Bis(4,4′-bipyridine-κN)bis(hydrogen phthalato)-κ 2O,O′;κO-zinc(II)

Article abstract of DOI:10.1107/S0108270104017184

Hydrogen bonding inetractions in [Zn(c₈H₅O ₄)₂ (C₁₀H₈N₂) ₂] were investigated using crystallographic analysis. It was observed that each Zn^Ii atom, having a distorted tetragonal geometry, was coordinated by two nitrogen atoms from 4,4′-bipy ligands. It was found that the compound had a one-dimensional double chain structure via hydrogen bonding interactions. The results show that Zn^II atom has a trigonal-bipyramidal geometry.

Full text of DOI:10.1107/S0108270104017184

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
Bis(4,40-bipyridine-jN)bis(hydrogen
phthalato)-j2O,O0;jO-zinc(II)
En Tang, Yu-Mei Dai and Shen Lin*
Institute of Chemistry and Materials, Fujian Normal University, Fuzhou 350007,
People's Republic of China, and State Key Laboratory of Structural Chemistry, Fujian
Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou, Fujian 350002, People's Republic of China
Correspondence e-mail: shenlin_fz@163.com
Figure 1
A view of the structure of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level.
Received 21 June 2004
Accepted 14 July 2004
Online 11 August 2004
organic coordination polymer, (I), obtained by the hydro-
thermal reaction of 4,40-bipy, H2pht and ZnSO4Á7H2O.
The present X-ray single-crystal diffraction study reveals
that compound (I) consists of one ZnII atom, two Hpht
ligands and two 4,40-bipy ligands. As shown in Fig. 1, each ZnII
atom is four-coordinated tetrahedrally by two O atoms from
two Hpht ligands, with ZnÐO bond lengt0hs of 1.921 (4) and
The title compound, [Zn(C8H5O4)2(C10H8N2)2], was obtained
by the hydrothermal reaction of ZnSO4Á7H2O with phthalic
acid (H2pht) and 4,40-bipyridine (4,40-bipy). Crystallographic
analysis shows that it has a one-dimensional double-chain
structure via hydrogen-bonding interactions. Each ZnII atom,
adopting a distorted tetrahedral geometry, is coordinated by
two N atoms from two 4,40-bipy ligands, with ZnÐN distances
Ê
Ê
2.019 (4) A, and by two N atoms of two 4,4 -bipy ligands, with
of 2.054 (4) and 2.104 (4) A, and by two O atoms from
symmetry-related Hpht ligands, with ZnÐO distances of
Ê
ZnÐN bond distances of 2.054 (4) and 2.104 (4) A. However,
Ê
the ZnÐO4 distance of 2.496 (4) A suggests a non-negligible
Ê
1.921 (4) and 2.019 (4) A.
interaction with the uncoordinated O atom, which may be
described as a semi-chelating coordination mode (Guilera &
Steed, 1999). Hence, the ZnII atom may also be regarded as
having a trigonal±bipyramidal geometry. The aforementioned
bond lengths agree with those observed in similar Zn
complexes (Wu et al., 2002). Each 4,40-bipy ligand acts as a
terminal ligand to link to one ZnII atom. Within each 4,40-bipy
molecule, the two pyridine rings are twisted by 33.61 and
44.88ꢀ relative to one another.
Comment
The design and construction of novel coordination polymers
based on covalent interactions (Fujita et al., 1994) or supra-
molecular contacts, such as hydrogen bonds and ꢀ±ꢀ stacking
interactions (Desiraju, 1995), is a rapidly developing research
area, due not only to their fascinating structures (Blake et
al., 1999; Batten & Robson, 1998) but also to their unexpected
properties for potential applications (Matsumoto et al., 1999;
Chui et al., 1999). The design of coordination polymers is
greatly in¯uenced by factors such as the coordination nature
As each Hpht and 4,40-bipy ligand acts as a terminal
ligand, the uncoordinated carboxylic acid groups from the
Hpht ligands link to the uncoordinated N atoms from the
4,40-bipy ligands via hydrogen bonding. The O1Á Á ÁN3 and
Ê
O8Á Á ÁN4 distances are 2.643 (5) and 2.665 (6) A, respectively,
indicating strong hydrogen bonds. The two C O bonds, viz.
Ê
C15ÐO2 and C8ÐO7, are 1.191 (6) and 1.218 (7) A, respec-
tively; these are much shorter than the other CÐO bonds.
It is interesting to note that two ZnII atoms, two 4,40-bipy
molecules and two Hpht anions produce a 30-membered
Ê
grid, with a ZnÁ Á ÁZn distance of 14.024 (7) A, via coordination
covalent bonds and hydrogen bonds. These grids, by sharing
ZnII atoms, extend to form double zigzag chains propagating
along the c axis (Fig. 2).
In contrast with other metal±organic frameworks
constructed with 4,40-bipy ligands and H2pht (Ma et al., 2003;
Lightfoot & Sneddon, 1999; Suresh et al., 2001), 4,40-bipy acts
as a terminal ligand in (I) instead of as a ꢁ2-bridging ligand
of the metal ion, the structural characteristics of the poly-
dentate organic ligand, the metal±ligand ratio, and the
possible counter-ion. We report here the title novel metal±
Acta Cryst. (2004). C60, m433±m434
DOI: 10.1107/S0108270104017184
# 2004 International Union of Crystallography m433

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
ZnÐO5
ZnÐO3
ZnÐN1
1.921 (4)
2.019 (4)
2.054 (4)
ZnÐN2
ZnÐO4
2.104 (4)
2.496 (5)
O5ÐZnÐO3
O5ÐZnÐN1
O3ÐZnÐN1
O5ÐZnÐN2
O3ÐZnÐN2
106.29 (19)
120.43 (19)
123.09 (16)
113.3 (2)
N1ÐZnÐN2
O5ÐZnÐO4
O3ÐZnÐO4
N1ÐZnÐO4
N2ÐZnÐO4
94.83 (16)
90.3 (2)
57.19 (14)
90.31 (15)
148.40 (16)
Figure 2
The double zigzag chains formed along the c axis of the crystal of (I), with
hydrogen bonds shown as dotted lines.
94.71 (15)
and this results in a different structural topology. This also
suggests that the combination of coordination covalent bonds
and hydrogen bonds is an important tool for the construction
of supramolecular architectures.
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O1ÐH1OÁ Á ÁN3i
0.83 (6)
0.83 (6)
1.82 (6)
1.84 (6)
2.643 (5)
2.665 (6)
175 (7)
172 (8)
O8ÐH8OÁ Á ÁN4ii
Experimental
A mixture of ZnSO4Á7H2O (0.144 g, 0.5 mmol), 4,40-bipy (0.080 g,
0.5 mmol) and H2pht (0.166 g, 0.5 mmol) in EtOH±H2O (1:8 v/v,
18 ml) was sealed in a Te¯on-lined stainless steel vessel and heated at
438 K for 36 h under autogeneous pressure. A large quantity of
colourless crystals of (I) (yield 56%) was obtained after the solution
had cooled to room temperature.
Symmetry codes: (i) 1 x; y; z; (ii) 1 x; y; 1 z.
(Siemens, 1994); program(s) used to re®ne structure: SHELXTL
(Siemens, 1994); molecular graphics: SHELXTL (Bruker, 2001);
software used to prepare material for publication: SHELXTL
(Bruker, 2001).
Crystal data
The authors are grateful for ®nancial support from the
Natural Science Foundation of Fujian Province, China (grant
No. 2002J001), the Foundation for University Key Teachers of
the Ministry of Education, and the Science Foundation of the
State Key Laboratory of Structural Chemistry (grant No.
030071).
[Zn(C8H5O4)2(C10H8N2)2]
Mr = 708.00
Triclinic, P1
a = 7.5100 (3) A
b = 10.0003 (4) A
Z = 2
Dx = 1.507 Mg m
Mo Kꢂ radiation
3
Ê
Cell parameters from 3960
re¯ections
Ê
Ê
c = 22.0821 (6) A
ꢅ = 0.9±25.0ꢀ
ꢁ = 0.85 mm
T = 293 (2) K
1
ꢂ = 84.307 (1)ꢀ
ꢃ = 88.084 (1)ꢀ
ꢄ = 71.020 (1)ꢀ
Block, colourless
0.56 Â 0.26 Â 0.18 mm
3
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SQ1166). Services for accessing these data are
described at the back of the journal.
Ê
V = 1560.52 (10) A
Data collection
Siemens SMART CCD area-
detector diffractometer
' and ! scans
Absorption correction: empirical
(SADABS; Sheldrick, 1996)
Tmin = 0.767, Tmax = 0.858
8036 measured re¯ections
5502 independent re¯ections
4273 re¯ections with I > 2ꢆ(I)
Rint = 0.029
References
ꢅmax = 25.0ꢀ
Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460±1494.
Blake, A. J., Champness, N. K., Hubbersley, P., Li, W. S., Withersly, M. A. &
Schoder, M. (1999). Coord. Chem. Rev. 183, 117±138.
Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison,
Wisconsin, USA.
Chui, S. S.-Y., Lo, S. M.-F., Charmant, S. P. H., Orpen, A. G. & Williams, L. D.
(1999). Science, 283, 1148±1150.
Desiraju, G. R. (1995). Angew. Chem. Int. Ed. Engl. 34, 2311±2327.
Fujita, M., Kwon, Y.-J., Washizu, S. & Ogura, K. (1994). J. Am. Chem. Soc. 116,
1151±1152.
h = 5 ! 8
k = 11 ! 11
l = 23 ! 26
Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.063
wR(F2) = 0.177
S = 1.07
5390 re¯ections
448 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[ꢆ2(Fo2) + (0.0795P)2
+ 3.685P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢆ)max < 0.001
Guilera, G. & Steed, J. W. (1999). Chem. Commun. pp. 1563±1564.
Lightfoot, P. & Snedden, A. (1999). J. Chem. Soc. Dalton Trans. pp. 3549±3551.
Ma, C., Chen, C., Liu, Q., Liao, D., Li, L. & Sun, L. (2003). New J. Chem. 27,
890±894.
3
Ê
Áꢇmax = 0.75 e A
3
Ê
0.64 e A
Áꢇmin
=
Matsumoto, N., Sunatsuki, Y., Miyasaka, H., Hashimoto, Y., Luneau, D. &
Tuchagues, J.-P. (1999). Angew. Chem. Int. Ed. 38, 171±173.
H atoms bonded to C atoms were positioned geometrically and
Ê
re®ned using a riding model [CÐH = 0.93 A and Uiso(H) =
È
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
Siemens (1994). SAINT and SHELXTL (Release 5.03). Siemens Analytical
X-ray Instruments Inc., Madison, Wisconsin, USA.
Siemens (1996). SMART. Version 4.0. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Suresh, E., Boopalan, K., Jasra, R.-V. & Bhadbhade, M.-M. (2001). Inorg.
Chem. 40, 4078±4080.
1.2Ueq(C)]. The hydroxy H atoms were located from difference maps.
Their coordinates were re®ned subject to OÐH distance restraints of
Ê
0.83 (6) A and with the Uiso values ®xed at 1.5Ueq(O).
Data collection: SMART (Siemens, 1996); cell re®nement: SMART
and SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL
(Siemens, 1994); program(s) used to solve structure: SHELXTL
Wu, C.-D., Lu, C.-Z., Yang, W.-B., Zhuang, H.-H. & Huang, J.-S. (2002). Inorg.
Chem. 41, 3302±3307.
ꢁ
m434 Tang, Dai and Lin [Zn(C8H5O4)2(C10H8N2)2]
Acta Cryst. (2004). C60, m433±m434