One-dimensional channels encapsulated in supramolecular networks constructed of zinc(II), manganese(II), or nickel(II) atoms with 3-(Carboxymethyl)-2, 7-dimethyl-3H-benzo[d]imidazole-5-carboxylic Acid

Article abstract of DOI:10.1002/zaac.201300154

Four complexes with supramolecular architectures, namely, MZCA·3H₂O (1), [Zn(H₂O)₆] ²⁺·[MZCA]₂·[H₂O]₆ (2), [Mn(MZCA)₂(H₂O)₄]·2H₂O (3), and [Ni(MZCA)₂(H₂O)₄]·2H₂O (4) [MZCA = 3-(carboxymethyl)-2, 7-dimethyl-3H-benzo[d]imidazole-5-carboxylic acid], were synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Complexes 1 and 2 display a remarkable 3D network with 1D hydrophilic channels. Complexes 3 and 4 are isostructural and exhibit a 3D structure encapsulating 1D 24-membered ring microporous channels. The UV/Vis and fluorescent spectra were measured to characterize complexes 1-4. The thermal stability of complexes 2-4 were also examined.

Full text of DOI:10.1002/zaac.201300154

ARTICLE
DOI: 10.1002/zaac.201300154
One-Dimensional Channels Encapsulated in Supramolecular Networks
Constructed of Zinc(II), Manganese(II), or Nickel(II) Atoms with
3-(Carboxymethyl)-2,7-dimethyl-3H-benzo[d]imidazole-5-carboxylic Acid
Mingxia Zhao,[a] Liqin Xiong,[a] Shilei Li,[a] Jin Chang,[a] Hongyu Ning,[a] and
Chuanmin Qi*[a]
Keywords: Hydrogen bonding; Channels; Water chains; X-ray diffraction; Fluorescence
Abstract. Four complexes with supramolecular architectures,
plexes 1 and 2 display a remarkable 3D network with 1D hydrophilic
namely, MZCA·3H2O (1), [Zn(H2O)6]2+·[MZCA]2·[H2O]6 (2), channels. Complexes 3 and 4 are isostructural and exhibit a 3D struc-
[Mn(MZCA)2(H2O)4]·2H2O (3), and [Ni(MZCA)2(H2O)4]·2H2O (4) ture encapsulating 1D 24-membered ring microporous channels. The
[MZCA = 3-(carboxymethyl)-2,7-dimethyl-3H-benzo[d]imidazole-5- UV/Vis and fluorescent spectra were measured to characterize com-
carboxylic acid], were synthesized and characterized by elemental
plexes 1–4. The thermal stability of complexes 2–4 were also exam-
analysis, IR spectroscopy, and single-crystal X-ray diffraction. Com- ined.
proteins, and other biological systems.[11] During the last dec-
Introduction
ade, the structure of benzimidazole carboxylate was widely
used in the design of therapeutic agents, such as diuretic and
natriuretic,[12] antiparasitic, serotonin antagonist, antineoplas-
tic and antiflarial,[13] herbicidal, and antihypertensive com-
pounds.[14] The analysis of various interactions in drugs has
attracted considerable interest for their wide-ranging antiviral
activity and the possibility of forming supramolecular aggre-
gates with transition metal ions. However, reports on the coor-
dination behavior of benzimidazole carboxylate compounds re-
main scarce.[15] To the best of our knowledge, supramolecular
frameworks constructed by 3-(carboxymethyl)-2,7-dimethyl-
3H-benzo[d]imidazole-5-carboxylic acid (MZCA) have not yet
been reported.
The rational design of microporous solids based on supra-
molecular architectures have attracted considerable interest in
recent years, mainly due to the potential use of their resulting
cavities and channels in nanotechnology, including shape- and
size-selective molecular recognition,[1] separation,[2] ion ex-
change,[3] storage, adsorption,[4] catalysis,[5] electronic and
magnetic properties.[6] However, the control of crystal and net-
work structures in a predictable manner still remains an elusive
task because of the delicate balance and competition between
directional noncovalent interactions such as hydrogen bonds
and nondirectional noncovalent interactions such as van der
Waals (dispersive) packing forces. The formation of hydrogen-
bonded and metal coordination networks with large cavities
often results in self-interpenetration to fill the voids in the ini-
tial host structure.[7]
From a structural point of view, MZCA has three interesting
characteristics: (i) the nitrogen atom in benzimidazole ring and
the oxygen atoms in carboxylate group are both potential sites
The understanding of different molecular interactions plays
a major role in supramolecular chemistry and crystal engineer- of hydrogen bonding interactions, given that the presence of
ing.[8] Hydrogen bonding and π–π stacking interactions are by
solvent molecules, such as water or methanol, might serve as
far the most well-studied interactions.[9] They are employed
to control the conformational and topological features of the
molecular assembly in the solid state.[10] Many scientists have
been involved in the analysis of weak interactions focusing
on benzimidazole derivatives due to their relevance to DNA,
possible hydrogen-bond donors;[16] (ii) due to the benzimid-
azole rings, we can predict that the π–π interactions might de-
vote to the formation of crystal structures;[17] (iii) the relatively
large π-conjugated system in benzimidazole ring might con-
tribute much to the desirable fluorescence property.
Herein, we report the syntheses and structures of four new
compounds MZCA·3H2O (1), [Zn(H2O)6]2+·[MZCA]2·[H2O]6
(2), [Mn(MZCA)2(H2O)4]·2H2O (3), and [Ni(MZCA)2(H2O)4]·
2H2O (4) [MZCA = 3-(carboxymethyl)-2,7-dimethyl-3H-
benzo[d] imidazole-5-carboxylic acid]. Complexes 1 and 2
both have remarkable hydrogen-bonded 3D networks encapsu-
lating 1D hydrophilic channels. Complexes 3 and 4 are iso-
structural and both have unusual hydrogen-bonded 3D net-
* Prof. Dr. C. M. Qi
Fax: +86-10-58802075
E-Mail: qicmin@sohu.com
[a] Key Laboratory of Radiopharmaceuticals
Ministry of Education, College of Chemistry
Beijing Normal University
Beijing, 100875, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201300154 or from the au-
thor.
Z. Anorg. Allg. Chem. 2014, 640, (1), 159–167
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
159

M. Zhao, L. Xiong, S. Li, J. Chang, H. Ning, C. Qi
ARTICLE
works encapsulating 1D 24-membered ring microporous chan-
nels.
Results and Discussion
MZCA·3H2O (1)
The overall structure of the crystal for 1 with atom labeling
is shown in Figure 1. One carboxylic group [O(1), C(1), O(2)]
of MZCA is coplanar with the molecular plane: the dihedral
angle between the benzimidazole ring and the O(1)/C(1)/O(2)
plane is 3.3(4)°. The other carboxylic group [O(3), C(12),
O(4)] is almost perpendicular to the molecular plane: the dihe-
dral angle between the benzimidazole ring and the O(3)/C(12)/
O(4) plane is 72.8(4)°. In the structure of MZCA, one carbox-
ylic acid group is deprotonated and the nitrogen atom is pro-
Figure 1. Molecular structure of 1 showing 30% probability displace-
ment ellipsoids and the atom-numbering scheme.
Hydrogen bond lengths and angles are listed in Table 1. As
tonated. Therefore, MZCA is in the inner-salt form. A similar shown in Figure 2a, the hydrogen bonds [O(5)–H(5E)···O(3) =
feature has been reported in the complex N-(2-oxopyrrolidin- 2.690(4) Å, O(2)–H(2)···O(5) = 2.548(4) Å] bridge molecules
1-ylmethyl)-l-valine·2H2O.[18]
forming a 1D helical chain along the b axis, which is intercon-
Table 1. Hydrogen bonding parameters /Å,° for compounds 1–4.
D–H···A
d(D–H)
d(H···A)
d(D···A)
Є(D–H···A)
a)
1
2
O(2)–H(2)···O(5)
0.82
0.88
0.86
0.88
0.86
0.85
0.89
0.86
1.75
2.04
1.84
1.93
1.87
2.27
2.21
1.84
2.548(4)
2.666(4)
2.690(4)
2.760(5)
2.681(5)
2.886(10)
2.874(4)
2.702(3)
165
127
171
155
157
129
130
177
O(5)–H(5D)···O(6)i
O(5)–H(5E)···O(3)ii
O(6)–H(6A)···O(7)iii
O(6)–H(6B)···O(4)
O(7)–H(7A)···O(7)iv
O(7)–H(7B)···O(1)v
N(2)–H(2A)···O(4)vi
b)
OW(1)–HW(1)···O(1)
0.76
0.86
0.75
0.82
0.85
0.80
0.85
0.81
0.84
0.82
0.88
0.85
0.86
1.93
1.87
1.99
2.02
2.07
1.90
1.87
2.18
1.87
2.09
1.80
1.86
1.91
2.655(3)
2.708(4)
2.732(4)
2.795(4)
2.914(4)
2.685(3)
2.720(4)
2.947(4)
2.701(4)
2.899(4)
2.674(4)
2.709(5)
2.768(4)
159
164
174
158
177
165
171
157
170
167
170
177
172
OW(2)–HW(2A)···O(2)
OQ(1)–HQ(1A)···O(3)
OQ(2)–HQ(2B)···O(3)
OQ(3)–HQ(3C)···O(2)
OW(1)–HW(1B)···O(1)i
OW(2)–HW(2B)···OQ(3)ii
OW(3)–HW(3A)···OQ(2)iii
OW(3)–HW(3B)···O (4)iv
OQ(1) –HQ(1B)···OW(1)v
OQ(2) –HQ(2A)···OQ(1)vi
OQ(3) –HQ(3B)···O(4)vii
N(2) –HN(2)···OQ(2)viii
c)
3
4
N(2)–H(2A)···O(7)i
O(5)–H(5D)···O(4)i
O(5)–H(5E)···O(4)ii
O(6)–H(6A)···O(3)iii
O(6)–H(6B)···O(2)
O(7)–H(7A)···O(3)iii
O(7)–H(7B)···O(2)iv
0.89
0.85
0.85
0.86
0.86
0.85
0.85
1.77
1.90
1.86
2.01
1.87
1.85
1.96
2.639(3)
2.728(3)
2.680(3)
2.826(3)
2.723(3)
2.673(3)
2.793(3)
164
163
161
159
170
164
166
d)
OW(1)–HW(1A)···O(4)i
OW(1)–HW(1B)···O(4)ii
OW(2)–HW(2A)···O(2)
OW(2)–HW(2B)···O(3)iii
OW(3)–HW(3A)···O(3)iv
OW(3)–HW(3B)···O(2)v
N(1)–HN(1)···OW(3)
0.96
0.89
0.86
0.87
0.90
0.99
0.92
1.78
1.80
1.98
1.98
1.81
1.81
1.76
2.737(3)
2.684(3)
2.716(3)
2.846(3)
2.680(3)
2.787(3)
2.630(3)
173
170
143
170
161
168
157
Symmetry codes: a) (i), –x+1/2, y–1/2, –z+1/2; (ii), –x+1/2, y+1/2, –z+1/2; (iii), x+1/2, y–1/2, z; (iv), –x, y+2, –z–1; (v), x, y+1, z; (vi) x, –y,
z+1/2. b) (i), –x+1, –y, –z; (ii), –x, –y–1, –z; (iii), –x, –y, –z; (iv), x, y, z+1; (v), x, y, z–1; (vi), –x+1, –y, –z–1; (vii), –x, –y–1, –z–1; (viii), x,
y–1, z. C) (i), –x+3/2, y+1/2, –z+3/2; (ii), x+1/2, –y+1/2, z+1/2; (iii), –x+3/2, –y+1/2, –z+1; (iv), x, –y, z–1/2. d) (i), –x+1/2, y–1/2, –z+1/2; (ii),
x–1/2, –y+1/2, z–1/2; (iii), –x+1/2, –y+1/2, –z+1; (iv), x, –y, z–1/2; (v), –x+1/2, –y+1/2, –z.
160
www.zaac.wiley-vch.de
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 159–167

Supramolecular Networks with ZnII, MgII, or NiII Atoms
nected by the hydrogen bonds [N(2)–H(2A)···O(4)
=
2.702(3) Å] and π–π stacking interactions, giving rise to a 2D
helical architecture. Furthermore, the 2D structure is extended
through the water molecules into a 3D network with 1D hydro-
philic channels (Figure 2b), in which water chains containing
acyclic water hexamers are observed. Each water chain con-
sists of acyclic water hexamers, interlinked by hydrogen bonds
[O(5)–H(5D)···O(6)
= 2.666(4) Å, O(6)–H(6A)···O(7) =
2.760(5) Å, and O(7)–H(7A)···O(7Ј) = 2.886(10) Å] and short
contacts [O(6)···O(6Ј) = 2.590(5) Å]. In the water hexamer, the
average O···O distance is 2.771 Å. This distance is slightly
longer than the corresponding values in ice Ih (2.759 Å)[19] and
the calculated value of 2.718 Å for cyclic water hexamer and
comparable to that in water trapped in organic compound of
DMNY·2.5H2O (2.776 Å, DMNY
=
2,4-bimethyl-5-
aminobenzo[b]-1,8-naphthyridine).[20] However, it is shorter
than that observed in the metal-organic framework of
[Pr(pdc)-(Hpdc)(H2O)2]·4H2O (2.783 Å, pdc = pyridine-2,6-
dicarboxylic acid)[21] and in liquid water (2.854 Å) and the
ring water hexamer with a planar arrangement (2.905 Å).[22]
The water molecules O(6) and O(7) in the cluster are in a
tetrahedral arrangement with three water–water interactions
and one water–carboxylate interaction. Meanwhile, the water
molecule O(5) involves one water–water interaction and two
water–carboxylate interactions. Therefore, the water molecule
O(5) acts as single-hydrogen-bond donor, the water molecule
O(6) acts as single-hydrogen-bond donor and single-hydrogen-
bond acceptor, and the water molecule O(7) functions as sin-
gle-hydrogen-bond donor and double-hydrogen-bond ac-
ceptors in the water hexamer (Figure 2c).
Figure 2. (a) Projection of the 2D structure of 1. Hydrogen atoms not
involved in hydrogen bonding are omitted for clarity and hydrogen
bonds are shown as dashed lines. (b) Space-filling diagram shows the
hydrogen-bonded 3D network of 1 viewed along the c axis, with water
molecules and all hydrogen atoms are omitted for clarity. (c) Projection
of the 1D water chain and its coordination environment of 1. Dashed
lines indicate hydrogen bonds.
[Zn(H2O)6]2+·[MZCA–]2·[H2O]6 (2)
The asymmetric unit of complex 2 contains one MZCA mo-
lecule, half a ZnII, three coordinated water molecules, and
three lattice water molecules (Figure 3). The central zinc atom
is hexacoordinated by six oxygen atoms from water molecules
with bond length of 2.067(2)–2.129(2) Å, MZCA molecules
connect zinc atoms by the hydrogen bonds between the car-
boxylic oxygen atoms from MZCA molecules and oxygen
atoms from water molecules. Each MZCA molecule loses two
protons from the carboxylic acid group and one of the two
protons transfers to the nitrogen atom. Therefore, each MZCA
molecule provides one negative charge. The dihedral angles
between the benzimidazole ring and the carboxylic groups are
9.9(4)° for O(3)/C(11)/O(4) and 82.0(4)° for O(1)/C(10)/O(2),
respectively, these values are larger than those observed in 1.
As shown in Figure 4a, one [Zn(H2O)6]2+ cation is attached
to the other [Zn(H2O)6]2+ cation by hydrogen bonds with the
water molecules as bridges [OW(3)–HW(3A)···OQ(2) =
2.947(4) Å, OQ(2)–HQ(2A)···OQ(1) = 2.674(4) Å, OQ(1)–
HQ(1B)···OW(1) = 2.899(4) Å], forming a 1D linear metal–
water chain along the a axis with the intermolecular Zn···Zn
distance is 7.566 Å. Interestingly, the metal–water chain con-
Figure 3. Asymmetric unit of complex 2 showing 30% probability
displacement ellipsoids and the atom-numbering scheme.
sists of the acyclic (H2O)4 cluster and the [Zn(H2O)4]2+ 1,3-bis(4-pyridyl)propane and NaH2sip = 5-sulfoisophthalic
cation. This conformation contrasts with that in the acid monosodium salt], in which the infinite chain consists of
{[Cd(dpp)(sip)(H2O)3]·0.5Cd(H2O)6·5H2O}n complex [dpp = the water decamer and [Cd(H2O)4]2+.[23]
Z. Anorg. Allg. Chem. 2014, 159–167
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
161

M. Zhao, L. Xiong, S. Li, J. Chang, H. Ning, C. Qi
ARTICLE
drogen bonds [OQ(3)–HQ(3A)···O(2) = 2.914(4) Å, OQ(3)–
HQ(3B)···O(4) = 2.709(5) Å] and π–π stacking interactions,
giving rise to a 2D structure, which are further interlinked to
the [Zn(H2O)6]2+ cations by hydrogen bonds [OW(3)–HW(3B)
···O(4) = 2.701(4) Å, OQ(1)–HQ(1B)···OW(1) = 2.899(4) Å,
OW(2)–HW(2A)···O(2) = 2.708(4) Å] into a 3D network (Fig-
ure 4c). Interestingly, a hydrophilic channel is observed, being
enclosed by the MZCA molecules. The [Zn(H2O)6]2+ cations
and water molecules OQ(3) are accommodated in each chan-
nel.
[Mn(MZCA)2(H2O)4]·2H2O (3) and [Ni(MZCA)2(H2O)4]·
2H2O (4)
X-ray diffraction revealed that complexes 3 and 4 are iso-
structural. Both structures contain two MZCA molecules, one
metal atom, four coordinated water molecules, and two lattice
water molecules. Two MZCA molecules are almost perpendic-
ular to each other; the dihedral angles between two benzimid-
azole rings are 69.43(8) and 68.87(8)° for 3 and 4, respectively.
The coordination arrangement around the metal ion, compris-
ing of two oxygen atoms belonging to two monodentate carb-
oxylate groups from two MZCA located at the axial positions,
and four oxygen atoms from water molecules located at the
equatorial plane, can be described as a distorted octahedral.
The average M–O bond lengths are 2.179 and 2.068 Å for 3
and 4, respectively. The overall structure of the crystal for 3 is
shown in Figure 5. Similar to 2, each MZCA provides one
negative charge. One carboxylic group [O(1), C(1), O(2)] of
MZCA is coplanar with the benzimidazole ring: the dihedral
angles between the benzimidazole ring and the O(1)/C(1)/O(2)
plane are 3.4(4)° for 3 and 1.8(3)° for 4, these values are sim-
ilar to those observed in 1, and smaller than those observed in
2. The other carboxylic group [O(3), C(12), O(4)] is almost
perpendicular to the benzimidazole ring: the dihedral angles
between the benzimidazole ring and the O(3)/C(12)/O(4) plane
are 87.9(4)° for 3 and 88.1(4)° for 4, these values are larger
than those observed in 1 and 2.
Figure 4. (a) Projection of the 1D linear metal-water chain formed by
[Zn (H2O)6]2+ cations in 2 viewed along the a axis. Hydrogen atoms
not involved in hydrogen bonding are omitted for clarity and hydrogen
bonds are shown as dashed lines. (b) Projection of the 2D network
formed by MZCA molecules in 2. Hydrogen atoms not involved in
hydrogen bonding are omitted for clarity and hydrogen bonds are
shown as dashed lines. (c) Space-filling diagram shows the hydrogen-
bonded 3D network of 2 viewed along the b axis, with [Zn(H2O)6]2+
cations, water molecules and all hydrogen atoms are omitted for clar-
ity.
As shown in Figure 4b, one MZCA molecule is attached to
the other molecule via hydrogen bonds with the water
Figure 5. Molecular structure of 3 showing 30% probability displace-
ment ellipsoids and the atom-numbering scheme. Symmetry code
(A): –x, y, –z+1/2.
molecules OQ(2) as bridges [OQ(2)–HQ(2B)···O(3)
2.795(4) Å, N(2)–HN(2)···OQ(2) = 2.768(4) Å], forming a 1D
chain along the axis, which is further interlinked
through water molecules OQ(1) by hydrogen bonds [OQ(1)–
HQ(1A)···O(3) 2.732(4) Å, OQ(2)–HQ(2A)···OQ(1)
=
b
As shown in Figure 6a, the molecules are connected to each
other by hydrogen bonds with distances of O(5)–H(5D)···O(4)
=
=
4
2.674(4) Å] and form a graph-set motif of R6 (12). These = 2.728(3) Å and O(6)–H(6A)···O(3) = 2.826(3) Å, resulting
chains are interconnected by water molecules OQ(3) via hy- in 1D ribbons along the b axis and forming a graph-set motif
162
www.zaac.wiley-vch.de
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 159–167

Supramolecular Networks with ZnII, MgII, or NiII Atoms
2
of R2 (8). On the other hand, there exist π–π stacking interac-
tions in complexes 3 and 4 with distances of 3.497 and
3.482 Å, respectively (Figure S1, Supporting Information).
Hydrogen bonds [O(7)–H(7B)···O(2) = 2.793(3) Å, N(2)–
H(2A)···O(7) = 2.639 (3) Å] and π–π stacking interactions
bridge molecules forming 1D chains along the a axis, and fur-
ther interconnect the ribbons into 2D layer structures (Fig-
ure 6b), in which the grid-like 22-membered ring (22-MR)
cavities is observed.
As shown in Figure 6c, hydrogen bonds [O(7)–H(7A)···O(3)
= 2.673(3) Å, O(7)–H(7B)···O(2) = 2.793(3) Å, O(5)–H(5D)···
O(4) = 2.728(3) Å] bridge molecules forming a 2D architec-
6
ture, and form a graph-set motif of R8 (24) which shares the
C–O and M–O bond. The 2D structure is further extended
into a 3D supramolecular network by hydrogen bonds [N(2)–
H(2A)···O(7) = 2.639(3) Å, O(6)–H(6A)···O(3) = 2.826(3) Å,
O(5)–H(5E)···O(4) = 2.680(3) Å]. The interesting feature, a
24-MR microporous channel running along the c axis, is ob-
served in the 3D network (Figure 6d).
UV/Vis and Fluorescence Spectroscopy
The UV/Vis spectra of MZCA and complexes 2–4 in
CH3OH were measured at room temperature (Figure S2, Sup-
porting Information). MZCA shows a broad absorption at
270 nm. Because the absorption bands of complexes 2–4
are similar to that of the free MZCA ligand with a slight
bathochromic shift, it should be assigned to the πǞπ* transi-
tion of the MZCA ligand.
The fluorescence properties of MZCA and complexes 2–4
in CH3OH were measured at room temperature (Figure S3,
Supporting Information). It can be observed that the free
MZCA has an emission at 335 nm when excited at 278 nm. In
contrast, complexes 2–4 exhibit an intense broad emission
peak at 341 nm when excited at 277, 280, and 281nm, respec-
tively. Generally, the intraligand fluorescence emission wave-
length is determined by the energy gap between the π and π*
molecular orbitals of the free ligand, which is simply related
to the extent of conjugation in the system. As for the metal
complexes, the bathochromic shift of the band in contrast to
that of ancillary ligand should be attributed to the intraligand
(π–π*) fluorescent emission.
PXRD and Thermogravimetric Analysis
To confirm the phase purity of the complexes, the original Figure 6. (a) Projection of the 1D ribbon of 3 viewed along the b axis.
Hydrogen atoms not involved in hydrogen bonding are omitted for
samples are characterized by X-ray powder diffraction
clarity and hydrogen bonds are shown as dashed lines. (b) Projection
(PXRD) at room temperature. The peak positions simulated
of the 2D layer structure of 3 viewed along the b axis. Hydrogen atoms
from the single-crystal X-ray data of complexes are in good
not involved in hydrogen bonding are omitted for clarity and hydrogen
agreement with those observed (Figure S4–S7, Supporting In-
formation).
In order to examine the thermal stability of the complexes,
thermal gravimetric (TG) analyses are carried out for 2–4 (Fig-
ure S8, Supporting Information). The TG curve of complex 2
bonds are shown as dashed lines. (c) Projection of the 2D network of
3 viewed along the c axis, with all hydrogen atoms are omitted for
clarity. Dashed lines indicate hydrogen bonds. (d) View of 3D network
of 3 with 1D channel down the c axis.
exhibits two weight loss stages. The first weight loss of 27.2% cules. The residue remains stable up to 298 °C and then upon
(calcd. 27.8%) from 30 to 165 °C corresponds to the loss of further heating decomposes to unidentified products. The TG
six lattice water molecules and six coordinated water mole- curve of complex 3 exhibits two main weight loss steps. The
Z. Anorg. Allg. Chem. 2014, 159–167
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
163

M. Zhao, L. Xiong, S. Li, J. Chang, H. Ning, C. Qi
ARTICLE
spectra were recorded with a Varian 500 Bruker spectrometer in
[D6]DMSO or CDCl3.
first with a value of 16.2% (calcd. 16.4%) from 30 to 86 °C
corresponds to the loss of two lattice water molecules and four
coordinated water molecules. The dehydrated compound re-
mains stable up to 313 °C and then upon further heating de-
composes to unidentified products. The thermogravimetric
studies of complex 4 indicate two main steps of weight losses.
The first step starts at approximately 100 °C and completes at
approximately 210 °C. The observed weight loss of 16% is
corresponding to the loss of two lattice water molecules and
Synthesis of MZCA: To a solution of 1a (70 g, 0.386 mol) in CH3OH
(200 mL) was slowly added concentrated H2SO4 (20 mL). The solution
was heated to reflux for 24 h and cooled to room temperature, to yield
a yellow precipitate. Intermediate 2a was obtained by filtration and
crystallization from methanol (54.7 g, 72.6%). M.p: 78–79 °C. IR
(KBr): ν˜ = 3005 (br), 1740 (m), 1620 (m), 1590 (m), 1520 (m), 1350
(m) cm–1. 1H NMR (CDCl3, 500 MHz): δ = 8.03(br., 1 H, Ar–H),
four coordinated water molecules (calcd. 16.3%). The dehy- 7.9(m, 2 H, Ar–H), 3.97(s, 3 H, CH3O), 2.63(s, 3 H, PhCH3).
drated compound remains stable up to 300 °C and then upon
Pd/C (0.4 g, 5%) was added to a methanol solution (150 mL) of 2a
(7 g, 35.9 mmol) under hydrogen. The mixture was stirred at room
temperature for 6 h and afterwards passed through Celite. The filtrate
further heating decomposes to unidentified products.
was concentrated to give a brown solid of 3a (5.286g, 89.1%).
Conclusions
M.p:188–121 °C. IR (KBr): ν˜ = 3452 (br), 3370 (m), 1686 (m), 1597
(m) cm–1. 1H NMR (CDCl3, 500 MHz): δ = 7.76(s, 1 H, Ar–H),
In this work, the ligand 3-(carboxymethyl)-2,7-dimethyl-
3H-benzo[d]imidazole-5-carboxylic acid (MZCA) was em- 7.74(d, 3JH,H = 8.21Hz, 1 H, Ar–H), 6.64 (d, 3JH,H = 8.20Hz, 1 H, Ar–
ployed to construct coordination polymers with ZnII, MnII, and
H), 4.15(br., 2 H, NH2), 3.85(s, 3 H, CH3O), 2.17(s, 3 H, PhCH3).
NiII in solutions. The MZCA molecules in 1 form 1D helical
chains through hydrogen bonds. These chains are further ex-
tended through the water molecules and π–π stacking interac-
tions into 3D networks with 1D hydrophilic channels. The
MZCA anions in 2 form interesting 2D network by hydrogen
bonds and π–π stacking interactions, which are further inter-
linked to the [Zn(H2O)6]2+ cations by hydrogen bonds into
Acetyl chloride (12 mL) was added dropwise to a solution of 3a (10 g,
60.5 mmol) in CH2Cl2 (100 mL) and Et3N (22 mL). The solution was
allowed to cool to 0–8 °C during the addition, and stirred at r t for 5 h.
After filtration, the mixture was washed with water, NaHCO3 aqueous
solution, water, dried (Na2SO4), and the solvent was removed in vacuo
to afford the crude product, which was recrystallized from EtOAc to
give a white solid of 4a (9.804 g, 78.2%). M.p:130–133 °C. IR
three dimensions with 1D hydrophilic channels. Complexes 3
(KBr): ν˜ = 3289 (br), 2941 (m), 1719 (m), 1656 (m), 1527 (m), 891
and 4 are isostructural. The M(MZCA)2(H2O)4 (M = Mn, Ni) (m) cm–1. 1H NMR ([D6]DMSO, 500 MHz): δ = 9.31(s, 1 H, NH),
3
7.80(s, 1 H, Ar–H), 7.77 (d, 2 H, JH,H = 9.60Hz, Ar–H), 3.83
molecules in complexes 3 and 4 form 1D ribbons, which are
further extended through hydrogen bonds and π–π stacking
interactions into a 3D network containing a 24-membered ring
microporous channel.
(s, 3 H, –COOCH3), 2.28(s, 3 H, –COCH3), 2.12 (s, 3 H, Ar–CH3).
To a solution of fuming HNO3 (10.2 mL) at –15 °C was slowly added
4a (3 g, 14.5 mmol). After stirring for 1 h, the mixture was poured
into ice water to yield a white precipitate, which was filtered and
washed with ice water, NaHCO3 aqueous solution, and water, and
dried to afford the crude product. This was recrystallized from EtOAc
Experimental Section
Materials and General Methods: The ligand 3-(carboxymethyl)-2,7- to give a white solid of 5a (2.29 g, 62.6%). m.p:174–176 °C. IR
dimethyl-3H-benzo[d]imidazole-5-carboxylic acid (MZCA) was pre-
pared according to the pathway shown in Scheme 1. Other commer-
cially available chemicals were of analytical grade and were used with-
out further purification. Powder X-ray diffraction measurements were
carried out with a Bruker D8 Focus X-ray diffractometer to check
(KBr): ν˜ = 3259 (br), 2953 (m), 1723 (s), 1667 (m), 1579 (m), 1534
1
(m), 1512 (m) cm–1. H NMR ([D6]DMSO, 500 MHz): δ = 10.13 ( s,
1 H, NH), 8.17(s, 1 H, Ar–H), 8.15(s, 1 H, Ar–H), 3.89(s, 3 H,
–COOCH3), 2.38(s, 3 H, –NHCOCH3), 2.09(s, 3 H, Ar–CH3).
phase purity. Elemental analyses (C, H, N) were determined with an Pd/C (0.1 g, 5%) was added to the methanol solution (20 mL) of 5a
Elementar vario EL elemental analyzer. UV/Vis spectra were measured (1.35 g, 5.4 mmol) under hydrogen. The mixture was stirred at room
with a GBC Cintra 10e UV/Vis spectrophotometer in MeOH solution. temperature for 7 h. The solution was passed through Celite. The fil-
Photoluminescence analyses were performed with a RF-5301PC fluo-
rescence spectrometer in MeOH solution. Thermogravimetric analyses
trate was concentrated to give a white solid of 6a (0.85 g, 71.5%). IR
(KBr): ν˜ = 3415 (br), 3244 (m), 2948 (m), 1704 (m), 1649 (m), 1512
were conducted on a ZRY-2P Thermal Analyses using a heating rate (m) cm–1.
of 20 K·min–1 from room temperature to 800 °C under nitrogen. The
IR spectra were recorded with a Nicolet-AVATAR 360 FT-IR spec-
To a solution of glacial AcOH (30 mL) was added 6a (3 g, 13.5 mmol),
trometer using KBr pellets in the 4000–400 cm–1 regions. 1H NMR
the mixture was heated to reflux for 2 h and afterwards cooled to room
temperature. The solvent was removed under reduced pressure to yield
a yellow oil, which was dissolved in water (10 mL). Ammonia was
added until a pH of about 9 to yield a white precipitate, which was
filtered and dried to afford the product of 7a (1.7 g, 61.6%). M.p:174–
176 °C. Elemental analysis for C11H12O2N2: calcd. C 64.69; H 5.92;
N 13.72%; found: C 64.71; H 5.89; N 14.73%. IR (KBr): ν˜ = 3422
(br), 3282 (br), 1727 (m), 1682 (m), 1616 (m) cm–1. 1H NMR
([D6]DMSO, 500 MHz): δ = :7.96(s, 1 H, Ar–H), 8.10(s, 1 H, Ar–H),
3.96(s, 1 H, –COOCH3), 2.70(s, 3 H, –NHCOCH3), 2.63(s, 3 H,
–Ar–CH3).
Scheme 1. Synthetic pathway for MZCA.
164
www.zaac.wiley-vch.de
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 159–167

Supramolecular Networks with ZnII, MgII, or NiII Atoms
To a solution of 7a (0.78 g, 3.819 mmol) in THF (50 mL) at 0 °C
was added dropwise with constant stirring to a CH3CH2OH–H2O (2:1,
was added NaH (0.6 g, 25 mmol). The mixture was stirred at room 6 mL) solution of MZCA (0.0248 g, 0.1 mmol). The pH of the mixture
temperature for 1 h, afterwards BrCH2COOEt (0.8 mL) was added and was adjusted to 5–6 with a CH3OH solution (2 mL) of pyridine
stirring was continued for 2 h. The solvent was removed under reduced (16 μL), The resulting mixture was heated at reflux for 1 h, cooled to
pressure to give a white solid, which was purified by column room temperature, and stirred at room temperature for 4 h. Afterwards
chromatography (silica; petroleum ether/ethyl acetate; 20:1) to afford the reaction mixture was filtered and the green block-shaped crystals
8a (0.77 g, 69.4%). M.p: 104–107 °C. IR (KBr): ν˜ = 3392 (br), 1734
(s), 1701 (s), 1520 (m), 1424 (m), 1350 (m), 1279 (m), 1217 (m), 1021
(m), 766 (m) cm–1. 1H NMR ([D6]DMSO, 500 MHz): δ = 7.84(s, 1
of 4 were obtained from the filtrate at room temperature after a few
days in 62% Yield (based on MZCA). Elemental analysis for
C24H34N4NiO14: calcd. C 43.59; H 5.18; N 8.47%; found: C 43.56; H
H, Ar–H), 7.81(s, 1 H, Ar–H), 4.88(s, 2 H, –CH2–COOC2H5), 4.27 5.16; N 8.51%. IR (KBr): ν˜ = 3424 (br), 1630 (m), 1568 (m), 1396
3
(q, 2 H, JH,H = 7.10Hz, –COOCH2CH3), 3.96 (s, 3 H, –COOCH3), (m), 1313 (w), 793 (m) cm–1.
2.69 (s, 3 H, imidazole–CH3), 2.65(s, 3 H, Ar–CH3), 1.31(t, 3 H, 3JH,H
= 7.10Hz, –COOCH2CH3).
X-ray Crystallography: Crystal diffraction intensities for complexes
1 and 3 were collected with a Bruker SMART 1000 CCD dif-
To a solution of 8a (0.72 g, 2.48 mmol) in CH3OH (20 mL) was added
fractometer with graphite monochromatized Mo-Kα radiation (λ =
10% NaOH (20 mL). The mixture was heated to reflux for 3 h and
0.71073 Å) at 294(2) K. Semi-empirical absorption corrections were
next cooled to room temperature. Water (10 mL) was added followed
applied using the SADABS program. The structures were solved by
by HCl (0.5 m) until the solution reached pH 7–8 to yield a white
direct methods and refined by full-matrix least-squares on F2 using the
precipitate, which was filtered and dried to afford the product of
SHELXS-97 and SHELXL-97 programs.[24] All non-hydrogen atoms
MZCA (0.527 g, 85.6%). Elemental analysis for C12H12N2O4: calcd.
were refined anisotropically. Hydrogen atoms bound to carbon atoms
C 58.06; H 4.87; N 11.28%; found: C 58.03; H 4.89; N 11.31%. IR
were placed in calculated positions and allowed to ride at distances of
(KBr): ν˜ = 3407 (br), 1738 (m), 1686 (s), 1557 (m), 1516 (m), 1427
0.93 Å (C–H aromatic), 0.96 Å (CH3) and 0.97 Å (CH2); whereas
(s), 1346 (m), 1276 (m), 1209 (s) and 769 (m) cm–1. 1H NMR
those of the aqua molecules were first located in difference Fourier
([D6]DMSO, 500 MHz): δ = 13.32(br., 1 H, Ar–COOH), 11.67 (br., 1
maps, and then fixed at the calculated positions and included in the
H, –CH2–COOH), 7.93 (s, 2 H, Ar–H), 7.62 (s, 1 H, Ar–H), 5.17 (s,
final refinement. Crystal diffraction intensities for complexes 2 and 4
2 H, –CH2–COOH), 2.52 (s, 3 H, Ar–CH3).
were collected with a Rapid-AUTO diffractometer with graphite mo-
nochromatized Mo-Kα radiation (λ = 0.71073 Å) at 293(2) K. Abscor-
Synthesis of MZCA·3H2O (1): A water solution (3 mL) of Zn(NO3)2·
Empirical Absorption Corrections were based on Fourier Series
6H2O (0.0297 g, 0.1 mmol) was added dropwise to CH2Cl2–CH3OH
Approximation. The structures were solved by direct methods and re-
(1:4) solution (5 mL) of MZCA (0.0248 g, 0.1 mmol). The resulting
fined by full-matrix least-squares on F2 using the SHELXS-97 and
mixture was filtered and colorless block-shaped crystals of 1 were ob-
SHELXL-97 programs. All non-hydrogen atoms were refined aniso-
tained from the filtrate at room temperature after a few days in 73%
tropically. Hydrogen atoms bound to carbon atoms were placed in cal-
Yield (based on MZCA). Elemental analysis for C12H18N2O7: calcd.
culated positions and allowed to ride at distances of 0.93 Å (C–H aro-
C 47.68; H 6.00; N 9.27%; found: C 47.66; H 5.97; N 9.31%. IR
(KBr): ν˜ = 3420 (w), 2925 (w), 2533 (br), 1707 (s), 1649 (s), 1625
matic), 0.96 Å (CH3) and 0.97 Å (CH2); whereas those of the aqua
molecules were first located in difference Fourier maps, and then fixed
(s), 1363 (m), 1268 (s), 1220 (m), 1174 (s), 771 (m) cm–1.
at the calculated positions and included in the final refinement. The
Synthesis of [Zn(H2O)6]2+·[MZCA]2·[H2O]6 (2): A solution of
Zn(NO3)2·6H2O (0.0297 g, 0.1 mmol) in CH3OH–H2O (1:1, 2 mL)
was added dropwise to a CH2Cl2–CH3OH (1:1, 8 mL) solution of
MZCA (0.0248 g, 0.1 mmol). The pH of the resulting mixture was
adjusted to 4.5 with a CH3OH solution (2 mL) of pyridine (8 μL). The
reaction mixture was filtered and the colorless block-shaped crystals
of 2 were obtained from the filtrate at room temperature after a few
days in 35% Yield (based on MZCA). Elemental analysis for
C24H46N4O20Zn: calcd. C 37.15; H 5.97; N 7.22%; found: C 37.11; H
5.94; N 7.26%. IR (KBr): ν˜ = 3448 (br), 1637 (m), 1569 (w), 1384
(vs), 1323 (w), 792 (v) cm–1.
crystallography details for complexes 1–4 are presented in Table 2.
Selected bond lengths and angles are listed in Tables S1–S4 (Support-
ing Information).
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
Copies of the data can be obtained free of charge on quoting the de-
pository numbers CCDC-288684, -284063, -602559and -290069.
(Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk)
Synthesis of [Mn(MZCA)2(H2O)4]·2H2O (3): To a CH3CH2OH solu-
tion (8 mL) of MZCA (0.0248 g, 0.10 mmol), CH3OH–H2O (1:1) solu-
tions (10 mL) of MnSO4 (0.0151 g, 0.10 mmol) and Mg(ClO4)2
(0.0446 g, 0.20 mmol) were added dropwise with constant stirring. The
pH of the mixture was adjusted to 5 with a 0.1 m NaOH solution, the
resulting mixture was stirred at room temperature for 0.5 h. The reac-
tion mixture was filtered and the colorless block-shaped crystals of 3
were obtained from the filtrate at room temperature after a few days
in 65% Yield (based on MZCA). Elemental analysis for
C24H34MnN4O14: calcd. C 43.84; H 5.21; N 8.52%; found: C 43.81;
H 5.19; N 8.56%. IR (KBr): ν˜ = 3335 (br), 1622 (s), 1567 (m), 1396
(s), 1313 (m), 794 (m) cm–1.
Supporting Information (see footnote on the first page of this article):
Diagram of π···π stacking interactions in complexes 3 and 4 (Figure
S1), UV/Vis spectra for 1–4 (Figure S2), fluorescence spectra for 1–4
(Figure S3), PXRD patterns for 1–4 (Figures S4–7), thermogravimetric
analyses (TGA) for 2–4 (Figure S8), and selected bond lengths and
angles for compounds 1–4 (Tables S1–S4).
Acknowledgements
This work is supported by the National Natural Science Foundation of
China (No. 21071022) and the Fundamental Research funds for the
Central Universities. We especially thank Ms. LiQin Xiong for her ex-
cellent work and kind help in preparing this paper.
Synthesis of [Ni(MZCA)2(H2O)4]·2H2O (4):
A solution of
NiCl2·6H2O (0.0238 g, 0.1 mmol) in CH3CH2OH–H2O (2:1, 6 mL)
Z. Anorg. Allg. Chem. 2014, 159–167
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
165

M. Zhao, L. Xiong, S. Li, J. Chang, H. Ning, C. Qi
ARTICLE
Table 2. Crystal data and details of structure determination of compounds 1–4.
1
2
3
4
Empirical formula
Formula weight
C12H18N2O7
302.28
C24H46N4O20Zn
776.02
C24H34MnN4O14
657.49
C24H34N4NiO14
661.26
Crystal system
Space group
monoclinic
C2/c
triclinic
P1
monoclinic
C2/c
monoclinic
C2/c
¯
Crystal size /mm
a /Å
b /Å
c /Å
0.22ϫ0.18ϫ0.10
24.678(4)
7.3698(19)
16.045(4)
90
0.50ϫ0.15ϫ0.10
7.5659(15)
9.757(2)
11.634(2)
95.82(3)
0.26ϫ0.22ϫ0.16
22.391(4)
11.369(2)
11.821(2)
90
0.50ϫ0.20ϫ0.08
22.223(4)
11.413(2)
11.731(2)
90
α /°
β /°
100.367(4)
90
2870.5(12)
8
1.399
0.116
98.05(3)
94.63(3)
842.1(3)
1
1.530
0.819
102.535(3)
90
2937.5(9)
4
1.487
0.524
103.43(3)
90
2894.0(10)
4
1.518
0.746
γ /°
V /Å3
Z
Dc /g·cm–3
μ /mm–1
θ range /°
2.58–26.43
7821/2937
1.022
0.0369
0.0618, 0.1718
0.1079, 0.2079
1.78–27.48
6392/3653
1.005
1.86–26.37
8093/2995
0.930
2.55–27.48
11390/3308
0.966
Reflns collected /unique
GOF on F2
Rint
0.0564
0.0318
0.0594
b)
R1a), wR2 [I Ͼ 2σ(I)]
0.0488, 0.1093
0.0813, 0.1170
0.336, –0.378
0.0469, 0.1318
0.0723, 0.1552
0.376, –0.573
0.0441, 0.0945
0.0786, 0.1002
0.354, –0.400
R1, wR2 (all data)
Largest diff. peak, hole /e·Å–3 0.436, –0.391
2
2 2
2 2
a) R1 = Σ||Fo|–|Fc||/Σ|Fo|. b) wR2 = {Σ[w(Fo –Fc ) ]/Σ[w(Fo ) ]}1/2
.
Int. Ed. 2002, 41, 281; d) C. Serre, F. Millange, C. Thouvenot,
M. Nogues, G. Marsolier, D. Louèr, G. Férey, J. Am. Chem. Soc.
2002, 124, 13519.
References
[1] a) K. Endo, T. Sawaki, M. Koyanagi, K. Kobayashi, H. Masuda,
Y. Aoyama, J. Am. Chem. Soc. 1995, 117, 8341; b) K. T. Holman,
A. M. Pivovar, J. A. Swift, M. D. Ward, Acc. Chem. Res. 2000,
33, 107.
[2] K. Uemura, S. Kitagawa, M. Kondo, K. Fukui, R. Kitaura, H. C.
Chang, T. Mizutani, Chem. Eur. J. 2002, 8, 3587.
[7] T. Dewa, K. Endo, Y. Aoyama, J. Am. Chem. Soc. 1998, 120,
8933.
[8] a) K. M. Dethlefs, P. Hobza, Chem. Rev. 2000, 100, 143; b) C. B.
Aakeroy, Acta Crystallogr., Sect. B 1997, 53, 569; c) T. N.
Guru Row, Coord. Chem. Rev. 1999, 183, 81.
[3] a) O. M. Yaghi, H. L. Li, J. Am. Chem. Soc. 1995, 117, 10401; b)
O. M. Yaghi, H. L. Li, J. Am. Chem. Soc. 1996, 118, 295; c) A.
Kamiyama, T. Noguchi, T. Kajiwara, T. Ito, Angew. Chem. Int.
Ed. 2000, 39, 3130.
[9] a) L. Pauling, The Nature of Chemical Bond, Cornell University
Press, Ithaca, NY, 1960; b) C. A. Hunter, Angew. Chem. Int. Ed.
Engl. 1993, 32, 1584; c) C. A. Hunter, Chem. Soc. Rev. 1994, 23,
101.
[4] a) M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T. M. Reineke, M.
O’Keeffe, O. M. Yaghi, Acc. Chem. Res. 2001, 34, 319; b) S.
Noro, S. Kitagawa, M. Kondo, K. Seki, Angew. Chem. Int. Ed.
2000, 39, 2082; c) M. Eddaoudi, J. Kim, N. L. Rosi, D. T. Vodak,
J. Wachter, M. O’Keeffe, O. M. Yaghi, Science 2002, 295, 469;
d) N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M.
O’Keeffe, O. M. Yaghi, Science 2003, 300, 1127; e) D. N. Dybt-
sev, H. Chun, S. H. Yoon, D. Kim, K. Kim, J. Am. Chem. Soc.
2004, 126, 32; f) L. Pan, M. B. Sander, X. Y. Huang, J. Li, M.
Smith, E. Bittner, B. Bochrath, J. K. Johnson, J. Am. Chem. Soc.
2004, 126, 1308; g) P. M. Forster, J. Eckert, J. S. Chang, S. E.
Park, G. Férey, A. K. Cheetham, J. Am. Chem. Soc. 2003, 125,
1309; h) M. Latroche, C. Serre, F. Millange, T. Loiseau, G. Férey,
Chem. Commun. 2003, 2976; i) A. Hazra, P. Kanoo, S. Mohapa-
tra, G. Mostafa, T. K. Maji, CrystEngComm 2010, 12, 2775.
[5] a) M. Fujita, Y. J. Kwon, S. Washizu, K. Ogura, J. Am. Chem.
Soc. 1994, 116, 1151; b) K. Endo, T. Koike, T. Sawaki, O. Haya-
shida, H. Masuda, Y. Aoyama, J. Am. Chem. Soc. 1997, 119,
4117; c) T. Sawaki, K. Endo, K. Kobayashi, O. Hayashida, Y.
Aoyama, Bull. Chem. Soc. Jpn. 1997, 70, 3075; d) J. S. Seo, D.
Whang, H. Lee, S. I. Jun, J. Oh, Y. J. Jeon, K. Kim, Nature 2000,
404, 982; e) L. Pan, H. M. Liu, X. G. Lei, X. Y. Huang, D. H.
Olson, N. J. Turro, J. Li, Angew. Chem. Int. Ed. 2003, 42, 542; f)
G. Férey, Nat. Mater. 2003, 2, 136.
[10] a) S. Subramanian, M. J. Zawarotko, Coord. Chem. Rev. 1994,
137, 357; b) C. B. Aakeroy, M. Nieuwenhuyzen, J. Am. Chem.
Soc. 1994, 116, 10983; c) I. Weissbuch, R. Popovitz-Biro, M.
Lahav, L. Leiserowitz, Acta Crystallogr., Sect. B 1995, 51, 115;
d) R. Kadirvelraj, A. M. Umarji, W. T. Robinson, S. Bhattacharya,
T. N. Guru Row, Chem. Mater. 1996, 8, 2313; e) K. Fuji, T. Fu-
ruta, T. Otsubo, K. Tanaka, Tetrahedron Lett. 1999, 40, 3001; f)
C. Dai, P. Nguyen, T. B. Marder, A. J. Scott, W. Clegg, C. Viney,
Chem. Commun. 1999, 2493; g) G. W. Coates, A. R. Dunn, L. M.
Henling, D. A. Dougherty, R. H. Grubbs, Angew. Chem. Int. Ed.
Engl. 1997, 36, 248.
[11] a) C. A. Hunter, J. K. M. Sanders, J. Am. Chem. Soc. 1990, 112,
5525; b) P. Hobza, H. L. Selzle, E. W. Schlag, J. Am. Chem. Soc.
1994, 116, 3500; c) W. S. Zielinski, L. E. Orgel, Nature 1987,
327, 346; d) K. T. O’Neil, R. H. Hoess, W. F. Degrado, Science
1990, 249, 774.
[12] E. Palosi, K. Dezso, M. Erzsebet, I. Szvoboda, H. Laszlo, S.
Gyorgy, V. Sandor, G. Vera, M. Katalin, European Patent, Appl.
EP, 324, 988, Chem. Abstr. 1990, 112, 55864w.
[13] S. Ram, D. S. Wise, L. L. Wotring, J. W. McCall, L. B. Townsend,
J. Med. Chem. 1992, 35, 539.
[14] K. Kubo, Y. Inada, Y. Kohara, Y. Sugiura, M. Ojima, K. Itoh, Y.
Furukawa, N. Nishikawa, T. Naka, J. Med. Chem. 1993, 36, 1772.
[15] a) Z. Liu, Y. Chen, P. Liu, J. Wang, M. H. Huang, J. Solid State
Chem. 2005, 178, 2306; b) Z. G. Guo, D. Q. Yuan, W. H. Bi, X. J.
Li, Y. Q. Wang, R. Cao, J. Mol. Struct. 2006, 782, 106.
[16] a) H. W. Roesky, A. Marius, Coord. Chem. Rev. 2003, 236, 91;
b) G. R. Desiraju, Chem. Commun. 2005, 2995.
[6] a) V. R. Thalladi, S. Brasselet, H. C. Weiss, D. Bläser, A. K. Katz,
H. L. Carrell, R. Boese, J. Zyss, A. Nangia, G. R. Desiraju, J.
Am. Chem. Soc. 1998, 120, 2563; b) E. Coronado, J. R. Galan-
Mascaros, C. J. Gómez-Garcıà, V. Laukhin, Nature 2000, 408,
447; c) K. Barthelet, J. Marrot, D. Riou, G. Férey, Angew. Chem.
166
www.zaac.wiley-vch.de
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 159–167

Supramolecular Networks with ZnII, MgII, or NiII Atoms
[17] a) C. Janiak, J. Chem. Soc. Dalton Trans. 2000, 3885; b) R. Hal-
dar, K. V. Rao, S. J. George, T. K. Maji, Chem. Eur. J. 2012, 18,
5848.
[21] S. K. Ghosh, P. K. Bharadwaj, Inorg. Chem. 2003, 42, 8250.
[22] J. N. Moorthy, R. Natarajan, P. Venugopalan, Angew. Chem. Int.
Ed. 2002, 41, 3417.
[23] Q. Y. Liu, L. Xu, CrystEngComm 2005, 7, 87.
[24] G. M. Sheldrick, SHELXS-97 and SHELXL-97, Program for the
Solution and Refinement of Crystal Structures, University of
Göttingen, Germany, 1997.
[18] Y. Liang, X. Li, Z. M. Wang, C. H. Yan, L. P. Jin, J. Mol. Struct.
2002, 643, 1.
[19] D. Eisenberg, W. Kauzmann, The Structure and Properties of
Water, Oxford University, Oxford, U. K., 1969.
[20] R. Custelcean, C. Afloroaei, M. Vlassa, M. Polverejan, Angew.
Chem. Int. Ed. 2000, 39, 3094.
Received: March 13, 2013
Published Online: September 6, 2013
Z. Anorg. Allg. Chem. 2014, 159–167
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
167