Syntheses, crystal structures, and properties of lead(II), zinc(II), and manganese(II) complexes constructed from 2, 3, 5, 6-tetraiodo-1, 4-benzenedicarboxylic acid

Article abstract of DOI:10.1002/zaac.201200210

Three new coordination compounds, [Pb(HBDC-I₄) ₂(DMF)₄](1) and [M(BDC-I₄)(MeOH) ₂(DMF)₂]_n (M = Zn^II for 2 and Mn^II for (3) (H₂BDC-I₄ = 2, 3, 5, 6-tetraiodo-1, 4-benzenedicarboxylic acid), were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and X-ray single crystal structure analysis. Single-crystal X-ray diffraction reveals that 1 crystallizes in the monoclinic space group C2/c and has a discrete mononuclear structure, which is further assembled to form a two-dimensional (2D) layer through intermolecular O-H···O and C-H···O hydrogen bonding interactions. The isostructural compounds 2 and 3 crystallize in the space group P2₁/c and have similar one-dimensional (1D) chain structures that are extended into three-dimensional (3D) supramolecular networks by interchain C-H···π interactions. The Pb^II and Zn ^II complexes 1 and 2 display similar emissions at 472 nm in the solid state, which essentially are intraligand transitions. Copyright

Full text of DOI:10.1002/zaac.201200210

Job/Unit: Z12210
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ARTICLE
DOI: 10.1002/zaac.201200210
Syntheses, Crystal Structures, and Properties of Lead(II), Zinc(II), and
Manganese(II) Complexes Constructed from 2,3,5,6-Tetraiodo-1,4-
benzenedicarboxylic Acid
Meng Hu,[a] Sheng-Chun Chen,*[a,b] Zhi-Hui Zhang,[a] Liang Wang,[a] Fu-An Sun,[a]
Ai-Jun Cui,[a] Ming-Yang He,[a] and Qun Chen*[a,b]
Keywords: Coordination compounds; Tetraiodoterephthalates; Crystal structure; Luminescence; Manganese; Lead; Zinc
Abstract. Three new coordination compounds, [Pb(HBDC-I4)2(DMF)4] through intermolecular O–H···O and C–H···O hydrogen bonding inter-
(1) and [M(BDC-I4)(MeOH)2(DMF)2]n (M = ZnII for 2 and MnII for actions. The isostructural compounds 2 and 3 crystallize in the space
(3) (H2BDC-I4 = 2,3,5,6-tetraiodo-1,4-benzenedicarboxylic acid), were group P21/c and have similar one-dimensional (1D) chain structures
synthesized and characterized by elemental analysis, IR spectroscopy, that are extended into three-dimensional (3D) supramolecular networks
thermogravimetric (TG) analysis, and X-ray single crystal structure by interchain C–H···π interactions. The PbII and ZnII complexes 1 and
analysis. Single-crystal X-ray diffraction reveals that 1 crystallizes in
the monoclinic space group C2/c and has a discrete mononuclear struc-
ture, which is further assembled to form a two-dimensional (2D) layer
2 display similar emissions at 472 nm in the solid state, which essen-
tially are intraligand transitions.
field, increasing numbers of investigations have been focused
on the self-assembly of metal-carboxylate systems based on
perhalogen-substituted BDC derivatives, such as 2,3,5,6-tetra-
fluoro-1,4-benzenedicarboxylate,[19–21] 2,4,5,6-tetrafluoro-1,3-
benzenedicarboxylate,[22,23] 3,4,5,6-tetrafluoro-1,2-benzened-
Introduction
The increasing interest in the design and synthesis of new
discrete or polymeric metal-organic coordination architectures
is prompted by the discovery of intriguing topologies and crys-
tal packing motifs as well as by their potential application as
functional materials.[1–6] One of the feasible approaches to
achieve such complexes is based upon the appropriate choice
of well-designed organic ligands as spacers or terminal groups
and metal ions or clusters as nodes.[7–9] Among various or-
ganic ligands, aromatic dicarboxylate species such as 1,2-, 1,3-,
and 1,4-benzenedicarboxylate (BDC), are widely used for the
construction of functional crystalline solids.[10–17] As Yaghi et
al. have demonstrated, the addition of polarizable functional
groups to the aromatic ring of ligand is expected to increase
the strength of the interaction between the host coordination
framework and guest species.[18] Because their polarizability
increases with increasing atomic size, the substitution with
halogen atoms (fluorine, chlorine, bromine, and iodine) pro-
icarboxylate,[24]
2,3,5,6-tetrachloro-1,4-benzenedicarboxyl-
ate,[25–27] and 2,3,5,6-tetrabromo-1,4-benzenedicarboxylate.[28]
Notably, it has been demonstrated that the presence of halogen
substituent on the BDC-type ligands can significantly affect
the rotation of carboxylate out of the benzene plane to give
different binding modes upon metal complexation owing to the
steric hindrance effect. In this context, very recently, BDC-
type ligands modified by one heavy iodine substituent (e.g. 2-
iodo-1,4-benzenedicarboxylic acid,[29] 5-iodo-1,3-benzened-
icarboxylic acid,[30] and so on) could be used as good building
blocks for constructing polymeric systems with unique struc-
tures and properties.
As a continuation of our research on the coordination
vides a straightforward way to study the effects of polarizabil- assemblies based on perhalogen-substituted BDC li-
gands,[20,24–27] we focus on a periodo-BDC ligand, namely,
2,3,5,6-tetraiodo-1,4-benzenedicarboxylic acid (H2BDC-I4),
which may offer different structure features and attractive
properties.[31] Herein, we report the synthesis and crystal struc-
tures of three new complexes [Pb(HBDC-I4)2(DMF)4] (1) and
[M(BDC-I4)(MeOH)2(DMF)2]n (M = ZnII for 2 and MnII for
3) assembled from H2BDC-I4 with the corresponding metal
salts under similar conditions (see Scheme 1). In addition, so-
lid-state properties like thermal stability and fluorescence were
also investigated for these crystalline materials.
ity on crystal engineering and host-guest chemistry. In this
* Dr. S.-C. Chen
Fax: +86-519-86330251
E-Mail: cscczu@yahoo.com
* Prof. Q. Chen
E-Mail: chenqunjpu@yahoo.com
[a] Key Laboratory of Fine Petro-chemical Technology
Changzhou University
Changzhou 213164, P. R. China
[b] School of Chemical Engineering
Nanjing University of Science & Technology
Nanjing 210094, P. R. China
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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ARTICLE
temperature, and partly change to the amorphous substance. So the
data of them were collected under mineral oil. Further crystal data and
structural refinement parameters are summarized in Table 1, and the
selected bond lengths and angles are listed in Table 2.
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 depository
numbers CCDC-879567, CCDC-879568, and CCDC-879569 (Fax:
Scheme 1.
Experimental Section
+44-1223-336-033;
E-Mail:
deposit@ccdc.cam.ac.uk,
http://
www.ccdc.cam.ac.uk).
Reagents and Instruments: All chemicals were commercially available
and used as received. The Fourier transform (FT) IR spectra (KBr pellet)
were taken with a Nicolet ESP 460 FT-IR spectrometer in the range of
4000–400 cm–1. Elemental analyses were performed with a PE-2400II
(Perkin-Elmer) analyzer. Thermogravimetric analysis (TGA) experi-
ments were carried out in the temperature range of 25–800 °C with a
Dupont thermal analyzer in a nitrogen atmosphere at a heating rate of
10 K·min–1. Luminescent spectra in the solid state were measured at
room temperature with a Varian Cary Eclipse spectrometer.
Results and Discussion
Syntheses and General Characterization
The ligand H2BDC-I4 is insoluble in water and soluble in
common polar organic solvents, such as MeOH, EtOH, DMF,
and DMSO. Complexes 1–3 were achieved in a MeOH/DMF
mixed media by assembling H2BDC-I4 with different transition
salts with a 1:1 stoichiometric metal/ligand ratio at room tem-
perature. When the sources of central metal atoms such as
Zn(OAc)2, Zn(ClO4)2, MnCl2, and Mn(ClO4)2 were used,
complexes 2 and 3 could also be isolated by the same pro-
cedure (confirmed by IR spectroscopy and X-ray structural
analysis), which suggests that such products are indeed inde-
pendent of the counteranions. For the IR spectra of 1–3, the
broad peak appearing in the region of 3000–3500 cm–1 corre-
sponds to the O–H stretching frequencies. All complexes show
characteristic bands of carboxylate groups appearing in the re-
gion of 1580–1650 cm–1 for the antisymmetric stretching vi-
brations and at 1380–1450 cm–1 for the symmetric stretching
vibrations, respectively. In addition, the strong peak at
1703 cm–1 in the IR spectra of 1 reveals the presence of the
free carboxyl group, which is also confirmed by the X-ray sin-
gle-crystal structure analysis.
Synthesis of [Pb(HBDC-I4)2(DMF)4] (1): In a 25 mL vial, a mixture
of Pb(NO3)2 (33.1 mg, 0.1 mmol) and H2BDC-I4 (67.0 mg, 0.1 mmol)
was dissolved in DMF (6 mL) and diluted with methanol (12 mL).
After stirring for 20 min, the reaction solution was filtered and left to
stand at room temperature. Colorless block-shaped crystals of 1 suit-
able for X-ray diffraction were obtained by slow evaporation of the
solvents after 5 d in ca. 65% yield (59.7 mg, based on H2BDC-I4).
C28H30I8N4O12Pb: calcd. C 18.31; N 3.05; H 1.65%; found: C, 18.23;
N 3.09; H 1.61%. IR (KBr): ν˜ = 3444 br. s, 2930 m, 1703 s, 1628 s,
1484 m, 1428 s, 1383 vs, 1267 m, 1112 m, 1014 m, 1046 m, 792 m,
747 s, 677 m, 530 m cm–1.
Synthesis of [Zn(BDC-I4)(MeOH)2(DMF)2]n (2): The same synthetic
procedure as that for 1 was used except that Pb(NO3)2 was replaced by
Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol), giving colorless block-shaped
crystals of 2 in ca. 42% yield (39.6 mg, based on H2BDC-I4). C16H22I-
4N2O8Zn: calcd. C 20.37; N 2.97; H 2.35%; found: C 20.45; N 2.91;
H 2.33%. IR (KBr): ν˜ = 3418 br. s, 2925 m, 1642 s, 1603 vs, 1462
m, 1424 s, 1397 vs, 1302 s, 1267 m, 1214 w, 1095 m, 1024 m, 931
w, 815 m, 775 w, 662 w, 565 m, 538 m cm–1.
Structure Descriptions of Complexes 1–3
Synthesis of [Mn(BDC-I4)(MeOH)2(DMF)2]n (3): The same syn-
thetic procedure as that for 1 was used except that Pb(NO3)2 was re-
placed by Mn(OAc)2·4H2O (24.5 mg, 0.1 mmol), affording colorless
block-shaped crystals of 3 in ca. 53% yield (49.4 mg, based on
H2BDC-I4). C16H22I4N2O8Mn: calcd. C 20.60; N 3.00; H 2.38%;
found: C 20.75; N 2.93; H 2.41%. IR (KBr): ν˜ = 3482 br. s, 2923 m,
1638 s, 1598 vs, 1478 m, 1418 s, 1396 vs, 1307 s, 1256 m, 1120 m,
1065 m, 1024 m, 927 w, 815 m, 756 w, 566 m, 538 m cm–1.
[Pb(HBDC-I4)2(DMF)4] (1)
X-ray crystallographic analysis shows that compound 1,
which crystallizes in the space group C2/c, is a discrete mono-
nuclear complex with twofold symmetry. The asymmetric unit
is composed of one PbII ion, two monodeprotonated HBDC-I4
anions, and four DMF molecules. As shown in Figure 1a, the
central PbII atom is hemidirected and hexacoordinated by two
X-ray Crystallography: Single-crystal X-ray diffraction measure-
ments of 1–3 were performed with a Bruker Apex II CCD dif- oxygen donors (O1 and O1A) from two HBDC-I4 ligands with
fractometer at the ambient temperature with Mo-Kα radiation (λ =
0.71073 Å). In each case, a semiempirical absorption correction was
applied using SADABS, and the program SAINT was used for integra-
tion of the diffraction profiles.[32] The structures were solved by the
direct methods using SHELXS program of SHELXTL packages and
refined anisotropically for all non-hydrogen atoms by full-matrix least-
squares on F2 with SHELXL.[33] Carbon-bound hydrogen atoms were
placed in geometrically calculated positions by using a riding model.
Oxygen-bound hydrogen atoms were firstly localized by difference
Fourier maps and fixed geometrically with isotropic temperature fac-
a Pb–O distance of 2.623(3) Å and four oxygen atoms (O5,
O6, O5A, and O6A) from four terminal DMF molecules with
Pb–O distances of 2.398(4) and 2.605(4) Å. In 1, within the
HBDC-I4 anion entity, only one carboxylate group is deproton-
ated to coordinate to the central PbII atom in a terminal fash-
ion. Owing to the steric hindrance of the bulk iodine atoms
located at the ortho positions of carboxylate, the rotation angle
between the carboxylate groups and the tetaiodinated central
benzene ring is 84.2(2) and 85.4(2)°, respectively, which is
tors. Crystals of 2 and 3 are not stable when exposed to air at room similar to those of other carboxylate compounds with periodin-
2
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Pb,II Zn,II and MnII Complexes with 2,3,5,6-Tetraiodo-1,4-benzenedicarboxylic Acid
Table 1. Crystal data and structure refinements for compounds 1–3.
1
2
3
Empirical formula
Formula weight
Crystal size /mm3
Crystal system
Space group
a /Å
C28H30I8N4O12Pb
1836.95
0.26ϫ0.24ϫ0.24
monoclinic
C2/c
26.923(3)
C16H22I4N2O8Zn
943.33
0.28ϫ0.26ϫ0.26
monoclinic
P21/n
8.728(2)
C16H22I4N2O8Mn
932.90
0.28ϫ0.26ϫ0.26
monoclinic
P21/n
8.699(2)
b /Å
9.631(1)
13.662(3)
13.801(3)
c /Å
19.242(2)
11.414(3)
11.539(2)
α /°
90.00
90.00
90.00
β /°
116.481(2)
100.087(4)
101.913(4)
γ /°
90.00
4466.0(9)
90.00
1340.0(5)
90.00
1355.6(5)
V /Å3
Z
4
2
2
Dcalc /mg·m–3
2.732
9.364
2.338
5.564
2.286
5.081
μ /mm–1
F(000)
3312
876
866
Total reflections
Independent reections
Rint
11851
3914
0.0373
1.098
R1 = 0.0265,wR2 = 0.0716
R1 = 0.0282,wR2 = 0.0725
1.021 and –1.269
7866
3071
0.0531
1.038
R1 = 0.0843,wR2 = 0.2387
R1 = 0.0946,wR2 = 0.2518
3.150 and –3.538
11810
2299
0.0737
1.084
R1 = 0.0729,wR2 = 0.2304
R1 = 0.0922,wR2 = 0.2613
2.929 and –2.222
Goodness-of-t on F2
Final R indices [I Ͼ 2σ(I)]
R indices (all data)
Residuals /e·Å–3
ated backbone.[34,35] Each complex unit is connected by inter- within BDC-I4 ligand in 2 are almost perpendicular to the cen-
molecular O3–H3···O2i hydrogen bonds (H···O/O···O distance: tral tetraiodinated benzene plane with the dihedral angle of
1.78/2.547(5) Å, angle: 154.4(2)°; i = x, –y + 1, z – 1/2) be- 89.3(7)°, which is similar to those observed for the tetrafluori-
tween uncoordinated carboxylate O2 atoms and undeproton- nated BDC complexes.[19,22,23] Each coordinated methanol
ated carboxylate group to generate a 1D ladder-like array along molecule is involved in the strong intramolecular hydrogen
the c axis (Figure 1b). Within the 1D pattern, the neighboring bond (O3–H3···O2, H···O/O···O distances: 1.86/2.657(8) Å, an-
Pb···Pb separation is 10.234(1) Å and the Pb···Pb···Pb angle is gle: 163°) to the uncoordinated carboxylate O2 atom of BDC-
140.2°. Meanwhile, these adjacent 1D motifs are further con- I4, which helps to stabilize such 1D coordination motifs. Be-
nected through intermolecular C–H···O hydrogen bond interac- tween the adjacent chains, the occurrence of weak edge-to-face
tions (see Table 3) between the DMF molecules and undepro- C–H···π [C8–H8B···Cg1i (Cg1
=
C2–C4, C2A–C4A):
tonated carboxylate O3 atoms of HBDC-I4, leading to the for- H8B···Cg1, 2.76 Å, C8···Cg1, 6.07(2) Å, i = –x+1/2, y–1/2,
mation of a 2D supramolecular architecture, as illustrated in –z+1/2] intermolecular interactions results in a 3D supra-
Figure 1c.
molecular network (see Figure 2c). Notably, similar 1D chains
of [M(tfBDC)(H2O)4] (M = Zn, Co, Ni; tfBDC = tetrafluo-
roterephthalate) have been reported to have dissimilar 2D hy-
drogen-bonding networks, which may be caused by slight dif-
ference of coordinated solvent molecules.[19]
[M(BDC-I4)(MeOH)2(DMF)2]n (M = ZnII for 2 and MnII for 3)
Single-crystal X-ray diffraction analysis reveals that com-
plexes 2 and 3 are isostructural (see Table 1) and thus herein,
only the crystal structure of 2 is described in detail. Complex
2 crystallizes in the space group P21/c and shows a 1D poly-
meric coordination chain structure. The asymmetric unit of 2
Thermal Stability
Thermogravimetric analysis (TGA) experiments were con-
consists of one ZnII ion, one BDC-I4 dianion with centrosym- ducted to examine the thermal stabilities of complexes 1–3.
metry, two MeOH ligands, and two DMF molecules. In the The corresponding curves are depicted in Figure 3. For 1, the
structure of 2 (see Figure 2a), the central ZnII atom is six-coor- TGA curve shows that the first weight loss of 15.2% in the
dinated octahedrally by two oxygen atoms (O1 and O1A) from range of 85–200 °C corresponds to the elimination of four co-
two trans BDC-I4 ligands, two oxygen atoms (O3 and O3A) ordinated DMF molecules (calculated: 15.9%). The residual
from two MeOH molecules, and two oxygen atoms (O4 and solid starts to decompose at 230 °C with a series of consecu-
O4A) from two terminal DMF molecules. The Zn–O bond tive weight losses that do not stop until the heating end. The
lengths are in the range of 2.085(5)–2.134(6) Å. Each BDC-I4 TGA curves of 2 and 3 are similar for their isostructural nature.
dianion bridges two ZnII ions in a bis-monodentate fashion to The first weight loss of 21.9% (45–180 °C) for 2 and 23.4%
form a 1D linear chain (see Figure 2b). Within each linear (40–185 °C) for 3 indicates the exclusion of coordinated meth-
chain, the distance between successive ZnII ions is anol and DMF molecules (calculated: 22.3% and 22.5%). Py-
11.414(3) Å, and the closest Zn···Zn separation between the rolysis of the residual components for 2 and 3 starts at 220
neighboring strands is 8.728(2) Å. The two carboxylate groups and 200 °C, respectively, which does not stop until the heating
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Table 2. Selected bond lengths /Å and angles /° for complexes 1–3.
1
Pb1–O1
Pb1–O5
Pb1–O6
2.623(3)
2.398(4)
2.605(4)
140.5(2)
142.9(1)
112.4(1)
79.2(1)
78.1(2)
72.6(1)
112.4(1)
146.5(2)
Pb1–O1#1
Pb1–O5#1
Pb1–O6#1
O1–Pb1–O5
O1–Pb1–O6
O1#1–Pb1–O5#1 74.1(1)
O5–Pb1–O1#1
O5–Pb1–O6
2.623(3)
2.398(4)
2.605(4)
74.1(1)
O1–Pb1–O1#1
O1–Pb1–O5#1
O1–Pb1–O6#1
O1#1–Pb1–O6#1
O5–Pb1–O5#1
O5–Pb1–O6#1
O6–Pb1–O1#1
O6–Pb1–O6#1
79.2(1)
142.9(1)
81.5(1)
O5#1–Pb1–O6#1 81.5(1)
O6–Pb1–O5#1
72.6(2)
2
Zn1–O1
Zn1–O3
Zn1–O4
2.085(5)
2.134(6)
2.102(6)
180
89.3 (2)
90.7 (2)
90.7 (2)
89.3 (2)
180
Zn1–O1#2
Zn1–O3#2
Zn1–O4#2
O4#2–Zn1–O3
O4–Zn1–O3
O1#2–Zn1–O3#2 87.5 (2)
O1–Zn1–O3#2 92.5 (2)
O4#2–Zn1–O3#2 90.8 (3)
O4–Zn1–O3#2
O3–Zn1–O3#2
2.085(5)
2.134(6)
2.102(6)
89.2 (3)
90.8 (3)
O1#2–Zn1–O1
O1#2–Zn1–O4#2
O1–Zn1–O4#2
O1#2–Zn1–O4
O1–Zn1–O4
O4#2–Zn1–O4
O1#2–Zn1–O3
O1–Zn1–O3
89.2 (3)
180
92.5 (2)
87.5 (2)
3
Mn1–O1
Mn1–O3
Mn1–O4
2.155(8)
2.198(8)
2.16(1)
180
89.7 (3)
90.3 (3)
90.3 (3)
89.7 (3)
180
Mn1–O1#3
Mn1–O3#3
Mn1–O4#3
O4#3–Mn1–O3
O4–Mn1–O3
O1–Mn1–O3#3
O1#3–Mn1–O3#3 91.3 (3)
O4#3–Mn1–O3#3 89.1 (4)
2.155(8)
2.198(8)
2.16(1)
90.9 (4)
89.1 (4)
88.7 (3)
O1–Mn1–O1#3
O1–Mn1–O4#3
O1#3–Mn1–O4#3
O1–Mn1–O4
O1#3–Mn1–O4
O4#3–Mn1–O4
O1–Mn1–O3
O1#3–Mn1–O3
O4–Mn1–O3#3
O3–Mn1–O3#3
90.9 (4)
180
91.3 (3)
88.7 (3)
Symmetry transformations used to generate equivalent atoms: For 1,
#1: –x, y, –z+1/2. For 2, #2: –x, –y+1, –z+1. For 3, #3: –x+1, –y,
–z+2.
Figure 1. (a) The coordination environment of the central PbII atom
in 1; (b) the 1D supramolecular double-chain in 1 (irrelevant iodine
and nitrogen atoms are omitted for clarity); (c) 2D supramolecular
layer along the bc plane (hydrogen bonds interactions are shown as
dashed lines; irrelevant iodine and part of hydrogen atoms are omitted
for clarity).
end. The residual solids have the weights of 8.4% and 6.7%
of the original samples for 2 and 3, respectively, which can be
properly assigned to zinc oxide (calculated: 8.6%) and manga-
nese oxide (calculated: 7.6%).
Luminescent Properties
may be assigned to the increased rigidity of the deprotonated
ligand upon complexation that will reduce the nonradiative de-
cay of the intraligand (π Ǟ π*) excited state.[38,39]
Inorganic-organic hybrid coordination complexes, especially
for those that comprise the central d10 metal atom and aro-
matic-containing system, have now been a powerful tool for
achieving new luminescent materials.[36,37] In this work, solid-
state fluorescent spectra of the PbII and ZnII complexes 1 and
2 as well as the free ligand H2BDC-I4 were recorded at room
temperature (see Figure 4). The free ligand exhibits an emis-
Conclusions
Three new PbII, ZnII, and MnII complexes constructed from
sion maximum at 474 nm upon excitation at 336 nm, which a periodinated benzenedicarboxylate ligand H2BDC-I4 were
could be ascribed to the π Ǟ π* and/or n Ǟ π* transitions. For prepared and structurally characterized by X-ray single crystal
complexes 1 and 2, the maximum emission bands are similarly structure analysis. On the one hand, H2BDC-I4 can be depro-
observed at 472 nm (λex = 336 nm), which are tentatively at- tonated at different levels, so it may serve as either a terminal
tributed to the ligand-centered transitions. Furthermore, the ef- or bridging connector to construct discrete or infinite coordina-
fective enhancement of the luminescent intensity for 1 and 2 tion structures. On the other hand, intramolecular/intermo-
4
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Pb,II Zn,II and MnII Complexes with 2,3,5,6-Tetraiodo-1,4-benzenedicarboxylic Acid
Table 3. Possible hydrogen-bonding arrangements in the crystal structures of 1–3.
Complex
D–H···A
H···A /Å
D···A /Å
D–H···A /°
Symmetry code
1
O3–H3···O2
C9–H9···O1
O3–H3···O2
O3–H3···O2
1.78
2.36
1.86
1.87
2.547(5)
2.957(6)
2.657(8)
2.671(9)
154
122
163
165
–x+1/2, y–1/2, –z+1/2
2
3
Figure 3. Thermogravimetric profiles for complexes 1–3.
Figure 4. Solid-state fluorescent emission spectra of complexes 1 and
2 as well as the free ligand 1,4-H2BDC-I4.
Figure 2. (a) The coordination environment of the central ZnII atom
in 2; (b) the 1D linear chain of 2 (irrelevant hydrogen atoms are omit-
ted for clarity); (c) 3D supramolecular architecture along the ab plane
(C–H···π interactions are shown as dashed lines; irrelevant iodine
atoms and hydrogen atoms are omitted for clarity).
efforts on the design and preparation of novel coordination
networks with various halogenated benzenedicarboxylate tec-
tons are underway in our lab.
Acknowledgements
We gratefully acknowledge financial support by the Project Funded
by the Priority Academic Program Development of Jiangsu Higher
Education Institutions (PAPD) and the Open Foundation of Jiangsu
Province Key Laboratory of Fine Petrochemical Technology (KF
lecular weak interactions, such as hydrogen bonding and C–
H···π interactions, play an important role in the formation of
complexes, especially linking the discrete subunits or low-di-
mensional entities into high-dimensional frameworks. Further 1005).
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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Date: 29-08-12 10:28:55
Pages: 7
S.-C. Chen, Q. Chen et al.
ARTICLE
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Received: May 7, 2012
Published Online: ᭿
6
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Job/Unit: Z12210
/KAP1
Date: 29-08-12 10:28:55
Pages: 7
Pb,II Zn,II and MnII Complexes with 2,3,5,6-Tetraiodo-1,4-benzenedicarboxylic Acid
M. Hu, S.-C. Chen,* Z.-H. Zhang, L. Wang, F.-A. Sun,
A.-J. Cui, M.-Y. He, Q. Chen* .......................................... 1–7
Syntheses, Crystal Structures, and Properties of Lead(II),
Zinc(II), and Manganese(II) Complexes Constructed from
2,3,5,6-Tetraiodo-1,4-benzenedicarboxylic Acid
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
7