci., 2004, 6, 1421; (e)
D. F. Sun, Y. X. Ke, T. M. Mattox, B. A. Ooro and H. C. Zhou, Chem. Commun.,
2005, 5447; (f) B. Zheng, H. Dong, J. F. Bai, Y. Z. Li, S. H. Li and M. Scheer, J.
Am. Chem. Soc., 2008, 130, 7778; (g) P. Kanoo, K. L. Gurunatha and T. K. Maji,
Cryst. Growth Des., 2009, 9, 4147.
10 (a) O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi and J.
Kim, Nature, 2003, 423, 705; (b) X. Shi, G. S. Zhu, X. H. Wang, G. H. Li, Q. R.
Fang, X. J. Zhao, G. Wu, G. Tian, M. Xue, R. W. Wang and S. L. Qiu, Cryst.
Growth Des., 2005, 5, 341; (c) C. B. Aakeröy, N. C. Schultheiss, A. Rajbanshi, J.
Desper and C. Moore, Cryst. Growth Des., 2009, 9, 432; (d) J. H. Jia, X. Lin, C.

CrystEngComm
Page 22 of 44
View Article Online
469
470
471
472
473
474
475
476
477
478
479
480
481
482
483
484
485
486
487
488
489
490
Wilson, A. J. Blake, N. R. Champness, P. Hubberstey, G. Walker, E. J. Cussena
and M. Schröder, Chem. Commun., 2007, 840; (e) M. X. Li, Z. X. Miao, M. Shao,
S. W. Liang and S. R. Zhu, Inorg. Chem., 2008, 47, 4481; (f) A. H. Yuan, R. Q.
Lu, H. Zhou, Y. Y. Chen and Y. Z. Li, CrystEngComm, 2010, 12, 1382.
11 (a) B. Dey, S. R. Choudhury, P. Gamez, A. V. Vargiu, A. Robertazzi, C. Y. Chen,
H. M. Lee, A. D. Jana and S. Mukhopadhyay, J. Phys. Chem. A, 2009, 113, 8628;
(b) A. Das, A. D. Jana, S. K. Seth, B. Dey, S. R. Choudhury, T. Kar, S.
Mukhopadhyay, N. J. Singh, I. C. Hwang and K. S. Kim, J. Phys. Chem. B, 2010,
114, 4166; (c) G. Mezei, P. Baran and R. G. Raptis, Angew. Chem., Int. Ed., 2004,
43, 574; (d) H. K. Liu, X. H. Huang, T. H. Lu, X. J. Wang, W. Y. Sun and B. S.
Kang, Dalton Trans., 2008, 3178; (e) Y. Cui, O. R. Evans, H. L. Ngo, P. S. White
and W. B. Lin, Angew. Chem., Int. Ed., 2002, 41, 1159; (f) O. M. Yaghi, M.
O’Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi and J. Kim, Nature, 2003,
423, 705; (g) R. Carballo, B. Covelo, E. M. VázquezꢀLópez, E. GarcíaꢀMartínez,
A. Castiñeiras and J. Niclós, Z. Anorg. Allg. Chem., 2005, 631, 785; (h) D. L.
Reger, R. P. Watson and M. D. Smith, Inorg. Chem., 2006, 45, 10077; (i) F. Luo,
Y. X. Che and J. M. Zheng, Cryst. Growth Des., 2009, 9, 1066.
12 (a) D. N. Dybtsev, H. Chun and K. Kim, Chem. Commun., 2004, 1594; (b) Y. B.
Dong, H. X. Xu, J. P. Ma and R. Q. Huang, Inorg. Chem., 2006, 45, 3325; (c) L.
H. Weng and D. Y. Zhao, Chem. ꢀEur. J., 2007, 13, 4146; (d) R. Sarma, D. Kalita
and J. B. Baruah, Dalton Trans., 2009, 7428; (e) R. Cao, D. F. Sun, Y. C. Liang,
M. C. Hong, K. Tatsumi and Q. Shi, Inorg. Chem., 2002, 41, 2087; (f) J. C.

Page 23 of 44
CrystEngComm
View Article Online
491
492
493
494
495
496
497
498
499
500
501
502
503
504
505
506
507
508
509
510
511
512
MacDonald, T. J. M. Luo and G. T. R. Palmore, Cryst. Growth Des., 2004, 4,
1203; (g) P. Mahata and S. Natarajan, Inorg. Chem., 2007, 46, 1250; (h) Z. W.
Wang, C. C. Ji, J. Li, Z. J. Guo, Y. Z. Li and H. G. Zheng, Cryst. Growth Des.,
2009, 9, 475.
13 (a) S. Masaoka, D. Tanaka, Y. Nakanishi and S. Kitagawa, Angew. Chem., Int. Ed.,
2004, 43, 2530; (b) D. F. Sun, Y. X. Ke, T. M. Mattox, B. A. Ooro and H. C. Zhou,
Chem. Commun., 2005, 5447; (c) B. Zheng, H. Dong, J. F. Bai, Y. Z. Li, S. H, Li
and M. Scheer, J. Am. Chem. Soc., 2008, 130, 7778; (d) P. Kanoo, K. L.
Gurunatha and T. K. Maji, Cryst. Growth Des., 2009, 9, 4147.
14 (a) V. S. S. Kumar, F. C. Pigge and N. P. Rath, New J. Chem., 2004, 28, 1192; (b)
A. J. Blake, N. R. Brooks, N. R. Champness, M. Crew, A. Deveson, D. Fenske, D.
H. Gregory, L. R. Hanton, P. Hubberstey and M. Schröder, Chem. Commun., 2001,
1432; (c) Y. J. Qi, Y. H. Wang, C. W. Hu, M. H. Cao, L. Mao and E. B. Wang,
Inorg. Chem., 2003, 42, 8519.
15 (a) X. L.Wang, C. Qin, E. B. Wang, Z. M. Su, L. Xu and S. R. Batten, Chem.
Commun., 2005, 4789; (b) B. Chen, F. R. Fronczek, B. H. Courtney and F. Zapata,
Cryst. Growth Des., 2006, 6, 825; (c) C. A. Williams, A. J. Blake, P. Hubberstey
and M. Schröder, Chem. Commun., 2005, 5435.
16 (a) Z. H. Zhou, J. M. Yang and H. L. Wan, Cryst. Growth Des., 2005, 5, 1825; (b)
S. L. Childs, L. J. Chyall, J. T. Dunlap, V. N. Smolenskaya, B. C. Stahly and G. P.
Stahly, J. Am. Chem. Soc., 2004, 126, 13335; (c) P. Vishweshwar, A. Nangia and
V. M. Lynch, Cryst. Growth Des., 2003, 3, 783; (d) A. Dimos, D. Tsaousis, A.

CrystEngComm
Page 24 of 44
View Article Online
513
514
515
516
517
518
519
520
521
522
523
524
525
526
527
528
529
530
531
532
533
534
Michaelides, S. Skoulika, S. Golhen, L. Ouahab, C. Didierjean and A. Aubry,
Chem. Mater., 2002, 14, 2616; (e) D. T. de Lill, N. S. Gunning and C. L. Cahill,
Inorg. Chem., 2005, 44, 258; (f) L. A. Borkowski and C. L. Cahill, Inorg. Chem.,
2003, 42, 7041.
17 (a) Y. X. Tan, Y. P. He and J. Zhang, Inorg. Chem., 2012, 51, 9649; (b) Y. X. Tan,
F. Wang, Y. Kang and J. Zhang, Chem. Commun., 2011, 47, 770; (c) S. Q. Zhang,
F. L. Fang, M. Y. Wu, J. Ma, Y. Bu and M. C. Hong, Cryst. Drowth Des., 2012, 12,
1452; (d) C. Ren, P. Liu, Y. Y. Wang, W. H. Huang and Q. Z. Shi, Eur. J. Inorg.
Chem., 2010, 5545; (e) G. X. Liu, K. Zhu, H. M. Xu, S. Nishihara, R. Y. Huang
and X. M. Ren, CrystEngComm, 2010, 12, 1175; (f) H. L. Wang, K. Wang, D. F.
Sun, Z. H. Ni and J. Z. Jiang, CrystEngComm, 2011, 13, 279; (g) S. Q. Zang, J. B.
Li, Q. Y. Li, H. W. Hou and T. C. W. Mak, CrystEngComm, 2010, 12, 2907; (h) G.
X. Liu, R. Y. Huang, L. F. Huang, X. J. Kong and X. M. Ren, CrystEngComm,
2009, 11, 643.
18 (a) Y. L. Lu, W. J. Zhao, Y. Liu, B. Liu, X. Feng, J. T. Tan, X. Li and X. W. Yang,
J. Solid State Chem., 2012, 192, 144; (b) G. X. Liu, Y. Q. Huang, Q. Chu, T. ꢀa.
Okamura, W. Y. Sun, H. Liang and N. Ueyama, Cryst. Growth Des., 2008, 8,
3233; (c) W. H. Zhang, Z. Dong, Y. Y. Wang, L. Hou, J. C. Jin, W. H. Huang and
Q. Z. Shi, Dalton Trans., 2011, 40, 2509; (d) G. P. Yang, Y. Y. Wang, P. Liu, A. Y.
Fu, Y. N. Zhang, J. C. Jin and Q. Z. Shi, Cryst. Growth Des., 2010, 10, 1443; (e)
S. N. Wang, H. Xing, Y. Z. Li, J. F. Bai, Y. Pan, M. Scheer and X. Z. You, Eur. J.
Inorg. Chem., 2006, 3041.

Page 25 of 44
CrystEngComm
View Article Online
535
536
537
538
539
540
541
542
543
544
545
546
547
548
549
550
551
552
553
554
555
19 (a) Y. Wang, F. H. Zhao, Y. X. Che and J. M. Zheng, Inorg. Chem. Commun.,
2012, 17, 180; (b) L. L. Wen, J. B. Zhao, K. L. Lv, Y. H. Wu, K. J. Deng, X. K.
Leng and D. F. Li, Cryst. Growth Des., 2012, 12, 1603; (c) F. Wang, X. H. Ke, J.
Zhao, K. J. Deng, X. K. Leng, Z. F. Tian, L. L. Wen and D. F. Li, Dalton Trans.,
2011, 40, 11856; (d) S. Y. Zhang, J. B. Lan, Z. H. Mao, R. G. Xie and J. S. You,
Cryst. Growth Des., 2008, 8, 3134.
20 (a) J. Fan and B. E. Hanson, Chem. Commun., 2005, 2327; (b) Y. H. So,
Macromolecules, 1992, 25, 516.
21 (a) R. L. Carlin, Magnetochemistry, SpringerꢀVerlag, Berlin, Heidelberg, 1986; (b)
O. Kahn, Molecular Magnetism, VCH Publishers, Weinheim, 1993.
22 SAINT, Version 6.02a; Bruker AXS Inc., Madison, W1, 2002.
23 G. M. Sheldrick, SADABS, Program for Bruker Area Detector Absorption
Correction, University of Göttingen, Göttingen, Germany, 1997.
24 (a) G. M. Sheldrick, SHELXSꢀ97, Program for Crystal Structure Solution,
University of Göttingen, Göttingen, Germany, 1997. (b) G. M. Sheldrick,
SHELXLꢀ97, Program for Crystal Structure Refinement, University of Göttingen,
Göttingen, Germany, 1997.
25 (a) K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordinated
Compounds, 5th edn, Wiley & Sons, New York, 1997; (b) C. G. Wang, Y. H. Xing,
Z. P. Li, J. Li, X. Q. Zeng, M. F. Ge and S. Y. Niu, Cryst. Growth Des., 2009, 9,
1525.

CrystEngComm
Page 26 of 44
View Article Online
556
557
558
559
560
561
562
563
564
565
566
567
568
569
570
571
572
573
574
575
576
577
26 (a) Y. Liu, Y. Qi, Y. Y. Lv, Y. X. Che and J. M. Zheng, Cryst. Growth Des., 2009,
9, 4797; (b) J. Yang, J. F. Ma, S. R. Batter and Z. M. Su, Chem. Commun., 2008,
2233; (c) B. K. Tripuramallu, P. Manna, S. N. Reddy and S. K. Das, Cryst.
Growth Des., 2012, 12, 777; (d) S. Q. Zang, M. M. Dong, Y. J. Fan, H. W. Hou
and T. C. W. Mak, Cryst. Growth Des., 2012, 12, 1239; (e) J. Q. Liu, Y. Y. Wang,
T.Wu and J. Wu, CrystEngComm, 2012, 14, 2906.
27 (a) L. F. Ma, L. Y. Wang, D. H. Lu, S. R. Batten and J. G. Wang, Cryst. Growth
Des., 2009, 9, 1741; (b) W. Q. Kan, J. Yang, Y. Y. Liu and J. F. Ma,
CrystEngComm, 2012, 14, 6934.
28 (a) Y. Y. Liu, J. F. Ma, J. Yang and Z. M. Su, Inorg. Chem., 2007, 46, 3027; (b) Y.
Liu, Y. Qi, Y. Y. Lv, Y. X. Che and J. M. Zheng, Cryst. Growth Des., 2010, 10,
4797.
29 (a) M. O’Keeffe, O. M. Yaghi, Reticular Chemistry Structure Resource; Arizona
State University: Tempe, AZ, 2005; http://okeeffews1.la.asu.edu/rcsr/home.htm;
(b) I. A. Baburin, V. A. Blatov, L. Carluccib, G. Ciani and D. M. Proserpio, J.
Solid State Chem., 2005, 178, 2452; (c) V. A. Blatov, 2006,
http://www.topos.ssu.samara.ru/starting.html.
30 (a) L. Pan, D. H. Olson, L. R. Ciemnolonski, R. Heddy and J. Li, Angew. Chem.
Int. Ed., 2006, 45, 616; (b) W. B. Yang, X. Lin, A. J. Blake, C. Wilson, P.
Hubberstey, N. R. Champness and M. Schröder, Inorg. Chem., 2009, 48, 11067.
31 (a) S. W. Lee, H. J. Kim, Y. K. Lee, K. Park, J. H. Son and Y. U. Kwon, Inorg.
Chim. Acta, 2003, 353, 151; (b) E. Y. Choi, K. Park, C. M. Yang, H. Kim, J. H.

Page 27 of 44
CrystEngComm
View Article Online
578
579
580
581
582
583
584
585
586
587
588
589
590
591
592
593
594
595
596
597
598
Son, S. W. Lee, Y. H. Lee, D. Min and Y. U. Kwon, Chem. –Eur. J., 2004, 10,
5535; (c) S. A. Hilderbrand and S. J. Lippard, Inorg. Chem., 2004, 43, 5294; (d)
H. Chun, H. Jung and J. Seo, Inorg. Chem., 2009, 48, 2043; (e) Q. X. Yao, J. L.
Sun, K. Li, J. Su, M. V. Peskov and X. Z. You, Dalton Trans., 2012, 41, 3953.
32 (a) L. Han, Y. Zhao, W. N. Zhao, X. Li and Y. X. Liang, Cryst. Growth Des., 2009,
9, 660; (b) P. Pachfule, C. Dey, T. Panda and R. Banarjee, CrystEngComm, 2010,
12, 1600; (c) C. C. Ji, L. Qin, Y. Z. Li, Z. J. Guo and H. G. Zheng, Cryst. Growth
Des., 2011, 11, 480.
33 (a) Q. Ye, Y. M. Song, G. X. Wang, K. Chen, D. W. Fu, P. W. H. Chan, J. S. Zhu,
S. D. Huang and R. G. Xiong, J. Am. Chem. Soc., 2006, 128, 6554; (b) H. Zhang,
D. E. Zelmon, G. E. Price and B. K. Teo, Inorg. Chem., 2000, 39, 1868; (c) Y. S.
Chang, H. Xu, S. P. Xie, J. P. Li, X. L. Xue and H. W. Hou, Inorg. Chem.
Commun., 2010, 13, 959.
34 (a) D. W. Fu, Y. M. Song, G. X. Wang, Q. Ye, R. G. Xiong, T. Akutagawa, T.
Nakamura, P. W. H. Chan and S. D. Huang, J. Am. Chem. Soc., 2007, 129, 5346;
(b) T. Okubo, R. Kawajiri, T. Mitani and T. Shimoda, J. Am. Chem. Soc., 2005,
127, 17598; (c) T. Sivakurnar, H. Y. Chang, J. Baek and P. S. Halasyamani, Chem.
Mater., 2007, 19, 4710; (d) D. L. de Murillas, R. Pinol, M. B. Ros, J. L. Serrano,
T. Sierra and M. R. de la Fuente, J. Mater. Chem., 2004, 14, 1117.
35 (a) L. Song, S. W. Du, J.D. Lin, H. Zhou, T. Li, Cryst. Growth Des., 2007, 7,
2268; (b) X. Q. Liang, J. T. Jia, T. Wu, D. P. Li, L. Liu, Tsolmon and G. S. Zhu,

CrystEngComm
Page 28 of 44
View Article Online
599
600
601
602
603
604
605
606
607
608
CrystEngComm, 2010, 12, 3499; (c) Z. Su, M. S. Chen, J. Fan, M. Chen, S. S.
Chen, L. Luo and W. Y. Sun, CrystEngComm, 2010, 12, 2040.
36 (a) F. Luo, Y. X. Che and J. M. Zheng, Cryst. Growth Des., 2009, 9, 1066; (b) Y.
Wang, F. H. Zhao, A. H. Shi, Y. X. Che and J. M. Zheng, Inorg. Chem. Commun.,
2012, 20, 23; (c) Y. Y. Liu, J. F. Ma, J. Yang and Z. M. Su, Inorg. Chem., 2007, 46,
3027; (d) L. F. Ma, L. Y. Wang, Y. Y. Wang, S. R. Batten and J. G. Wang, Inorg.
Chem., 2009, 48, 915; (e) M. X. Yao, M. H. Zeng, H. H. Zou, Y. L. Zhou and H.
Liang, Dalton Trans., 2008, 2428.
37 O. Sengupta, B. Gole, S. Mukherjee and P. S. Mukherjee, Dalton Trans., 2010, 39,
7451.
609
610
38 K. R. MitchellꢀKoch and A. Matzger, J. Pharm. Sci., 2008, 97, 2121.

Page 29 of 44
CrystEngComm
View Article Online
611
612
Table 1 Xꢀray crystallographic data for complexes 1 ꢀ 3
Complex
1
2
3
Formula
C32H22N4O6SCo
649.53
C43H29N6O11SCo2
955.64
C26H17F6N2O5Co
610.35
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
293(2)
293(2)
293(2)
Monoclinic
Cc
Monoclinic
C2/c
Monoclinic
P2/c
22.707(3)
10.2165(11)
15.1394(16)
90
49.698(4)
7.2513(6)
21.8865(19)
90
14.909(3)
7.1963(15)
24.592(5)
90
b (Å)
c (Å)
α (º)
β (º)
124.5430(10)
90
93.5130(10)
90
104.312(2)
90
γ (º)
V (Å3)
2892.9(5)
4
7872.6(12)
8
2556.5(9)
4
Z
Dcalc (Mg/m3)
ꢂ (mmꢀ1)
1.491
1.613
1.586
0.719
0.969
0.756
F(000)
1332
3896
1232
θ range (º)
2.27ꢀ25.50
10927
2.41ꢀ25.50
30070
2.47ꢀ26.00
19735
Reflections collected
Independent reflections (Rint)
Data/restraints/parameters
Goodnessꢀofꢀfit
R indices [I > 2σ(I)]a,b
5274 (0.0184)
5274 / 2 / 397
1.022
7325 (0.0598)
7325 / 14 / 576
1.039
5025 (0.0138)
5025 / 2 / 359
1.025
R1 = 0.0283
wR2 = 0.0723
R1 = 0.0299
wR2 = 0.0735
R1 = 0.0510
wR2 = 0.1237
R1 = 0.0772
wR2 = 0.1390
R1 = 0.0468
wR2 = 0.1152
R1 = 0.0570
wR2 = 0.1165
R indices (all data)
613
614
a R1 =Σ||Fo| ꢀ |Fc||/Σ|Fo|.
b wR2 = |Σw(|Fo|2 ꢀ |Fc|2)|/Σ|w(Fo)2|1/2
615