Unusual double layer coordination polymers constructed from metal(II)-3-fluorophthalate helices and M-tib honeycom layers (tib = 1,3,5-tris(1-imidazolyl)benzene)

Article abstract of DOI:10.1016/j.inoche.2012.02.029

Two coordination polymers, [M(Fpht)tib]·H₂O (M = Cd 1, Co 2; H₂Fpht = 3-fluorophthalic acid and tib = 1,3,5-tris(1-imidazolyl) benzene) have been synthesized and structurally characterized by single crystal X-ray diffraction. They po

Full text of DOI:10.1016/j.inoche.2012.02.029

Inorganic Chemistry Communications 20 (2012) 108–111
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Unusual double layer coordination polymers constructed from
metal(II)-3-fluorophthalate helices and M–tib honeycom
layers (tib=1,3,5-tris(1-imidazolyl)benzene)
⁎
Yu-E Cha, Xue Ma, Xia Li , Han-Zhu Shi, Hua-Lu Tan, Yuan Meng
Department of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
Two coordination polymers, [M(Fpht)tib]·H2O (M=Cd 1, Co 2; H2Fpht=3-fluorophthalic acid and
tib=1,3,5-tris(1-imidazolyl)benzene) have been synthesized and structurally characterized by single crystal
X-ray diffraction. They possess unusual double layer structures constructed from M–Fpht helices and (3, 3)
Received 24 January 2012
Accepted 24 February 2012
Available online 6 March 2012
⁎
M–tib honeycom layers. The fluorescence of the complexes maybe arise from the intraligand π –π transition.
© 2012 Elsevier B.V. All rights reserved.
Keywords:
Coordination polymer
3-Fluorophthalic acid
1,3,5-Tris(1-imidazolyl)benzene
Crystal structure
Fluorescence
In the past decade, metal–organic frameworks (MOFs) have been
studied extensively. These polymeric frameworks show a variety of
interesting structures and variety of properties such as magnetic
and luminescent properties and optoelectronic effects, imparting
promising applications [1–11]. Vast numbers of coordination poly-
mers have been obtained by the reaction of transition metal salts
with carboxylate ligands in the presence of various N-ligands, leading
to different extended structures or coordination networks with larger
cavities and interpenetrating structures [10–15]. Another interest of
network is the construction of compounds with helical attributes.
The special functional properties for helices structure are bioactivity
and are also important in advanced materials such as optical devices
and asymmetric catalysis [16–18]. Benzenedicarboxylate ligands and
their derivatives are among the most commonly employed linkers
in the construction of coordination polymers due to their structural
rigidity and diversity. The phthalic acid (H2pht) ligand has proven
to be an efficacious choice for the generation of novel coordination
polymers [19,20]. So, the 3-fluorophthalic acid (H2Fpht) is a good
candidate to produce unique structural motifs with beautiful aes-
thetics and useful functional properties. It must be considered that
the acidity of H2Fpht is significantly higher than that of H2pht due
to the electron-withdrawing nature of the fluorine atoms. In addition,
the carboxylate groups are twisted out of the plane of the benzene
ring due to the electrostatic repulsion between the fluorine atoms
and the carboxylate oxygen atoms. Hulvey et al. in this regard, have
explored metal complexes with perfluorinated or nonfluorinated
benzenedicarboxylate ligand. A significant difference between the
carboxylate torsion angles of the fluorinated and nonfluorinated li-
gands leads to the formation of markedly different structures for the
two groups of materials [21]. However, only one example of complex
containing H2Fpht ligand has been reported [22]. 1,3,5-Tris(1-imida-
zolyl)benzene (tib) is a rigid planar molecule containing three imid-
azole groups arranged symmetrically around the benzene ring, thus
forming a trigonal ligand, which can be used as a building block in
the synthesis of some MOFs [23–34]. In the present case, using
H2Fpht and tib as ligands, the complexes [M(Fpht)tib]·H2O (M=Cd
1 and Co 2) were obtained. The two complexes possess double layer
structures, which are observed for the first time, for tib-complexes.
Herein, we report the syntheses [35], structures [36] and luminescent
properties of the two complexes.
Complex 1 features a double layer structure constructed from Cd–
Fpht helical chains and (3, 3) Cd–tib layers (Fig. 1). The asymmetric
unit comprises one divalent cadmium ion, one Fpht, one tib ligand
and free water molecule. The coordination environment of Cd(II)
ion is a distorted octahedron with three oxygen atoms (O1C, O2C
and O3) from two Fpht dianions, three nitrogen atoms (N2, N4A
and N6B) from three tib ligands (Fig. 1a). The bond distances of
Cd1―O and Cd1―N range from 2.281(3) to 2.485(3)
Å and
2.299(3) to 2.329(3) Å, respectively. Each tib ligand connects three
Cd(II) ions and each Cd(II) ion connects three tib ligands to generate
(3, 3) Cd–tib honeycom network (Fig. 1b). Three Cd(II) ions and three
tib ligands form a 30-membered macrocyclic ring through the Cd–N
coordination bonds with the distances Cd…Cd of 10.310, 12.165,
and 13.007 Å. The dihedral angles between each imidazole ring and
⁎
Corresponding author. Tel.: +86 10 68902320; fax: +86 10 68902320.
E-mail address: xiali@mail.cnu.edu.cn (X. Li).
1387-7003/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2012.02.029

Y.-E. Cha et al. / Inorganic Chemistry Communications 20 (2012) 108–111
109
a)
b)
Fig. 1. View of the structure of complex 1. (a) Coordination environment of Cd(II) ion. Selected bond distances (Å): Cd1-O3, 2.281(3); Cd1-N2, 2.299(3); Cd1-N6B, 2.302(3);
Cd1-N4A, 2.329(3); Cd1-O2C, 2.353(2), Cd1-O1C, 2.485(3). Symmetry code: A x+1/2, −y+3/2, z−1/2, B x+1/2, −y+1/2, z−1/2, C −x+1/2, y−1/2, −z+1/2. (b) 2D double
layer architecture constructed from the (3, 3) Cd–tib layer (top and bottom) and Cd–Fpht left- and right-handed helices (left and right). All hydrogen atoms and free water molecule
are omitted for clarity.
central benzene ring of tib ligand are 40.5°, 7.3° and 49.6°. So, the
honeycom network is corrugated. The Fpht ligand adopts
conformation variation, but the coordinated carboxylate groups
have the bigger dihedral angles relative to the plane of the aromatic
ring. The Cd–Fpht helix is maybe mainly caused by the significant dif-
ference of the dihedral angles between the two carboxylate groups.
Interestingly, the (3, 3) Cd–tib layers are linked by Cd–Fpht helices
into double layer architecture parallel to the (1 0 1)-plane. In the
layer, the right- and left-handed helical chains are in an alternate
array and joined together by the tib ligands leading to the formation
of achiral 2D layer. The distance between the layers separated by
a
bidentate-chelating/monodentate coordination mode and its two car-
boxylate groups are twisted relative to their benzene ring by 7.4° and
91.2°. It is worthy to note that the Cd(II) ions are linked together by
the Fpht ligands to furnish Cd–Fpht single-stranded helices along
the b direction. Each turn of the helix contains two Fpht ligands and
two Cd(II) ions with a pitch of 10.310 Å. It is also interesting to note
that H2Fpht molecule is planar and rigid ligand, and there is no

110
Y.-E. Cha et al. / Inorganic Chemistry Communications 20 (2012) 108–111
Fpht ligand is 6.852 Å based the distance Cd⋅⋅⋅Cd. Therefore, the dou-
ble layer structure of 1 can also be viewed as a structure constructed
from Cd–Fpht right- and left-handed single-stranded helices and Cd–
tib honeycom layers. Each Fpht, tib and Cd(II) are considered as two-,
three-, and five-connector, respectively, the layer can be simplified to
a (2, 3, 4)-connected 3-nodal net, and its Schläfli symbol is {63}{66.84}
{6}. The free water molecule (O5) bonds to the layer through weak
hydrogen bonds (O5―H5⋅⋅⋅O3, 3.080(5) Å and O5―H5⋅⋅⋅O4 [−x+
1/2, y−1/2, −z+1/2], 3.075(5) Å). Furthermore, the double layers
are stacked in an AAA parallel fashion by C―H⋅⋅⋅π bonds between
the C―H groups of Fpht and the imidazole rings (H⋅⋅⋅centroid dis-
tance, 2.924 Å; the angle of C―H⋅⋅⋅centroid, 147.5°), resulting in an
overall 3D array (Fig. S1).
acid analog. The two complexes show similar ligand-based lumines-
cent behavior.
Acknowledgments
This work is supported by the National Natural Science Founda-
tion of China (21071101).
Appendix A. Supplementary materials
Crystallographic data for the complexes has been deposited with the
Cambridge Crystallographic Data Centre, CCDC reference number is
851841 for 1 and 851840 for 2. Copies of the information may be
obtained free of charge from The Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (Tel: (44) 01223 762910; fax: (44) 01223
336033; email: deposit@ccdc.cam.ac.uk or visit website: http://www.
ccdc.cam.ac.uk/deposit). Supplementary data to this article can be
found online at doi:10.1016/j.inoche.2012.02.029.
The structure of complex 2 is similar to that of 1 (Fig. S2), the cor-
responding bond distances and bond angles are differences (Table
S3). Compared the distances of the M―N, M―O and M…M for the
two complexes, reveals that the corresponding distances decrease
as the ionic radius of the M2+ ions decrease in the order of Cd2+
>
Co2+. In 2, the C―H⋅⋅⋅π interaction is not observed between the
C―H groups of Fpht and the imidazole rings, since H⋅⋅⋅centroid (π)
distance of 3.111 Å is longer (normal value of H⋅⋅⋅π distances below
3.0 Å) [39,40]. The week π⋅⋅⋅π interaction is found between the
aromatic rings of Fpht ligands from the neighboring layers (the
face-to-face distance, 3.962 Å).
References
[1] J. Rocha, L.D. Carlos, F.A. Almeida Paz, D. Ananias, Luminescent multifunctional
lanthanides-based metal–organic frameworks, Chem. Soc. Rev. 40 (2011)
926–940.
[2] O. Shekhah, J. Liu, R.A. Fischer, C. Woell, MOF thin films: existing and future appli-
cations, Chem. Soc. Rev. 40 (2011) 1081–1106.
[3] M.D. Allendorf, A. Schwartzberg, V. Stavila, A.A. Talin, A roadmap to implement-
ing metal–organic frameworks in electronic devices: challenges and critical direc-
tions, Chem. Eur. J. 17 (2011) 11372–11388.
[4] J.-R. Li, Y. Ma, M.C. McCarthy, J. Sculley, J. Yu, H.-K. Jeong, P.B. Balbuena, H.-C.
Zhou, Carbon dioxide capture-related gas adsorption and separation in metal–
organic frameworks, Coord. Chem. Rev. 255 (2011) 1791–1823.
[5] S. Qiu, G. Zhu, Molecular engineering for synthesizing novel structures of metal–
organic frameworks with multifunctional properties, Coord. Chem. Rev. 253
(2009) 2891–2911.
[6] J. Lee, O.K. Farha, J. Roberts, K.A. Scheidt, S.T. Nguyen, J.T. Hupp, Metal–organic
framework materials as catalysts, Chem. Soc. Rev. 38 (2009) 1450–1459.
[7] S. Natarajan, P. Mahata, Metal–organic framework structures—how closely are
they related to classical inorganic structures? Chem. Soc. Rev. 38 (2009)
2304–2318.
[8] H.E. Toma, K. Araki, A.D.P. Alexiou, S. Nikolaou, S. Dovidauskas, Monomeric and
extended oxo-centered triruthenium clusters, Coord. Chem. Rev. 219 (2001)
187–234.
The fluorescent spectra of the two complexes and the free ligands
in the solid state were recorded at room temperature upon the exci-
tation wavelength at 365 nm (Fig. 2). The emission spectrum of tib
ligand shows a broad band at 423 nm, while the emission spectrum
of H2Fpht ligand splits at 417 and 438 nm. The complex 1 displays a
broad emission band at 430 nm. For 1, no emission originating from
metal-centered MLCT/ LMCT excited states are expected, since
Cd(II) ion is difficult to oxidize or reduce due to its d10 configuration.
Complex 2 shows a emission band at 427 nm, similar to that of 1. In
comparison to that of the free ligands, the emission bands of com-
plexes 1 and 2 are little shifted arising from the coordination interac-
tions of the organic ligands to metal(II) ions. Thus, the fluorescence of
⁎
the two complexes can be attributed to the π –π transition of the li-
gands [41–43].
In conclusion, based on 3- fluorophthalic acid (H2Fpht) as ligand,
along with tripodal rigid 1,3,5-tris(1-imidazolyl)benzene (tib) ligand,
we synthesized two coordination polymers [M(Fpht)tib]·H2O
(M=Cd 1 and Co 2). Unique double layer structural motifs are char-
acterized, which are scantily reported. The M–Fpht helical motifs are
observed in the ternary systems of M/Fpht/tib. This is the first metal–
H2Fpht framework containing mixed ligands where the substituent
3-fluoro-phthalic acid forms a different structure to that of phthalic
[9] M. Koeberl, M. Cokoja, W.A. Herrmann, F.E. Kuehn, From molecules to materials:
molecular paddle-wheel synthons of macromolecules, cage compounds and
metal–organic frameworks, Dalton Trans. 40 (2011) 6834–6859.
[10] N. Roques, V. Mugnaini, J. Veciana, Magnetic and porous molecule-based mate-
rials, Top. Curr. Chem. 293 (2010) 207–258.
[11] M. Mikuriya, D. Yoshioka, M. Handa, Magnetic interactions in one-, two-, and
three-dimensional assemblies of dinuclear ruthenium carboxylates, Coord.
Chem. Rev. 250 (2006) 2194–2211.
[12] B.I. Kharisov, P. Elizondo Martinez, V.M. Jimenez-Perez, O.V. Kharissova, B. Najera
Martinez, N. Perez, Recent advances on ditopic ligands, J. Coord. Chem. 63 (2010)
1–25.
[13] S. Friedle, E. Reisner, S.J. Lippard, Current challenges of modeling diiron enzyme
active sites for dioxygen activation by biomimetic synthetic complexes, Chem.
Soc. Rev. 39 (2010) 2768–2779.
[14] X.-Q. Lu, J.-J. Jiang, C.-L. Chen, B.-S. Kang, C.-Y. Su, 3D coordination polymers with
nitrilotriacetic and 4,4′-bipyridyl mixed ligands: structural variation based on
dinuclear or tetranuclear subunits assisted by Na−O and/or O−H···O interac-
tions, Inorg. Chem. 44 (2005) 4515–4521.
[15] Y.-P. Cai, C.-Y. Su, C.-L. Chen, Y.M. Li, B.-S. Kang, A.S.C. Chan, W. Kaim, Formation of
racemate and mesocate complexes from an achiral tripodal ligand containing
three benzimidazole groups, Inorg. Chem. 42 (2003) 163–168.
[16] X.-M. Chen, G.-F. Liu, Double-stranded helices and molecular zippers assembled
from single-stranded coordination polymers directed by supramolecular interac-
tions, Chem. Eur. J. 8 (2002) 4811–4817.
[17] W.-G. Lu, J.-Z. Gu, L. Jiang, M.-Y. Tan, T.-B. Lu, Achiral and chiral coordination poly-
mers containing helical chains: the chirality transfer between helical chains,
Cryst. Growth Des. 8 (2008) 192–199.
[18] U. Siemeling, I. Scheppelmann, B. Neumann, A. Stammler, H.-G. Stammler, J.
Frelekc, Spontaneous chiral resolution of a coordination polymer with distorted
helical structure consisting of achiral building blocks, Chem. Commun. (2003)
2236–2237.
[19] K.M. Elkins, D.J. Nelson, Spectroscopic approaches to the study of the interaction
of aluminum with humic substances, Coord. Chem. Rev. 228 (2002) 205–225.
[20] W. Macyk, K. Szacilowski, G. Stochel, M. Buchalska, J. Kuncewicz, P. Labuz,
Titanium(IV) complexes as direct TiO(2) photosensitizers, Coord. Chem. Rev.
254 (2010) 2687–2701.
3000
2500
2000
1500
1000
500
H2Fpht
1
tib
2
0
400
450
500
550
600
650
Wavelength (nm)
Fig. 2. The emission spectra of the complexes and ligands in solid state (λex=365 nm).

Y.-E. Cha et al. / Inorganic Chemistry Communications 20 (2012) 108–111
111
[21] Z. Hulvey, J.D. Furman, S.A. Turner, M. Tang, A.K. Cheetham, Dimensionality
trends in metal–organic frameworks containing perfluorinated or nonfluorinated
benzenedicarboxylates, Cryst. Growth Des. 10 (2010) 2041–2043.
[22] D. Rishmawi, K. Lewis, M.D. Smith, L. Peterson Jr., H.-C. zur Loye, Poly diaqua (μ4-
3-fluorophthalato-kappa κ4O: O: O': O'') cadmium(II), Acta Crystallogr. Sect. E 63
(2007) m695–m697.
container and heated at 160°C for 3 days. After being cooled to room tempera-
ture, colorless block crystals were collected. Yield: about 68% based on the Cd.
Anal. Calcd for C23H17CdFN6O5 (%):C: 46.91; H: 2.91; N: 14.27 Found(%): C:
46.61; H: 2.67; N: 14.55. IR (KBr pellet, cm−1): 3431(m,br ), 1617(s), 1585(s),
1557(s), 1503(s), 1445(s), 1309(m), 1290(m), 1247(m), 1113(m), 1074(m),
1014(m), 858(m), 763(m), 686(m), 619(m), 466 (w). Preparation of [Co(Fpht)
[23] Z. Su, Z.-B. Wang, W.-Y. Sun, Counteranion-directed assembly of zinc(II) coordi-
nation polymers with 1,3,5-tris(1-imidazolyl)benzene, Inorg. Chem. Commun.
13 (2010) 1278–1280.
[24] Z. Su, J. Fan, T. Okamura, M.-S. Chen, S.-S. Chen, W.-Y. Sun, N. Ueyama, Interpene-
trating and self-penetrating zinc(II) complexes with rigid tripodal mmidazole-
containing ligand and benzenedicarboxylate, Cryst. Growth Des. 10 (2010)
1911–1922.
[25] Z. Su, J. Fan, T.-a. Okamura, W.-Y. Sun, N. Ueyama, Ligand-directed and pH-
controlled assembly of chiral 3d-3d heterometallic metal-organic frameworks,
Cryst. Growth Des. 10 (2010) 3515–3521.
tib]·H2O (2): A mixture of tib (0.0278 g, 0.1 mmol), H2Fpht (0.0185 g,
0.1 mmol), CoCl2·6H2O (0.0235 g, 0.1 mmol), and 2molL−1NaOH (0.1 ml) in
H2O(10 ml) was sealed in a 25 ml Teflon-lined stainless steel container and heat-
ed at 150°C for 3 days. After being cooled to room temperature, purple block crys-
tals were collected. Yield: about 79% based on the Co. Anal. Calcd for
C
23H17CoFN6O5 (%):C: 51.60; H: 3.20; N: 15.70. Found (%): C: 51.42; H: 3.13; N:
15.56. IR (KBr pellet, cm−1): 3471(m,br), 1615(s), 1582(s), 1506(s), 1472(m),
1447(m), 1405(s), 1382(s), 1309(m), 1284(m), 1259(m), 1233(m), 1112(m),
1071(m), 870(w), 769(m), 726(w), 690(w), 578(w), 471(w).
[36] Crystal data for [Cd(Fpht)tib]·H2O (1): monoclinic, space group P2(1)/n,
[26] Z. Su, J. Xu, J. Fan, D.-J. Liu, Q. Chu, M.-S. Chen, S.-S. Chen, G.-X. Liu, X.-F. Wang, W.-Y.
Sun, Synthesis, crystal structure, and photoluminescence of coordination polymers
with mixed ligands and diverse topologies, Cryst. Growth Des. 9 (2009) 2801–2811.
[27] X.-F. Wang, Y. Lv, T.-A. Okamura, H. Kawaguchi, G. Wu, W.-Y. Sun, N. Ueyama,
Structure variation of mercury(II) halide complexes with different imidazole-
containing ligands, Cryst. Growth Des. 7 (2007) 1125–1133.
[28] C.-C. Ji, J. Li, Y.-Z. Li, Z.-J. Guo, H.-G. Zheng, Solvothermal synthesis, structures and
physical properties of four new complexes constructed from multi-variant tricar-
boxylate ligand and pyridyl-based ligands, CrystEngComm 13 (2011) 459–466.
[29] Z.-R. Pan, X.-Q. Yao, H.-G. Zheng, Y.-Z. Li, Z.-J. Guo, S.R. Batten, Unusual three-
dimensional coordination networks with WS4Cu6 cluster nodes and α-C3N4 to-
pology, CrystEngComm 11 (2009) 605–609.
a
=13.7132(12), b=10.3099(9), c=16.1767(15) Å; β=99.6160(10)°, V=
2255.0(3)Å3, Dc=1.734 mg·m−3
Z=4, F(000)=1176, R1=0.0214,
,
wR2=0.0417 for 2986 independent reflections. Crystal data for [Co(Fpht)tib]·
H2O (2): monoclinic, space group P2(1)/c, a=14.0215(8), b=10.1661(5), c=
19.1828(8)Å; β=127.676(3)°, V=2164.21(19)Å3, Z=4, Dc=1.643 mg·m−`3
,
F(000)=1092, R1 =0.0214, wR2=0.0417 for 2986 independent reflections. The
X-ray single crystal data collections for the complexes were performed on a Bruker
ApexII CCD diffractometer equipped with using a graphite monochromatized Mo Kα
radiation (λ=0.71073 Å) at 298(2) K. Semi-empirical absorption corrections were
applied. The structures were solved by direct methods and refined by full-matrix
least-squares method on F2 using the SHELXS 97 and SHELXL-97 programs
[37,38]. All non-hydrogen atoms in the complexes were refined anisotropically.
The hydrogen atoms were generated geometrically and treated by a mixture of inde-
pendent and constrained refinement. A summary of the crystallographic data and
details of the structures refinements are listed in Table S1. Selected bond distances
and bond angles for the complexes are listed in Table S2 and S3.
[30] Z. Su, M.-S. Chen, J. Fan, M. Chen, S.-S. Chen, L. Luo, W.-Y. Sun, Spontaneous reso-
lution of two homochiral ferroelectric cadmium(II) frameworks and an achiral
framework from a one-pot reaction involving achiral rigid ligands, CrystEngComm
12 (2010) 2040–2043.
[31] Z. Su, Y. Song, Z.-S. Bai, J. Fan, G.-X. Liu, W.-Y. Sun, Unprecedented three-
dimensional 10-connected bct nets based on trinuclear secondary building
units and their magnetic behavior, CrystEngComm 12 (2010) 4339–4346.
[32] J. Xu, Z. Pan, T. Wang, Y. Li, Z. Guo, S.R. Batten, H. Zheng, Syntheses, structures,
photoluminescence and magnetic properties of five compounds with 1,3,5-
benzenetricarboxylate acid and imidazole ligands, CrystEngComm 12 (2010)
612–619.
[33] W. Zhao, J. Fan, Y. Song, H. Kawaguchi, T. Okamura, W.Y. Sun, N. Ueyama, Synthe-
ses, crystal structures and properties of novel copper(II) complexes obtained by
reactions of copper(II) sulfate pentahydrate with tripodal ligands, Dalton Trans.
(2005) 1509–1517.
[37] G.M. Sheldrick, SHELXTL Version 5.1, Bruker Analytical X-ray Instruments Inc.,
Madison, Wisconsin, USA, 1998.
[38] G.M. Sheldrick, SHELX-97, PC Version, University of Göttingen, Germany, 1997.
[39] S.V. Lindeman, D. Kosynkin, J.K. Kochi, Unusually short (C―H⋅⋅⋅π) hydrogen
bonds for effective supramolecular (aromatic/aromatic) organization in edge-
to-face motifs, J. Am. Chem. Soc. 120 (1998) 13268–13269.
[40] D. Braga, F. Grepioni, E. Tedesco, X―H⋅⋅⋅π(X O, N, C) Hydrogen bonds in organo-
metallic crystals, Organometallic 17 (1998) 2669–2672.
[41] Y.-K. Gu, X. Li, H. Liang, X.-B. Deng, A novel addition complex composed of single
and double chain constructed from btb–Cd–SO4 units (btb=1,4-bis(1,2,4-triazol-
1-yl)butane), Inorg. Chem. Commun. 14 (2011) 52–55.
[34] J. Fan, W.Y. Sun, T. Okamura, W.X. Tang, N. Ueyama, Novel metal–organic frame-
works with specific topology from new tripodal ligands: 1,3,5-tris(1-imidazolyl)
benzene and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene, Inorg. Chem.
42 (2003) 3168–3175.
[42] G.A. Farnum, C.M. Gandolfo, R.M. Supkowski, R.L. LaDuca, Divalent metal aliphatic
tricarboxylate dipyridylamine coordination polymers with new or rare binodal
topologies, Cryst. Growth Des. 11 (2011) 4860–4875.
[43] X. Li, Y.-K. Gu, X.-B. Deng, K. Zhao, L.-P. Jin, Effect of anions on architecture of tran-
sition metal complexes with 1,4-bis(1,2,4-triazol-1-yl)butane), CrystEngComm
13 (2011) 6665–6673.
[35] Preparation of [Cd(Fpht)tib]·H2O (1): A mixture of tib (0.0278 g ,0.1 mmol),
H2Fpht (0.0184 g ,0.1 mmol), CdSO4 (0.0257 g ,0.1 mmol), and 2 mol.L−1NaOH
(0.2 ml) in H2O (10 ml) was sealed in
a 25 ml Teflon-lined stainless steel