Spectroscopic studies and crystal structure of four-coordinate manganese(II) chloride complex

Article abstract of DOI:10.1080/15533174.2011.618756

High-spin new, manganese-(II) L₂MnCl₂, complex has been synthesized and its structure was elucidated by using elemental analysis, FT-IR, DTA-TG, ¹H-NMR, ¹³C-NMR, and UV-Visible spectroscopic techniques. The structure of the compound has also been examined crystallographically. The title compound crystallizes in the triclinic space group P-1, with unit cell parameters: a = 11.354(1), b = 11.868(1), c = 12.080(1) A, V = 1548.9(1)A³, D_x = 1.270g.cm^-3, and Z = 2, respectively. The Mn atom was tetra-coordinated to form a distorted tetrahedral geometry by two oxygen atoms of L₂ and two chloride atoms of MnCl₂.4H₂O in the complex.

Full text of DOI:10.1080/15533174.2011.618756

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Spectroscopic Studies and Crystal Structure of Four-
Coordinate Manganese(II) Chloride Complex
Hava Özay a , Mustafa Yıldız a b , Hüseyin Ünver c & Nazan Ocak İskeleli d
a Department of Chemistry , Faculty of Science and Arts, Çanakkale Onsekiz Mart
University , Çanakkale , Turkey
b Nanoscience and Technology Research and Application Center (NANORAC) , Çanakkale
Onsekiz Mart University , Çanakkale , Turkey
c Department of Physics , Faculty of Science, Ankara University , Beşevler-Ankara , Turkey
d Department of Science Education , Ondokuz Mayıs University , Kurupelit , Turkey
Accepted author version posted online: 18 Apr 2012.Published online: 11 Jul 2012.
To cite this article: Hava Özay , Mustafa Yıldız , Hüseyin Ünver & Nazan Ocak İskeleli (2012) Spectroscopic Studies and
Crystal Structure of Four-Coordinate Manganese(II) Chloride Complex, Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry, 42:6, 872-877
To link to this article: http://dx.doi.org/10.1080/15533174.2011.618756
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:872–877, 2012
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.618756
Spectroscopic Studies and Crystal Structure
of Four-Coordinate Manganese(II) Chloride Complex
1
1,2
3
4
¨
¨
˙
Hava Ozay, Mustafa Yıldız, Hu¨seyin Unver, and Nazan Ocak Iskeleli
1Department of Chemistry, Faculty of Science and Arts, C¸ anakkale Onsekiz Mart University,
C¸ anakkale, Turkey
2Nanoscience and Technology Research and Application Center (NANORAC), C¸ anakkale Onsekiz Mart
University, C¸ anakkale, Turkey
3Department of Physics, Faculty of Science, Ankara University, Bes¸evler-Ankara, Turkey
4Department of Science Education, Ondokuz Mayıs University, Kurupelit, Turkey
The tautomerism in the Schiff base ligands plays an
important role for distinguishing their photochromic and
thermochromic characteristics.[12–14] It has been proposed
that molecules showing thermochromism are planer, while
those showing photochromism are non-planer.[15] However,
both appearances being associated with a proton transfer.[16]
Therefore the structures of this kind of compounds, which are
showed as tautomeric form, are relevant due to the possibility
of finding them in the solid state or in solution as ketoamine
or phenolimine forms. In the solid state, salicylaldimine
compounds tend to form two (N. . .H-O or N-H. . .O) types of
hydrogen bonding, respectively.[17–24]
The Schiff bases of 2-hydroxy-3-methoxy-1-benzaldehyde
(o-vanillin) have been studied previously[25–36] and used as
ionophores in a Cu(II) selective electrochemical sensor.[37]
These compounds as well as their metal complexes have been
found to possess biological activity.[38] Antibacterial activity has
also been reported for the ruthenium(II) complex of the Schiff
base of 2-hydroxy-3-methoxy-1-benzaldehyde.[39]
High-spin new, manganese-(II) L2MnCl2, complex has been
synthesized and its structure was elucidated by using elemental
analysis, FT-IR, DTA-TG, 1H-NMR, 13C-NMR, and UV-Visible
spectroscopic techniques. The structure of the compound has also
been examined crystallographically. The title compound crystal-
lizes in the triclinic space group P-1, with unit cell parameters:
a = 11.354(1), b = 11.868(1), c = 12.080(1) Å, V = 1548.9(1) Å3,
Dx = 1.270 g.cm−3, and Z = 2, respectively. The Mn atom was
tetra-coordinated to form a distorted tetrahedral geometry by two
oxygen atoms of L2 and two chloride atoms of MnCl2.4H2O in the
complex.
Keywords crystal structure, DTA-TG, four-coordinated man-
ganese(II), NMR, spectroscopic studies
INTRODUCTION
The compounds of manganese play an essential structural
and catalytic role in many proteins. The active Mn sites of many
enzymes have been shown to bind with imidazole nitrogen from
histidine residues.[1–4] There has been considerable interest in
the coordination chemistry of manganese compounds because
of their potential utilities as model compounds of manganese
containing proteins that exhibit significant involvement of man-
ganese in various biological systems.[5–11] Manganese(II) ion
takes usually a high-spin d5 electronic configuration, which
gives no crystal field stabilization energies for any coordina-
tion geometries. However, most of the manganese(II) complexes
have an octahedral geometry and few examples are known to
have the other coordination geometries.
In the present study, four-coordinated manganese(II) chloride
compound was synthesized (Scheme 1), and then the structure
of the compound was enlightened by using data obtained from
1
13
element analysis, FT-IR, H-NMR, C-NMR, DTA-TG, and
X-ray crystallographic techniques.
EXPERIMENTAL
The 1H-, 13C-NMR spectra were recorded on a Bruker DPX
FT-NMR spectrometers operating at 500 and 125.7 MHz. In-
frared absorption spectra were recorded on a Perkin-Elmer BX
II spectrometer in KBr discs. UV-vis spectra were recorded on a
Shimadzu 1201 series spectrometer. Carbon, hydrogen, and ni-
trogen analyses were performed on a LECO CHNS-932 C-, H-,
N-analyzer. Melting point was measured on an Electro Thermal
IA 9100 apparatus using a capillary tube. The DTA-TG mea-
surements were performed between 25 and 1000◦C (in air, rate
10◦C/min, Seiko SII TG&DTA 6300). 2-Chlorobenzylamine,
Received 2 June 2011; accepted 25 August 2011.
The authors thank C¸ anakkale Onsekiz Mart University Grants Com-
mission for a research grant (Project Number: 2011/004).
Address correspondence to Mustafa Yıldız, Department of Chem-
istry, Faculty of Science and Arts, C¸ anakkale Onsekiz Mart University,
TR-17100, C¸ anakkale, Turkey. E-mail: myildiz@comu.edu.tr
872

SPECTROSCOPIC STUDIES AND CRYSTAL STRUCTURE STUDIES
873
H
CH3
H3C
H
O
O
N
O
O
N
H
H
MnCl2.4H2O
MeOH
Cl
Cl
Enol-imine
Keto-amine
H
Cl
N
CH3
H
O
O
Cl
Mn
O
Cl
O
H3C
H
N
Cl
H
SCH. 1. Synthesis of the Mn(II) complex.
2-hydroxy-3-methoxy-1-benzaldehyde(o-vanillin),
THF,
Crystallography
DMSO, MeOH, and MnCl2.4H2O were purchased from Merck
(Germany).
The data collection for the title complex was performed
on a STOE IPDS-2 diffractometer employing graphite-
monochromatized MoKα radiation (λ = 0.71073Å). Data col-
lection, reduction, and corrections for absorption and crystal
decomposition were achieved by using X-AREA, X-RED soft-
ware.[40] The structure was solved by SHELXS-97 and refined
with SHELXL-97.[41,42] The positions of the H atoms bonded to
C atoms were calculated (C-H distance 0.96Å), and refined by
using a riding model. All atoms (except hydrogen) were located
from a difference Fourier map and refined anisotropically. The
details of the X-ray data collection, structure solution and struc-
ture refinements are given in Table 1. Selected bond distances
and angles are listed in Table 2. The molecular structure with
the atom-numbering scheme is shown in Figure 1.[43]
Synthesis of Bis[(Z)-6-((2-chlorobenzylamino)methylene)-
2-methoxycyclohexa-2,4-dienone] Manganese(II)
Chloride
MnCl2.4H2O (0,5 g; 2.5 × 10−3 mol) was added to a
dry MeOH (100 mL) solution of (Z)-6-((2-chlorobenzylamino)
methylene)-2-methoxycyclohexa-2,4-dienone[36] (1,39 g; 5.0 ×
10−3 mol). The reaction mixture was stirred under reflux for
3 h, then was filtered off, and the filtrate was kept undisturbed
for a few days. Bright, red crystalline product was filtered off
and washed with methanol and finally was dried in air, m.p.
218–220◦C, 1.62 g (95%) yield. Found: C, 53.17; H, 4.13; N,
4.14. Anal. Calcd. for C30H28Cl4MnN2O4: C, 53.18; H, 4.14; N,
4.14%. IR (KBr, cm−1): νN-H, 3398 m; νAr-H, 3055 w; νC-H,
2972 w; νC O, 1653 s; νC C, 1607 s; νC N, 1457 s; νAr-O-
C, 1232–1213-1170–1053 s; νMn-O, 450 s. 1H NMR (DMSO):
δ ppm, 12.88 (s-broad, 2H, Ar-NH); 6.69 (s-broad, 16H,
Ar-H + Ar CH); 4.21 (s-broad, 4H, ArCH2); 3.28 (s-broad,
6H, OCH3).
RESULTS AND DISCUSSION
FT-IR, 1H-NMR, 13C-NMR, UV-Visible Spectroscopic, and
Thermal studies
The structure of free ligand was studied by using FT-IR,
1H NMR, 13C NMR, UV-vis, and X-ray crystallographic tech-
niques in order to study the hydrogen bonding and tautomeric

¨
H. OZAY ET AL.
874
TABLE 1
Crystal and experimental data
TABLE 2
Some selected bond lengths (Å), bond angles (◦), and torsion
angles (◦)
Formula
C30 H28 Cl4Mn N2 O4
Mn-O3
Mn-O2
Mn-Cl2
Mn-Cl3
Cl1-C1
O3-C16
O2-C14
C9-C14
C13-O1
2.062(2) O1-C15
2.063(2) O4-C17
2.402(1) O4-C18
2.405(1) N2-C23
1.735(4) N2-C24
1.302(4) C6-C7
1.303(4) C8-N1
1.410(4) N1-C7
1.373(4) C24-C25
1.426(5)
1.369(4)
1.422(5)
1.284(4)
1.467(5)
1.506(5)
1.293(4)
1.462(5)
1.505(5)
Formula weight
Crystal system
Space group
Crystal dimension
Temperature collection
Unit cell parameters
677.28
Triclinic
P-1
0.30 × 0.38 × 0.45 mm3
293(2) K
a = 11.354(1)Å
b = 11.868(1)Å
β = 73.975(3)◦
c = 12.080(1)Å
1548.9(1)Å3
2
O3-Mn-O2
O3-Mn-Cl2
O2-Mn-Cl2
O3-Mn-Cl3
O2-Mn-Cl3
Cl2-Mn-Cl3
134.9(1) C16-O3-Mn
113.2(1) C14-O2-Mn
95.9(1) C13-O1-C15
94.0(1) C17-O4-C18
110.4(1) C23-N2-C24
106.6(1) C8-N1-C7
125.8(2)
125.8(2)
117.4(3)
118.7(4)
125.3(4)
125.4(3)
V
Z
Dc (g cm−3
µ(MoKα)
F(000)
)
1.270 g cm−3
0.632 mm−1
610
2 θmax
h, k, l range
52.00◦
O2-Mn-O3-C16
Cl2-Mn-O3-C16
78.0(3) Mn-O3-C16-C17
–47.9(3) C24-N2-C23-C22 177.1(3)
–23.3(4)
–14 ≤ h ≤ 14
–14 ≤ k ≤ 14
–14 ≤ l ≤ 14
22287
Cl3-Mn-O3-C16 –157.8(3) C9-C8-N1-C7
O3-Mn-O2-C14 74.4(3) Mn-O2-C14-C9
Cl2-Mn-O2-C14 –154.1(3) Mn-O2-C14-C13
Cl3-Mn-O2-C14
Mn-O3-C16-C22 157.2(2) C8-N1-C7-C6
178.1(4)
154.1(3)
–26.8(4)
No. of measured reflections
No. of independent
reflections
No. of observed reflections
Goodness-of-fit on F2
R, Rw (I > 2σ(I))
6088
–43.9(3) C23-N2-C24-C25 –120.4(4)
–126.3(4)
4112
1.046
0.051, 0.079
1.326, –0.334 e. Å−3
(ꢀρ)max, (ꢀρ)min
methylenecyclohexa-2,4-dienone Ar O bond. The nonligand
IR frequencies observed in the region of 600–400 cm−1 are at-
tributed to νMn-O IR stretching frequencies. The Mn-O strong
bond was observed at 450 cm−1 for the complex.
equilibrium (enolimine or ketoamine forms) in both the solution
and also solid states.[36] UV-vis, H NMR, 13C NMR, and X-
1
ray results show that in the solution and solid states free ligand
exists in the enolimine form.[36]
The FT-IR spectrum of the compound is given in synthetic
procedures (Figure 2). The IR spectra of the metal complex ex-
hibit characteristic changes in the functional group frequencies
when compared with the spectrum of the ligand.[36] The OH and
C N vibration band are observed at 3414 and 1635 cm−1 of
free ligand, respectively. The absorption is not observed in the
region of 600–400 cm−1 for free ligand. These can be correlated
to the specific coordination positions of the ligand. The infrared
spectrum shows a band at 3398 cm−1 that is assigned to νN-H
vibration. In this spectrum, the band characteristic of νN-H is
almost unperturbed, indicating that it is not involved in the co-
ordination.[44] The stretching frequency observed at 2835 cm−1
in compound shows the presence of N-H.. . .O intramolecu-
lar hydrogen bond.[19–20] The C O bond that is accountable
partially for the existence of ketoamine form can also be in-
ferred from the FT-IR spectra of the compound. The compound
with strong band at 1653 cm−1 possesses highest percentage
of ketoamine tautomer due to the stabilization of 2-methoxy-6-
FIG. 1. The molecular structure of the title complex. The intramolecular hy-
drogen bonds have been indicated by dashed lines (color figure available online).

SPECTROSCOPIC STUDIES AND CRYSTAL STRUCTURE STUDIES
875
114
110.6
144.8
124.1
118.8
127.1
59.9
H
129.7
130.0
130.5
O
130.1
135.8
170.9
N
O
Cl
H
132.5
52.7
Mn
Cl
Cl
SCH. 2. 13C-NMR Chemical shifts of the complex in solution media.
FIG. 2. FT-IR spectrum of the title complex in the solid state (color figure
available online).
According to the 13C-NMR spectra complex has 15 signals
(Figure 4). 13C-NMR Chemical shifts are given in Scheme 2 for
the complex. The ArC-OH carbon is observed at δ = 151.6 ppm
for free ligand,[36] while it is observed at δ = 170.9 ppm for
the complex. The ArC-OH carbon show absorption in the range
greater than δ = 151.6 ppm in solution for the complex. It
should be pointed out that the high absorption band belongs to
the ketoamine form of the Schiff bases with the OH group in
the ortho position to the imino group in the solution.
1
The H NMR data for free ligand show that the tautomeric
equilibrium favors the enolimine in CDCl3. The OH and azome-
thine protons are observed at δ = 13.60 and 8.41 ppm singlets
for the free ligand, respectively.[36] The phenyl protons resonate
at δ = 7.36, 7.21, 6.94, and 6.79 ppm multiplet, the ArCH2
and OCH3 protons of the compound gave a singlet at δ = 4.87
1
and 3.88 ppm for free ligand, respectively. The H-NMR data
It can be stated as a conclusion that 1H-NMR and 13C-NMR
results clearly show the existence of the ligand in the ketoamine
form in the complex.
for complex shows that the tautomeric equilibrium favors the
ketoamine in DMSO. The N-H proton is observed 12.88 ppm
broad-singlet for complex (Figure 3). The azomethine proton is
not observed for complex. The phenyl protons resonate at δ =
6.69 ppm broad-singlet and the Ar = CH protons of the complex
gave a broad-singlet at δ = 4.21 ppm. The ArCH2 and OCH3
protons of the complex are observed a singlet at δ = 3.28 ppm.
The UV-visible studies of the ligand and complex was done
in DMSO solvent (Figure 5). The UV-vis spectrum of the ligand
FIG. 4. 13C-NMR spectrum of the title complex.
FIG. 5. UV-vis spectrum of the free ligand and its complex in DMSO (color
figure available online).
FIG. 3. 1H-NMR spectrum of the title complex.

¨
H. OZAY ET AL.
876
Intramolecular hydrogen bond occurs between N1-H1. . .O2
[2.584(3) Å] and N2-H2. . .O3 [2.590(3) Å] atoms for the title
molecule (Figure 1), respectively. The sum of the Van der Waals
radius of the O and N atoms (3.07 Å) is significantly longer than
the intramolecular O. . .N hydrogen bond length.[46]
The compounds which have C-N group seem to have a weak
electron withdrawing character. Thus, in the title complex, O2-
C14 and O3-C16 bond distances of 1.303(4) Å and 1.302(4) Å is
also consistent with the C O double bonding. The C O bond
distance Å indicates the presence of the keto form, with a partial
double bond character of the CO group (>C O ↔C+-O−). X-
ray structure determinations reveal that the ketoamine tautomer
is favored over the enolimine tautomer for the ligand. This is
evident from the observed O-C bond distance of 1.303(4) Å and
1.302(4) Å, which is consistent with the O C double bond;
similarly the N-C distance of N1-C8 1.293(4) Å and N2-C23
1.284(4) Å is also consistent with the N-C single bonding.[36]
The ligand exists as dominant form of ketoamines in solid state.
FIG. 6. DTA-TG spectrum of the title complex (color figure available online).
shows only two broad band at 265 nm and 331 nm, which is
assigned to the π–π∗and n–π∗ transition of the C C and C N.
On complexation, these bands are not changed. The complex
showed same UV-vis spectrum with the ligand. The complex
does not show any d-d transitions but display charge transfer
SUPPLEMENTARY MATERIALS
Further information may be obtained from: Cambridge Crys-
tallographic Data Center (CCDC), 12 Union Road, Cambridge
CB21EZ, UK, by quoting the depository numbers CCDC
691504 & 691505, E-mail: deposit@ccdc.cam. ac.uk.
bands at 37735 and 30211 cm−1
.
Thermal studies (DTA-TG) of the Mn(II) complex was per-
formed in the temperature range 25–1000◦C, at a heating rate of
10◦C/min in a air atmosphere (Figure 6). The complex decom-
poses in two stages. The first step 225–590◦C resulted in a mass
loss of 45.10%, corresponding to the loss of 2-chlorobenzylamin
groups. In the second step, two chloride molecules and aldehyde
groups were lost in the 590–900◦C range from the Mn(II) com-
plex, with a mass loss of 42.5%. A plateau was obtained after
heating above 900◦C, which corresponds to the formation of
stable MnO2. The weight of MnO2 amounted to 12.4%, which
shows a good agreement with the metal analysis.
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