Synthesis, crystal structure and magnetic properties of a new 1D cobalt(II) complex with 1,10-phenanthroline and 3,5-dinitrosalicylate acid ligands

Article abstract of DOI:10.1016/j.inoche.2005.07.015

A new cobalt(II) complex, [Co^II(phen){3,5-(NO₂) ₂sal^2-}]_n (1) (3,5-(NO₂) ₂sal^2- = 3,5-dinitrosalicylate anion, phen = 1,10-phenanthroline), the first cobalt(II) complex with 1,10-phenanthroline and 3,5-dinitrosalicylate acid ligands, has been prepared by hydrothermal synthesis and characterized by single crystal X-ray analysis, IR, XPS spectra, TG-DTA analysis and elemental analysis. This compound displays a linear one-dimensional (1D) chain though cobalt atoms and bridging carboxylate groups of 3,5-dinitrosalicylic acid ligands with Co?Co distance of 4.085 ?. Magnetic susceptibility measurements show weak antiferromagnetic interactions in the complexes.

Full text of DOI:10.1016/j.inoche.2005.07.015

Inorganic Chemistry Communications 8 (2005) 983–987
www.elsevier.com/locate/inoche
Synthesis, crystal structure and magnetic properties of a new
1D cobalt(II) complex with 1,10-phenanthroline and
3,5-dinitrosalicylate acid ligands
a
a
a
a
a,
*
Xin He , Ya-Nan Li , Guang-Hua Li , Ya-Zhuo Li , Ping Zhang
,
Jia-Ning Xu ,a, Yue Wang
b
*
a
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China
b
Key Laboratory for Supramolecular Structure and Materials of Ministry of Education, Jilin University, Changchun 130012, PR China
Received 13 May 2005; accepted 21 July 2005
Available online 9 September 2005
Abstract
A new cobalt(II) complex, [CoII(phen){3,5-(NO2)2sal2À}]n (1) (3,5-(NO2)2sal2À = 3,5-dinitrosalicylate anion, phen = 1,10-phe-
nanthroline), the first cobalt(II) complex with 1,10-phenanthroline and 3,5-dinitrosalicylate acid ligands, has been prepared by
hydrothermal synthesis and characterized by single crystal X-ray analysis, IR, XPS spectra, TG-DTA analysis and elemental anal-
ysis. This compound displays a linear one-dimensional (1D) chain though cobalt atoms and bridging carboxylate groups of 3,5-
˚
dinitrosalicylic acid ligands with CoÁ Á ÁCo distance of 4.085 A. Magnetic susceptibility measurements show weak antiferromagnetic
interactions in the complexes.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: Hydrothermal syntheses; Cobalt(II); 3,5-Dinitrosalicylate acid ligands; Magnetic properties
Molecular and supramolecular materials have been
of most interest due to their potential applications and
intriguing structural features [1,2]. Among these materi-
als, a lot of attention has been paid to the metal salicy-
late owing to their biological applications [3–8],
spectroscopic and electrochemical behaviors [9,10]. In
contrast to aromatic dicarboxylate compounds, the
presence of the hydroxyl group in salicylic acid ligand
allows the formation of six-membered rings which can
stabilize the solid networks. Metal–organic frame-
works with salicylic acid ligand and nitrogen-containing
ligands were found to display multipoint diverse struc-
ture types such as discrete clusters [11–21] and one-
dimensional (1D) chain compounds [22–24]. However,
substituted salicylic acid such as 3,5-dinitrosalicylic acid
ligand [25] is much less applied compared with salicylic
acid ligand [26–34]. Recently, 1,10-phenanthroline li-
gand has shown interesting properties for it has two
nitrogen donors and often acts as a chelating ligand
due to their high affinity to metal ions [35,36]. Using
the mixed ligands of 1,10-phenanthroline or its deriva-
tives and multicarboxylate, many discrete clusters and
one-dimensional metal–organic complexes [37,38] have
been prepared. It has been well-documented that the
introduction of terminal ligands into the carboxylate
system can result in the formation of low dimensional
frameworks owing to the terminal ligands reducing the
available metal-ion binding sites to interdict polymer
growth in other directions [39]. Taking advantage of
some interesting properties of 1,10-phenanthroline and
3,5-dinitrosalicylic acid ligands, herein we report a novel
mental–organic complex [CoII(phen){3,5-(NO2)2sal2À}]n
*
Corresponding author. Tel.: +(86) 431 5168471.
E-mail address: zhangping@jlu.edu.cn (P. Zhang).
1387-7003/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2005.07.015

984
X. He et al. / Inorganic Chemistry Communications 8 (2005) 983–987
1, which possesses linear one-dimensional (1D) chain
structure.
as a bridging ligand between two cobalt atoms. This
connection mode (l) of salicylic acid or its derivatives be-
tween metal centers is one of the interesting connection
modes (Scheme 1). There are five examples in this con-
nection mode in the literatures [26,28,45,46]. 1 is the first
example with a linear one-dimensional chain structures
compared to other clusters with this connection mode.
The cobalt atoms are joined together forming an infinite
chain by bridging carboxylate groups of 3,5-dinitrosali-
Compound 1 was synthesized hydrothermally [40].
Single crystal X-ray structural analysis as well as the
composition and thermal analysis revealed the formula
of [CoII(phen){3,5-(NO2)2sal2À}]n [41]. The crystal
structure of 1 was constructed from a linear one-dimen-
sional chain consisting of CoII(phen){3,5-(NO2)2sal2À
}
entities (Fig. 1). In 1, each Co atom is in distorted octa-
hedral environment, coordinated by two nitrogen atoms
and four oxygen atoms. Each 1,10-phenanthroline li-
gand as a terminal ligand provides two nitrogen atoms
˚
cylic acid ligands with CoÁ Á ÁCo distance of 4.085 A.
Thus, each 3,5-dinitrosalicylic acid ligand links two
cobalt atoms and each cobalt atom connects two 3,5-
dinitrosalicylic acid ligands to form a linear one-
dimensional chain (Fig. 2). These one-dimensional
chains are parallel to each other along the c axis of the
cell. The linear one-dimensional chain structure of 1 is
similar to three complexes with 1,10-phenanthroline li-
gands [Cu (phen)(H2O)2SO4]n [47], [Zn(Hmal)(1,10-
phen)(H2O)]n [38] and {[Cu(phen)(l4-bta)1/2] Æ H2O}n
[38]. In addition, multipoint very weak hydrogen-bonds
also exist among the linear one-dimensional chains be-
tween C atoms of 1,10-phenanthroline ligands and nitro
O atoms of 3,5-dinitrosalicylic acid ligands. The 2+ oxi-
dation state of cobalt in 1 is consistent with the bond
valance sum (BVS = 2.27) [48]. Photoelectron spectrum
(XPS) measurements of 1 in the energy regions of
˚
with a typical Co–N distance [2.112(4) and 2.134(4) A]
and a N–Co–N chelating angle [78.32(16)°] similar to
some reported examples of Co(II) complexes with
1,10-phenanthroline ligands [43]. Four oxygen atoms
come from 3,5-dinitrosalicylate anion, one from a phe-
nolate group, one from a monodentate carboxylate
group and two from a bidentate bridging carboxylate
group. The Co–O bond lengths ranging from 1.997(3)
˚
to 2.262(3) A are comparable to the Co–O bond lengths
in [Co(1,3-BDC)(bipyen)] [44]. In 1, the 3,5-dinitrosali-
cylic acid has lost both of its two protons and behaves
1=2
2p
3=2
2p
Co and Co
show one peak at 780.8 eV (Fig. S2)
that confirms the valence of Co2+ atoms [49]. The differ-
ence oxidation state of cobalt between the starting mate-
rial ([Co(NH3)6]Cl3) and the title compound may be
attribute to the complexity of hydrothermal synthesis.
A similar example has been found [50]. The IR spectrum
of 1 reveals two strong bonds of the carboxylic groups
at 1608 and 1435 cmÀ1 for the asymmetric vibrations
and symmetric vibrations, respectively. The difference
between the asymmetric and symmetric stretching vibra-
tions (Dm = mas(COOÀ) – ms(COOÀ)) of 173 cmÀ1 indi-
cates that the 3,5-dinitrosalicylate anions coordinated
as a bidentate chelating, or bridging carboxylic group
[51]. The absent of d(O–H) of phenolic group at
1485 cmÀ1 and m(C–OH) at 1255 cmÀ1 shows the –OH
coordinate to Co atoms. A bond at 1520 cmÀ1 is as-
signed to mas(aromatic NO2), a band at 1315 cmÀ1 is as-
signed to ms(aromatic NO2) and a band at 849 cmÀ1 is
assigned to C@N stretching vibration of 1,10-phenan-
throline (Fig. S3). The thermal behavior of the com-
pound was studied from 20 to 800 °C. The TG–DTA
curve indicates that 1 is stable to 300 °C (Fig. S4). A
weight loss of 80.26% (Calc. 82.80%) and an intense exo-
thermic peak between 300 °C to 422 °C represent the
lose and decompositions of a 1,10-phenanthroline ligand
and a 3,5-dinitrosalicylate acid ligand per [CoII(phen)
{3,5-(NO2)2sal2À}]n.
Fig. 1. ORTEP drawing (30% probability level) with the atom-labeling
scheme of a monomer fragment of the one-dimensional chain. H atoms
˚
have been omitted for clarity. Selected band distances (A) and angles
(°): Co1–O3 1.997(3), Co1–O1 2.037(3), Co1–N1 2.112(4), Co1–N2
2.134(4), Co1–O2A 2.152(3), Co1–O1A 2.262(3) and N1–Co1–N2
78.32(16), O3–Co1–O1 88.95(12), O3–Co1–N1 92.44(15), O1–Co1–N1
101.27(14), O3–Co1–N2 169.97(16), O1–Co1–N2 96.62(14).
The variable-temperature magnetic susceptibility for
1 was measured from 2 to 300 K at 5000 Oe. The exper-
imental data plotted as the thermal variation of vM, vMT

X. He et al. / Inorganic Chemistry Communications 8 (2005) 983–987
985
a
e
c
b
d
OH
OH
OH
OH
O
O
O
O
O
O
O
M
O
O
HO
O
M
M
M
M
M
M
f
g
M
O
H
O
O
O
M
O
H
O
M
j
k
l
h
i
O
O
O
O
M
M
O
M
M
O
O
O
O
O
O
O
O
M
O
O
M
M
M
M
n
p
o
m
M
O
O
O
O
M
M
M
M
O
O
O
O
O
O
O
O
M
M
M
M
M
M
M
M
M
Scheme 1. Two groups of co-ordination modes of salicylic acid or its derivatives between metal centers: (1) hydrogensalicylate (HsalÀ): (a) l1 ([3–
5,16,19,21]); (b) l1 ([4,16,17,20,23]); (c) l1 ([21,32]); (d) l2 ([20,23]); (e) l2 ([30]); (f) l2 ([22]); (g) l2 ([15,25,34]). (2) Salicylate ions (sal À): (h) l1
([3,6,9,10]); (i) l2 ([24]); (j) l2 ([25,26]); (k) l2 ([7]); (l) l2 ([26,28,45,46], this work); (m) l3 ([45]); (n) l3 ([8]); (o) l4 ([6]); (p) l4 ([29]).
in Fig. 3(a) and vÀM1 in Fig. 3(b). The value of vMT at
room temperature is 1.98 emu molÀ1 K (leff = 3.97
lB), which is slightly larger than expected for the spin-
only value of high-spin CoII (vMT = 1.87 emu molÀ1
K; S = 3/2) (leff = 3.87 lB; lSO = [4S(S + 1)]1/2; S = 3/
2). This indicates that there is little orbital contribution
[52]. The temperature dependence of vM below 20 K
suggests a ferromagnetic transition or a development
Fig. 2. The infinite one-dimensional chain structure of 1.

986
X. He et al. / Inorganic Chemistry Communications 8 (2005) 983–987
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Appendix A. Supplementary data
Supplementary data associated with this article can
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X. He et al. / Inorganic Chemistry Communications 8 (2005) 983–987
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˚
˚
monoclinic, space group Cc, a = 12.1447(10) A, b = 22.372(2) A,
c = 8.1016(7) A, b = 123.367(5)°, V = 1838.4(3) m3, Z = 4,
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