A novel parallel inter-penetrating two-dimensional (4,4) network: Poly[[2-1,4-bis-(imidazol-1-ylmeth-yl)benzene](2-naphthalene-1,4-dicarboxyl-ato) zinc(II)]

Article abstract of DOI:10.1107/S0108270109029084

In the title coordination compound, [Zn(C12H6O4)(C14H14N4)] n , the two Zn^II centers exhibit different coordination environments. One Zn ^II center is four-coordinated in a distorted tetra-hedral environment surrounded by two carboxyl

Full text of DOI:10.1107/S0108270109029084

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Generally, the topology of a coordination polymer can often
be controlled and modified by selecting the coordination
geometry preferred by the metal ion and the chemical struc-
ture of the organic ligand chosen (Batten, 2001). Flexible N-
donor ligands are good candidates for the assembly of versa-
tile entangled structures, owing to their propensity to form
large voids; in particular, bis(imidazole) ligands are a good
choice. Using these ligands, many intriguing varieties of
interpenetrating architectures and topologies have been
constructed (Sun et al., 2009). Among the bis(imidazole) lig-
ands, 1,4-bis(imidazol-1-ylmethyl)benzene (1,4-bix) is parti-
cularly interesting. For example, the flexible bridging 1,4-bix
gives an unusual extended two-dimensional polyrotaxane
network when it is reacted with Cd(SO4)ꢀ6H2O (Carlucci et al.,
2005). An unusual triply interpenetrating ꢀ-polonium top-
ology is produced when it is reacted with Cd(NO3)2ꢀ6H2O
(Abrahams et al., 2002). In the present study, 1,4-bix assembles
with zinc naphthalene-1,4-dicarboxylate (1,4-ndc) to furnish a
1:1:1 adduct, [Zn(1,4-ndc)(1,4-bix)]2n (I), which exists as a
twofold interpenetrating (4,4) topology.
ISSN 0108-2701
A novel parallel interpenetrating two-
dimensional (4,4) network: poly[[l2-
1,4-bis(imidazol-1-ylmethyl)benzene]-
(l2-naphthalene-1,4-dicarboxylato)-
zinc(II)]
Ya-Ping Li,a Da-Jun Sun,b* Hu Zang,c Guan-Fang Sua and
Yu-Lin Lid
aDepartment of Ophthalmology, The Second Hospital of Jilin University, Changchun
130041, People’s Republic of China, bDepartment of Vascular Surgery, The China–
Japan Union Hospital of Jilin University, Changchun 130033, People’s Republic of
China, cDepartment of Orthopedics, The China–Japan Union Hospital of Jilin
University, Changchun 130033, People’s Republic of China, , and dLaboratory
Teaching of Pathology, Norman Bethune Medical College, Jilin University,
Changchun 130041, People’s Republic of China
Correspondence e-mail: li_yp2002@yahoo.com.cn
Received 5 July 2009
Accepted 22 July 2009
Online 15 August 2009
In the title coordination compound, [Zn(C12H6O4)(C14-
H14N4)]n, the two ZnII centers exhibit different coordination
environments. One ZnII center is four-coordinated in a
distorted tetrahedral environment surrounded by two
carboxylate O atoms from two different naphthalene-1,4-
dicarboxylate (1,4-ndc) anions and two N atoms from two
distinct 1,4-bis(imidazol-1-ylmethyl)benzene (1,4-bix) ligands.
The coordination of the second ZnII center comprises two N
atoms from two different 1,4-bix ligands and three carboxylate
O atoms from two different 1,4-ndc ligands in a highly
distorted square-pyramidal environment. The 1,4-bix ligand
and the 1,4-ndc anion link adjacent ZnII centers into a two-
dimensional four-connected (4,4) network. The two (4,4)
networks are interpenetrated in a parallel mode.
The asymmetric unit of (I) (Fig. 1 and Table 1) contains two
crystallographically independent ZnII centers, two unique 1,4-
ndc anions and two unique 1,4-bix ligands. The two ZnII
centers exhibit different coordination environments. Zn1 is
four-coordinated in a distorted tetrahedral environment
surrounded by two carboxylate O atoms from two different
1,4-ndc anions and two N atoms from two distinct 1,4-bix
ligands. The coordination of atom Zn2 comprises two N atoms
from two different 1,4-bix ligands and three carboxylate O
atoms from two different 1,4-ndc ligands in a highly distorted
square-pyramidal environment. One N atom (N5) and three O
atoms (O1, O7ii and O8ii) constitute the base of the square-
pyramid, whereas one N atom (N8iii) occupies the apical
Comment
The current interest in polymeric coordination networks is
rapidly expanding not only because of their potential appli-
cations in medical chemistry, host–guest chemistry, ion
exchange, artificial eye lenses, gas storage and nonlinear
optics, but also for their intriguing variety of topologies
(Carlucci et al., 2003; Eddaoudi et al., 2001). It is well known
that structural diversity in coordination polymers can occur as
a result of various processes, including supramolecular
isomerism and interpenetration. In this regard, inter-
penetrating networks, as an important subject in the area of
entanglement, have provided a long-standing fascination for
chemists (Batten & Robson, 1998; Ockwig et al., 2005).
iii
˚
position with a Zn—N8 distance of 2.046 (3) A. The average
Zn—O and Zn—N distances in (I) (Table 1) are comparable
to those observed for [Zn(OAc)(TITMB)](OH)ꢀ8.5H2O
[TITMB is 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethyl-
benzene and OAc is the acetate anion; Fan et al., 2003]. As
depicted in Fig. 2, each ZnII center is bridged by the 1,4-ndc
dianions and 1,4-bix ligands to give a two-dimensional four-
connected (4,4) network. Along the c axis, adjacent ZnII
centers are linked via the two carboxylate groups of the 1,4-
ndc ligands to form one-dimensional chains. The 1,4-bix
m340 # 2009 International Union of Crystallography
doi:10.1107/S0108270109029084
Acta Cryst. (2009). C65, m340–m342

metal-organic compounds
Figure 1
A view of the local coordination of the ZnII cations in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 20%
probability level. One of the H atoms on C42 is wholly obscured by its parent atom. [Symmetry codes: (i) x ꢁ 1, y ꢁ 1, z; (ii) x, y, 1 + z; (iii) x + 1, y + 1, z.]
Figure 2
A view of the two-dimensional (4,4) network in the (110) plane.
Figure 3
A view of the parallel interpenetrating (4,4) networks of (I) in the (110)
plane.
ligands further extend these chains along the b axis, yielding
the final two-dimensional (4,4) network. Interestingly, the two
(4,4) networks are interpenetrated in a parallel mode in the
(110) plane (Fig. 3). The two interpenetrating networks are
individually generated by translation and they are related by
inversion.
exhibit interpenetration. The structure of (I) is also entirely
different from that of the related polymer [Zn(SO4)(bis)1.5-
(H2O)]ꢀ6H2O [bis is 1,10-(butane-1,4-diyl)bis(imidazole); Ma
et al., 2000]. In that structure, the networks are interpenetrated
in an inclined mode by symmetry-related identical networks to
give an interlocked three-dimensional structure. This com-
pound may be a good candidate for artificial eye lenses.
It is noteworthy that the structure of (I) is entirely different
from those of the two related structures [Cu(1,3-bdc)2(1,4-
bix)][Cu(1,4-bix)2(H2O)2]ꢀ4H2O (1,3-bdc is benzene-1,3-di-
carboxylate) and [Cu(1,4-ndc)(1,2-bix)2]ꢀ2H2O (Yang et al.,
2008). The reported complex [Cu(1,3-bdc)2(1,4-bix)][Cu(1,4-
bix)2(H2O)2]ꢀ4H2O consists of two types of coordination
polymers, namely two-dimensional (4,4) grids of [Cu(1,4-bix)2-
Experimental
(H2O)2]2+ and linear chains of [Cu(1,3-bdc)2(1,4-bix)]2ꢁ
.
Zinc chloride (0.068 g, 0.5 mmol), naphthalene-1,4-dicarboxylic acid
(0.108 g, 0.5 mmol) and 1,4-bix (0.119 g, 0.5 mmol) were placed in
water (12 ml), and triethylamine was added until the pH value of the
The structure of [Cu(1,4-ndc)(1,2-bix)2]ꢀ2H2O contains two-
dimensional (4,4) networks. However, this structure does not
ꢂ
Acta Cryst. (2009). C65, m340–m342
Li et al.
[Zn(C12H6O4)(C14H14N4)] m341

metal-organic compounds
solution was 5.8. The solution was heated in a 25 ml Teflon-lined
stainless-steel autoclave at 450 K for 5 d. The autoclave was allowed
to cool to room temperature over a period of several hours. Colorless
blocks were isolated in about 42% yield.
Table 1
Selected geometric parameters (A, ).
ꢃ
˚
Zn1—O4
Zn1—O5
Zn1—N1
Zn1—N4i
Zn2—O1
1.960 (3)
1.958 (2)
2.038 (3)
2.035 (3)
1.950 (2)
Zn2—O7ii
Zn2—O8ii
Zn2—N5
Zn2—N8iii
2.224 (4)
2.256 (4)
2.053 (3)
2.046 (3)
Crystal data
[Zn(C12H6O4)(C14H14N4)]
Mr = 517.83
Triclinic, P1
ꢂ = 100.628 (4)ꢃ
V = 2249.95 (18) A
Z = 4
Mo Kꢀ radiation
ꢃ = 1.13 mmꢁ1
T = 293 K
0.33 ꢄ 0.27 ꢄ 0.22 mm
˚
O5—Zn1—O4
O5—Zn1—N4i
O4—Zn1—N4i
O5—Zn1—N1
O4—Zn1—N1
N4i—Zn1—N1
O1—Zn2—N8iii
O1—Zn2—N5
131.58 (11)
98.42 (12)
108.08 (12)
115.50 (11)
97.48 (12)
102.78 (12)
111.14 (12)
99.11 (12)
N8iii—Zn2—N5
O1—Zn2—O7ii
N8iii—Zn2—O7ii
N5—Zn2—O7ii
O1—Zn2—O8ii
N8iii—Zn2—O8ii
N5—Zn2—O8ii
O7ii—Zn2—O8ii
100.87 (13)
140.89 (14)
86.96 (15)
111.53 (15)
100.20 (14)
143.68 (15)
91.51 (14)
56.80 (15)
3
˚
a = 10.4112 (5) A
˚
b = 11.5745 (5) A
˚
c = 19.1907 (9) A
ꢀ = 96.319 (4)ꢃ
ꢁ = 93.869 (5)ꢃ
Symmetry codes: (i) x ꢁ 1; y ꢁ 1; z; (ii) x; y; z þ 1; (iii) x þ 1; y þ 1; z.
Data collection
Bruker APEX diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.680, Tmax = 0.775
22060 measured reflections
9159 independent reflections
4749 reflections with I > 2ꢄ(I)
Rint = 0.051
References
Abrahams, B. F., Hoskins, B. F., Robson, R. & Slizys, D. A. (2002). CrystEng-
Comm, 4, 478–482.
Batten, S. R. (2001). CrystEngComm. 18, 1–7.
Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460–1494.
Bruker (1997). SMART. Version 5.622. Bruker AXS Inc., Madison, Wisconsin,
USA.
Refinement
R[F2 > 2ꢄ(F2)] = 0.046
wR(F2) = 0.096
S = 0.83
631 parameters
H-atom parameteꢁrs3 constrained
˚
Áꢅmax = 0.74 e A
ꢁ3
˚
9159 reflections
Áꢅmin = ꢁ0.44 e A
Bruker (1999). SAINT. Version 6.02. Bruker AXS Inc., Madison, Wisconsin,
USA.
H atoms were treated as riding atoms in geometrically idealized
˚
positions, with C—H distances of 0.93 (aromatic) and 0.97 A
(methylene), and Uiso(H) values of 1.2Ueq(C).
Carlucci, L., Ciani, G. & Proserpio, D. M. (2003). Coord. Chem. Rev. 246, 247–
289.
Carlucci, L., Ciani, G. & Proserpio, D. M. (2005). Cryst. Growth Des. 5,
37–39.
Eddaoudi, M., Moler, D. B., Li, H., Chen, B., Reineke, T. M., O’Keeffe, M. &
Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330.
Fan, J., Zhu, H.-F., Okamura, T.-A., Sun, W.-Y., Tang, W.-X. & Ueyama, N.
(2003). Inorg. Chem. 42, 158–162.
Ma, J.-F., Liu, J.-F., Xing, Y., Jia, H.-Q. & Lin, Y.-H. (2000). J. Chem. Soc.
Dalton Trans. pp. 2403–2407.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT
(Bruker, 1999); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
SHELXTL-Plus (Sheldrick, 2008); software used to prepare material
for publication: publCIF (Westrip, 2009).
Ockwig, N. W., Delgado-Friedrichs, O., O’Keeffe, M. & Yaghi, O. M. (2005).
Acc. Chem. Res. 38, 176–182.
We thank the China–Japan Union Hospital of Jilin
University for generously supporting this study.
¨
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sun, L.-X., Qi, Y., Che, Y.-X., Batten, S. R. & Zheng, J.-M. (2009). Cryst.
Growth Des. 9, 2995–2998.
Westrip, S. P. (2009). publCIF. In preparation.
Yang, J., Ma, J.-F., Liu, Y.-Y., Ma, J.-C. & Batten, S. R. (2008). Cryst. Growth
Des. 8, 4383–4393.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GD3296). Services for accessing these data are
described at the back of the journal.
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m342 Li et al. [Zn(C12H6O4)(C14H14N4)]
Acta Cryst. (2009). C65, m340–m342