Synthesis and crystal structure of a novel polymeric manganese(IV) complex derived from the schiff base 2-ethoxy-6-[(2-hydroxyethylimino)methyl]phenol

Article abstract of DOI:10.1080/15533174.2012.684228

A novel polymeric manganese(IV) complex, [Mn(L)(HL)(N₃)] _n ·_nCH₃OH, has been synthesized from the Schiff base 2-ethoxy- 6-[(2-hydroxyethylimino)methyl]phenol (H₂L) with manganese chloride and sodium azide in methanol. The complex was characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The Mn atom in the complex is coordinated by two phenolic oxygen, two imino nitrogen, and one hydroxyl oxygen atoms from two Schiff base ligands, and by one azido N atom, giving an octahedral coordination. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2012.684228

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Synthesis and Crystal Structure of A Novel Polymeric
Manganese(IV) Complex Derived From the Schiff Base
2-Ethoxy-6-[(2-hydroxyethylimino)methyl]phenol
De-Suo Yang a
a Department of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences ,
Baoji , P. R. China
Accepted author version posted online: 27 Jul 2012.Published online: 05 Oct 2012.
To cite this article: De-Suo Yang (2012) Synthesis and Crystal Structure of A Novel Polymeric Manganese(IV) Complex Derived
From the Schiff Base 2-Ethoxy-6-[(2-hydroxyethylimino)methyl]phenol, Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry, 42:10, 1459-1462, DOI: 10.1080/15533174.2012.684228
To link to this article: http://dx.doi.org/10.1080/15533174.2012.684228
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:1459–1462, 2012
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.684228
Synthesis and Crystal Structure of A Novel Polymeric
Manganese(IV) Complex Derived From the Schiff Base
2-Ethoxy-6-[(2-hydroxyethylimino)methyl]phenol
De-Suo Yang
Department of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji,
P. R. China
OH
N
A novel polymeric manganese(IV) complex, [Mn(L)(HL)(N3)]n
·nCH3OH, has been synthesized from the Schiff base 2-ethoxy-
OH
6-[(2-hydroxyethylimino)methyl]phenol (H2L) with manganese
chloride and sodium azide in methanol. The complex was char-
acterized by elemental analysis, IR spectrum, and single-crystal
X-ray diffraction. The Mn atom in the complex is coordinated
by two phenolic oxygen, two imino nitrogen, and one hydroxyl
oxygen atoms from two Schiff base ligands, and by one azido N
atom, giving an octahedral coordination.
OEt
SCH. 1. H2L.
EXPERIMENTAL
Materials and Measurements
Keywords crystal structure, manganese, polymeric complex, Schiff
3-Ethoxysalicylaldehyde and 2-aminoethanol were pur-
chased from Aldrich with AR grade (China). Other chemicals
were obtained commercial, and were used as received. The anal-
yses of carbon, hydrogen, and nitrogen were performed with a
Perkin-Elmer 240C elemental analyzer (USA). Infrared spectra
were recorded in KBr pellets with a Perkin-Elmer 597 infrared
diffraction grating spectrophotometer (USA) in the range
base, synthesis
INTRODUCTION
Schiff bases derived from salicylaldehde and similar deriva-
tives have attracted much interest in recent years, especially
for their application in coordination chemistry.[1–3] The Schiff
bases derived from salicylaldehyde with 2-aminoethanol and
similar derivatives have been widely used to prepare complexes
with metal ions.[4–6] However, the transition metal complexes
with the Schiff base derived from 3-ethoxysalicylaldehyde
4000–400 cm−1
.
Caution: Sodium azide is potentially explosive, and only a
small quantity should be used and handled with great care.
Synthesis of 2-Ethoxy-6-[(2-hydroxyethylimino)methyl]
phenol (H2L)
and
2-aminoethanol,
2-ethoxy-6-[(2-hydroxyethylimino)
To
a
warm methanol solution (20 mL) of 3-
methyl]phenol (H2L; Scheme 1), have never been reported.
In this article, the synthesis and crystal structure of a novel
manganese(IV) complex, [Mn(L)(HL)(N3)]n·nCH3OH, are
reported.
ethoxysalicylaldehyde (1.0 mmol, 166 mg), 2-aminoethanol
(1.0 mmol, 61 mg) in methanol (10 mL) was added dropwise.
The yellow solution was maintained under reflux for 1 h, and
the methanol was evaporated to give a yellow solid product. It
was washed with methanol, and dried in vacuo. Anal. Calcd. for
C11H15NO3 (%): C, 63.1; H, 7.2; N, 6.7. Found (%): C, 62.9;
H, 7.3; N, 6.8.
Synthesis of the Complex [Mn(L)(HL)(N3)]n·nCH3OH
To a warm methanol solution (10 mL) of H2L (0.1 mmol,
20.9 mg) and NaN3 (0.1 mmol, 6.5 mg), MnCl2·4H2O
(0.1 mmol, 19.8 mg) dissolved in methanol (10 mL) was added
dropwise. The resulting solution was refluxed for 30 min.
The brown crystals were filtered off, washed with methanol,
and dried in vacuo. Yield, 37.0 mg, 68%. Anal. Calcd. for
Received 19 October 2011; accepted 8 April 2012.
The author acknowledges the project supported by the Office of
Science and Technology of Shanxi Province (Grant No. 2009K01-
51), and the project supported by the Key Research Item of the Baoji
University of Arts and Sciences (Grant No. ZK1040).
Address correspondence to De-Suo Yang, Department of Chemistry
and Chemical Engineering, Baoji University of Arts and Sciences,
Baoji 721007, P. R. China. E-mail: desuoyang@yahoo.com.cn
1459

1460
D.-S. YANG
TABLE 1
Crystallographical and experimental data for the complex
TABLE 2
Selected bond lengths (Å) and angles (◦) for the complex
Empirical formula
Formula weight
Crystal shape/color
Temperature/K
Wavelength/Å
Crystal size/mm
Crystal system
Space group
C23H31MnN5O7
544.5
Block/brown
298(2)
Bond lengths
Mn1-O1
Mn1-O4
Mn1-N2
1.857 (4)
1.854 (4)
2.041 (5)
Mn1-O3A
Mn1-N1
Mn1-N3
2.360 (4)
2.045 (4)
2.367 (6)
Bond angles
0.71073
O4-Mn1-O1
O1-Mn1-N2
O1-Mn1-N1
O4-Mn1-O3A
N2-Mn1-O3A
O4-Mn1-N3
N2-Mn1-N3
O3A-Mn1-N3
175.00 (18)
89.56 (19)
90.21 (17)
86.21 (17)
90.9 (2)
O4-Mn1-N2
O4-Mn1-N1
N2-Mn1-N1
O1-Mn1-O3A
N1-Mn1-O3A
O1-Mn1-N3
N1-Mn1-N3
90.96 (19)
89.17 (17)
178.8 (2)
88.81 (16)
87.91 (16)
92.05 (19)
91.38 (19)
0.20 × 0.20 × 0.18
Monoclinic
P21/n
a/Å
b/Å
12.453(3)
11.674(3)
17.814(3)
103.275(2)
2520.6(9)
4
92.92 (19)
89.8 (2)
c/Å
β/◦
V/Å3
178.88 (17)
Z
Symmetry code for A: 3/2 – x, 1/2 + y, 3/2 – z.
Dc/g cm−3
1.435
0.576
1140
µ/mm−1 (Mo-Kα)
F(000)
RESULTS AND DISCUSSION
θ ranges/◦
2.10–25.50
−15,15/−8,14/−17,21
4436
The condensation of 3-ethoxysalicylaldehyde with 2-
aminoethanol gave the yellow Schiff base. The Schiff base was
identified by its IR spectrum, where replacement of the car-
bonyl by the imine group results in lowering of the energy of
the ν(C O) stretch. The Schiff base prepared in this way was
formed in quantitative yield and was of high purity. The man-
ganese(IV) complex was prepared by the reaction of the Schiff
base, sodium azide, and manganese chloride in methanol. The
Mn atom with +2 oxidate number in manganese chloride was
oxidized to +4 in the complex by oxygen. The azide ligand
is a versatile bridging groups in the construction of polymeric
structures,[10–12] however, in the present complex, it acts as sim-
ple terminal ligand. The results of the elemental analyses are
in accord with the composition suggested for the Schiff base
and the complex. The Schiff base and the complex are soluble
in acetonitrile, methanol, and ethanol. It should be noticed that
the single crystals of the complex can only be formed from
methanol system.
h/k/l
Independent reflections
Observed reflections [I ≥ 2σ(I)]
Tmin and Tmax
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I ≥ 2σ(I)]
2705
0.8935 and 0.9034
4436/19/330
01.035
R1 = 0.0832
wR2 = 0.2036
R1 = 0.1345
wR2 = 0.2385
R indices (all data)
C23H31MnN5O7 (%): C, 50.7; H, 5.7; N, 12.9. Found (%): C,
50.5; H, 5.9; N, 12.8.
Crystal Structure Determination
A well-shaped brown crystal of the complex suitable for
X-ray crystallographic analysis was selected following exam-
ination under a microscope. Diffraction data were collected
on a Bruker APEXII CCD diffractometer (Germany) using
MoKα radiation. The collected data were reduced using the
SAINT program (Bruker, Germany),[7] and were corrected
for Lorentz and polarization effects and for absorption us-
ing the SADABS program (Bruker, Germany).[8] The struc-
ture was solved by direct method and the structure solution
and refinement were based on F2 with the SHELXTL program
(Bruker, Germany).[9] All non-hydrogen atoms were refined
with anisotropic displacement parameters whereas hydrogen
atoms were placed in calculated positions and given isotropic
U values 1.2 or 1.5 times those of the atoms to which they
are bonded. The crystal data and data collection parameters
of the complex are listed in Table 1. Selected bond lengths
and angles are listed in Table 2. Hydrogen bonds are listed in
Table 3.
IR Spectra
The broad absorption bands centered at 3417 and 3372 cm−1
in the free Schiff base and at 3408 cm−1 in complex are assigned
to the OH group vibrations. For the Schiff base, the strong band
at 1623 cm−1 is assigned to the azomethine group vibration.[13]
The band is shifted to lower wave number (1609 cm−1) in
the complex. This change shows that the imine nitrogen atom
TABLE 3
Hydrogen-bond geometry (Å, ◦) for the complex
D−H···A
D−H
0.82
0.82
H···A
2.09
2.43
D···A
2.840 (10)
2.869 (12)
D−H···A
O7−H7···N3#1
152
115
O6−H6···N5#2
Symmetry codes: #1: x, 1 + y, z; #2: 1/2 – x, 1/2 + y, 3/2 – z.

A NOVEL POLYMERIC MANGANESE(IV) COMPLEX
1461
FIG. 1. Molecular structure of the complex at 30% probability displacement.
coordinated to the manganese atom. The middle absorption bridged polymeric manganese(IV) complex and methanol
band at 1222 cm−1 is attributed to the phenolic stretch. The molecules of crystallization. One Schiff base ligand is monoan-
band is observed at lower wave number by 23 cm−1 relative to ionic form, and the other is dianionic form. The Mn atom in
the free Schiff base, suggesting involvement of the oxygen atom the complex is six-coordinated in an octahedral geometry, with
of the Ph–O group in the coordination.[14] The complex shows two phenolic O and two imino N atoms from two Schiff base
characteristic intense IR band for coordinated azide groups at ligands defined the equatorial plane, and with one hydroxyl O
2053 cm−1. The weak bands in the range 535–405 cm−1 are atom of a Schiff base ligand, and one azido N atom occupy-
assigned to the stretching vibrations of the Mn–O and Mn–N ing the two axial positions. The MnN3O3 coordination forms a
bonds.
slightly distorted octahedral geometry, with the three trans an-
gles subtended at the Mn atom in the range 175.0(2)–178.9(2)◦,
and with the remaining angles subtended at the Mn atom in
the range 86.2(2)–92.9(2)◦. All the bond lengths and angles
related to the Mn atom in the complex are comparable to the
Structure Description of the Complex
The view of the molecular structure of the complex is de-
picted in Figure 1. The compound contains a hydroxyl oxygen-
FIG. 2. Molecular packing arrangement of the complex, viewed along the c-axis.

1462
D.-S. YANG
values observed in the manganese(IV) complexes with Schiff
bases.[5,15–17]
In the crystal structure of the complex, molecules are linked
through intermolecular O−H···N hydrogen bonds, forming a
three-dimensional network, as shown in Figure 2.
4. Dey, M.; Rao, C.P.; Saarenketo, P.K.; Rissanen, K. Mono-, di- and tri-
nuclear Ni(II) complexes of N-, O-donor ligands: structural diversity and
reactivity. Inorg. Chem. Commun. 2002, 5, 924–928.
5. Asada, H.; Ozeki, M.; Fujiwara, M.; Matsushita, T. Structures of four
types of novel high-valent manganese complexes obtained by the reac-
tions of KMnO4 with tridentate Schiff base ligands. Polyhedron 2002, 21,
1139–1148.
6. Boskovic, C.; Rusanov, E.; Stoeckli-Evans, H.; Gudel, H.U. New tri- and
tetranuclear transition metal spin clusters incorporating a versatile polyden-
tate Schiff base ligand. Inorg. Chem. Commun. 2002, 5, 881–886.
7. Bruker, SMART and SAINT. Bruker AXS Inc.: Madison, Wisconsin, 2002.
8. Sheldrick, G.M. SADABS. Program for Empirical Absorption Correction
of Area Detector, University of Go¨ttingen: Germany, 1996.
9. Sheldrick, G.M. SHELXTL V5.1 Software Reference Manual; Bruker AXS,
Inc.: Madison, Wisconsin.
CONCLUSIONS
A novel manganese(IV) complex derived from the Schiff
base 2-ethoxy-6-[(2-hydroxyethylimino)methyl]phenol has
been synthesized and characterized by elemental analysis, IR
spectra, and single-crystal X-ray crystallography. The Schiff
base ligand coordinates to the Mn atom through the phenolic O,
imino N, and/or hydroxyl O atoms.
10. Qian, H.-Y.; You, Z.-L. Synthesis and crystal structures of a pair of azido-
bridged polynuclear Schiff base zinc(II) complexes. Synth. React. Inorg.
Met.-Org. Nano-Met. Chem. 2009, 39, 193–198.
11. Mondal, K.C.; Mukherjee, P.S. An antiferromagnetic Mn(II)-azido chain:
Synthesis and characterization. Synth. React. Inorg. Met.-Org. Nano-Met.
Chem. 2007, 37, 735–739.
12. Hoshino, N.; Ito, T.; Nihei, M.; Oshio, H. Inorg. Chem. Commun. 2003, 6,
377–?.
13. Tu¨mer, M.; Ko¨ksal, H.; Serin, S. Antimicrobial activity studies of mononu-
clear and binuclear mixed-ligand copper(II) complexes derived from Schiff
base ligands and 1,10-phenanthroline. Transition Met. Chem. 1999, 24,
13–17.
SUPPLEMENTARY MATERIALS
Crystallographic data for the complex have been deposited
with the Cambridge Crystallographic Data Centre (CCDC
848870).
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