Construction of an unusual 2Dchiral/2Dchiral→ 2Dachiral network based on a V-shaped pyridyl ligand

Article abstract of DOI:10.1016/j.mencom.2013.07.018

A new interpenetrating 2D coordination polymer {[Zn(dpb)(glu)]}_n was prepared under hydrothermal conditions, and an X-ray diffraction study showed that it is an unusual ABAB stacked 2D_chiral/2D _chiral → 2D_achiral network.

Full text of DOI:10.1016/j.mencom.2013.07.018

Mendeleev
Communications
Mendeleev Commun., 2013, 23, 229–230
Construction of an unusual 2Dchiral/2Dchiral ®2Dachiral
network based on a V-shaped pyridyl ligand
Jin-Song Hu,*a,b Zhang Lei,a Hong-Long Xing,a Xiao-Mei Zhang,a Jian-Jun Shia and Jie Hea
a School of Chemical Engineering, Anhui University of Science and Technology, Huainan 232001, P. R. China.
E-mail: jshu@aust.edu.cn
b State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. China
DOI: 10.1016/j.mencom.2013.07.018
A new interpenetrating 2D coordination polymer {[Zn(dpb)(glu)]}n was prepared under hydrothermal conditions, and an X-ray
diffraction study showed that it is an unusual ABAB stacked 2Dchiral /2Dchiral ®2Dachiral network.
The rational design of coordination polymers (CPs) from various
a
molecular building blocks connected by coordination bonds and
N(1#1)
O(#2)
b
N(1)
O(1#2)
c
supramolecular contacts have attracted great attention not only
for their structural diversity1,2 but also for their explosive applica-
tions in photochemical areas,3,4 gas adsorption and separation,5,6
molecular magnetism7,8 and heterogeneous catalysis.9,10 Entangled
systems are of considerable interest for supramolecular chem-
istry11,12 due to their esthetic architectures and topologies. Inter-
penetration as an important branch of entangled systems has
attracted more and more attention, and a great number of inter-
penetrating nets have been reported.13,14 Interpenetration is an
approach of nature to avoid voids or open space in a single
network. The interpenetrating structure depends upon not only
the metal coordination geometry but also the shapes and lengths
of special ligands. Recently, a great deal of mixed-ligand CPs
have been reported,15,16 but the design of the frameworks is still
challenging, the occurrence of interpenetration sometimes requires
that different bridging ligands match each other in shape and
length.17,18 To continue our previous work with the V-shaped
pyridyl ligand 1,3-dipyridylbenzene (1,3-dpb),19 we tried to explore
the assembly of dpb and carboxylic acids. Here, we report a
new 2Dchiral /2Dchiral ®2Dachiral network based on dpb and flexible
glutaric acid (H2glu).†
O(4)
Zn(1)
N(2)
O(1)
O(3)
O(2)
Figure 1 Coordination environment of 1. The hydrogen atoms are omitted
for clarity. Symmetry codes: #1 = –x, –0.5 + y, 0.5 – z; #2 = 2 – x, 0.5 + y,
0.5 – z. Selected bond lengths (Å): Zn(1)–N(1#1) 2.082(4), Zn(1)–N(2)
2.095(4), Zn(1)–O(3) 2.133(4), Zn(1)–O(4) 2.272(4), Zn(1)–O(1#2) 2.075(4),
Zn(1)–O(2#2) 2.430(5); selected bond angles (°): O(1#2)–Zn(1)–N(1#1)
139.86(15), O(1#2)–Zn(1)–N(2) 103.26(15), N(1#1)–Zn(1)–N(2) 94.07(14),
O(1#2)–Zn(1)–O(3) 111.82(16), N(1#1)–Zn(1)–O(3) 103.66(16), N(2)–
Zn(1)–O(3) 91.00(15), O(1#2)–Zn(1)–O(4) 91.65(15), N(1#1)–Zn(1)–O(4)
91.73(15), N(2)–Zn(1)–O(4) 148.69(15), O(3)–Zn(1)–O(4) 57.76(15), O(1#2)–
Zn(1)–O(2#2) 55.68(13), N(1#1)–Zn(1)–O(2#2) 87.47(14), N(2)–Zn(1)–
O(2#2) 94.43(16), O(3)–Zn(1)–O(2#2) 167.26(16), O(4)–Zn(1)–O(2#2)
116.57(17).
between phenyl and pyridyl rings are 23.8° and 41.0°, and the
dihedral angle between pyridyl rings is 40.3°.
X-ray crystallography analysis‡ reveals that the asymmetric
unit of 1 contains an independent Znii cation, a dpb ligand and
a glu2– anion. As shown in Figure 1, Zn(1) has an octahedral
coordination environment with two N atoms from two dpb and
four O atoms from two glu2–. The Zn–N bond lengths are 2.082(4)
and 2.095(4) Å, and the Zn–O lengths are 2.075(4)–2.430(5) Å,
which are similar to those in other Znii complexes containing
the glu2– anion ([Zn–O]: 1.918–2.574 Å). The dihedral angles
The neighbouring Zn(1) ions linked V-shaped dpb into an
infinitely helical chain, the adjacent Zn(1)···Zn(1) distance is
8.622 Å. Glu2– anions adopt cis-configuration, also linked Zn(1)
ions to form an infinitely helical chain, the adjacent distance
of Zn(1)···Zn(1) is 13.168 Å. These two kinds of helical chains
further form a wavelike 2D layer by sharing the Znii ions. There
are irregular windows in 2D layer, which has a 40-membered
and c = 17.439(3) Å, b = 101.818(2)°, V = 1906.8(6) Å3, Z = 4, dcalc
=
= 1.490 g cm–3, m(MoKa) = 1.318 mm–1, F(000) = 1248. 13122 reflec-
tions were measured and 3348 independent reflections (Rint = 0.054) were
used in further refinement. The refinement converged to wR2 = 0.1624 and
GOF = 1.08 for all independent reflections [R1 = 0.0532 was calculated
against F for 2524 observed reflections with I > 2s(I)]. The measure-
ments were made on a Bruker Apex Smart CCD diffractometer with
graphite-monochromated MoKa radiation (l = 0.71073Å). The structure
was solved by direct methods, and the non-hydrogen atoms were located
from the trial structure and then refined anisotropically with SHELXTL
using full-matrix least-squares procedures based on F2 values.20 Hydrogen
atom positions were fixed geometrically at calculated distances and allowed
them to ride on the parent atoms.
† Commercial reagents and solvents were used as received. The IR absorp-
tion spectra of complexes were recorded in a range of 400–4000 cm–1 on
a Nicolet (Impact 410) spectrometer with KBr pellets (5 mg sample in
500 mg of KBr). C, H, and N analyses were carried out with a Perkin–
Elmer 240C elemental analyzer.
General procedure for the preparation of compound 1. A mixture of
Zn(NO3)2 (0.15 mmol), 1,3-dpb and glu2– (0.1 mmol) was dissolved in
8 ml of DMF–MeOH–H2O (1:1:2, v/v). The final mixture was placed in a
Parr Teflon-lined stainless steel vessel (15 ml) and heated at 110°C for
3 days, colourless crystals were obtained (52% yield based on 1,3-dpb).
IR (KBr, n/cm–1): 3425 (m), 3068 (w), 2848 (w), 2359 (m), 1580 (s),
1515 (s), 1394 (s), 1226 (s), 1156 (w), 1056 (s), 964 (w), 852 (w), 757 (m),
674 (m), 536 (m). Found (%): C, 59.06; H, 4.13; N, 6.41. Calc. for
C21H18N2O4Zn (%): C, 58.96; H, 4.24; N, 6.55.
CCDC 936250 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2013.
‡
Crystal data. Crystal of 1 (C21H18N2O4Zn, M = 427.76) is mono-
clinic, space group P21/c, at 296 K: a = 7.7163(13), b = 14.477(3),
© 2013 Mendeleev Communications. All rights reserved.
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Mendeleev Commun., 2013, 23, 229–230
b
b
b
b
c
a
a
a
Figure 4 Interpenetrating 2Dchiral + 2Dchiral ® 2Dchiral sheet, which stacked
in the ABAB manner to generate a 2Dachiral network.
Science Fund of Education Department of Anhui Province (grant
no. KJ2011A091), the Natural Science Foundation of Anhui
Province (grant no. 1308085QB34) and the Research Fund of
Key Laboratory for Advanced Technology in Environmental
Protection of Jiangsu Province (grant no. AE201107).
Figure 2 Neighbouring Znii ions linked dpb or glu2– into infinitely helical
chains, the helical directions of (dpb–Zn–dpb)n or (glu–Zn–glu)n chains are
the same.
loop composed of four metal ions, two dpb linkers and two glu2–
anions. In this layer, the helical directions of all (dpb–Zn–dpb)n
or all (glu–Zn–glu)n chains are the same, so the 2D layer can be
regarded as a 2Dchiral layer (Figure 2).
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In complex 1, a pair of adjacent 2D layers interpenetrated
each other to generate a 2D + 2D ® 2D sheet (Figure 3); because
the helical directions of two interpenetrating 2D layers are the
same, the sheet can be regarded as 2Dchiral + 2Dchiral ® 2Dchiral
sheet. The helical chains of (dpb–Zn–dpb)n and (glu–Zn–glu)n
in the interpenetrating 2D sheet coincide to form a double helical
chain. The adjacent interpenetrating 2Dchiral sheets are stacked in
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ligands in length.
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under solvothermal conditions. Complex 1 is an interpenetrating
2Dchiral + 2Dchiral ® 2Dchiral sheet, which further stacked to generate
a 2Dachiral network. The results demonstrate that the lengths and
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Received: 30th April 2013; Com. 13/4115
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