Synthesis and structural characterization of iron(iii) complexes with 2-hydroxyphenones

Article abstract of DOI:10.1002/zaac.200900016

Four iron(III) complexes [Fe(2-OH-phenone)₃] (1-4), in which 2-OH-phenone is the anion of the ligands 2-OH-acetophenone(Hapo) (1′), 2-OH-propiophenone(Hppo) (2′), 2-OHbenzophenone(Hbpo) (3′) and 2-OH, 4-OCH₃-benzophenone(Hopo) (4′),

Full text of DOI:10.1002/zaac.200900016

ARTICLE
DOI: 10.1002/zaac.200900016
Synthesis and Structural Characterization of Iron(III) Complexes with
2-Hydroxyphenones
Maria Lalia-Kantouri,*[a] Theodor Dimitriadis,[a] Christos D. Papadopoulos,[a]
Maria Gdaniec,[b] Agnieszka Czapik,[b] and Antonios G. Hatzidimitriou[a]
Keywords: Iron chelates; 2-Hydroxyphenones; Crystal structure; Thermochemistry
Abstract. Four iron(III) complexes [Fe(2-OH-phenone)3] (1Ϫ4), in
which 2-OH-phenone is the anion of the ligands 2-OH-aceto-
phenone(Hapo) (1Ј), 2-OH-propiophenone(Hppo) (2Ј), 2-OH-
[Fe(ppo)3] revealed a facial octahedral arrangement of the ligands
around the iron(III) atom. The thermal decomposition for the com-
pounds 2 and 4 was studied in nitrogen atmosphere, from ambient
benzophenone(Hbpo) (3Ј) and 2-OH, 4-OCH3-benzophenone- temperature to 1000 °C, by using the TG/DTG-DTA technique.
(Hopo) (4Ј), were synthesized and characterized by physicochemi-
cal and spectral (IR, UV/Vis, Mössbauer) data. The X-ray diffrac-
tion study of compound 2, tris(2-hydroxypropiophenone)iron(III)
The compounds are very stable at ambient temperature but
unstable upon heating giving as residue carbonaceous iron oxide.
with vanadium octahedral coordination [VO(3-OCH3-
salo)2(H2O)] [9]. The bidentate coordination mode of the
ligand 3-OCH3-saloH is retained when mixed-ligands are
involved, e.g. [Co(salo)2(α-diimine)] (α-diimine is a bipyri-
dine or phenanthroline molecule) [10, 11], but there is no
reference of any salicylaldehyde or 2-hydroxy-phenone com-
plex with trivalent 3d metal structurally characterized.
However, it was recently found by us that under proper con-
ditions, 3-OCH3-salicylaldehyde can coordinate with FeIII
ions in two different modes as bridging ligand, forming
polynuclear complexes [12].
For a better understanding of the bonds and properties
in these complexes we have recently initiated a research pro-
ject with the metal ions cobalt(II, III) or iron(III) and li-
gands with nitrogen and/or oxygen donor atoms [13]. In
this paper, our approach to the field concerns the synthesis
and characterization (physicochemical and spectroscopic by
IR, UV/Vis, Mössbauer methods) of four iron(III) com-
plexes with the general formula [Fe(2-OH-phenone)3]
(1Ϫ4). The crystal and molecular structure for one com-
pound, [Fe(ppo)3] (2), was studied by X-ray diffraction
analysis. The deprotonated ligands ppoϪ coordinate to the
FeIII ion with the bidentate chelating mode from the
carbonyl and phenolic oxygens adopting an octahedral
arrangement. The thermal stability and decomposition
mode for two of the new complexes (2 and 4) were studied
in nitrogen atmosphere by using TG/DTG-DTA technique.
The 2-OH-phenones presented in this work have the
molecular formula 2-OH- C6H4C(R)O, in which R ϭ CH3,
C2H5 or C6H5, commonly known and abbreviated as 2-OH-
acetophenone(Hapo) (1Ј), 2-OH-propiophenone(Hppo)
1. Introduction
Among all metals, iron earns a relevant position due to
its indispensability in life, since it takes part in processes
such as oxygen transport and electron transfer and DNA
syntheses. Iron metal complexes with oxygen atoms possess
a variety of structures and are of current interest not only
in bioinorganic chemistry [1] (the iron storage protein ferri-
tin has been extensively studied as a biological prototype in
the organic systems [2]) but also in material science, since
they can find technological applications due to their pro-
mising magnetic, electronic and catalytic properties [3, 4],
that are related to their structural characterization.
Besides, the strong coordinating properties of 2-hydroxy-
phenones or 2-hydroxy-benzaldehydes (salicylaldehyde,
saloH) and their derivatives with 3d transition metals have
stimulated research in these compounds, which find appli-
cations in both pure [5] and applied chemistry fields,
especially in extractive metallurgy as analytical reagents [6].
These ligands are known to coordinate in a bidentate
manner with divalent transition metals in the mono-anionic
form, adopting square-planar arrangement, [Zn(salo)2],
[Zn-5-Br-salo] [7], [Cu(5-Br-salo)2] [8a], [Fe(salo)2] [8b] or
* Prof. Dr. M. Lalia-Kantouri
E-Mail: lalia@chem.auth.gr
[a] Department of Chemistry
Lab. of Inorganic Chemistry
P.O.Box 135, Aristotle University
Thessaloniki-54124, Greece
[b] Faculty of Chemistry
Adam Mickiewicz University
´
60780 Poznan, Poland
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M. Lalia-Kantouri, T. Dimitriadis, C. D. Papadopoulos, M. Gdaniec, A. Czapik, A. G. Hatzidimitriou
ARTICLE
(2Ј), 2-OH-benzophenone(Hbpo) (3Ј) and 2-OH, 4-OCH3- 2.3. Preparation of the Complexes [FeL3]
benzophenone(Hopo) (4Ј), respectively (Scheme 1).
2.3.1. Preparation of [Fe(apo)3] (1)
A freshly prepared methanol solution of Fe(SCN)3, [derived from
the reaction of FeCl3 ·6H2O (270.5 mg, 1 mmol) and NaSCN
(243 mg, 3 mmol) after the elimination by filtration of the white
NaCl] was added dropwise to a stirred methanol solution of 2-OH-
acetophenone (Hapo, 408 mg, 3 mmol) in the presence of excess
sodium methoxide (CH3ONa, 162 mg, 3 mmol) at room tempera-
ture. The color of the solution turned gradually darker and after 2
hours to dark red. The solution mixture was left at rest and a few
days later dark red microcrystals of compound 1 were formed. The
microcrystals obtained were collected by filtration, washed with
ethyl ether, dried in vacuo and recrystallized from dichloromethane.
The resulting solid analyzed as Anal. Calc. % for 1 (C24H21O6Fe):
C: 62.23 (calcd. 62.47), H: 4.52 (calcd. 4.55); Fe: 12.03 (calcd.
12.13). Yield 267 mg, 58 %. The conductivity in freshly prepared
CH3CN solutions was found equal to 16 µS/cm, denoting the neu-
tral character of the compound. The magnetic value at room temp.
(µeff) for compound 1 was found equal to 2.26 µB. IR (KBr), selec-
ted peaks: 1603 vs, 1342 m, 604 m cmϪ1
.
Scheme 1. Structural formulae of the 2-hydroxyphenone ligands.
2.3.2. Preparation of [Fe(ppo)3] (2)
The procedure followed was the same as described above, by
replacing only the ligand 2-OH-acetophenone, by 2-OH-
propiophenone (Hppo, 450 mg 3 mmol). The microcrystalline com-
pound obtained analyzed as Anal. Calc. % for 2 (C27H27O6Fe): C:
63.94 (calcd. 64.41), H: 5.35 (calcd. 5.36); Fe: 11.02 (calcd. 11.20).
Yield 276 mg, 55 %. Conductivity in CH3CN solutions was equal
to 14 µS/cm and µeff ϭ 2.63 µB. IR (KBr), selected peaks: 1602 s,
2. Experimental Section
2.1. Materials
2-Hydroxyphenone ligands 1ЈϪ4Ј, FeCl3 ·6H2O and NaSCN were
obtained as reagent grade from Aldrich and used as received. For
physical measurements solvents of “extra pure” quality were ob-
tained from Fluka and used without further purification.
1341 m, 603 m cmϪ1
.
2.3.3. Preparation of [Fe(bpo)3] (3)
2.2. Instrumentation and Analytical Procedures
The procedure followed was the same as described above, by re-
placing only the ligand 2-OH-acetophenone, by 2-OH-benzo-
Microanalyses were carried out with a Perkin-Elmer 240 B CHN
microanalyzer and Perkin-Elmer 5100 PC Atomic Absorption phenone (Hbpo, 594 mg, 3 mmol). The microcrystalline compound
Spectrophotometer for the metal content.
obtained analyzed as Anal. Calc. % for 3 (C39H27O6Fe): C: 71.83
(calcd. 72.33), H: 4.15 (calcd. 4.17); Fe: 8.63 (calcd. 8.65). Yield
Infrared spectra were recorded with a Perkin-Elmer 1600 FT-IR
spectrometer in KBr discs at room temperature and are reported
in cmϪ1. Electronic absorption spectra in CH3CN solutions were
obtained with a Shimatzu 160 A spectrometer. Molar conductivit-
ies were measured in CH3CN solutions, employing a WTW con-
ductivity bridge and a calibrated dip type cell. Magnetic suscepti-
bility measurements on powdered samples were performed at 25 °C
employing the Faraday method on a home-build balance calibrated
against Hg[Co(SCN)4].
297.6 mg, 46 %. Conductivity in CH3CN 12 µS/ cm and µeff
ϭ
2.67 µB. IR (KBr), selected peaks: 1608 s, 1368 m, 604 m cmϪ1
.
2.3.4. Preparation of [Fe(opo)3] (4)
The procedure followed was the same as described above, by re-
placing only the ligand 2-OH-acetophenone, by 2-OH-4-OCH3-
benzophenone (Hopo, 684 mg, 3 mmol). The microcrystalline com-
pound obtained analyzed as Anal. Calc. % for 4 (C42H33O9Fe): C:
67.84 (calcd. 68.38), H: 4.42 (calcd. 4.47); Fe: 7.50 (calcd.7.59).
Yield 309.5 mg, 42 %. Conductivity in CH3CN 15 µS/ cm and
µeff ϭ 2.59 µB. IR (KBr), selected peaks: 2837 m, 1607 s, 1371 m,
57Fe Mössbauer spectra were obtained at room temperature
with a conventional constant acceleration spectrometer using a
57Co(Rh-matrix) source. The spectrometer was calibrated with a
metallic α-Fe spectrum at room temperature and the isomer shift
values are given relative to metallic iron at room temperature.
604 m cmϪ1
.
The thermal behavior of the title compounds was studied in nitro-
gen with the simultaneous TG/DTG-DTA technique, over the tem-
2.4. X-ray Crystallography
perature range ambientϪtoϪ1000 °C, using a Setaram Model Single crystals of the [Fe(ppo)3] were obtained by recrystallization
Setsys-1200 thermogravimetric analyzer. The samples, with a mass
of about 12 mg were heated in platinum crucibles, at a heating rate
10 °C/min.
from dichloromethane solution at ambient temperature. Diffraction
data were collected at 130 K with a KumaCCD single-crystal dif-
fractometer equipped with an Oxford Cryostream device. Data col-
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Synthesis and Structural Characterization of Iron (III) Complexes
lection and reduction were performed with CrysAlis CCD [14] and
CrysAlis RED [14], respectively. As initial attempts to solve the
crystal structure in different trigonal space groups and a P lattice
were unsuccessful, twinning was considered as a source of the fail-
ure. More careful analysis of the diffraction pattern pointed to an
obverse/reverse twinning [15]. In layers with l ϭ 3n only every third
reflection was observed, whereas in all the other layers one third
of the reflections was absent (a typical manifestation of the obverse/
reverse twinning) and therefore data integration was repeated on
Their magnetic moments at room temperature (µeff
ϳ 2.49 µB), corroborate with low-spin octahedral coordi-
nation of the iron(III) ion [18].
ϭ
Fe(SCN)3 ϩ 3 (2-OH-phenoneH) ϩ 3 CH3ONa Ǟ
[Fe(2-OH-phenone)3] ϩ 3 CH3OH ϩ 3 NaSCN (1)
The coordination mode and the arrangement around the
metal ion of the 2-hydroxy-phenone ligands in the newly
prepared complexes were examined by different spectro-
scopic methods (IR and electronic excitation spectra, as
well as Mössbauer for one representative complex).
¯
an R lattice. The structure was solved in the space group R3 by
direct methods with the SHELXSϪ97 program [16] and refined by
full-matrix least-squares method on F2 with SHELXLϪ97 [17]. In
the refinement process obverse/reverse twinning was taken into ac-
count with the help of the “HKLF 5” instruction of SHELXL-97.
The BASF parameter refined to 0.420(2). Hydrogen atoms bound
to carbon atoms were generated geometrically in idealized posi-
tions. Their displacement parameters were set equal to 1.5Ueq(C)
for the methyl groups and 1.2Ueq(C) for the remaining hydrogen
atoms. The crystal data and some details of data collection and
structure refinement are given in Table 1. CCDC-713969 contains
the supplementary crystallographic data for this paper.
3.2. Infrared Spectra (IR)
From a plethora of discrete bands in the IR spectra of
the compounds studied we selected those that are important
for the elucidation of the coordination mode of the ligands
with the metal ion.
Table 1. Crystal data for [Fe(ppo)3].
In the spectra of the free 2-hydroxyphenone ligands the
intense bands stemming from the stretching and bending
vibrational modes of the phenolic OH around 3200 cmϪ1
and 1410 cmϪ1, respectively, disappear from the spectra of
all complexes indicating the ligand deprotonation [19].
Also, the bands originating from the CϪO stretching
vibrations at 1245Ϫ1285 cmϪ1 in the complexes exhibit
positive shifts at 1342Ϫ1385 cmϪ1, whereas their intensity
is enhanced appreciably denoting coordination through the
carbonyl oxygen of the phenone ligand. The band at
ϳ1660 cmϪ1 attributable to the carbonyl bond v(CϭO) of
the free ligand, upon coordination, in the complexes is
shifted to lower frequencies at ϳ 1603 cmϪ1 thus denoting
the bidentate mono-anionic character of the studied hy-
droxyl-phenone ligands. The medium intensity bands at
about 604 cmϪ1 are attributed to the Fe-O coordination
bonds [20].
Empirical formula
(C9H9O2)3Fe
Formula weight
Temperature /K
503.34
130 (2)
0.71073
trigonal
¯
R3
˚
Wavelength /A
Crystal system
Space group
Unit cell dimensions
˚
a /A
13.3184(1)
13.3184(1)
46.4459(9)
7134.80(16)
12
1.406
3156
0.2 ϫ 0.2 ϫ 0.15
4.16Ϫ25.02
Ϫ15 Յ h Յ 7, Ϫ7 Յ k Յ 15,
Ϫ54 Յ l Յ 55
13978 / 2797
2797 / 0 / 206
99.4 %
˚
b /A
˚
c /A
3
˚
Volume /A
Z
Density calculated /g·cmϪ3
F(000)
Crystal size /mm
θ range for data collection /°
Limiting indices
Reflection collected / unique
Data / restraints / parameters
Completeness θ ϭ 25.02°
Goodness-of-fit on F2
1.131
Final R indices [I > 2σ(I)]
R indices (all data)
R1 ϭ 0.0404, wR2 ϭ 0.0923
R1 ϭ 0.0510, wR2 ϭ 0.0975
0.506 and Ϫ0.512
3.3. Electronic Spectra (UV/Vis)
Ϫ3
˚
∆
ρmax
and ∆ρmin /e·A
The UV/Vis spectra of all compounds studied in CH3CN
solutions presented five dominant bands in the region
200Ϫ1000 nm. The intense bands in the ultraviolet region,
appearing at around 220 nm (Band I), 265 nm (Band II),
and 330 nm (Band III), were assigned to π*ǟπ or π*ǟη
intra ligand transitions, evidence arising from the position
and intensity, as well as from the comparison with the cor-
3. Results and Discussion
3.1. Synthesis and Characterization
The reaction of a methanol solution of Fe(SCN)3 with responding free 2-hydroxy-phenones spectra.
the anion of a 2-OH-phenone ligand, in a metal-to-ligand
In the visible region the band appearing at around
ratio 1:3 [Equation (1)], in air at room temperature, led to ϳ 430 nm (Band IV) with the shoulder at ϳ 480 nm
the formation of four dark red microcrystalline iron com- (Band V) can be assigned to charge transfer, probably from
pounds. They are stable in air, soluble in almost all organic phenolate ligand to metal (LMCT), responsible for the deep
solvents but insoluble in ethyl ether and water. Their el- red color of the compounds [21, 22].
emental analyses and the absence of electrical conductivity
The expected band at ϳ 600 nm due to the (dϪd) metal
in CH3CN solutions (ΛM ഠ 14 µS/cm) indicated neutral transition is not apparent in the spectra of these complexes,
compounds of the general formula [Fe(2-OH-phenone)3]. probably obscured from the more intense CT band. A rep-
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M. Lalia-Kantouri, T. Dimitriadis, C. D. Papadopoulos, M. Gdaniec, A. Czapik, A. G. Hatzidimitriou
ARTICLE
resentative UV/Vis spectrum for the compound [Fe(apo)3] carbonyl group and therefore the tris-chelate [Fe(ppo)3]
is given in Figure 1.
molecules could, in principle, assume meridional and facial
arrangements. However, C3 symmetry of the complex mol-
ecules in the studied crystal allows for facial isomers only.
In both symmetry independent molecules, the FeO6 units
show distorted octahedral arrangement (Table 2) with the
trans OϪFeϪO angles of 165.42(8)° and 168.21(8)° in mol-
ecules A and B, respectively. Larger distortions in the mol-
ecule A are also observed for the cis OϪFeϪO angles which
fall in the range 80.53(8)Ϫ100.13(7)°. The equatorial coor-
dination planes present no deviation within the experimen-
tal error for the atoms forming them and both FeIII ions
˚
are placed slightly lower with distances 0.13 and 0.17 A.
The corresponding FeϪO distances in both molecules are
equal within an experimental error, with the mean
˚
FeϪO(phenolato) length of 1.914(2) A significantly shorter
˚
than the mean FeϪO(carbonyl) distance, 2.070(2) A. This
arrangement is in a good agreement with that observed in
some complexes formed by FeIII with salicylate-based
tripodal ligands [24]. A significantly smaller difference be-
tween the distances of the metal ion to phenolato and car-
bonyl oxygen atoms was observed in the meridional [Ru(s-
alo)3] complex [25].
Figure 1. Electronic excitation (UV/Vis) spectrum for the com-
pound [Fe(apo)3], C ϭ 10Ϫ4 M in CH3CN.
3.4. Mössbauer
˚
Table 2. Selected interatomic distances /A and angles /° for
The RT Mössbauer spectrum of the compound
[Fe(ppo)3] (Figure 2) consists of one non-equivalent doublet
with hyperfine parameters (isomer shift value δ(Fe) ϭ
0.28 mm/s and quadrupolar splitting ∆Eq ϭ 0.66 mm/ s)
corresponding to FeIII in distorted octahedral environment
with probability of low-spin complexes [23].
[Fe(ppo)3].
Bond/angle
Molecule A
Molecule B
Fe1ϪO1
Fe1ϪO2
O1ϪC1
O2ϪC7
1.9135(19)
2.0766(19)
1.313(3)
1.244(3)
100.13(7)
86.07(8)
91.66(8)
165.42(8)
80.53(8)
1.9155(19)
2.0632(19)
1.312(3)
1.252(3)
96.94(7)
85.72(7)
94.13(8)
168.21(8)
82.63(8)
O1ϪFe1ϪO1(i)
O1ϪFe1ϪO2
O1ϪFe1ϪO2(i)
O1ϪFe1ϪO2(ii)
O2ϪFe1ϪO2(ii)
Symmetry codes: (i) 1Ϫy, 1 ϩ xϪy, z; (ii) 1Ϫx ϩ y, 1Ϫx, z.
The crystal packing is shown in Figure 4a. Two types of
(0001) layers, composed solely of similarly arranged mol-
ecules A or B, alternate along the z axis (Figure 4bϪd). The
crystal structure is mainly stabilized by CϪH-π interactions
between the phenyl rings belonging to the same layer and
by CϪH···O(phenolate) interactions between the molecules
from neighboring layers.
3.6. Thermal Behavior
Figure 2. Mössbauer spectrum of the compound [Fe(ppo)3] at
The decomposition mode of the complexes [Fe(ppo)3]
and [Fe(opo)3] was studied in nitrogen atmosphere by using
the simultaneous thermogravimetric and differential ther-
mal analysis technique (TG/DTG-DTA) from ambient tem-
perature up to 1000 °C. The thermal decomposition mode
of the two complexes under investigation seems to follow
room temp.
3.5. Crystal Structure of [Fe(ppo)3] (2)
¯
[Fe(ppo)3] crystallizes in the space group R3 with two similar models. Representative thermoanalytical curves are
symmetry independent molecules in the unit cell, A and B, depicted for [Fe(ppo)3] in Figure 5. It is obvious that there
situated on a threefold axis (Figure 3). The ppo ligand is a is no crystallized water or alcohol solvent molecule in the
bidentate O,O donor, with one oxygen atom belonging to compound. The melting, deduced from the sharp intense
the phenolate group and the second oxygen atom to the endothermic peak on DTA curve at 205 °C, was followed
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Synthesis and Structural Characterization of Iron (III) Complexes
immediately by decomposition. The first decomposition
stage proceeds with a sudden and considerable mass loss
(30 %) with maximum decomposition rate (DTGmax) at
250 °C, which is attributed to the elimination of one Hppo
ligand molecule (29.62 % calcd.). The second stage, sepa-
rated in several steps as deduced from the DTG curve, fol-
lows successively with the rupture of both coordination
bonds and bonds inside the ligands. The experimental mass
loss for this stage (36 %) involves possibly elimination of a
second ligand plus one ethane molecule from the third one
at DTG maxima 300 and 350 °C (35.60 % calcd.).
Figure 3. Ortep plot of the two symmetry independent molecules
of [Fe(ppo)3] with 50 % probability ellipsoids. Atomic labels are
shown for asymmetric unit and hydrogen atoms have been omitted
for clarity.
Figure 5. Thermoanalytical (TG/DTG-DTA) curves for compound
[Fe(ppo)3] in nitrogen.
Figure 4. Crystal packing of [Fe(ppo)3]: (a) view along the z axis; (b) view along the b axis showing alternating layers of molecules A
and B and arrangement of the molecules within the layers for molecues A (c) and B (d). Hydrogen atoms have been omitted for clarity.
Z. Anorg. Allg. Chem. 2009, 2185Ϫ2190
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M. Lalia-Kantouri, T. Dimitriadis, C. D. Papadopoulos, M. Gdaniec, A. Czapik, A. G. Hatzidimitriou
[9] J. C. Pessoa, I. Cavaco, I. Correia, I. Tomaz, T. Duarte, P. M.
ARTICLE
The intermediates formed are further decomposed at
700 °C leading to the formation of carbonaceous (4 % in
carbon) iron oxide, Fe2O3, confirmed by its infrared spec-
trum and X-ray diffraction pattern as final product at
1000 °C [26, 27].
Matias, J. Inorg. Biochem. 2000, 80, 35.
[10] C. D. Papadopoulos, A. G. Hatzidimitriou, G. P. Voutsas, M.
Lalia-Kantouri, Polyhedron 2007, 26, 1077.
[11] C. D. Papadopoulos, M. Lalia-Kantouri, J. Jaud, A. G. Hatzid-
imitriou, Inorg. Chim. Acta 2007, 360, 3581.
[12] M. Lalia-Kantouri, C. D. Papadopoulos, A. G. Hatzidimitriou,
S. Skoulika, Struct. Chem. 2008, in press, DOI: 10.1007/
s11224-008-9397-5.
4. Conclusions
[13] C. D. Papadopoulos, Ph. D. Thesis, Aristotle University of
Thessaloniki, Greece 2007.
The characterization of the newly synthesized iron(III)
complexes [Fe(2-OH-phenone)3] was made by stoichio-
metric analysis, molar conductivity and magnetic measure-
ments at room temperature. The infrared spectroscopic data
gave evidence for the bidentate coordination mode (through
the phenolate and carbonyl oxygen atoms) of the 2-
hydroxyphenone ligands, whereas Mössbauer data verified
the trivalent character of the iron atom in the studied com-
plexes. The X-ray study of complex 2 revealed a facial octa-
hedral arrangement of the ppoϪ ligands around the
iron(III) atom. The thermal data of the complexes 2 and 4,
in nitrogen, gave as residues at 1000 °C the carbonaceous
oxide Fe2O3.
[14] Oxford Diffraction. CrysAlis CCD and CrysAlis RED Ver.
1.171.31. Oxford Diffraction Ltd., Abingdon, Oxfordshire,
England 2006.
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Received: January 20, 2009
Published Online: April 8, 2009
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