A novel metal-organic ternary topology constructed from triangular, square and tetrahedral molecular building blocks

Article abstract of DOI:10.1039/b712905j

A novel metal-organic network [Cu₄(5-NH₂-1,3-bdc) ₄(pyridine)₂(H₂O)₂]_n, displaying an unprecedented topology has been constructed utilizing the different coordinating functional groups of 5-NH₂-1,3-bdc to generate a ternary network based upon vertex-linked triangular, square and tetrahedral molecular building blocks (MBBs). The Royal Society of Chemistry.

Full text of DOI:10.1039/b712905j

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A novel metal–organic ternary topology constructed from triangular,
square and tetrahedral molecular building blocks
Gregory J. McManus, Zhenqiang Wang, Derek A. Beauchamp and Michael J. Zaworotko*
Received (in Cambridge, UK) 21st August 2007, Accepted 3rd October 2007
First published as an Advance Article on the web 16th October 2007
DOI: 10.1039/b712905j
building block in 1 is a pseudo-tetrahedral MBB. The five-
coordinate Cu(RCO2)2(RNH2)2L chromophore is present in over
50 crystal structures in the CSD.
A
novel metal–organic network [Cu4(5-NH2-1,3-bdc)4-
(pyridine)2(H2O)2]n, displaying an unprecedented topology has
been constructed utilizing the different coordinating functional
groups of 5-NH2-1,3-bdc to generate a ternary network based
upon vertex-linked triangular, square and tetrahedral molecular
building blocks (MBBs).
USF-5 is closely related to the previously reported USF-412 in
that each triangular MBB is linked to one square MBB and two
pseudo-tetrahedral MBBs which in turn are each linked to four
triangular MBBs (Fig. 2). However, USF-5 is significantly different
than USF-4 and previously reported (3,4)-connected networks, the
long vertex symbols, (4?82?8)4(8?8?82?82?128?128) (4?4?8?8?8?1213)2
being hitherto unprecedented.15 Analysis of the physical properties
observed in 1 and other ternary nets remains an ongoing study in
our laboratory.
Crystal engineering1 offers a paradigm for the self-assembly of
infinite and discrete nanoscale organic2 and metal–organic/
coordination3 structures via a bottom-up ‘‘molecular building
block (MBB) approach’’.4 Structure–function relationships with
properties such as magnetism,5 luminescence,6 and permanent
porosity7 have thereby been developed in a systematic manner.
Wells catalogued network structures in crystals8 and spawned the
‘‘node-and-spacer’’ methodology9 which simplifies design since it
reduces MBBs into topological points and lines. Interpretation and
design of nets can also take into account the geometrical shape
of the MBBs by representing nets as vertex-linked polygons or
polyhedra (VLPP).10
When the experimental conditions of 1 were altered to utilize
4-picoline instead of pyridine we obtained two products: green
crystals isostructural to 1;16 and yellow crystals of [Cu(5-NH2-1,3-
bdc)(4-picoline)]n, 2. The 2-D honeycomb framework of 2 is
composed of 3-connected 5-NH2-1,3-bdc ligands and five-
coordinate Cu(II) metal centers which also serve as 3-connected
nodes. A series of Zn(II) analogues of this structure has recently
been reported.17
Topologically the simplest nets are unitary nets comprised of
only one type of MBB for which the topology of the net is directed
by the geometry and arrangement of the MBBs: (10,3)-a
(triangular MBBs), diamondoid (tetrahedral MBBs), NbO (square
MBBs), and primitive cubic (octahedral MBBs) nets. The VLPP
approach comes into its own for binary nets sustained by pairs of
polygonal or polyhedral MBBs and even the simplest combina-
tions of MBBs can result in structural diversity as exemplified by
(3,4)-connected nets.11 Nevertheless, the design of novel topologies
remains challenging and is a dominant theme in crystal engineering
since new topologies can serve as ‘‘blueprints’’ for the design of
new classes of materials. We have proposed a design strategy based
upon the VLPP approach for the synthesis of ternary nets
sustained by a combination of three distinct polygons or
polyhedra12 utilizing zinc(II), which is known to offer structural
diversity. In this communication we delineate how 3-connected
triangular MBBs with different coordinating functional groups
such as, 5-NH2-1,3-bdc (5-amino-1,3-benzenedicarboxylate)13 can
promote the formation of two distinct metal centers and a ternary
net (Fig. 1) with a new topology, USF-5: [Cu4(5-NH2-1,3-bdc)4-
(pyridine)2(H2O)2]n, 1.{
In summary, we have demonstrated a second simple strategy
for the design of ternary nets, i.e. triangular MBBs containing
different coordinating functional groups (i.e. carboxylates and
amines) which promote the formation of geometrically and
chemically distinct metal centers. Further studies will investigate
the design of ternary nets from a wider range of geometrical and
chemical MBBs, including preformed MBBs.
The square MBB utilized in 1 is based upon the ubiquitous
dicopper tetracarboxylate, Cu2(RCO2)4L2, or ‘‘paddlewheel’’
which is present in over 600 crystal structures in the Cambridge
Structural Database (CSD).14 The Cu(5-NH2-1,3-bdc)4/3(H2O)]n.
Fig. 1 Molecular building blocks (MBBs) employed in the ternary net
USF-5: (a) 5-NH2-1,3-bdc – triangular MBB; (b) Cu2(RCO2)4L2 – square
MBB; (c) Cu(RCO2)2(RNH2)2L – pseudo-tetrahedral MBB.
Department of Chemistry, University of South Florida, 4202 E. Fowler
Ave., CHE 205, Tampa, Florida, 33620, USA. E-mail: xtal@usf.edu;
Fax: 1 813 974 3203; Tel: 1 813 974 4129
5212 | Chem. Commun., 2007, 5212–5213
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Data were collected on a Bruker SMART-APEX CCD diffractometer
˚
using Mo-Ka radiation (l = 0.71073 A). Crystal data were corrected for
Lorentz and polarization effects, and the SADABS program was used for
absorption correction. The structures were solved by direct methods and
the structure solution and refinement was based on |F2|. All non-hydrogen
atoms were refined with anisotropic displacement parameters, whereas
hydrogen atoms were placed in calculated positions and given isotropic U
values 20% higher than the atom to which they are bonded. All
crystallographic calculations were conducted with the SHELXTL software
suite.
CCDC 658210 and 658211. For crystallographic data in CIF or other
electronic format see DOI: 10.1039/b712905j
1 (a) G. M. J. Schmidt, Pure Appl. Chem., 1971, 27, 647; (b) R. Pepinsky,
Phys. Rev., 1955, 100, 971; (c) B. Moulton and M. J. Zaworotko, Chem.
Rev., 2001, 101, 1629; (d) D. Braga, Chem. Commun., 2003, 2751.
2 (a) L. R. MacGillivray and J. L. Atwood, Nature, 1997, 389, 469; (b)
O. Ugono and K. T. Holman, Chem. Commun., 2006, 2144; (c) H. M. El-
Kaderi, J. R. Hunt, J. L. Mendoza-Cortes, A. P. Coˆte´, R. E. Taylor,
M. O’Keeffe and O. M. Yaghi, Science, 2007, 316, 268; (d)
P. K. Thallapally, G. O. Lloyd, T. B. Wirsig, M. W. Bredenkamp,
J. L. Atwood and L. J. Barbour, Chem. Commun., 2005, 5272.
3 (a) S. Kitagawa, R. Kitaura and S. Noro, Angew. Chem., Int. Ed., 2004,
116, 2388; (b) M. Fujita, K. Umemoto, M. Yoshizawa, N. Fujita,
T. Kusukawa and K. Biradha, Chem. Commun., 2001, 509; (c) C. Janiak,
Dalton Trans., 2003, 2781; (d) A. Y. Robin and K. M. Fromm, Coord.
Chem. Rev., 2006, 250, 2127; (e) S. L. James, Chem. Soc. Rev., 2003, 32,
276.
4 (a) Y. Liu, V. Ch. Kravtsov, R. Larsen and M. Eddaoudi, Chem.
Commun., 2006, 1488; (b) J. J. Perry, V. Ch. Kravstov, G. J. McManus
and M. J. Zaworotko, J. Am. Chem. Soc., 2007, 129, 10076.
5 (a) S. R. Batten, B. F. Hoskins, B. Moubaraki, K. S. Murray and
R. Robson, J. Chem. Soc., Dalton Trans., 1999, 2977; (b) C. S. Campos-
Fernandez, R. Clerac and K. R. Dunbar, Angew. Chem., Int. Ed., 1999,
38, 3477; (c) M. Kurmoo and C. J. Kepert, New J. Chem., 1998, 22,
1515.
6 (a) G. J. McManus, J. J. Perry, M. Perry, B. D. Wagner and
M. J. Zaworotko, J. Am. Chem. Soc., 2007, 129, 9094; (b) W. J. Rieter,
K. M. Taylor and W. Lin, J. Am. Chem. Soc., 2007, 129, 9852.
7 (a) M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keeffe
and O. M. Yaghi, Science, 2002, 295, 469; (b) S. Hasegawa, S. Horike,
R. Matsuda, S. Furukawa, K. Mochizuki, Y. Kinoshita and
S. Kitagawa, J. Am. Chem. Soc., 2007, 129, 2607; (c) X. Zhao,
B. Xiao, A. J. Fletcher, K. M. Thomas, D. Bradshaw and M. J.
Rosseinsky, Science, 2004, 306, 1012; (d) K. L. Mulfort and J. T. Hupp,
J. Am. Chem. Soc., 2007, 129, 9604.
Fig. 2 (a) Triangular 5-NH2-1,3-bdc units linked to one square MBB
and two pseudo-tetrahedral MBBs. (b) Crystal structure of 1 viewed down
the [100] axis in stick representation (pyridine and H2O ligands have been
deleted for clarity). (c) Schematic representation of 1 in VLPP format
viewed down the [100] axis.
The authors gratefully acknowledge the financial support of the
National Science Foundation (DMR-0101641).
8 A. F. Wells, Three-Dimensional Nets and Polyhedra, Wiley, New York,
1977.
9 S. R. Batten and R. Robson, Angew. Chem., Int. Ed., 1998, 37, 1460.
10 (a) J. Lu, A. Mondal, B. Moulton and M. J. Zaworotko, Angew. Chem.,
Int. Ed., 2001, 40, 2113; (b) G. J. McManus, Z. Wang and M. J.
Zaworotko, Cryst. Growth Des., 2004, 4, 11; (c) H. Chun, D. Kim,
D. N. Dybtsev and K. Kim, Angew. Chem., Int. Ed., 2004, 116, 989.
11 (a) B. Chen, M. Eddaoudi, S. T. Hyde, M. O’Keeffe and O. M. Yaghi,
Science, 2001, 291, 1021; (b) S. S. Y. Chui, S. M. F. Lo, J. P. H.
Charmant, A. G. Orpen and I. D. Williams, Science, 1999, 283, 1148; (c)
B. F. Abrahams, S. R. Batten, H. Hamit, B. F. Hoskins and R. Robson,
Angew. Chem., Int. Ed. Engl., 1996, 35, 1690; (d) D. N. Dybtsev,
H. Chun and K. Kim, Chem. Commun., 2004, 1594; (e) S. Hong, Y. Zou,
D. Moon and M. S. Lah, Chem. Commun., 2007, 1707; (f) Y. H. Liu
and M. T. Ding, Acta. Crystallogr., Sect. E., 2007, 63, m1828.
12 Z. Wang, V. Ch. Kravtsov and M. J. Zaworotko, Angew. Chem., Int.
Ed., 2005, 44, 2877.
Notes and references
{ Experimental data for 1: Green crystals form in 38% yield within one day
of layering a 10.0 mL methanolic solution of Cu(NO3)2?2.5H2O (116 mg,
0.499 mmol) through a 10.0 mL methanol buffer layer onto a 10.0 mL
methanolic solution containing 5-amino-1,3-benzenedicarboxylic acid
(91 mg, 0.50 mmol) and pyridine (0.12 mL, 1.5 mmol). Experimental data
for 2: Green (compound 1) and yellow (compound 2) crystals form within
one day of layering a 10.0 mL methanolic solution of Cu(NO3)2?2.5H2O
(116 mg, 0.499 mmol) through a 10.0 mL methanol buffer layer onto a
10.0 mL methanolic solution containing 5-amino-1,3-benzenedicarboxylic
acid (91 mg, 0.50 mmol) and 4-picoline (0.15 mL, 1.5 mmol).
Crystallographic data for 1: C21H30Cu2N3O15.50, Mr = 699.56, orthor-
˚
hombic, space group Ibam, a = 14.669(7), b = 16.833(8), c = 24.743(11) A,
3
13 There are 23 crystal structures containing 5-amino-1,3-benzenedi-
carboxylate coordinated to metal centers deposited in the CSD V5.28
(Nov. 2006 + 2 updates)—none of which can be interpreted as a
ternary net.
V = 6109(5) A , Z = 8, Dc = 1.521 g cm23, m = 1.464 mm21, F(000) = 2872,
˚
2hmax = 50.22u (217 ¡ h ¡ 16, 28 ¡ k ¡ 20, 229 ¡ l ¡ 29), T = 298(2)
K, 14695 measured reflections, R1 = 0.0671 for 1283 reflections (I . 2s(I)),
wR2 = 0.1883 for 2787 independent reflections (all data) and 201
parameters, GOF = 0.882. Crystallographic data for 2: C14H12CuN2O4,
14 F. H. Allen, Acta Crystallogr., Sect. B, 2002, 58, 380.
15 (a) O. V. Dolomanov, A. J. Blake, N. R. Champness and M. Schro¨der,
J. Appl. Crystallogr., 2003, 36, 1283; (b) M. O’Keeffe, M. Eddaoudi,
H. Li, T. Reineke and O. M. Yaghi, J. Solid State Chem., 2000, 152, 3;
(c) M. O’Keeffe and S. T. Hyde, Zeolites, 1993, 13, 592.
Mr = 335.80, monoclinic, space group P21/n, a = 12.7210(18), b =
3
˚
˚
7.7387(11), c = 14.005(2) A, b = 108.106(2)u, V = 1310.4(3) A , Z = 4, Dc =
1.702 g cm23, m = 1.684 mm21, F(000) = 684, 2hmax = 50.28u (213 ¡ h ¡
15, 29 ¡ k ¡ 9, 216 ¡ l ¡ 16), T = 298(2) K, 6452 measured reflections,
R1 = 0.0447 for 1776 reflections (I . 2s(I)), wR2 = 0.1139 for 2316
independent reflections (all data) and 191 parameters, GOF = 1.041.
˚
16 Unit cell parameters: a = 14.526(2), b = 17.382(3), c = 24.444(4) A,
3
V = 6171.9(17) A .
˚
17 K. O. Kongshaug and H. Fjellva˚g, Inorg. Chem., 2006, 45, 2424.
This journal is ß The Royal Society of Chemistry 2007
Chem. Commun., 2007, 5212–5213 | 5213