Hydrothermal synthesis, structure, and magnetic properties of a three-dimensional polymeric NiII complex, [Ni(bpp)(NIP)(H 2O)]n (bpp = 1,3-di(4-pyridyl)propane, NIP = 5-nitroisophthalate)

Article abstract of DOI:10.1002/zaac.200500199

A three-dimensional polymeric Ni^II complex, [Ni(bpp)-(NIP) (H₂O)]_n (bpp = 1,3-di(4-pyridyl)propane and NIP = 5-nitro-isophthalate), has been synthesized and characterized. The coordination number of the nickel atom is six (NiN₂O₄) and the coordination environment around the Ni^II atom may be described as a distorted octahedron in which two nitrogen atoms of bpp ligand occupy the cis positions. The effective magnetic moment for this complex indicate that the interactions between two Ni^II atoms through the effective exchange media are antiferromagnetic. Self-assembly of these compounds in the solid state via π-π-stacking interactions is discussed.

Full text of DOI:10.1002/zaac.200500199

Hydrothermal Synthesis, Structure, and Magnetic Properties of a
Three-dimensional Polymeric NiII Complex, [Ni(bpp)(NIP)(H2O)]n
(bpp ؍ 1,3-di(4-pyridyl)propane, NIP ؍ 5-nitroisophthalate)
Hong-Ping Xiaoa, Jia-Guo Wanga, Xin-Hua Lia, and Ali Morsali*,b
a Wenzhou/ China, School of Chemistry and Materials Science, Wenzhou Normal College
b Tehran/Iran, Department of Chemistry, School of Sciences, Tarbiat Modarres University
Received April 25th, 2005.
Abstract. A three-dimensional polymeric NiII complex, [Ni(bpp)-
(NIP)(H2O)]n (bpp ϭ 1,3-di(4-pyridyl)propane and NIP ϭ 5-nitro-
isophthalate), has been synthesized and characterized. The coordi-
nation number of the nickel atom is six (NiN2O4) and the coordina-
tion environment around the NiII atom may be described as a di-
storted octahedron in which two nitrogen atoms of “bpp” ligand
occupy the cis positions. The effective magnetic moment for this
complex indicate that the interactions between two NiII atoms
through the effective exchange media are antiferromagnetic. Self-
assembly of these compounds in the solid state via πϪπ-stacking
interactions is discussed.
Keywords: Nickel; 5-Nitroisophthalate; 1,3-Di(4-pyridyl)propane;
Three-dimensional polymer; Magnetic properties
The design of crystal structures and control of molecular arrange-
ments of coordination polymers has attracted much attention in
recent years [1Ϫ10]. The metal-organic coordination polymers of
1,3-di(4-pyridyl)propane (bpp) have attracted continuous attention
in recent years [11Ϫ13]. This is a flexible ligand and it has three
different conformations, TT, TG and GG (Figure 1). The polytypic
5-nitroisophethalate (NIP) anion is also an interesting ligand, with
both carboxylate and nitro groups available as coordinating group-
s.The incorporation of the flexible ligand such as “bpp” and the
polytypic ligand such as “NIP” in the design and preparation of
new coordination polymers is of considerable interest for potential
application in control of the properties of metal-organic coordi-
nation polymers. In this paper, we report the synthesis, structure
and magnetic properties of a 3D polymeric NiII complex of 1,3-
di(4-pyridyl)propane (bpp) and 5-nitroisophthalate (NIP) ligands,
[Ni(bpp)(NIP)(H2O)]n.
Experimental Section
Infrared spectra were measured on a Perkin Elmer 2000 system in
the range 4000Ϫ400 cmϪ1 with KBr disk technique. C, H and N
were analyzed using a Carlo-Erba 1112 Elemental Analyzer. Vari-
able-temperature magnetic susceptibilities were determined with a
crystalline sample in the temperature 2-300 K on a Quantum De-
sign MPMS SQUID magnetometer at 2T. The field dependent
magnetizations were measured at 2K in the field range 1-50 T. Cor-
rections were applied for diamagnetism calculated from Pascal con-
stants. Effective magnetic moments were calculated by the equation
μeff ϭ 2.828(χMT)1/2, where χM is the magnetic susceptibility per
formula unit. Crystallographic measurements of a singly crystal of
dimensions 0.28 x 0.12 x 0.09 mm were made at 298(2) K on a
Bruker APEX area-detector diffractometer. The intensity data were
collected within the range 1.66° Յ θ Յ 26.00° using graphite mon-
˚
ochromated MoKa radiation (λ 0.71073 A). Accurate unit-cell par-
ameters and an orientation matrix for data collection were ob-
tained from least-squares refinement. The intensities of 22463 un-
ique reflections were collected, from which 4150 with I > 2σ(I) were
used in the refinement. The structure was solved by direct methods
and refined by full-matrix least-squares techniques on F2. The posi-
tions of the H-atoms were idealized and included in the calcu-
lations of the structure factors as fixed contributions. Each H-atom
was assigned an isotopic thermal parameter. R and Rw with good-
ness of fit on F2 1.369 are 0.1275 and 0.2325. The reason for the
relatively high values of the R factors is the poor quality of the
crystal.
Fig. 1 The general structure of the “NIP” ligand and different con-
formations of “bpp“.
Preparation of [Ni(bpp)(NIP)(H2O)]n
Nickel(II) acetate tetrahydrate (0.5 mmol), 5-nitroisophthalic acid
(0.5 mmol) and 1,3-di(4-pyridyl)propane (0.5 mmol) were placedin
a 30 ml, Teflon-lined, stainless-steel Parr bomb together with water
(20 ml). The bomb was heated at 423K for six days. The bomb was
cooled slowly to room temperature to furnish green crystals. Yield:
0.125g, 52 %, (Found: C: 52.13, H: 3.97, N: 8.59: calculated for
C21H19N3NiO7; C: 52.05, H: 3.92, N: 8.67 %).
* Dr.Ali Morsali
Department of Chemistry, School of Science
Tarbiat Modarres University
P.O.Box 14155-4838
Tehran / Iran
E-mail: Morsali a@yahoo.com
2976
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
DOI: 10.1002/zaac.200500199
Z. Anorg. Allg. Chem. 2005, 631, 2976Ϫ2978

Three-dimensional Polymeric NiII Complex
Fig. 2 The coordination sphere of the nickel atom in [Ni(bpp)(NI-
P)(H2O)]n.
ii
˚
Selected bond lengths/A and bond angles/°: Ni1-O3 2.03(5), Ni1-
O7 2.08(6), Ni1-N1 2.08(6), Ni1-O1 2.09(5), Ni1-N2i 2.10(7), Ni1-
O2 2.30(6), O3ii-Ni1-O7 87.2(2), O3ii-Ni1-N1 91.8(2), O7-Ni1-N1
91.6(3), O3ii-Ni1-O1 172.6(2), O7-Ni1-O1 88.1(2), N1-Ni1-O1
94.1(2), O3ii-Ni1-N2i 91.4(3), O7-Ni1-N2i 175.2(2), N1-Ni1-N2i
93.1(3), O1-Ni1-N2i 92.7(3), O3i-Ni1-O2 114.3(2), O7-Ni1-O2
86.2(2), N1-Ni1-O2 153.6(2), O1-Ni1-O2 59.6(2), N2i-Ni1-O2
90.2(3).
Fig. 3 A view of the [100] layer of the coordination polymer
[Ni(bpp)(NIP)(H2O)]n
˚
Table 1 Hydrogen bonds (in A and °) for [Ni(bpp)(NIP)(H2O)]n.
i: Ϫxϩ1/2,yϩ1/2,Ϫzϩ1/2 ii: xϩ1/2, y,Ϫz
D-H...A
d(D-H)
0.82
0.81(2)
d(H...A)
2.05
1.84(3)
d(D...A)
2.763(8)
2.653(8)
<(DHA)
144.9
173(11)
O(7)-H(7B)...O(2)v
O(7)-H(7C)...O(4)vi
IR (cmϪ1) selected bonds: 3431(s), 3088(m), 2946(w), 1630(vs),
1543(s), 1460(s), 1359(vs), 1223(m), 1079(m), 1023(w), 928(w),
817(m), 790(m) and 725(s).
v: Ϫx,Ϫyϩ2,Ϫzϩ1; vi: ϪxϪ1/2,Ϫyϩ2,z
The [Ni(bpp)(NIP)(H2O)]n is involved in hydrogen bonding. The
coordinated water molecule is involved in hydrogen bonding acting
as hydrogen-bond acceptors with O atoms of carboxylate group
from “NIP” as potential hydrogen-bond donors and the hydrogen
bond parameters are given in the Table 1.
Results and Discussion
Determination of the structure of the [Ni(bpp)(NIP)(H2O)]n by
XϪray crystallography showed [14] the complex in the solid state
(Fig.3) to be a polymeric species and is 3D coordination polymer.
The nickel atoms are linked by oxygen and nitrogen atoms and can
be considered to be sixϪcoordinate with O4N2 donor atoms array.
The coordination around Ni atom is distorted octahedral and three
oxygen atoms of “NIP“, two nitrogen atoms of the “bpp” ligands
and one oxygen atom of the water molecule chelate the Ni atom.
Two nitrogen atoms from “bpp” ligands are in cis position (the N1-
Ni1-N2ii angle is 93.1(3)°). The intraϪchain Ni···Ni distances by
There is both face-to-face and edge-to-face π-π stacking [17Ϫ19]
interactions between aromatic rings belonging to adjacent chains
in this network, as shown in Figure 3. The phenyl groups of “NIP”
ligands are almost parallel and separated by a distance of about
˚
3.5 A, close to that of the layers in graphite. Parallel arrays of the
planes of the aromatic moieties indicate that these interactions are
of the face-to-face “π -stacking” type, rather than “edge-to-face”
or “vertex-to-face” types [20Ϫ22]. The centroid-centroid distance
˚
“bpp” and “NIP” ligands are 11.18 and 8.87 A, respectively.
˚
Each “NIP” anion acts as a three-dentate ligand, connecting two
Ni2ϩ ions. The one of carboxylate groups of the “NIP” ligand act
as bidentate and other carboxylate group of this ligand act only as
monodentate mode. The oxygen atoms of the nitro group is not
coordinated to Ni atoms. This is consistent with the assumption
that carboxylate group is the stronger binding ligand than the nitro
of phenyl groups is 3.71 A and angle between the ring normal and
the centroid vectors is 18.99°. There is also edge-to-face interac-
˚
tions between the “bpp” ligands and slippage distance is 3.78 A.
The plot of χmT versus T for the title complex is shown in Figure
4a. The χmT value at 300 K is 0.92 cm3 K molϪ1, which decreases
smoothly from 300 to 10 K and decreases sharply to reach 0.41
μB cm3 K molϪ1 at 2K. The μeff value of per NiII ion (2.72 μB) at
room temperature is slightly lower than the spin-only value for NiII
(2.83 μB). The data fit the Curie-Weiss law χ ϭ C(T - Θ)Ϫ1, with
the parameters of Θ ϭ Ϫ1.26 K and C ϭ 0.925, indicating that the
interactions between two NiII atoms through the effective exchange
media are antiferromagnetic. The M value increases from 0.11 Nβ
at 1 T to 1.00 Nβ at 10 T (Figure 4b), consistent with the expected
value for an Ni magnetic moments with spin ST ϭ 1. With the
increasing of the magnetic field, the M value increases sharply to
reach the value of 3.11 Nβ at 50 T, indicating that the spins have
Ϫ
group (-CO2 > NO2Ϫ).
There are three conformations of the “bpp” ligand. This flexible
ligand usually assumes TT, TG or GG conformations (Figure 1)
with quite different N-to-N distances (within the 6.7-10.1 A range)
[14]. The TT and TG conformations have been fairly widely enco-
untered and such structures tend to pack efficiently, whereas the
GG conformations are quite rare in the context of coordination
polymers [15Ϫ16]. Self-assembly of “bpp” ligand in this complex
˚
˚
is the GG conformation type with a N-to-N distance of 8.30 A
(Figure 3).
Z. Anorg. Allg. Chem. 2005, 631, 2976Ϫ2978
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2977

H.-P. Yiao, J.-G. Wang, X.-H. Li, A. Morsali
[3] S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem. 2004, 116,
2388; Angew. Chem. Int. Ed. 2004, 43, 2334.
[4] C. Janiak, J. Chem. Soc., Dalton Trans. 2003, 2781.
[5] S. L. James, Chem. Soc. Rev. 2003, 32, 276.
[6] M. Eddaoudi, J. Kim, D. Vodak, A. Sudik, J. Wachter, M.
O’Keeffe, O. M. Yaghi, PNAS 2002, 99, 4900.
[7] S.-L. Zheng, X.-M. Chen, Aust. J. Chem. 2004, 57, 703.
[8] D. Maspoch, D. Ruiz-Molina, J. Veciana, J. Mater. Chem.
2004, 14, 2713.
[9] S. R. Batten, K. S. Murray, Coord. Chem. Rev. 2003, 246, 103.
[10] L. Carlucci, G. Ciani, D. Proserpio, Coord. Chem. Rev. 2003,
246, 247.
[11] M. J. Plater, M. R. St. J. Foreman, T. Gelbrich, S. J. Coles, M.
B. Hursthouse, J. Chem. Soc., Dalton Trans. 2000, 3065.
[12] M.-L. Tong, Y.-M. Wu, J. Ru, X.-M. Chen, H. C. Chang, S.
Kitagawa, Inorg. Chem. 2002, 41, 4846.
Fig. 4 (a) Plot of χmT at 2T and χmϪ1T vs T of the complex, (b)
Magnetization (solid square) of the complex at 2K as a function
of the applied magnetic field (1-50 T).
[13] E.-Q. Gao, S.-Q. Bai, Z.-M. Wang, C.-H. Yan, J. Chem. Soc.,
Dalton Trans. 2003, 1759.
[14] Crystal Data: C21H19N3NiO7, M 484.10, orthorhombic, space
deviated from the antiferromagnetic coupling and aligned with the
applied field.
group Pnna,
a
ϭ
16.8886(19),
b
ϭ
13.9336(16),
c
ϭ
3
˚
˚
17.941(2) A, V ϭ 4221.8(8) A , Dc (Z ϭ 8 f.u.) ϭ 1.523 Mg/
m3, F(000) 2000. Specimen: 0.28 x 0.12 x 0.09 mm; R(wR) ϭ
0.1275 (0.2325) for 4150 reflections with I>2σ(I).
[15] L. Carlucci, G. Ciani, D. M. Proserpio, S. Rizzato, Cryst. Eng.
Comm. 2002, 4, 121.
Supplementary material: Crystallographic data for the structure re-
ported in the paper have been deposited with the Cambridge Crys-
tallographic Data Centre as supplementary publication no, CCDC-
267309. Copies of the data can be obtained on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [Fax: ϩ
44Ϫ1223/336033; eϪmal: deposit@ccdc.cam.ac.uk].
[16] F. M. Tabellion, S. R. Seidel, A. M. Arif, P. J. Stang, J. Am.
Chem. Soc., 123 2001, 123, 11982.
Acknowledgement. The authors acknowledge financial support by
Zhejiang Provincial Natural Science Foundation (No. Y404294),
Wenzhou science and technology project of China (No.
S2003A008), the ’551’ Distinguished Person Foundation of
Wenzhou and by Tarbiat Modarres University.
[17] R. D. Hancock, M. S. Shaikjee, S. M. Dobson, J. C. A. Boey-
ens, Inorg. Chim. Acta 154 (1988) 229.
[18] I. G. Dance, M. L. Scudder, J. Chem. Soc., Dalton Trans.
1996, 3755.
[19] Z.-H. Liu, C.-Y. Duan, J.-H. Li, Y.-J. Liu, Y.-H. Mei, X.-Z.
You, New J. Chem. 2000, 1057.
[20] T. M. Barclay, A. W. Cordes, J. R. Mingie, R. T. Oakley, K.
[1] M. J. Zaworotko, Chem. Soc. Rev. 1994, 283.
[2] T. K. Maji, K. Uemura, H.-C. Chang, R. Matsuda, S. Kita-
gawa, Angew. Chem. 2004, 116, 3331; Angew. Chem. Int. Ed.
2004, 43, 3269.
E. Preuss, Cryst. Eng. Comm. 2000, 80.
[21] C. A. Hunter, J. K. M. Sanders, J. Am. Chem. Soc. 1990,
112, 5525.
[22] C. Janiak, J. Chem. Soc., Dalton Trans. 2000, 3885.
2978
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 2976Ϫ2978