Synthesis, crystal structures and magnetic properties of two iron (II) tris(pyridyl)phosphine selenides complexes

Article abstract of DOI:10.1080/10426507.2017.1417295

We reported the synthesis of tris(pyridyl)phosphine selenide (TppSe) and tris(4-methylpyridin-2-yl)phosphine selenide (MeTppSe), which were prepared by a simple and straightforward one-pot method with red phosphorus in a KOH/DMSO suspension, and treatment of resulted phosphines with selenium in hot toluene. These compounds were characterized by mass spectroscopy, ¹H, ¹³C and ³¹P NMR spectroscopies and the structure of MeTppSe was characterised by a single-crystal X-ray diffraction. Furthermore, The reactions of selenides with Fe(ClO₄)₂·6H₂O afforded two new iron(II) mononuclear metal complexes [Fe(TppSe)₂][ClO₄]₂·3DMF (1) and [Fe(MeTppSe)₂][ClO₄]₂·2DMF (2). Detailed structural analyses and magnetic susceptibility measurements confirm no spin transition from low-spin to the high-spin state between 2 and 300?K in two iron(II) complexes.

Full text of DOI:10.1080/10426507.2017.1417295

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Synthesis, crystal structures and magnetic
properties of two iron (II) tris(pyridyl)phosphine
selenides complexes
Xuecheng Hu, Tingquan Sun & Chunyang Zheng
To cite this article: Xuecheng Hu, Tingquan Sun & Chunyang Zheng (2017): Synthesis, crystal
structures and magnetic properties of two iron (II) tris(pyridyl)phosphine selenides complexes,
Phosphorus, Sulfur, and Silicon and the Related Elements, DOI: 10.1080/10426507.2017.1417295
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Date: 17 December 2017, At: 00:12

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Synthesis, crystal structures and magnetic properties of two iron
(II) tris(pyridyl)phosphine selenides complexes
a, b
a
a, b
Xuecheng Hu Tingquan Sun and Chunyang Zheng*
Hubei Collaborative Innovation Center for Rare Metal Chemistry, Hubei Key Laboratory
a
of Pollutant Analysis and Reuse Technology, Institute for Advanced Materials, Hubei Normal
University, Huangshi 435002, P. R. China.
b
Department of Chemistry, The School of Art and Science of Hubei Normal University,
Huangshi 435002, P. R. China.
E-mail: zcy800204@163.com
Abstract: We reported the synthesis of tris(pyridyl)phosphine selenide (TppSe) and tris(4-
methylpyridin-2-yl)phosphine selenide (MeTppSe), which were prepared by a simple and
straightforward one-pot method with red phosphorus in a KOH/DMSO suspension, and
treatment of resulted phosphines with selenium in hot toluene. These compounds were
1
13
31
characterized by mass spectroscopy, H, C and P NMR spectroscopies and the structure of
MeTppSe was characterised by a single-crystal X-ray diffraction. Furthermore, The reactions of
selenides with Fe(ClO ) ·6H O afforded two new iron(II) mononuclear metal complexes
4
2
2
[
Fe(TppSe) ][ClO ] ·3DMF (1) and [Fe(MeTppSe) ][ClO ] ·2DMF (2). Detailed structural
2 4 2 2 4 2
analyses and magnetic susceptibility measurements confirm no spin transition from low-spin to
the high-spin state between 2 and 300 K in two iron(II) complexes.
Introduction
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Over the last decade, organophosphorus compounds and their chalcogenides derivatives
attracted much attention because of their unique chemical and physical properties and their
1
-3
applications in a variety of advanced materials. Among them, pyridyl-substituted phosphines
have been extensively used in metal ion coordination chemistry for their ease of
functionalization and the electronic properties that they impart to metal complexes used for
catalysis purposes. Tris(2-pyridyl)phosphine exhibits rich coordination capabilities, forming a
variety of complexes owing to its high-performance group combining molecular flexibility, and a
large number of metal complexes have been found, in which the pyridylphosphines ligands bind
4
-11
to the metal.
On the other hand, the coordination chemistry of tris(2-pyridyl)phosphine
chalcogenides is poorly investigated, and only several example based on tris(2-
5
pyridyl)phosphine selenide have been prepared. However, to the best of our knowledge, no
study about iron (II) complex has been reported so far based on the tris(2-pyridyl)phosphine
selenide ligands.
On the other hand, magnetic bistability induced by external stimuli (such as temperature,
pressure, magnetic field or light) has attracted much attention because of their potential
technological applications. We recently synthesized a cyano-bridged {Fe Co } grid and two
2
2
III
2
II
2
mixed-valence {Fe Fe } clusters, which exhibited reversible thermally intramolecular charge
1
2, 13
transfer induced spin transition (CTIST) and spin crossover (SCO) properties, respectively.
According to the relevant literature, we find that substituted tris(pyrazolyl)borate and
tris(pyrazolyl)methane ligands induce a variety of electronic spin-state behaviors in iron
14-16
complexes,
which led us to undertake an extensive investigation of the iron (II) complexes
formed with other tripodal ligands. Herein, we report the first iron(II) mononuclear metal
2
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complexes with tris(pyridyl)phosphine selenide and thoroughly characterize them by single-
crystal X-ray diffraction and magnetic susceptibility measurements.
Result and discussion
Synthesis
Two tris(pyridyl)phosphine ligands are synthesized by the reaction of 2-bromopyridine or
2
1
-bromo-4-methylpyridine with red phosphorus in a superbasic KOH/DMSO(H O) suspension at
2
20 °C for 1 h to afford tris(2-pyridyl) phosphine (Tpp) and tris(4-methylpyridin-2-yl)phosphine
9
, 17, 18
(MeTpp).
Two phosphines are easily oxidized by treatment of appropriate phosphine with
elemental selenium in refluxing toluene to afford the corresponding phosphine chalcogenides
1
0, 19
TppSe and MeTppSe,
crystallographically. The synthesis of two metal complexes 1 and 2 are performed by reaction of
equiv of TppSe or MeTppSe with the appropriate Fe(ClO ) ·6H O salt in DMF under an N
2
and the identity of MeTppSe, 1 and 2 were also confirmed
2
4
2
2
atmosphere in good yields (Scheme 1). The mass spectra of complexes 1 and 2 in CH OH
3
2
+
(
Figure S3 and S4) show strong peaks at m/z = 373.14, and 414.73, for [Fe(TppSe)2] and
2
+
[
Fe(MeTppSe) ] , respectively, indicating that two iron(II) mononuclear metal complexes are
2
stable in solution.
NMR spectral studies
1
13
31
H NMR, C NMR and P NMR spectra of Tpp, TppSe, MeTpp and MeTppSe are given
1
in the supplemental materials. The comparison of the H NMR spectra for phosphines and
selenides reveals that the selenium atom does not obviously effect on δ values. However, some
H
of C resonance on pyridine split into doublets indicating that there exist the P-C couplings based
1
3
on C NMR spectra of four ligands (see below experimental part and supplemental materials).
3
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1
The coupling constants of J in phosphines ligands are significantly different comparing with
C,P
1
selenides ligands. The J value in selenides ligands (105.6 Hz in TppSe and 105.3 Hz in
C,P
1
MeTppSe) are larger than those of phosphines ligands ( JC,P = 12.1 Hz in Tpp and MeTpp).
Phosphorus with different chemical valence (tervalence in phosphines ligands and pentavalence
2
0
in selenides ligands) has different effects on P-C coupling constants. Furthermore, the
31
resonance in the P NMR spectra of Tpp, MeTpp and TppSe, MeTppSe appears at –0.78, -
.35 and 28.97, 29.00 ppm, respectively, and the δ values of selenides ligands are also larger
0
P
than those of phosphines ligands. These chemical shifts are similar to the related phosphines and
9
, 19
selenides that were previously reported in the literature.
Single crystal X-ray studies
Details of the crystal data and structure refinement parameters for MeTppSe, 1 and 2 are
summarized in Table 1. Selected bond distances and angles are included in Table 2. ORTEP of
MeTppSe is presented in Figure 1, and the asymmetric unit (Monoclinic, P2 /n) contains two
1
independent molecules. In two molecules, the nitrogen atoms (N2, N3 and N5, N6) point to the
opposite direction as the selenium atoms (Se1 and Se2), respectively, while the remaining
nitrogen atoms (N1 and N4) point in the same direction. This type of arrangement has been
previously seen in the structure of tris(2-pyridyl)phophine oxide and tris(2-pyridyl)phophine
1
9
sulphide. However, in the reported tris(2-pyridyl)phophine selenide structure,
all nitrogen
atoms point in the same direction as the Se atom, which can be related to the steric requirement
in the structure of MeTppSe bearing a methyl group at the 4-position of the pyridyl ring. The P-
Se bond distances, 2.1043(13) Å and 2.1066(14) Å, are comparable with similar structures found
1
9
in the literature showing typical double bond character.
4
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The molecular structures of complexes 1 and 2 are determined by X-ray crystallography at
2
96 K and 100 K, respectively. Complex 1 and 2 crystallize in the Monoclinic space group P21
and triclinic space group P-1 with three DMF molecules in 1 and two DMF molecules in 2,
respectively. As shown in Figure 2, the crystal structures of 1 and 2 are similar. TppSe and
II
MeTppSe act as tripodal ligands, and the Fe atoms lie on an inversion center and are
octahedrally coordinated by the N atoms of two tridentate ligands with expected six-coordinate
geometry. The three pyridine planes of each ligand are parallel to the P-Fe-P axis.
It should be noted that the coordination bond lengths in 1 (av. 2.008 Å) and 2 (av. 2.004 Å)
2
+
2+
(
Table 1) are slightly longer than those of the [Fe{N(py) } ] (1.982 Å), [Fe{CH(py) } ]
3
2
3 2
2+
2+
22, 22, 23
(
1.949 Å), [Fe{CH C(py) } ] (1.973 Å) and [Fe(TppO) ) ] (1.982 Å)
, but similar with
3
3 2
2 2
2
+
2+
other reported average [Fe-N(py)6]
bond lengths in [Fe(TppO)2] based on tris(2-
2
4
pyridyl)phosphine oxide ligand. In addition, the distortion parameter values Σ of geometries
II
II
around Fe ions are 20.2° for 1 and 19.9°, 19.3° for 2, respectively. In general, high spin Fe ions
tend to form more distorted octahedra and thus have larger Σ values than their low spin
II
counterparts. According to above analysis, we can infer that the spin state of Fe ion in 1 and 2 is
the LS state, which is in accordance with the magnetic data (see below). The P=Se bond lengths
II
in the Fe complexes (2.079 Å, 2.091 Å for 1 and 2.085 and 2.077 Å for 2) are a litter shorter
than those in the free MeTppSe ligand (2.103 Å and 2.106 Å), which are due to the strong effect
II
of spin delocalization in 1 and 2. Furthermore, the CPC angles of two Fe complexes lie in the
range 100.7°–104.1°, comparable to 102.7°–107.8° Å in free MeTppSe ligand.
Magnetic properties
5
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Magnetic susceptibility measurements in a 1000 Oe field were performed on 1 and 2 in the
temperature range of 2–300 K, and are shown as χ T versus T plots (Figure 4). The  T values
M
M
of 1 and 2 do not change as the temperature increased from 30 K to 300 K, which shows a great
II
tendency to stabilize the LS state with S = 0 and is very similar to that observed for related Fe
complex systems chelating bis-tripodal ligands showing no temperature dependence (LS state) in
2
1, 22
the measuring temperature range.
Although the coordination bond lengths in 1 and 2 are
2+
2+
2+
slightly longer than those of the [Fe{CH(py) } ] , [Fe{CH C(py) } ] and [Fe(TppO) ) ] (See
3
2
3
3 2
2 2
above), the magnetic moments on 1 and 2 show that they are fully low spin at room temperature,
and the small differences noted in the Fe–N distances (Table 4) cannot be correlated with any
2+
differences in magnetic properties, which can be found in some of the similar [Fe-N(py)6]
II
compounds with such same phenomenon. In general, Fe complexes exist in either a high spin
or a low spin state, depending on the nature of the ligand field on the metal ions. We devote
ourselves to select and change the ligands with different electron-donating groups in order to
get intermediate ligand field, but spin transition from low-spin to the high-spin state is not
detected between 2 and 300 K in two complexes.
Conclusions
In summary, we report a simple and straightforward one-pot method for the synthesis of
tris(2-pyridyl)phosphines with red phosphorus in a KOH/DMSO suspension. Moreover, two
iron(II) mononuclear metal complexes based on the tris(2-pyridyl)phosphine selenide ligands in
a N,N',N''-tripodal mode have been successfully synthesized. Based on the detailed structural
analyses and magnetic susceptibility measurements, no spin transition happened from low-spin
to the high-spin state between 2 and 300 K in two iron(II) complexes. We think that our result
6
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for synthesizing two new iron(II) mononuclear metal complexes will have some impact for the
preparation of novel SCO molecular materials. Further studies on the fabrication of new iron(II)
metal complexes are ongoing.
Experimental
Materials and methods
All chemicals were commercial and purified according to standard procedures. All organic
1
13
31
solvents were dried and freshly distilled before use. The H NMR, C NMR and P NMR
spectra were recorded on Bruker AV 300 MHz and 400 MHz spectrometers using CDCl as the
3
1
13
solvent. Chemical shifts are given with respect to tetramethylsilane ( H, C) and phosphoric acid
3
1
31
(
P) and P spectra were calibrated externally and chemical shifts are expressed in δ (ppm).
Mass spectra were measured on a LCQ Advantage MAX (ESI). The melting points of the
synthesized compounds were recorded on a WRX-4 monocular microscope and were not
corrected. Magnetic susceptibility measurement was carried out on a Quantum Design MPMS
SQUID-VSM magnetometer in the temperature range of 2−300 K with a magnetic field of 2000
Oe and the magnetic susceptibilities of the two complexes were measured at a sweep rate of 3 K
-1
min . Magnetic data were calibrated with the sample holder and diamagnetic contributions. The
1
13
31
Supplemental Materials contains sample H, C, P NMR spectra and mass spectra for the
products.
Structural Studies
Single crystal structural data for MeTppSe, 1 and 2 were collected on a Bruker Apex-II
CCD diffractometer using graphite-collimated Mo Kα radiation (λ = 0.71073 Å). The structures
were solved by direct methods (SHELXL97) and completed by difference Fourier methods
7
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2
5
2
(
SHELXL97). Refinement was performed against F by weighted full-matrix least-squares
2
6
(
SHELXL97) and empirical absorption corrections (SADABS) were applied. Hydrogen atoms
were found in difference maps and subsequently placed at calculated positions using suitable
riding models with isotropic displacement parameters derived from their carrier atoms. Non-
hydrogen atoms were refined with anisotropic displacement parameters.
CCDC 1575133, 1575137 and 1575138 contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data
Centre via http://www.ccdc.cam.ac.uk.
Preparation of tris(pyridyl)phosphine ligands Tpp and MeTpp.
A mixture of 2-bromopyridine (20 mmol) or 2-bromo-4-methylpyridine, red phosphorus (50
mmol), powdered KOH (60 mmol), DMSO (30 mL), and H O (1 mL) was stirred for 1 h at 120
2
o
C under argon. The mixture was cooled to room temperature, diluted with H O (60 mL) and
2
extracted with CHCl (3 x 20 mL). The combined extract was washed with H O (3 x 20 mL) and
2
2
dried over MgSO . The solvent was removed under reduced pressure and the residue washed
4
with diethyl ether (10 mL) and dried in vacuo to afford pure phosphine product as a
microcrystalline powder.
19
1
Tris(2-pyridyl)phosphine Tpp: Yield: 1.52 g (86 %). m.p. 113 °C (lit. 113 °C). H NMR
(
300 MHz, CDCl ): δ ppm: 8.73 (d, 4.4 Hz, 3H), 7.61-7.66 (m, 3H), 7.43 (d, J = 7.7 Hz, 3H),
3
1
3
2
7
.21-7.25 (m, 3H). C NMR (CDCl , 75.4 MHz): δ = 122.8, 129.2 (d, J = 19.5 Hz), 135.9 (d,
3
C,P
3
1
3
31
JC,P = 3.9 Hz), 150.3 (d, J = 12.1 Hz), 161.2 (d, J = 2.8 Hz) ppm. P NMR (CDCl , 162
C,P
C,P
3
+
+
+
MHz): δ = -0.78 ppm. ESI-MS: m/z = 266.01 ([M+H] ), 288.02 ([M+Na] ), 552.92 ([2M+Na] ).
+
HRMS (ESI+, CH OH): m/z (%) = 266.0841 ([M+H] requires 266.0842).
3
8
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+
Tris(4-methylpyridin-2-yl)phosphine MeTpp: Yield: 1.68 g (82 %). m.p. 94 °C. MS (EI ,
+
Me +
Me
+ 1
7
0 eV): m/z (%): 307 (6) [M] , 215 (100) [M-Py ] , 200 (10) [M-Py -Me] . H NMR (300
MHz, CDCl ): δ ppm: 8.58 (t, J = 9.6 and 4.8 Hz, 3H), 7.30 (d, J = 9.6 Hz, 3H), 7.02 (d, J = 4.8
3
1
3
2
Hz, 3H), 2.28 (s, 9H). C NMR (CDCl , 75.4 MHz): δ = 21.1, 123.7, 130.1 (d, J = 21.2 Hz),
3
C,P
3
1
3
31
1
46.9 (d, J = 4.5 Hz), 150.1 (d, J = 12.1 Hz), 161.2 (d, J = 3.3 Hz) ppm. P NMR
C,P
C,P
C,P
+
+
(
CDCl , 162 MHz): δ = -0.35 ppm. ESI-MS: m/z = 308.16 ([M+H] ), 330.15 ([M+Na] ), 637.05
3
+
+
(
[2M+Na] ). HRMS (ESI+, CH OH): m/z (%) = 308.1311 ( [M+H] requires 326.1311).
3
Preparation of tris(pyridyl)phosphine selenide ligands TppSe and MeTppSe.
To a solution of Tpp or MeTpp (10 mmol) in degassed toluene (20 ml), powdered gray
selenium (14 mmol) was added and the suspension was refluxed for 10 h. After cooling to room
temperature the suspension was filtered via a syringe filter and the filtrate is evaporated to
dryness under vacuum. The crude product was washed with ethanol (20 mL). After drying in
vacuo a beige-colored powder was obtained.
19
Tris(2-pyridyl)phosphine selenide TppSe: Yield: 3.1 g (90 %). m.p. 176 °C (lit. 176-178
1
°
C). H NMR (CDCl , 300 MHz): δ = 8.72 (d, J = 4.5 Hz, 3H), 8.34 (t, J = 7.4 Hz, 3H), 7.78-
3
1
3
4
7
1
=
.85 (m, 3H), 7.32-7.37 (m, 3H), C NMR (CDCl , 75.4 MHz): δ = 125.1 (d, J = 2.9 Hz),
3 C,P
2
3
3
1
29.4 (d, J = 26.1 Hz), 136.4 (d, J = 10.6 Hz), 150.0 (d, J =18.9 Hz), 154.2 (d, J
C,P
C,P
C,P
C,P
3
1
+
105.6 Hz) ppm. P NMR (CDCl , 162 MHz): δ = 28.97 ppm. ESI-MS: m/z = 345.86 ([M+H] ),
3
+
+
7
12.62 ([2M+Na] ). HRMS (ESI+, CH OH): m/z (%) = 346.0005 ([M+H] requires 346.0007).
3
Tris(4-methylpyridin-2-yl)phosphine selenide MeTppSe: Yield: 3.3 g (86 %). m.p. 167-168
+
+
+
Me +
°
C. MS (EI , 70 eV): m/z (%): 387 (18) [M] , 306 (15) [M-Se] , 215 (100) [M-SePy ] , 200
9
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Me
+
Me + 1
(
13) [M-SePy -Me] , 92 (6) [Py ] . H NMR (CDCl , 300 MHz): δ = 8.57 (d, J = 4.8 Hz, 3H),
3
13
8
.14 (d, J = 7.2 Hz, 3H), 7.14 (d, J = 4.8 Hz, 3H), 2.39 (s, 9H) ppm. C NMR (CDCl , 75.4
3
4
4
2
MHz): δ = 21.2 (d, J = 1.3 Hz), 125.8 (d, J = 3.2 Hz), 130.1 (d, J = 26.2 Hz), 147.7 (d,
C,P
C,P
C,P
3
3
1
31
JC,P = 10.6 Hz), 149.8 (d, J =19.8 Hz), 154.3 (d, J =105.3 Hz) ppm. P NMR (CDCl ,
C,P
C,P
3
+
1
3
62 MHz): δ = 29.00 ppm. ESI-MS: m/z = 388.02 ([M+H] ). HRMS (ESI+, CH OH): m/z (%) =
3
+
88.0472 ([M+H] requires 388.0476).
Preparation of [Fe(TppSe) ][ClO ] ·3DMF (1)and [Fe(MeTppSe) ][ClO ] ·2DMF (2)
2
4 2
2
4 2
Under an argon atmosphere, A solution of Fe(ClO ) ·6H O (0.1 mmol) and TppSe or
4
2
2
MeTppSe (0.2 mmol) in DMF (4 mL) was stirred at room temperature for 2 h and left it under
the diffusion of diethyl ether vapor slowly without disturbance. Dark-red blocks crystals suitable
for X-ray structure analysis were obtained and isolated via filtration after about 3 d.
2+
[
Fe(TppSe) ][ClO ] ·3DMF 1: Yield: 95 mg (82 %). ESI-MS: [M] calculated for
2 4 2
2
+
[
Fe(TppSe) ] : 372.96; Found: 373.14. Elemental analysis (%) calculated for
2
C H Cl N O P Se Fe: C 40.30, H 3.90, N 10.84; Found: C 40.25, H 4.08, N 10.65.
39
45
2
9
11
2
2
2
+
[
Fe(MeTppSe) ][ClO ] ·2DMF 2: Yield: 94 mg (80 %). ESI-MS: [M] calculated for
2 4 2
2
+
[
Fe(MeTppSe) ] : 415.00; Found: 414.73. Elemental analysis (%) calculated for
2
C H Cl N O P Se Fe: C 42.99, H 4.29, N 9.55; Found: C 42.89, H 4.35, N 9.51.
42
50
2
8
10
2
2
Funding
This work was financially supported by the project of Educational Commission of
Hubei Province of China (No. B2017141) and the National Undergraduate Training
Program for Innovation and Entrepreneurship (No. 201613256001) and the open fund of
10
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Hubei Key Laboratory of Pollutant Analysis & Reuse Technology (No. PA160209) and the
key fund of The School of Art and Science of Hubei Normal University (No. Ky201701).
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Inorg. Chem. 2004, 16, 3345-3352.
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K.; Trofimov, B. A. Russ. J. Gen. Chem. 2012, 82, 1307-1308.
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Elem. 2010, 185, 2341-2347.
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22Santoro, A.; Sambiagio, C.; McGowan, P. C.; Halcrow, M. A. Dalton Trans. 2015, 44,
1060-1069.
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3Anderson, P. A.; Astley, T.; Hitchman, M. A.; Keene, F. R.; Moubaraki, B.; Murray, K.
S.; Skelton, B. W.; Tiekink, E. R. T.; Toftlund, H.; White, A. H. J. Chem. Soc., Dalton
Trans. 2000, 20, 3505-3512.
2
4Bakhoda, A.; Khavasi H. R.; Safari, N. Cryst. Growth Des. 2011, 11, 933-935.
5Sheldrick, G. M. SHELX-97. Programs for Crystal Structure Solution and Refinement;
2
University of Göttingen, Germany, 1997
6Sheldrick, G. M. SADABS-An empirical absorption correction program. Bruker
Analytical X-Ray Systems; Madison, Wisconsin, 1996
.
2
.
R
N
R
R
N
R
N
R
R
R
N
1
2
Se
P
KOH/DMSO
red selenium
Fe(ClO4)2
P
N
+
Pn
o
Ar , 120 C, 1h
o
2
80 C, 10h
Br
N
N
R = H :Tpp
R =CH : MeTpp
R = H :TppSe
R =CH : MeTppSe
1
: [Fe(TppSe) ][ClO ] ·3DMF
2 4 2
3
3
2: [Fe(MeTppSe) ][ClO ] ·2DMF
2 4 2
Scheme 1 Synthetic procedure for two metal complexes 1 and 2
Figure 1. Molecular structure of MeTppSe
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Figure 2. Molecular structure of the 1, anions, solvent molecules, and hydrogen atoms are
omitted for clarity
Figure 3. Molecular structure of the 2, anions, solvent molecules, and hydrogen atoms are
omitted for clarity
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0.4
0.3
0.2
0.1
0.0
1
2

0
50
100
150
200
250
300
T /K
Figure 4. Temperature dependence of  T plots for
1 and 2
M
Table 1. Crystal structure and data refinement parameters for compounds MeTppSe, 1 and 2
Compound
Temperature / K
Formula
Formula weight
Crystal system
Space group
a /Å
MeTppSe
1
2
298
100
298
C H N PSe C H Cl N O P Se Fe C H Cl N O P Se Fe
18
18
3
39 45
2
9
11
2
2
42 50
2
8
10
2
2
386.28
1162.45
1173.51
Monoclinic
Monoclinic
Triclinic
P2 /n
P21
P-1
1
14.154(3)
8.4907(19)
30.189(7)
90
11.5861(14)
17.224(2)
12.2355(15)
90
12.1451(12)
13.2797(13)
16.5383(16)
79.689(2)
b /Å
c /Å
α /º
β /º
97.841(4)
110.213(2)
73.4610(10)
90
γ /º
90
86.613(2)
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3
V / Å
3594.0(14)
8
2291.3(5)
2
2515.6(4)
2
Z
-
3
D calcd/g cm
1.428
2.181
18180
7032
1.685
2.173
15606
8671
1.549
−
1
μ / mm
1.978
Collected reflections
Unique reflections
23174
8803
Data / restraints / parameters 7032 / 0 / 421 8671 / 37 / 629
8803 / 84 / 696
1.072
2
GOF on F
1.131
1.081
R1 = 0.0547
R1 = 0.0289
R1 = 0.0399
Final R indices [I >2σ (I)]
wR = 0.1438
2
wR = 0.0796
wR = 0.1178
2
2
R1 = 0.0720
R1 = 0.0307
R1 = 0.0519
R indices (all data)
wR = 0.1507
2
wR = 0.0806
wR = 0.1374
2
2
Table 2. Selected bond distances (Å), angles () and structural parameters in these complexes
a
compound P=Se (Å)
CPC ()
FeNAverage (Å) Fe
b
TppSe
2.1050(15) 104.76(13); 104.76(13); 104.76(13)
2
2
2
2
2
2
.1043(13) 107.8(2); 102.7(2); 106.3(2)
.1066(14) 106.6(2); 105.7(2); 103.6(2)
.0787(9) 102.96(14); 101.70(14); 104.02(15)
.0907(9) 103.63(15); 103.59(14); 101.09(14)
MeTppSe
1
2
2.008(3)
20.2
.0851(9) 103.82(17); 100.69(16); 103.52(16) 2.004(3)
.0773(10) 103.39(15); 102.91(15); 102.54(15) 2.004(3)
19.9
19.3
a
b
Fe : the sum of the deviation from 90° of the 12 cis-angles of the FeN octahedron; TppSe :
6
Crystallographic data is obtained from CCDC number 720507.
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