Substituted groups-directed assembly of Cd(ii) coordination polymers based on 5-R-1,3-benzenedicarboxylate and 4,4'-bis(1-imidazolyl)bibenzene: Syntheses, structures and photoluminescent properties

Article abstract of DOI:10.1039/c2ce25677k

Hydrothermal reactions of CdCl₂·2.5H₂O with 4,4'-bis(1-imidazolyl)bibenzene (bimb) and 1,3-benzenedicarboxylate (1,3-H ₂BDC), 5-methyl-1,3-benzenedicarboxylate (5-Me-1,3-H₂BDC), 5-amino-1,3-benzenedicarboxylate (5-NH₂-1,3-H₂BDC), 5-hydroxy-1,3-benzenedicarboxylate (5-HO-1,3-H₂BDC), 5-nitro-1,3-benzenedicarboxylate (5-NO₂-H₂1,3-BDC), or 5-sulfo-1,3-benzenedicarboxylate (5-HSO₃-1,3-H₂BDC) resulted in the formation of six Cd(ii) coordination polymers, [Cd(5-R-1,3-BDC)(bimb)]_n (R = H (1), R = Me (2), R = NH₂ (3), R = OH (4)), {[Cd₂(H₂O)(5-NO₂-1,3-BDC) ₂(bimb)]·2H₂O}_n (5) and [Cd(5-SO ₃-1,3-HBDC)(bimb)]_n (6). Compounds 1-6 were characterized by elemental analysis, IR, powder X-ray diffraction and single-crystal X-ray diffraction. 1-4 exhibit similar 3D frameworks in which 2D [Cd ₄(5-R-1,3-BDC)₄]_n (R = H, Me, NH₂ and OH) layers are interlinked by bimb ligands. 5 has a two-fold interpenetrating 3D framework in which 1D [Cd₂(5-NO ₂-1,3-BDC)₂]_n chains are interconnected by bimb ligands. 6 shows a 3D (3,5)-connected framework in which 2D [Cd ₂(5-SO₃-1,3-HBDC)₂]_n networks are bridged by bimb ligands. The Schlaefli symbols for these six 3D nets are (4·6²)(4·6⁶·8³) (1-4), (4²·6)(4²·6·10²·12) (5) and (4·6·8)(4·6⁵·8 ³·10) (6). The solid state photoluminescent properties of 1-6 were also investigated.

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PAPER
Substituted groups-directed assembly of Cd(II) coordination polymers based
on 5-R-1,3-benzenedicarboxylate and 4,4’-bis(1-imidazolyl)bibenzene:
syntheses, structures and photoluminescent properties{
Hong-Jian Cheng,a Hong-Xi Li,a Zhi-Gang Ren,a Chun-Ning Lu¨,a Jing Shia and Jian-Ping Lang*ab
Received 2nd May 2012, Accepted 12th June 2012
DOI: 10.1039/c2ce25677k
Hydrothermal reactions of CdCl2?2.5H2O with 4,4’-bis(1-imidazolyl)bibenzene (bimb) and 1,3-
benzenedicarboxylate (1,3-H2BDC), 5-methyl-1,3-benzenedicarboxylate (5-Me-1,3-H2BDC),
5-amino-1,3-benzenedicarboxylate (5-NH2-1,3-H2BDC), 5-hydroxy-1,3-benzenedicarboxylate (5-
HO-1,3-H2BDC), 5-nitro-1,3-benzenedicarboxylate (5-NO2-H21,3-BDC), or 5-sulfo-1,3-
benzenedicarboxylate (5-HSO3-1,3-H2BDC) resulted in the formation of six Cd(II) coordination
polymers, [Cd(5-R-1,3-BDC)(bimb)]n (R = H (1), R = Me (2), R = NH2 (3), R = OH (4)),
{[Cd2(H2O)(5-NO2-1,3-BDC)2(bimb)]?2H2O}n (5) and [Cd(5-SO3-1,3-HBDC)(bimb)]n (6).
Compounds 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction and single-
crystal X-ray diffraction. 1–4 exhibit similar 3D frameworks in which 2D [Cd4(5-R-1,3-BDC)4]n (R =
H, Me, NH2 and OH) layers are interlinked by bimb ligands. 5 has a two-fold interpenetrating 3D
framework in which 1D [Cd2(5-NO2-1,3-BDC)2]n chains are interconnected by bimb ligands. 6 shows
a 3D (3,5)-connected framework in which 2D [Cd2(5-SO3-1,3-HBDC)2]n networks are bridged by
bimb ligands. The Schla¨fli symbols for these six 3D nets are (4?62)(4?66?83) (1–4), (42?6)(42?6?102?12)
(5) and (4?6?8)(4?65?83?10) (6). The solid state photoluminescent properties of 1–6 were also
investigated.
instance, solvothermal reactions of Co(NO3)2 with 2-R-1,4-
Introduction
benzenedicarboxylic acid (R = H and NH2) and 4,49-bipyridine
In past decades, much attention has been focused on the rational
(4,49-bipy) produced a 2-fold interpenetrating non-porous frame-
design and synthesis of functional coordination polymers due to
work [Co2(1,4-BDC)2(bpy)2] (1,4-BDC = 1,4-benzenedicarboxy-
their intriguing architectures1 and potential applications in
late) and a non-interpenetrating porous doubly pillared-layer
absorption,2 separation,3 magnetism,4 luminescence,5 catalysis,6
framework [Co2(2-NH2-1,4-BDC)2(bpy)2]?8DMF (2-NH2-1,4-
drug delivery7 and proton conduction,8 etc. Among the numerous
strategies for constructing coordination polymers, the employ-
ment of the self-assembly of transition metal salts with di- or
multi- carboxylic acids and/or multidentate N-donor ligands
under solvothermal conditions has become an effective approach.9
However, many factors, such as metal ions, organic multitopic
ligands, pH values, solvents, templates and temperatures, place a
great and delicate influence on the structures of the resulting
coordination polymers.10 It is noted that substituent groups of
carboxylate ligands also exert great impact on the formation of
coordination polymers with different topological structures.11 For
BDC = 2-amino-1,4-benzenedicarboxylate).11d However, research
in this respect is still less explored relative to those related to other
factors.
Recently, we have been interested in the syntheses, structures
and properties of coordination polymers derived from group IIB
and IB metals and polycarboxylates and multidentate N-donor
ligands.12,13 For example, hydrothermal reactions of Zn(NO3)2
with 5-R-1,3-BDC (R = OH, COOH, NO2, Me) and 1,4-bis[2-(4-
pyridyl)ethenyl]benzene (1,4-bpeb) produced four different
coordination polymers [Zn(H2O)(5-HO-1,3-BDC)(1,4-bpeb)]n
(1D), [{Zn2(1,3,5-HBTC)2}4]n (2D), [Zn4(5-NO2-1,3-BDC)4(1,4-
bpeb)4]n (2D) and [Zn4(5-Me-1,3-BDC)4(1,4-bpeb)4]n (3D).12d
The results revealed that changes on substituted R groups in the
5-position of 1,3-BDC ligands could lead to big changes in the
frameworks or the levels of interpenetration in the resulting
supramolecular arrays. As an extension of this work, we selected
six 5-R-1,3-benzenedicarboxylic acid derivatives (R = H, Me,
NH2, OH, NO2, SO3H) and another N-donor ligand, 4,49-bis
(1-imidazolyl)bibenzene (bimb) (Scheme 1), to react with
CdCl2 under the hydrothermal conditions. Six different 3D
aKey Laboratory of Organic Synthesis of Jiangsu Province, College of
Chemistry, Chemical Engineering and Materials Science, Soochow
University, Suzhou, 215123, P. R. China. E-mail: jplang@suda.edu.cn;
Fax: 86-512-65880089
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032,
P. R. China
{ Electronic supplementary information (ESI) available: CCDC refer-
ence numbers 874180–874185 for 1–6. For ESI and crystallographic data
in CIF or other electronic format see DOI: 10.1039/c2ce25677k
6064 | CrystEngComm, 2012, 14, 6064–6071
This journal is ß The Royal Society of Chemistry 2012

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3.59, N 4.88. IR (KBr, cm21): 2922 (w), 1616 (m), 1572 (s), 1514
(s), 1418 (s), 1363 (m), 1302 (m), 1247 (s), 1060 (s), 820 (s), 647
(s), 422 (m).
Preparation of Cd(5-NH2-1,3-BDC)(bimb)]n (3). Compound 3
was prepared as colorless crystals in a similar manner to that
described for 1, using CdCl2?2.5H2O (24 mg, 0.1 mmol), 5-NH2-
1,3-H2BDC (18 mg, 0.1 mmol), bimb (28 mg, 0.1 mmol) and
3 mL of H2O. Yield: 35 mg (61% yield based on Cd). Anal. calcd
for C26H19CdN5O4: C 54.04; H 3.31; N 12.12. Found: C 53.96, H
3.24, N 12.20. IR (KBr, cm21): 3462 (w), 3332 (w), 1608 (s), 1549
(s), 1510 (s), 1420 (s), 1368 (s), 1060 (s), 818 (s), 724 (s), 648 (m),
423 (m).
Preparation of [Cd(5-HO-1,3-BDC)(bimb)]n (4). To a 10 mL
Pyrex glass tube was added CdCl2?2.5H2O (24 mg, 0.1 mmol),
5-OH-1,3-H2BDC (18 mg, 0.1 mmol), bimb (28 mg, 0.1 mmol)
and 3 mL of H2O. After the pH value was adjusted to 4.8 by
addition of HNO3 (0.01 M, 10 mL), the tube was sealed and
heated in an oven to 170 uC for 1 d and then cooled to ambient
temperature at the rate of 5 uC h21 to form colorless crystals of
4, which were washed with water–methanol and dried in air.
Yield: 25 mg (43% yield based on Cd). Anal. calcd for
C26H18CdN4O5: C 53.95; H 3.13; N 9.68. Found: C 54.04, H
3.20, N 9.24. IR (KBr, cm21): 3272 (w), 1617 (s), 1580 (s), 1520
(s), 1419 (s), 1365 (s), 1272 (s), 1060 (s), 820 (s), 720 (s), 647 (s),
520 (m), 430 (m).
Scheme 1 The coordination modes of 5-R-1,3-BDC in 1–4 (a), 5-NO2-
1,3-BDC in 5 (b), 5-SO3-1,3-HBDC in 6 (c) and bimb in 1–6(d).
coordination polymers with three kinds of different topological
structures [Cd(5-R-1,3-BDC)(bimb)]n (R = H (1), R = Me (2), R
= NH2 (3), R = OH (4)), {[Cd2(H2O)(5-NO2-1,3-BDC)2(bimb)]?
2H2O}n (5) and [Cd(5-SO3-1,3-HBDC)(bimb)]n (6) were isolated.
Herein, we report their syntheses, crystal structures and photolu-
minescent properties.
Experimental
Materials and methods
The ligand bimb was prepared according to the literature
method.14 Other chemicals and reagents were obtained from
commercial sources and used as received. Elemental analyses for
C, H and N were performed on a Carlo-Erbo CHNO-S
microanalyzer. The IR spectra (KBr disc) were recorded on a
Nicolet MagNa-IR550 FT-IR spectrometer (4000–400 cm21).
The powder X-ray diffraction (PXRD) measurements were
carried out on a PANalytical X’Pert PRO MPD system
(PW3040/60). The emission/excitation spectra were measured
Preparation of {[Cd2(H2O)2(5-NO2-1,3-BDC)2(bimb)2]?2H2O}n
(5). Compound 5 was prepared as colorless crystals in a similar
manner to that described for 1, using CdCl2?2.5H2O (24 mg,
0.1 mmol), 5-NO2-1,3-H2BDC (22 mg, 0.1 mmol), bimb (28 mg,
0.1 mmol) and 3 mL of H2O. Yield: 19 mg (37% yield based on
Cd). Anal. Calcd. for C34H28Cd2N6O16: C 40.78; H 2.82; N 8.39.
Found: C 40.80, H 2.76 N 8.30. IR (KBr, cm21): 1617 (s), 1517
(s), 1454 (m), 1344 (s), 1251 (m), 1063 (s), 862 (m), 822 (m), 729
(m), 644 (s), 518 (m).
on
a Varian Cary Elipse fluorescence spectrophotometer
equipped with a continuous Xenon Lamp.
Preparation of [Cd(5-SO3-1,3-HBDC)(bimb)]n (6). Compound
6 was prepared as colorless crystals in a similar manner to that
described for 1, using CdCl2?2.5H2O (24 mg, 0.1 mmol),
5-HSO3-1,3-H2BDC (25 mg, 0.1 mmol), bimb (28 mg, 0.1 mmol)
and 3 mL of H2O. Yield: 26 mg (41% yield based on Cd). Anal.
calcd for C26H18CdN4O7S: C, 48.57; H, 2.82; N, 8.71. Found: C
48.62, H 2.92, N 8.81. IR (KBr, cm21): 3163 (m), 1707 (s), 1605
(s), 1516 (m), 1400 (s), 1121 (s), 1101 (s), 1037 (s), 812 (w), 692
(w), 621 (s).
Preparation of compounds 1–6
Preparation of [Cd(1,3-BDC)(bimb)]n (1). To a 10 mL Pyrex
glass tube was added CdCl2?2.5H2O (24 mg, 0.1 mmol), 1,3-
H2BDC (17 mg, 0.1 mmol), bimb (28 mg, 0.1 mmol) and 3 mL of
H2O. The tube was sealed and heated in an oven to 170 uC for
1 d and then cooled to ambient temperature at the rate of 5 uC h21
to form colorless crystals of 1, which were washed with water–
methanol and dried in air. Yield: 30 mg (53% yield based on Cd).
Anal. calcd for C26H18CdN4O4: C, 55.48; H, 3.22; N, 9.95. Found:
C 55.40, H 3.18, N 10.02. IR (KBr, cm21): 1610 (m), 1568 (s),
1551 (s), 1515 (s), 1375 (s), 1264 (s), 1060 (s), 820 (s), 724 (s),
649 (s), 423 (m).
X-ray crystallography
Single crystals of 1–6 suitable for X-ray analysis were obtained
directly from the above preparations. All measurements were
made on a Rigaku Mercury CCD X-ray diffractometer using
˚
graphite monochromated Mo-Ka (l = 0.71073 A). Single crystals
Preparation of [Cd(5-Me-1,3-BDC)(bimb)]n (2). Compound 2
was prepared as colorless crystals in a similar manner to that
described for 1, using CdCl2?2.5H2O (24 mg, 0.1 mmol), 5-Me-
1,3-H2BDC (18 mg, 0.1 mmol), bimb (28 mg, 0.1 mmol) and
3 mL of H2O. Yield: 26 mg (45% yield based on Cd). Anal. calcd
for C27H20CdN4O4: C 56.21; H 3.49; N 9.71. Found: C 62.63, H
of 1–6 were mounted with grease at the top of a glass fibre at
293 K (1 and 3–6) or 223 K (2) in a liquid nitrogen stream. Cell
parameters were refined on all observed reflections using the
program Crystalclear (Rigaku and MSc, ver. 1.3, 2001). The
collected data were reduced by the program CrystalClear and an
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absorption correction (multi-scan) was applied. The reflection
data were also corrected for Lorentz and polarization effects.
The crystal structures of 1–6 were solved by direct methods
and refined on F2 by full-matrix least-squares methods with the
SHELXL-97 program.15 In 3, the C8 and C9 atoms of one bimp
ligand are disordered over two sites with an occupancy factor of
0.33/0.67 for C8/C8A and C9/C9A. All of the non-H atoms were
refined anisotropically. The H atoms of the water molecule in 5
and the uncoordinated –COOH group in 6 were located from the
Fourier map. All other H atoms were placed in geometrically
0.01 M HNO3 up to 4.8. Such a resulting solution was preformed
by a hydrothermal treatment at 170 uC to afford colorless
crystals of 4 in 43% yield. As discussed later in this paper,
complexes 1–4 possess similar 3D structures, while complexes 5
and 6 have two different 3D structures. For 1–4, one carboxylate
group of the 5-R-1,3-BDC ligand takes a chelating bidentate
mode, while the other a bridging bidentate one (Scheme 1a). The
R (CH3, NH2, OH) group was not involved in the binding to Cd
centres. For 5, the 5-NO2-1,3-BDC ligand adopts monodentate
and m3-chelating/bridging coordination modes (Scheme 1b). For
6, one carboxylate group of the 5-HSO3-1,3-BDC ligand remains
intact, while the other takes a chelating bidentate fashion. In
addition, the SO32 group of this ligand coordinates at Cd atoms
through a bridging bidentate coordination mode (Scheme 1c).
The bimb ligand in three kinds of topological structures has the
same coordination mode, but somewhat different configurations
related to two imidazolyl groups. Thus, the substituent groups in
the 5-position of 1,3-BDC ligands in 1–6 did affect their
coordination modes, which subsequently leads to the formation
of the different topological structures of 1–6.
˚
idealized positions (C–H = 0.96 A for methyl groups, N–H =
˚
0.86 A for amino groups, O–H = 0.82 A for hydroxyl groups, or
˚
˚
C–H = 0.93 A for phenyl groups) and constrained to ride on
their parent atoms with Uiso(H) = 1.5Ueq(C) for methyl groups,
1.2Ueq(N) for amino groups, and 1.5Ueq(O) for hydroxyl groups.
All of the calculations were performed on a Dell workstation
using the Crystal Structure crystallographic software package
(Rigaku and MSC, ver. 3.60, 2004). A summary of the important
crystallographic information for 1–6 are summarized in Table 1.
Complexes 1–6 are air-stable and insoluble in common
solvents. The elemental analysis was consistent with their
chemical formulas of 1–6. The IR spectra of 1–6 showed strong
Results and discussion
Synthetic and spectral aspects
peaks in the range of 1550–1618 cm21 and 1314–1465 cm21
,
The hydrothermal reaction of CdCl2?2.5H2O with 1,3-H2BDC
and bimb in a 1 : 1 : 1 molar ratio at 170 uC for 1 day gave rise
to colorless crystals of 1 in 53% yield. Analogous reactions with
5-Me-1,3-H2BDC, 5-NH2-1,3-H2BDC, 5-NO2-1,3-H2BDC and
5-HSO3-1,3-H2BDC afforded colorless crystals of 2 (45% yield),
3 (61% yield), 5 (37% yield) and 6 (41% yield), respectively.
However, we could not isolate any Cd/5-HO-1,3-BDC/bimb
complexes from similar reactions of these three components with
1 : 1 : 1 and other molar ratios. Thus, the pH value of the
solution of a mixture containing CdCl2?2.5H2O, 5-HO-1,3-
H2BDC and bimb (molar ratio = 1 : 1 : 1) was adjusted by
indicating that they all contain coordinated carboxylic groups.
The strong peaks at ca. 1060 cm21 and 650 cm21 mean the
existence of imidazolyl groups in 1–6. The bands at 2922 cm21
,
3332 cm21, 3272 cm21, 1365 cm21 and 1707 cm21 could be
assigned to the vibrations of the –Me, –NH2, –OH, –NO2 and –
COOH groups, respectively.16 The PXRD showed that the
experimental patterns for each compound correlate well with its
simulated one generated from single-crystal X-ray diffraction
data (Fig. S1, ESI{). The identities of 1–6 were further confirmed
by single crystal X-ray diffraction analysis.
Table 1 A summary of crystal data and structure refinement parameters for 1–6
1
2
3
4
5
6
Empirical formula
Formula mass
Crystal system
Space group
C
562.85
monoclinic
P21/c
26H18CdN4O4
C27H20CdN4O4
576.88
monoclinic
P21/c
C26H19CdN5O4
577.87
monoclinic
P21/c
C26H18CdN4O5
578.85
monoclinic
P21/c
C34H28Cd2N6O16
1001.45
triclinic
C26H18CdN4O7S
642.92
monoclinic
C2/c
¯
Pi
Crystal dimensions (mm3) 0.4 6 0.1 6 0.1 0.26 6 0.24 6 0.18 0.6 6 0.4 6 0.2 0.4 6 0.3 6 0.3 0.3 6 0.25 6 0.1 0.6 6 0.3 6 0.3
˚
a/A
9.762(2)
13.486(3)
16.804(3)
9.857(2)
14.011(3)
16.884(3)
9.5702(19)
14.329(3)
16.631(3)
9.6647(19)
14.032(3)
16.543(3)
9.967(2)
12.179(2)
15.859(2)
96.41(3)
96.96(3)
104.19(3)
1832.5(6)
1.815
29.425(6)
9.4342(19)
20.233(4)
˚
b/A
˚
c/A
a (u)
b (u)
c (u)
100.04(3)
100.93(3)
98.75(3)
98.79(3)
123.71
3
˚
V/A
2178.3(8)
1.716
4
1.046
1128
2289.5(8)
1.674
4
0.998
1160
2254.1(8)
1.703
4
1.015
1160
2217.1(8)
1.734
4
1.034
1160
4672.2(23)
1.828
8
1.084
2576
Dc/g cm23
Z
2
1.245
996
m(Mo-Ka)/mm21
F(000)
Total reflections
Unique reflections
No. observations
No. parameters
23 311
4973
3712
20 898
5192
4442
21 176
4119
3735
21 086
4049
3708
17 804
6640
5269
21 883
4274
3749
317
325
344
325
523
356
a
R1
wR2
0.0608
0.1115
1.091
0.0674
0.1051
1.096
0.0423
0.0926
1.074
0.889, 20.422
2
0.0361
0.0863
1.036
0.0412
0.0918
1.069
0.0388
0.0858
1.103
b
GOFc
23
˚
Drmax/Drmin/e A
1.064, 20.734
0.580, 20.754
0.932, 20.795
0.918, 20.713
0.725, 20.445
a
b
2
c
R1 = S ||Fo| 2 |Fc||/S|Fo|. wR2 = {Sw(Fo 2 Fc2)2/Sw(Fo2)2}1/2
total numbers of parameters refined.
.
GOF = {Sw((Fo 2 Fc2)2)/(n 2 p)}1/2, where n = number of reflections and p =
6066 | CrystEngComm, 2012, 14, 6064–6071
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a
˚
Table 2 Selected bond lengths (A) and angles (u) for 1–4
1
2
3
4
Cd(1)–O(1)
Cd(1)–O(2)
Cd(1)–O(3C)
Cd(1)–O(4B)
Cd(1)–N(1)
Cd(1)–N(3A)
O(1)–Cd(1)–O(2)
O(1)–Cd(1)–O(4B)
O(1)–Cd(1)–O(3C)
O(2)–Cd(1)–O(3C)
O(2)–Cd(1)–O(4B)
2.339(3)
2.482(4)
2.245(3)
2.293(4)
2.314(4)
2.320(4)
54.41(11)
94.42(13)
2.380(3)
2.420(4)
2.239(3)
2.288(3)
2.306(4)
2.318(4)
54.88(11)
97.95(12)
2.338(3)
2.530(3)
2.245(3)
2.293(3)
2.312(4)
2.319(4)
53.68(9)
98.80(11)
2.298(2)
2.649(3)
2.243(3)
2.274(2)
2.301(3)
2.305(3)
52.40(8)
98.41(9)
147.48(13) 144.19(13) 140.72(11) 140.83(9)
93.14(13) 89.31(13) 87.36(10) 88.84(8)
148.63(13) 152.84(12) 151.27(11) 149.48(9)
O(3C)–Cd(1)–O(4B) 118.10(14) 117.85(13) 120.48(11) 120.76(9)
N(1)–Cd(1)–O(1)
N(1)–Cd(1)–O(2)
N(1)–Cd(1)–O(3C)
N(1)–Cd(1)–O(4B)
N(3A)–Cd(1)–O(1)
N(3A)–Cd(1)–O(2)
N(3A)–Cd(1)–O(3C)
N(3A)–Cd(1)–O(4B)
N(1)–Cd(1)–N(3A)
a
100.17(14)
98.83(15) 101.23(15)
99.73(14) 100.79(12)
98.84(10)
91.82(9)
94.83(12)
85.77(13)
81.41(12)
81.57(12)
91.70(12)
96.45(13)
91.94(13)
85.62(14)
81.84(14)
81.58(13)
89.11(15)
97.49(14)
89.57(15)
85.72(14)
81.84(14)
82.16(14)
87.43(15)
98.17(14)
88.78(15)
86.39(11)
83.54(10)
81.20(10)
92.23(10)
96.82(11)
91.38(11)
171.32(15) 170.59(16) 173.19(13) 174.88(11)
Symmetry codes: (A) x + 1, y, z + 1; (B) 2x + 1, y + 1/2, 2z + 5/2;
(C) x, 2y + 1/2, z 2 1/2 for 1. (A) x 2 1, y, z 2 1; (B) 2x + 1, y 2 1/
2, 2z + 1/2; (C) x, 2y + 1/2, z + 1/2 for 2. (A) x + 1, y, z + 1; (B) 2x
+ 1, 2y + 1/2, 2z + 3/2; (C) x, 2y + 1/2, z 2 1/2 for 3. (A) x + 1 , y,
z + 1; (B) 2x + 1, y 2 1/2, 2z + 3/2; (C) x, 2y + 3/2, z 2 1/2 for 4.
Crystal structures of 1–4
Being crystallized in the monoclinic space group P21/c, the
asymmetric units for 1–4 consist of one [Cd(1,3-BDC)(bimb)]
molecule (1), one [Cd(5-Me-1,3-BDC)(bimb)] molecule (2), one
[Cd(5-NH2-1,3-BDC)(bimb)] molecule (3), or one [5-HO-Cd(1,3-
BDC)(bimb)] molecule (4). As the structures of 1–4 are very
similar, only that of 1 is shown in Fig. 1. The selected bond
lengths and angles for 1–4 are compared in Table 2. In 1–4, each
Cd atom has a distorted octahedral coordination geometry,
coordinated by four O atoms from three 5-R-1,3-BDC ligands
and two N atoms from two different bimb molecules (Fig. 1a). In
1–4, the carboxylate groups of 5-R-1,3-BDC (R = H, Me, NH2
and OH) ligands show chelating bidentate and bridging
bidentate coordination modes (Scheme 1a). The mean bridging
˚
˚
Cd–O bond distances (2.269(3) A (1), 2.233(3) A (2), 2.269(3) A
˚
˚
(3) and 2.259(3) A (4)) are shorter than those of the chelating
˚
Cd–O bonds (2.410(3) A (1), 2.400(4) A (2), 2.434(3) A (3) and
˚
˚
˚
2.474(3) A (4)). The average Cd–O bond distances (2.340(4) A
˚
˚
˚
˚
(1), 2.340(3) A (2), 2.340(3) A (3), and 2.340(3) A (4)) are
comparable to those observed in {[Cd3(btc)2(bimb)2]?2H2O}n
17
(btc = 1,3,5-benzenetricarboxylate) (2.339(4) A). The mean
˚
Fig. 1 (a) A view of the coordination environment of Cd(1) in 1 with a
labelling scheme and 30% thermal ellipsoids. All H atoms have been
omitted for clarity. Symmetry codes: (A) x + 1, y, z + 1; (B) 2 x + 1, y +
1/2, 2 z + 1/2; (C) x, 2 y + 1/2, z 2 1/2. (b) A view of a 2D (4,82) network
that is constructed by Cd2(1,3-BDC)4 units (extending along the bc
plane). All of the bimb ligands are omitted for clarity. Each cyan
tetrahedron represents one Cd atom. The red and blue balls represent O
and N, respectively. (c) The 3D net of 1 (looking down the b axis). (d) A
schematic view of a (4?62)(4?66?83) topological net of 1. The cyan and
black balls represent 5-connecting Cd centres and 3-connecting 1,3-
HBDC ligands. Each pink line represents one bimb ligand.
˚
˚
˚
Cd–N bond lengths (2.317(4) A (1), 2.332 A (2), 2.352 A (3), and
˚
2.366 A (4)) are longer than the those of the corresponding ones
˚
of {[Cd3(btc)2(bimb)2]?2H2O}n (2.267(3) A). The dihedral angles
of the two imidazolyl groups of bimb in 1–4 are 21.48(2)u (1),
12.26(3)u (2), 14.94(2)u (3) and 23.36(2)u (4), respectively. In 1–4,
two Cd atoms are bridged by one pair of 5-R-1,3-BDC ligands to
form a [Cd2(5-R-1,3-BDC)2] unit. Four [Cd2(5-R-1,3-BDC)2]
units are linked by four 5-R-1,3-BDC ligands in a head-to-tail
way to form a [Cd2(5-R-1,3-BDC)2]4 grid with a dimension of
˚
˚
˚
˚
˚
˚
8.81 A 6 10.27 A (1), 8.96 A 6 10.30 A (2), 8.88 A 6 10.33 A
˚
˚
(3), or 8.80 A 6 10.30 A (4). Each grid is further connected to its
equivalent ones via four 1,3-BDC ligands to form a 2D (4,82)
layer extending along the bc plane (Fig. 1b). Each bimb ligand
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˚
acts as a pillar to link the adjacent 2D layers via N atoms,
thereby forming a 3D net (Fig. 1c). Topologically, if the 1,3-
BDC ligands and the Cd centers are considered as 3- and
5-connecting nodes, respectively, 1 may be considered as having
a 3D (3,5)-connected topological structure with a (4?62)(4?66?83)
Schla¨fli symbol (Fig. 1d). In 3 and 4, the NH2 (or OH) group of
5-NH2-1,3-BDC (or 5-OH-1,3-BDC) ligand interacts with O(4)
of another 5-NH2-1,3-BDC (or 5-OH-1,3-BDC) ligand to afford
between Cd(1) and O(4D) (2.740(3) A) or Cd(2) and O(10C)
(2.844(3) A) is observed (Fig. 2a).17 In 5, the carboxylate groups
˚
of 5-NO2-1,3-BDC ligand exhibits one monodentate mode and
one m3 chelating/bridging mode. (Scheme 1b). The mean
2
monodentate Cd–O(COO ) bond length (2.234(3) A) (Table 3)
are shorter than those of the chelating Cd–O(COO2) bonds
2
(2.423(3) A), the bridging Cd–O(COO ) bonds (2.520(3) A) and
˚
the Cd–O(H2O) bonds (2.331(3) A). The average Cd–O length
2
(2.458(3) A) of the chelating/bridging Cd–O(COO ) in 5 are
longer than that of Cd2(HL1)2(L3)4 (HL1 = 3-(2-pyridyl)pyr-
3
azole, HL = naphthalene–carboxylic acid) (2.395(2) A). The
˚
˚
˚
…
an intermolecular H-bonding interaction (O–H O (or N–
…
˚
H
O)) (Figs. S3 and S4, ESI{).
18
˚
Crystal structure of 5
˚
mean Cd–N bond length of 2.225(4) A is shorter than those
observed in 1–4. The two imidazolyl groups and the biphenyl
groups of bimb in 5 are almost linear. Two Cd(1) and Cd(2)
atoms are linked by a couple of 5-NO2-1,3-BDC ligands to form
a four-membered ring [Cd(1)–O(2)–Cd(1)–O(7)] unit with the
¯
Compound 5 crystallizes in the triclinic space group P1 and its
asymmetric unit consists of one [Cd2(OH2)2(5-NO2-1,3-
BDC)2(bimb)] molecule and two water solvent molecules.
Cd(1) and Cd(2) atoms adopt a distorted octahedral coordina-
tion geometry, coordinated by one O atom from the coordinated
H2O, four O atoms from three 5-NO2-1,3-BDC ligands and one
N atom from a bimb ligand, though a seventh weak interaction
…
˚
Cd(1) Cd(2) separation of 3.908 A. Such ‘‘Cd2O2’’ four-
membered rings are interlinked to adjacent ones by one pair of
5-NO2-1,3-BDC ligands, forming a 1D double chain (extending
Fig. 2 (a) A view of the coordination environments of Cd1 and Cd2 in 5 with a labelling scheme and 30% thermal ellipsoids. All H atoms except those
from coordinated water have been omitted for clarity. Symmetry codes: (A) 2x, 2y + 2, 2 z.; (B) 2x + 3, 2y + 1, 2z; (C) 2x + 1, 2y + 2, 2z + 1; (D)
2x + 2, 2y + 1, 2z + 1. (b) A view of a section of the 1D chain (extending along the a axis). The red and blue balls represent O and N atoms. Each cyan
tetrahedron represents one Cd atom. (c) A view of the 3D net of 5 (looking down the b axis). (d) A schematic view of a (42?6)(42?6?102?12) topological
net of 5. The cyan and black balls represent 4-connecting Cd centres and 3-connecting 5-NO2-1,3-HBDC ligands. Each blue line represents one bimb
ligand. (e) A view of the 2-fold interpenetrating mode of 5 looking down the b axis.
6068 | CrystEngComm, 2012, 14, 6064–6071
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a
˚
length (2.464(3) A) is between those of 1–3 and that of 4. The
˚
Table 3 Selected bond lengths (A) and angles (u) for 5 and 6
2
average Cd–O(SO3 ) length (2.371(4) A) is shorter than that
˚
Compound 5
observed in [Cd5(m2-OH)2(m3-OH)2(5-SO3-1,3-HBDC)2(H2O)5]n
Cd(2)–N(1)
Cd(2)–O(1)
Cd(1)–O(2)
Cd(2)–O(7)
Cd(2)–O(9C)
Cd(1)–O(14)
2.230(4) Cd(1)–N(3)
2.358(3) Cd(2)–O(2)
2.553(3) Cd(1)–O(7)
2.486(3) Cd(1)–O(8)
2.216(3) Cd(2)–O(13)
2.320(3) Cd(1)–O(3D)
2.220(4)
2.459(3)
2.305(3)
2.541(3)
2.342(3)
2.253(3)
2.844(3)
19
˚
˚
(2.467(2) A). The mean Cd–N bond length of 2.244(4) A is
shorter than those of 1–4. The dihedral angles of the two
imidazolyl groups of bimb in 6 are 23.61(2)u. For the 5-SO3-1,3-
HBDC ligand in 6, one COO2 group adopts a chelating mode,
…
…
2
Cd(1) O(4D)
2.740(3) Cd(2) O(10C))
while the other remains intact. The SO3 group takes a bridging
N(3)–Cd(1)–O(3D)
O(3D)–Cd(1)–O(14)
O(3D)–Cd(1)–O(7)
N(3)–Cd(1)–O(8)
O(14)–Cd(1)–O(8)
N(3)–Cd(1)–O(2)
O(14)–Cd(1)–O(2)
O(8)–Cd(1)–O(2)
O(9C)–Cd(2)–O(13)
O(9C)–Cd(2)–O(1)
O(13)–Cd(2)–O(1)
N(1)–Cd(2)–O(2)
O(1)–Cd(2)–O(2)
N(1)–Cd(2)–O(7)
O(1)–Cd(2)–O(7)
Compound 6
135.63(14) N(3)–Cd(1)–O(14)
90.23(13) N(3)–Cd(1)–O(7)
82.69(12) O(14)–Cd(1)–O(7)
93.91(13) O(3D)–Cd(1)–O(8)
79.82(12) O(7)–Cd(1)–O(8)
86.89(13) O(3D)–Cd(1)–O(2)
177.34(11) O(7)–Cd(1)–O(2)
100.86(11) N(1)–Cd(2)–O(13)
92.40(13) N(1)–Cd(2)–O(1)
84.40(13) O(9C)–Cd(2)–O(2)
82.95(13) O(13)–Cd(2)–O(2)
95.05(12) O(9C)–Cd(2)–O(7)
54.22(12) O(13)–Cd(2)–O(7)
85.98(13) O(2)–Cd(2)–O(7)
98.52(12)
95.64(14)
137.14(13)
103.81(12)
130.35(12)
53.80(11)
87.38(13)
74.73(11)
91.98(13)
144.97(14)
130.26(11)
106.55(12)
89.20(13)
177.93(11)
73.32(11)
bidentate mode. Two Cd atoms are coordinated by two 5-SO3-1,3-
HBDC ligands to generate a binuclear [Cd2(5-SO3-1,3-HBDC)2]
˚
˚
grid with dimensions of 3.51 A 6 7.77 A. Such a grid is linked to
its equivalent ones by a pair of 5-SO3-1,3-HBDC ligands, forming
a 2D 3-connected (4?82) network extending along the bc axis
(Fig. 3b). Each bimb ligand links the adjacent 2D layers to afford
a 3D framework (Fig. 3c). If the 5-SO3-1,3-HBDC ligand and the
Cd center are considered as 3- and 5-connecting nodes,
respectively, 6 has a 3D (3,5)-connected topological structure
with a (4?6?8)(4?65?83?10) Schla¨fli symbol (Fig. 3d). Within the
[Cd2(5-SO3-1,3-HBDC)2] grid, the centroid–centroid separation
˚
between imidazole rings of the two bimb ligands is 3.585 A, while
˚
that between phenyl rings is 3.796 A from such pairs of bimb
…
Cd(1)–N(1)
Cd(1)–O(1B)
Cd(1)–O(5)
2.243(4) N(3A)–Cd(1)
2.368(3) Cd(1)–O(2B)
2.418(4) Cd(1)–O(7C)
2.245(4)
2.559(3)
2.332(3)
ligands, indicating the presence of weak intermolecular p
p
interactions. In addition, the O(1) atom of one 5-SO3-1,3-HBDC
ligand acts as an acceptor to interact with the uncoordinated
carboxyl group of another 5-SO3-1,3-HBDC ligand to yield an
O(5)–Cd(1)–N(1)
N(1)–Cd(1)–N(3A)
N(1)–Cd(1)–O(7C)
O(5)–Cd(1)–O(1A)
N((3A)–Cd(1)–O(1B)
O(5)–Cd(1)–O(2B)
N(3A)–Cd(1)–O(2B)
O((1B)–Cd(1)–O(2B)
a
83.26(15) O(5)–Cd(1)–N(3A)
173.44(13) O(5)–Cd(1)–O(7C)
86.16(13) N(3A)–Cd(1)–O(7C)
91.14(13) N(1)–Cd(1)–O(1B)
90.83(13) O(7C)–Cd(1)–O(1B)
138.27(13) N(1)–Cd(1)–O(2B)
108.43(13) O(7C)–Cd(1)–O(2B)
52.91(11)
90.28(15)
130.95(13)
97.29(13)
90.44(13)
136.79(11)
84.47(11)
180.0
…
intermolecular hydrogen bond (O(3)–H(3B) O(1)).
Thermal and photoluminescent properties
Thermogravimetric (TGA) experiments were carried out to study
the thermal stability of 1–6 (Fig. S5, ESI{). The TGA analysis
revealed that 1–6 were stable up to 422 uC (1), 435 uC (2), 460 uC
(3), 429 uC (4) and 423 uC (6). For 1–4 and 6, only one weight
loss of 77.62% (1), 78.98% (2), 77.27% (3) 78.53% (4) and 79.37%
(6) in the range of 422–750 uC (1), 435–680 uC (2), 460–700 uC
(3), 429–730 uC (4) and 423–900 uC (6) amounts roughly to the
loss of the bimb and 5-R-1,3-BDC (R = H, Me, NH2, OH,
HSO3) ligands (calculated 77.19% for 1, 77.74% for 2, 77.78% for
3, 77.82% for 4 and 80.02% for 6). For 5, the first weight loss of
6.87% in the range of 45–119 uC corresponds roughly to the loss
of two uncoordinated and two coordinated water molecules per
formula (calculated 7.19%). The second weight loss of 67.63% in
the range of 367–780 uC approximately amounts to the loss of
the bimb and 5-NO2-1,3-BDC (calculated 67.17%). In all cases,
the remaining substance with a weight of 22.38% (1), 21.02% (2),
22.73% (3), 21.47% (4), 25.01% (5) and 20.63% (6) was assumed
to be CdO (calculated 22.81% for 1, 22.26% for 2, 22.22% for 3,
22.18% for 4, 25.64% for 5 and 19.97% for 6).
Symmetry codes: (C) 2x + 1, 2y + 2, 2z + 1; (D) 2x + 2, 2y + 1,
2z + 1 for 5. (A) x 2 1/2, y 2 1/2, z 2 1; (B) x, 2y + 2, z + 1/2; (C)
2x + 1/2, y 2 1/2, 2z + 1/2 for 6.
along the b axis) (Fig. 2b). Such a chain is further connected to
its equivalent ones by bimb ligands to give a 3D framework
(Fig. 2c). This single framework has 1D channels (its window
˚
˚
size being ca. 17.37 A 6 24.35 A) along the b axis. If the 5-NO2-
1,3-BDC ligands and the Cd centers are considered as 3- and
4-connecting nodes, respectively,
5
possesses
a 3D (3,4)-
connected topological structure with
a
(42?6)(42?6?102?12)
Schla¨fli symbol (Fig. 2d). The resulting channels are further
filled by interpenetration of one independent equivalent net,
generating a two-fold interpenetrating 3D architecture (Fig. 2e).
3
A total of 147.6 A (8.1% of the unit cell volume calculated by
˚
the Platon program) void in each unit cell is occupied by the
guest water molecules. The coordinated and uncoordinated
water molecules in the channels interact with the carboxyl groups
and NO2 groups to form complicated intra- and inter-molecular
H-bonding interactions.
The photoluminescent properties of 1–6 in the solid state were
investigated at ambient temperature (Fig. 4). For 1–6, upon
excitation at 327 nm (1), 307 nm (2), 330 nm (3), 312 nm (4),
300 nm (5) and 333 nm (6), they exhibited strong photolumines-
cence with emission maxima at ca. 377 nm (1), 349/364 nm (2),
394 nm (3), 354/366 nm (4), 372 nm (5) and 397 nm (6),
respectively. The emission peaks of 2 and 4 were similar to that
of the bimb ligand (lem = 348 nm and 361 nm, lex = 300 nm).
Their origins may be tentatively assigned to the p–p * intra-
ligand fluorescence.20 It is noted that the emission maxima of 1,
3, 5 and 6 are red-shifted compared to that of bimb. The bands
Crystal structure of 6
Compound 6 crystallizes in the monoclinic space group C2/c and
its asymmetric unit contains [Cd(5-SO3-1,3-HBDC)(bimb)] mole-
cule. As shown in Fig. 3a, each Cd atom is octahedrally
coordinated by two O atoms from two different SO32groups,
two O atoms from one COO2 groups and two N atoms from two
different bimb ligands. The average chelating Cd–O(COO2)
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Fig. 3 (a) A view of the coordination environment of Cd1 in 6 with a labelling scheme and 30% thermal ellipsoids. All H atoms except the carboxylic
H atoms have been omitted for clarity. Symmetry codes: (A) x 2 1/2, y 2 1/2, z 2 1; (B) x, 2 y + 2, z + 1/2; (C) 2x + 1/2, y 2 1/2, 2z + 1/2. (b) A view
of the 2D network (extending along the bc plane). Each cyan tetrahedron represents one Cd atom. The red, blue and yellow balls represent O, N and S
atoms, respectively. (c) A view of the 3D net of 6 (looking down the b axis). (d) A schematic view of a (4?6?8)(4?65?83?10) topological net of 6. The cyan
and yellow balls represent 5-connecting Cd centers and 3-connecting 5-SO3-1,3-HBDC ligands. Each pink line represents one bimb ligand.
might be assigned as the metal-to-ligand charge transfer (MLCT)
Conclusions
with electrons being transferred from the Cd(II) centres to the
In the work reported here, we demonstrated construction of six
unoccupied p* orbitals of the imidazolyl groups of bimb,
according to the literature.21
Cd(II) coordination polymers 1–6 from hydrothermal reactions
of CdCl2?2.5H2O with bimb and six 5-R-1,3-BDC derivatives
with differently sized substituted R (H, Me, NH2, OH, NO2,
SO3H) groups at the 5-position. Compounds 1–4 consist of
similar 3D frameworks with the Schla¨fli symbol (4?62)(4?66?83).
Compound 5 exhibits a two-fold interpenetrating 3D framework
with a Schla¨fli symbol of (42?6)(42?6?102?12). Compound 6 has a
3D framework with a Schla¨fli symbol of (4?6?8)(4?65?83?10). For
each dicarboxylate in 1–4, one carboxyl group takes a chelating
mode, while the other works as a bridging one. For 5, the two
carboxyl groups of 5-NO2-1,3-BDC serve as a monodentate
mode and a m3-chelating/bridging mode. For 6, one carboxyl
group of the 5-HSO3-1,3-BDC ligand is kept intact, while the
other exhibited a chelating bidentate coordination mode and its
2
SO3 group adopted a bridging bidentate coordination mode.
The structural diversities of 1–6 were greatly affected by different
coordination modes of dicarboxylates, though the role of the
bimb ligands showing different conformations in 1–6 may not be
Fig. 4 The solid state emission spectra of 1–6 along with bimb at
ambient temperature.
ruled out. These results may provide us an interesting insight
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into how the assembly of Cd(II) coordination polymers is
affected by the substituted groups of the ligands.
Acknowledgements
The authors thanked the National Natural Science Foundation of
China (20901054, 90922018 and 21171124), the Nature Science
Key Basic Research of Jiangsu Province for Higher Education
(09KJA150002), the Specialized Research Fund for the Doctoral
Program of higher Education of Ministry of Education
(20093201110017), the State Key Laboratory of Organometallic
Chemistry of Shanghai Institute of Organic Chemistry
(201201006) for financial support. J. P. Lang also highly
appreciated the support for the Qin-Lan and the 9933399 Projects
of Jiangsu Province, the Priority Academic Program Development
of Jiangsu Higher Education Institutions and the ‘‘SooChow
Scholar’’ Program of Suzhou University. The authors are grateful
to the useful comments of the reviewers and the editor.
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