Decamethyl- and octamethyl-ferrocenium salts of F1- and F 2-TCNQ: Effects of fluorine substitution on the crystal structures and magnetic interactions

Article abstract of DOI:10.1016/j.ica.2014.05.011

Decamethyl- and octamethyl-ferrocenium salts of F_nTCNQ (n = 1, 2) were prepared and their crystal structures characterized. The 2,5-F ₂TCNQ salts [Fe(C₅Me₅)₂](2,5-F ₂TCNQ) (1) and [Fe(C₅Me₄H)₂](2,5- F₂TCNQ) (2) exhibit one-dimensional ...[D]⁺[A] ^-[D]⁺[A]^-... mixed-stack structures, while the salts with polar acceptors [Fe(C₅Me₅)₂][A] (A = F₁TCNQ (3), 2,3-F₂TCNQ (4), 2,6-F₂TCNQ (5)) and [Fe(C₅Me₄H)₂][A] (A = 2,3-F₂TCNQ (6), 2,6-F₂TCNQ (7)) consist of [D]⁺[A₂] ^2-[D]⁺ units involving a diamagnetic dimer of the acceptors. These salts are isomorphous to the corresponding TCNQ salts. 1 and 2 exhibit small ferromagnetic interactions at low temperatures. 1 undergoes an antiferromagnetic phase transition at T_N = 3.9 K, which is higher than T_N = 2.1 K of the metamagnetic polymorph of [Fe(C ₅Me₅)₂](TCNQ).

Full text of DOI:10.1016/j.ica.2014.05.011

Inorganica Chimica Acta 419 (2014) 105–110
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Decamethyl- and octamethyl-ferrocenium salts of F1- and F2-TCNQ:
Effects of fluorine substitution on the crystal structures and magnetic
interactions
Yusuke Funasako a, Tomoyuki Mochida a, , Takahiro Akasaka a,b, Takahiro Sakurai c, Hitoshi Ohta d,
⇑
Yutaka Nishio e
a Department of Chemistry, Graduate School of Science, Kobe University, Kobe, Hyogo 657-8501, Japan
b Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan
c Center for Supports to Research and Education Activities, Kobe University, Kobe, Hyogo 657-8501, Japan
d Molecular Photoscience Research Center, Kobe University, Kobe, Hyogo 657-8501, Japan
e Department of Physics, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Decamethyl- and octamethyl-ferrocenium salts of FnTCNQ (n = 1, 2) were prepared and their crystal
structures characterized. The 2,5-F2TCNQ salts [Fe(C5Me5)2](2,5-F2TCNQ) (1) and [Fe(C5Me4H)2]
(2,5-F2TCNQ) (2) exhibit one-dimensional . . .[D]+[A]À[D]+[A]À. . . mixed-stack structures, while the salts
with polar acceptors [Fe(C5Me5)2][A] (A = F1TCNQ (3), 2,3-F2TCNQ (4), 2,6-F2TCNQ (5)) and [Fe(C5Me4H)2]
[A] (A = 2,3-F2TCNQ (6), 2,6-F2TCNQ (7)) consist of [D]+[A2]2À[D]+ units involving a diamagnetic dimer of
the acceptors. These salts are isomorphous to the corresponding TCNQ salts. 1 and 2 exhibit small
ferromagnetic interactions at low temperatures. 1 undergoes an antiferromagnetic phase transition at
TN = 3.9 K, which is higher than TN = 2.1 K of the metamagnetic polymorph of [Fe(C5Me5)2](TCNQ).
Ó 2014 Elsevier B.V. All rights reserved.
Received 21 February 2014
Received in revised form 30 April 2014
Accepted 12 May 2014
Available online 17 May 2014
Keywords:
Decamethylferrocene
FnTCNQ
Crystal structures
Magnetic properties
1. Introduction
is interesting from the viewpoint of crystal engineering [12]. In this
study, [Fe(C5Me5)2](FnTCNQ) and [Fe(C5Me4H)2](FnTCNQ) (n = 1, 2)
Metallocene-based charge-transfer (CT) salts have attracted a lot
of attention owing to their solid-state electronic properties such as
magnetism and electrical conductivities [1,2]. One of the most nota-
ble examples is [Fe(C5Me5)2](TCNQ) (decamethylferrocenium
7,7,8,8-tetracyano-p-quinodimethanide), which has three poly-
morphs: the metamagnetic phase (TN = 2.1 K), the ferromagnetic
phase (TC = 3.0 K), and the paramagnetic phase [3–8]. The former
two polymorphs have a one-dimensional (1-D) mixed-stack struc-
ture (. . .[D]+[A]À[D]+[A]À. . .), whereas the latter is a ‘‘dimeric phase’’
polymorph consisting of [D]+[A2]2À[D]+ units involving a diamag-
netic dimer of acceptors. Several related salts have been reported.
[Fe(C5Me4H)2](TCNQ) ([Fe(C5Me4H)2] = octamethylferrocene) has
a 1-D mixed-stack structure [9]. [Fe(C5Me5)2](F4TCNQ) is isomor-
phous to the dimeric phase of [Fe(C5Me5)2](TCNQ) [10].
were prepared to examine the effects of the fluorine substituents
(Fig. 1). The half-wave redox potentials (E1/2 in CH3CN, versus
SCE) of TCNQ, F1TCNQ, and 2,5-F2TCNQ are 0.22, 0.32, and 0.41 V,
respectively [13], and their use for CT complexes are well docu-
mented [14]. 2,3- and 2,6-F2TCNQ, which are polar isomers of
2,5-F2TCNQ [14], were also used to investigate the effect of
acceptor polarity. Herein, we report the preparation and crystal
structures of the salts 1–7 shown in Fig. 2. The magnetic properties
of 1 and 2 were also investigated.
2. Results and discussion
2.1. Preparation and general structural features
Our group recently investigated the effects of fluorine substitu-
ents on the assembled structures of alkylferrocenium salts of
FnTCNQ [11]. The packing structures of these salts were found to
vary depending on the number of fluorine atoms. This approach
Determination of the crystal structures revealed that 1 and 2,
which are the salts of the centrosymmetric acceptor 2,5-F2TCNQ,
exhibit 1-D mixed-stack structures. They are isomorphous to
[Fe(C5Me5)2](TCNQ) (metamagnetic polymorph) and [Fe(C5Me4H)2]
(TCNQ), respectively. In contrast, the salts with polar acceptors
(3–7) were isomorphous to the dimeric phase polymorph of
[Fe(C5Me5)2](TCNQ) (Fig. 2). All of the salts exhibit a 1:1 donor/
⇑
Corresponding author. Tel./fax: +81 78 803 5679.
E-mail address: tmochida@platinum.kobe-u.ac.jp (T. Mochida).
http://dx.doi.org/10.1016/j.ica.2014.05.011
0020-1693/Ó 2014 Elsevier B.V. All rights reserved.

106
Y. Funasako et al. / Inorganica Chimica Acta 419 (2014) 105–110
(2798.3 Å3, at 293 K) was 0.47% larger than that of the dimeric
phase polymorph of [Fe(C5Me5)2](TCNQ) (2785.1 Å3, at 293 K).
Therefore, the effect of fluorine substitution was found to be
smaller than that of temperature change; the thermal expansion
of 1 on increasing the temperature from 167 K (704.9 Å3) to
296 K (720.1 Å3) was 2.1%, and that of 3 on going from 173 K
(2743.3 Å3) to 293 K (2798.3 Å3) was 2.0%.
2.2. Crystal structures of mixed-stack salts 1 and 2
Fig. 1. Acceptors used in this study.
The packing diagrams of [Fe(C5Me5)2](2,5-F2TCNQ) (1) and
[Fe(C5Me4H)2](2,5-F2TCNQ) (2) are shown in Fig. 3a and b,
respectively. The structures of
1 and 2 consisted of a 1-D
. . .[D][A][D][A]. . . alternate stacking. The molecular planes of the
adjacent donor and acceptor moieties are canted with respect to
each other in 2 due to the asymmetric structure of the donor.
The donor–acceptor distance and Fe. . .Fe distance in the 1-D
stacked structure of 1 (3.47 Å, 10.48 Å) is shorter than those in 2
(3.55 Å, 10.29 Å) owing to the lack of methyl groups (Fig. 3). These
tendencies are also observed in the corresponding TCNQ salts [9].
The intermolecular Fe. . .Fe distances in the 1-D stacked struc-
ture of 1 (10.48 Å) and 2 (10.29 Å) are shorter by 0.07 Å than those
of the corresponding salts with TCNQ (Table 1), whereas the inter-
chain Fe. . .Fe distances are slightly longer. The acceptors form a
ribbon structure along the a-axis, i.e., perpendicular to the stacking
direction, via –CHÁ Á ÁNC– hydrogen-bond-like contacts [17], which
are shorter than the van der Waals distance by 0.2 Å (Fig. 4). This
acceptor arrangement in 1 and 2 results in much shorter NÁ Á ÁN dis-
tances between the acceptors (3.51 and 3.65 Å, respectively;
Table 1) than those in the corresponding TCNQ salts (4.08 and
3.89 Å, respectively). This was the most prominent change in
geometry caused by the fluorine substitution, which likely affects
intermolecular magnetic interactions (vide infra). There are no sig-
nificant intermolecular –CHÁ Á ÁF– interactions.
Fig. 2. General reaction scheme.
acceptor ratio, and the molecular geometries of the donors and
acceptors are consistent with those of monocations and monoa-
nions [15], respectively. We tried various crystallization condi-
tions, but these phases were obtained exclusively as single
crystals and no polymorphism was observed. It seems reasonable
that the polar acceptors favoring dimer formation produce the
dimeric phase structure. This is further supported by results of
the examination of the acceptor arrangements (vide infra). There
were no close FeÁ Á ÁNC– arrangements between the cation and
anion, although such arrangements are often observed in the ferro-
cenium salts of TCNQ [11] and [M(mnt)2]À [16].
2.3. Crystal structures of dimeric phase salts 3À7
The unit cell volumes and intermolecular distances of 1–7 and
related salts are listed in Table 1. The cell volume of 1 (704.9 Å3,
at 167 K) was 0.45% larger than that of the metamagnetic poly-
morph of [Fe(C5Me5)2](TCNQ) (701.8 Å3, at 167 K), and that of 3
[Fe(C5Me5)2][A] (A = F1TCNQ (3), 2,3-F2TCNQ (4), 2,6-F2TCNQ
(5)) and [Fe(C5Me4H)2][A] (A = 2,3-F2TCNQ (6), 2,6-F2TCNQ (7))
are isomorphous to the dimeric phase polymorph of [Fe(C5Me5)2]
(TCNQ), which consists of [D][A]2[D] units. The packing diagram
Table 1
Unit cell volumes and intermolecular distances in 1–7 and related compounds.
Compounds
V (Å3)
D–A (Å)a
A–A (Å)a
A–A (Å)b
Fe. . .Fe (Å)
N. . .N (Å)c
Temp. (K)d
One-dimensional phase
[Fe(C5Me5)](2,5-F2TCNQ) (1)
[Fe(C5Me4H)2](2,5-F2TCNQ) (2)
[Fe(C5Me5)](TCNQ)h,i
704.9
638.0
701.8
651.6
3.540
3.473
3.567
3.478
10.482e
10.288e
10.55e
10.36e
8.826f
8.659f
8.635f
8.636f
3.514
3.653
4.080
3.893
167
173
167
296
[Fe(C5Me4H)2](TCNQ)j
Dimeric phase
[Fe(C5Me5)](F1TCNQ) (3)d
[Fe(C5Me5)](2,3-F2TCNQ) (4)
[Fe(C5Me5)](2,6-F2TCNQ) (5)
[Fe(C5Me4H)2](2,3-F2TCNQ) (6)
[Fe(C5Me4H)2](2,6-F2TCNQ) (7)
[Fe(C5Me5)](TCNQ)h
2743.3
2783.2
2775.3
2612.0
2618.9
2785.1
2878.3
3.704
3.695
3.748
3.686
3.804
3.741
3.254
3.241
3.250
3.241
3.248
3.305
3.129
3.136
3.170
3.199
3.243
3.149
13.859g
13.843g
13.951g
13.896g
14.064g
13.993g
173
173
173
173
173
rt
[Fe(C5Me5)](F4TCNQ)k
rt
a
b
c
d
e
f
Distance between the centroids of adjacent rings.
Acceptor–acceptor interplane distances in the acceptor dimer.
The closest intermolecular N. . .N distance between adjacent acceptor molecules.
The temperature at which the unit cell volume was determined.
Intrachain Fe. . .Fe distance.
In-registry interchain Fe. . .Fe distance. See Ref. [7] for definition.
Intermolecular Fe. . .Fe distances in the DAAD unit.
Metamagnetic polymorph.
g
h
i
Ref. [4].
Ref. [8].
Ref. [9].
j
k

Y. Funasako et al. / Inorganica Chimica Acta 419 (2014) 105–110
107
of 3 is shown in Fig. 5. The C5Me5 rings of the cations in 3–5 that
face away from the acceptor exhibit a twofold rotational disorder,
where the occupancies of the dominant site are 0.8–0.9. The cat-
ions in 6–7 exhibit no disorder. There are –CCpHÁ Á ÁF– short contacts
between the donors and acceptors in 6 and 7, which are 2.53 and
2.45 Å, respectively. The orientation of the acceptor, namely the
position of the fluorine atom of F1TCNQ, in 3 is disordered over
two adjacent sites with an occupancy of 0.5:0.5; hence, its molec-
ular shape appears similar to that of 2,3-F2TCNQ. Similarly, the
acceptor orientations in 5–7 are disordered with occupancies of
0.72:0.28 (5), 0.88:0.12 (6), and 0.53:0.47 (7), while 2,3-F2TCNQ
in 4 is ordered. The acceptors in the centrosymmetric dimer are
slipped with respect to each other along the molecular short axis,
and hence, the energies of the dimer differ depending on the
acceptor orientations more significantly for 2,3-F2TCNQ than for
2,6-F2TCNQ (Fig. 6). This is probably the reason why the disorder
ratio of 2,3-F2TCNQ exhibits a larger deviation from 0.5:0.5 than
that of 2,6-F2TCNQ.
It is to be noted that the interplane distances between the
acceptors in the dimer (3.13–3.24 Å), the donor–acceptor inter-
plane distances (3.69–3.75 Å), and the Fe. . .Fe distances in the
[D][A]2[D] units (13.84–14.06 Å) vary slightly in these salts
(Table 1). These distances in the F1 and 2,3-F2TCNQ salts are
shorter than those in the 2,6-F2TCNQ and TCNQ salts. This ten-
dency indicates stronger intradimer interactions for the acceptors
having larger transverse dipole moments, which is again reflective
of acceptor polarity. The centroid–centroid distances between the
acceptors are 3.241–3.254 Å (Table 1), and there was no correlation
between the values and the substituent positions. The donor–
acceptor interplane distances in the salts with [Fe(C5Me5)2] and
[Fe(C5Me4H)2] are almost the same. This contrasts with the
tendency observed for 1 and 2.
2.4. Magnetic properties of 1 and 2
To investigate the effect of fluorine substitution on the mag-
netic transition of the metamagnetic polymorph of [Fe(C5Me5)2]
(TCNQ) [3a], we examined the magnetic property of the isomor-
phous salt 1. The temperature dependence of the magnetic suscep-
tibility (vT value) of this salt is shown in Fig. 7. The value at room
temperature was 1.14 emu K molÀ1, which corresponds to the sum
of the contribution by the decamethylferrocenium cation
(ꢀ0.7 emu K molÀ1) and the F2TCNQ anion (0.375 emu K molÀ1).
The value increased at temperatures below approximately 50 K,
and the magnetic susceptibility (v) exhibited a maximum at
4.5 K. This behavior closely resembles that of the metamagnetic
polymorph of [Fe(C5Me5)2](TCNQ) [3]. The antiferromagnetic
phase transition temperature (TN) determined from the maximum
Fig. 3. Packing diagrams of (a) [Fe(C5Me5)2](2,5-F2TCNQ) (1) and (b) [Fe(C5Me4-
H)2](2,5-F2TCNQ) (2) projected along the a-axis.
of d(vT)/dT was 3.9 K. The Weiss temperature (h) estimated from
the Curie–Weiss fitting was +1.6 K. The value was smaller
than those of the metamagnetic and ferromagnetic polymorphs
of [Fe(C5Me5)2](TCNQ), which are h = + 3 K [4] and +3.8 K [7],
Fig. 4. The arrangement of the acceptors in [Fe(C5Me5)2](2,5-F2TCNQ) (1) arranged along the a-axis. Dotted lines indicate intermolecular contacts shorter than the van der
Waals distances by 0.2 Å.

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Y. Funasako et al. / Inorganica Chimica Acta 419 (2014) 105–110
Fig. 8. Excess heat capacity and excess entropy of [Fe(C5Me5)2](2,5-F2TCNQ) (1).
Fig. 5. Packing diagrams of [Fe(C5Me5)2](F1TCNQ) (3). The C5Me5 rings and fluorine
atoms are disordered, and the disordered components are partly omitted.
Fig. 6. The acceptor arrangements in the dimers of (a) 2,3-F2TCNQ and (b) 2,6-
F2TCNQ. Form I was the dominant orientation in [Fe(C5Me5)2](2,3-F2TCNQ)2 (4) and
[Fe(C5Me4H)2](2,3-F2TCNQ)2 (6).
Fig. 9. Temperature dependence of the magnetic susceptibility
[Fe(C5Me4H)2](2,5-F2TCNQ) (2).
(vT value) of
NÁ Á ÁN distances between the acceptors, which likely to transmit
interchain magnetic interactions better [2a]. The values of TN and
HC in [Fe(C5Me5)2](TCNQ) increase with pressure (TC = 2.9 K and
HC (2 K) = 0.18 T, at 2.9 kbar) [3]. The lattice volume as well as the
interchain distance are larger in 1 than in [Fe(C5Me5)2](TCNQ);
hence, it was shown that the effect of fluorine substitution on the
magnetic property is not a simple negative chemical pressure effect.
We also examined the magnetic properties of 2 (Fig. 9). The vT
value at room temperature was 1.13 emu K molÀ1. The value
increased with decreasing temperature below approximately
50 K, and the value at 2 K was 2.00 emu K molÀ1. This behavior
indicates the presence of ferromagnetic interactions (h = +1.1 K).
No magnetic phase transition was observed down to 2 K.
3. Conclusion
Fig. 7. Temperature dependence of the magnetic susceptibility (vT value) of
[Fe(C5Me5)2](2,5-F2TCNQ) (1). The inset shows the magnetization curve for 1 at 2 K.
[Fe(C5Me5)](FnTCNQ) and [Fe(C5Me4H)](FnTCNQ) (n = 1 and 2)
formed either the 1-D . . .[D]+[A]À[D]+[A]À. . . mixed-stack structure
or the dimeric phase structure consisting of [D]+[A2]2À[D]+ units
although [Fe(C5Me5)](TCNQ) adopts both the crystal phases. The
assembled structures depended on the acceptor polarity; the non-
polar acceptor (2,5-F2TCNQ) formed the former structure, while
the polar acceptors (F1TCNQ, 2,3-F2TCNQ, and 2,6-F2TCNQ) formed
the latter structure. It seems reasonable that the polar acceptors
form dimers in order to cancel their dipole moments to form the
dimeric phase structure. The acceptor orientation, namely the
position of the fluorine atoms, was disordered in most salts.
The extent of disorder as well as the intermolecular distances in
the salts depended on the acceptor polarity. The use of FnTCNQ
provides an effective method to investigate chemical pressure
respectively. The coercive field (HC) at 2 K was determined to be
0.99 T from the magnetization curve (Fig. 7, inset). Specific heat
measurements revealed the presence of an excess heat capacity
that corresponds to the antiferromagnetic phase transition
(Fig. 8). The transition temperature and transition entropy were
determined to be TN = 3.9 K and
D
S = 9.6 J molÀ1 KÀ1, respectively.
The transition entropy is consistent with magnetic ordering, for
which, a value of 2R ln2 (11.5 J molÀ1 KÀ1) is expected.
Compared with the TC of [Fe(C5Me5)2](TCNQ) (TC = 2.1 K, HC
(2 K) = 0.13 T [3]), the TC of 1 is higher by ꢀ2 K and the HC is about
seven times larger, suggesting stronger intercolumn antiferromag-
netic interactions in 1. This is probably ascribed to the shorter

Y. Funasako et al. / Inorganica Chimica Acta 419 (2014) 105–110
109
effects. However, it was demonstrated that the effect of fluorine on
the magnetic interactions in [Fe(C5Me5)](TCNQ) and [Fe(C5Me4H)2]
(TCNQ) were not due to simple expansion of the cell volume, but
due to changes in the intermolecular arrangement.
bolometer with Apiezon N grease. A sample holder made of Stycast
1266 was located in the mixing chamber of a dilution refrigerator,
and a vacuum was created inside the holder using charcoal. It was
possible to measure the specific heat over a wide range of temper-
atures from 0.2 to 9 K because the heat-contact of the thermal bath
with a 3He–4He mixture in the mixing chamber was suppressed.
4. Experimental
4.1. Materials and physical measurements
4.2. Syntheses
Decamethylferrocene and octamethylferrocene were purchased
from Sigma-Aldrich and used after recrystallization from acetoni-
trile. FnTCNQs were prepared according to literature methods
[18]. FT-IR spectra were recorded as KBr pellets on a Thermo
Nicolet Avatar 360 spectrometer. Magnetic susceptibilities were
measured using a Quantum Design MPMS–2 SQUID susceptometer
in the temperature range of 2–300 K under a field of 1000 G.
Calorimetric measurements of single crystals were conducted
using a thermal relaxation method. The sample was attached to a
Single crystals of 1 and 2 were obtained by slow diffusion of
chloroform solutions of the donor and the acceptor. Single crystals
of 3–5 and 7 were obtained by diffusion of diethylether into aceto-
nitrile solutions of the components, and those of 6 by slow cooling
of acetonitrile solutions down to –40 °C. The use of different sol-
vents (ex. acetonitrile for 1) also produced the same crystal forms
but resulted in poor quality. 1: Yield 44%. 14.0 mg of 1 was
obtained from 18.2 mg (0.06 mmol) of the donor and 13.5 mg
(0.06 mmol) of the acceptor. IR:
m
= 3045, 2185(CN), 2168, 1518,
Table 2
Crystallographic parameters for 1–3.
[Fe(C5Me5)2](2,5-F2TCNQ) (1)
[Fe(C5Me4H)2](2,5-F2TCNQ) (2)
[Fe(C5Me5)2](F1TCNQ) (3)
Empirical formula
Formula weight
Crystal system
a (Å)
b (Å)
c (Å)
C32 H32 F2 Fe N4
566.47
triclinic
C30 H28 F2 Fe N4
538.41
triclinic
8.6593(6)
9.3659(6)
C32 H33 F Fe N4
548.47
monoclinic
9.6432(6)
12.1366(8)
23.52581(16)
8.8255(7)
9.3279(7)
10.2929(8)
64.365(2)
68.639(2)
74.2700(10)
704.93(9)
9.8807(6)
a
(°)
b (°)
(°)
99.2620(10)
107.0940(10)
117.2990(10)
638.04(7)
94.887(2)
c
V (Å)
Space group
2743.3(3)
P21/c
ꢀ
ꢀ
P1
P1
Z value
1
1
4
Dcalc (g cmÀ3
F (000)
)
1.334
296
1.401
280
1.328
1152
No. of reflections
No. of observations
Parameters
4616
2857
183
4779
3135
173
16142
5030
446
Temperature (K)
167
173
173
b
R1a, Rw (I > 2
r)
0.0328, 0.0822
0.0370, 0.0847
1.061
0.0293, 0.0784
0.0299, 0.0789
1.093
0.0718, 0.1627
0.0871, 0.1718
1.127
b
R1a, Rw (all data)
Goodness of fit
P
P
a
R1
=
||Fo| À |Fc||/ |Fo|.
P
P
b
Rw = [ w(Fo2 À F2c)2/ w(Fo2)2]1/2
.
Table 3
Crystallographic parameters for 4–7.
[Fe(C5Me5)2](2,3-F2TCNQ) (4)
[Fe(C5Me5)2](2,6-F2TCNQ) (5)
[Fe(C5Me4H)2](2,3-F2TCNQ) (6)
[Fe(C5Me4H)2](2,6-F2TCNQ) (7)
Empirical formula
Formula weight
Crystal system
a (Å)
b (Å)
c (Å)
C32 H32 F Fe N4
566.47
C32 H32 F Fe N4
566.47
C30 H28 F2 Fe N4
538.41
C30 H28 F2 Fe N4
538.41
monoclinic
9.6345(9)
12.2216(11)
23.709(2)
94.4540(10)
2783.2(4)
P21/c
monoclinic
9.7823(13)
12.1306(15)
23.484(3)
95.191(2)
2775.3(6)
P21/c
monoclinic
9.5244(11)
12.3182(14)
22.574(3)
99.524(2)
2612.0(5)
P21/c
monoclinic
9.8242(13)
11.9374(15)
22.774(3)
101.311(2)
2618.9(6)
P21/c
b (°)
V (Å)
Space group
Z value
4
4
4
4
Dcalc (g cmÀ3
F (000)
)
1.352
1184
1.356
1184
1.369
1120
1.366
1120
No. of reflections
No. of observations
Parameters
14208
5456
443
14167
5451
462
12655
4775
361
14168
5554
361
Temperature (K)
173
173
173
173
b
R1a, Rw (I > 2
r
)
0.0398, 0.1131
0.0422, 0.1148
1.004
0.0413, 0.1080
0.0505, 0.1133
1.044
0.0400. 0.1023
0.0423, 0.1039
1.094
0.0293, 0.0782
0.0323, 0.0800
1.044
b
R1a, Rw (all data)
Goodness of fit
P
P
a
R1
=
||Fo| À |Fc||/ |Fo|.
P
P
b
Rw = [ w(Fo2 À F2c)2/ w(Fo2)2]1/2
.

110
Y. Funasako et al. / Inorganica Chimica Acta 419 (2014) 105–110
1483, 1476, 1389, 1342, 1202, 1142, 1026, 901, 787. Anal. Calc. for
32H32F2FeN4 (566.47): C, 67.85; H, 5.69; N, 9.89. Found: C, 67.74;
Appendix A. Supplementary material
C
H, 5.67; N, 9.91%. 2: Yield 25%. 14.2 mg of 2 was obtained from
CCDC 942506 (1), 942507 (2), 942508 (3), 951723(4), 951724
(5), 953082 (6), and 953083 (7) contains the supplementary crys-
tallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at http://
dx.doi.org/10.1016/j.ica.2014.05.011.
31.5 mg of the donor and 25.2 mg of the acceptor. IR (cmÀ1):
m
= 3075, 3055, 2183 (CN), 2166 (CN), 2127 (CN), 1547, 1516,
1483, 1454, 1414, 1391, 1373, 1341, 1296, 1202, 1165, 1150,
1138, 1028, 887, 787. Anal. Calc. for C30H28F2FeN4 (538.41): C,
66.92; H, 5.24; N, 10.41. Found: C, 66.55; H, 5.13; N, 10.61%. 3:
Yield 55%. 15 mg of 3 was obtained from 15 mg of the donor and
11 mg of the acceptor. IR:
m = 2920, 2181 (CN), 2168 (CN), 1603,
1514, 1491, 1450, 1423, 1387, 1368, 1325, 1256, 1186, 1119,
1074, 1020, 982, 866, 818. Anal. Calc. for C32H33FFeN4 (548.47):
C, 70.07; H, 6.06; N, 10.22. Found: C, 69.87; H, 6.06; N, 10.34%. 4:
Yield 76%. 9 mg of 4 was obtained from 8 mg of the donor and
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m
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Bruker SMART APEX II CCD diffractometer using Mo K
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Acknowledgments
University of Göttingen, Göttingen, Germany, 1997;
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This work was financially supported by KAKENHI (Grant No.
23110719). We thank Dr. Y. Furuie (Kobe University) for elemental
analysis and Ms. Michiko Sato (Toho University) for her help with
specific heat measurements.