DOI: 10.1002/zaac.
200500472
Structural and Physicochemical Characteristics of Tetrabutylammonium
Tetrahalogenoferrates(III), [(C4H9)4N][FeBr4ⴚnCln]
Dariusz Wyrzykowskia, Rafał Kruszyńskib, Urszula Kucharskac, and Zygmunt Warnkea,*
a
Gdańsk/Poland, Faculty of Chemistry, University of Gdańsk
Łódź/Poland, b Institute of General and Ecological Chemistry and c Institute of General Food Chemistry, Technical University of Łódź
Received October 6th, 2005.
Abstract. A series of tetrahalogenoferrates(III), [FeBr4⫺nCln]⫺ (n⫽
0-4) stabilized with the tetrabutylammonium cation, of general for-
mula [(C4H9)4N][FeBr4⫺nCln], has been synthesized. The crystal
and molecular structure of [(C4H9)4N][FeCl4] was determined. The
iron cation adopts slightly distorted tetrahedral coordination with
two opposite angles smaller than tetrahedral one, two equal to te-
trahedral and two larger than tetrahedral. The bond valences were
computed. The total valence of iron atom is equal to 3.08. In the
structure can be found only one hydrogen bond C(1)⫺H···Cl.
Except mentioned there are no unusually intermolecular short
contacts between ions existing in the structure. All
[(C4H9)4N][FeBr4⫺nCln] (n⫽0-4) compounds are isostructural in
solid state.
1 Introduction
Tetrahalogenoferrate(III) anions form stable compounds
with quaternary aliphatic amine cations. Resulting salts can
provide ideal standardizing substances for standardization
of sodium thiosulfate solutions [1]. The advantages of these
compounds are: rapid crystallization in pure form, possibil-
ity of being dried undecomposed at temperatures up to ap-
prox. 120 °C, lack of hygroscopicity, and stability at ambi-
ent temperature over a year or longer. Furthermore, they
are freely soluble in water and have high molar masses.
For the first time the whole series of the compounds of
general formula [(C2H5)4N][FeBr4⫺nCln] (n ⫽ 0-4) contain-
ing mixed tetrahalogenoferrate(III) ions was prepared and
spectroscopically characterized by Clausen and Good [2].
Both charge transfer spectra and photographically recorded
X-ray powder diffraction patterns have shown that the
tetrahalogenoferrates(III) form pure single phases, rather
than mixtures of [FeCl4]⫺ and [FeBr4]⫺ ions. Apart from
the spectroscopic studies [3⫺5], considerable attention has
been focused on structural analysis [6] and magnetic
properties [7] of the [FeCl4]⫺ and [FeBr4]⫺ ions.
* Dr. Z. Warnke
Faculty of Chemistry, University of Gdańsk
Sobieskiego 18
PL-80-952 Gdańsk/Poland
Fax: ⫹48 58 3410357
e-mail: warnke@chem.univ.gda.pl
624  2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
On the basis of conductometric measurements, relative stabilities
of the anions have been estimated in methanol (MeOH), dimethyl
sulfoxide (DMSO), acetone (AC), acetonitrile (AN) and dichloro-
methane (CH2Cl2) representing both polar (including amphiprotic
and aprotic) as well as non-polar solvents. Further, the dissociation
constants of the compounds were calculated from the expanded
Pitt’s conductivity equation. The results of the conductometric me-
asurements were supported by electronic spectra.
Keywords: Tetrahalogenoferrates(III); Crystal structure; Conducto-
metric measurements
Our interest in the tetrahalogenoferrates(III) has been
sparked by studying their interactions with non-aqueous
solvents. Our previous work was confined to the synthesis,
spectroscopic investigation and conductometric measure-
ments of complexes incorporating the [FeCl4]⫺ and
[FeBr4]⫺ ions and cations of pyridinium, quinolinium, and
their methylated derivatives [8].
In this paper, crystal and molecular structure of
[(C4H9)4N][FeCl4], the results of X-ray powder diffraction
and conductometric measurements of the whole series of
mixed [FeBr4⫺nCln]⫺ (n ⫽ 0-4) ions stabilized by tetrabu-
tylammonium cation are presented.
2 Results and Discussion
2.1 Structural description
A perspective view of the [(C4H9)4N][FeCl4] structure to-
gether with the atom numbering scheme is shown in Figure
1. The iron and nitrogen atoms lie on two-fold rotation axis
along a direction (special positions 4d of Pnna space group
at x, 1/4, 1/4 [9]), thus the one molecule of title compound
occupies two asymmetric units. The iron cation is four coor-
dinated by chlorine anions, and it adopts slightly distorted
tetrahedral coordination with two opposite angles smaller
than tetrahedral one, two equal to tetrahedral and two
larger than tetrahedral. All Fe-Cl bond lengths are equal in
the range of experimental error (Table 2) and they are in
good agreement with the values found for
[(C2H5)4N][FeCl4] (Fe-Cl ⫽ 2.185(1) Å [6b]). The amine ni-
Z. Anorg. Allg. Chem. 2006, 632, 624⫺628
Tetrabutylammonium Tetrahalogenoferrates(III)

Table 1 Crystal data and structure refinement for

[(C4H9)4N][FeCl4].

Empirical formula C16H36Cl4NFe

Formula weight 440.11 g/mole
Temperature 290.0(2) K
Wavelength λ(MoKα) ⫽ 0.71073 Å
Crystal system, space group orthorhombic, Pnna
Unit cell dimensions a ⫽ 18.4370(13) Å
b ⫽ 11.5539(8) Å
c ⫽ 11.4345(8) Å
Volume 2435.8(3) Å3
Z, Calculated density 4, 1.200 Mg/m3
Absorption coefficient 1.056 mm⫺1
F(000) 932
Crystal size 0.425 x 0.511 x 0.577 mm
θ range for data collection 3.21 to 25.10°
Index ranges ⫺15ⱕhⱕ22, ⫺13ⱕkⱕ13, ⫺13ⱕ1ⱕ13
Fig. 1 Molecular structure of the [(C4H9)4N][FeCl4]. Displace- Completeness to 2θ ⫽ 50.22° 99.8 %
ment ellipsoids are drawn at the 50 % probability level. Hydrogen Reflections collected / unique 24258 / 2172 [R(int) ⫽ 0.049]
Completeness to 2θ ⫽ 25.11° 99.8 %
atoms are omitted for clarity. Refinement method full-matrix least-squares on F2
Max. and min. transmission 0.682 and 0.5470
trogen atom adopts very slightly distorted tetrahedral coor- Data / restraints / parameters 2172 / 0 / 104
Goodness-of-fit on F2 1.183
dination (with two opposite angles larger than tetrahedral Final R indices [I>2σ(I)] R1 ⫽ 0.0577, wR2 ⫽ 0.1610
one and four slightly smaller than tetrahedral). The indi- R indices (all data) R1 ⫽ 0.0638, wR2 ⫽ 0.1665
cated by C(5) atom butyl substituent atoms are coplanar in Largest diff. peak and hole 0.310 and ⫺0.349 e. Å⫺3
the range of three standard deviations, and the indicated by
C(1) atom butyl substituent atoms are little distorted from
planarity (maximum deviation of 0.036(3) Å occurs for C(3)
Table 2 Structural data for [(C4H9)4N][FeCl4]. Distances in Å,
atom). These least squares planes are inclined at 71.8(4)°. angles in deg.
The shortest Fe···Fe distance is 8.212(10) Å (second atom
obtained by ⫺x⫹1/2, ⫺y, z or ⫺x⫹1/2, ⫺y⫹1, z symmetry Fe(4)-Cl(1) 2.1843(11) Cl(1)-Fe(4)-Cl(2) 107.27(6)
transformations). The bond valences were computed as Fe(4)-Cl(2) 2.1882(14) Cl(2)#1-Fe(4)-Cl(2) 112.23(12)
N(2)-C(5) 1.516(3) C(5)#1-N(2)-C(5) 111.8(3)
νij ⫽ exp[(Rij-dij)/b] [10⫺12], where Rij is the bond-valence N(2)-C(1) 1.523(3) C(5)#1-N(2)-C(1) 108.39(15)
parameter (in the formal sense the Rij parameter value can C(1)-C(2) 1.496(4) C(5)-N(2)-C(1) 108.36(16)
be considered as an idealised single-bond length between i C(2)-C(3) 1.528(5) C(5)#1-N(2)-C(1)#1 108.36(16)
C(3)-C(4) 1.454(6) C(5)-N(2)-C(1)#1 108.39(15)
and j atoms). The RFe-Cl was taken as 2.09 [13] and b was C(5)-C(6) 1.500(4) C(1)-N(2)-C(1)#1 111.6(3)
taken as 0.37 [11, 12]. The computed bond valences of iron C(6)-C(7) 1.497(5) C(2)-C(1)-N(2) 117.2(2)
are νFe-Cl ⫽ 0.775 and 0.767 v.u. (valence units) and the C(7)-C(8)
Cl(1)#1-Fe(4)-Cl(1)
1.496(6)
111.15(7)
C(1)-C(2)-C(3)
C(4)-C(3)-C(2)
109.8(3)
114.8(4)
total valence of iron atom is equal to 3.08. The valence sum Cl(1)#1-Fe(4)-Cl(2)#1 107.27(6) C(6)-C(5)-N(2) 117.4(2)
rule states that the sum of the valences of the bonds formed Cl(1)-Fe(4)-Cl(2)#1 109.48(5) C(7)-C(6)-C(5) 110.7(3)
Cl(1)#1-Fe(4)-Cl(2) 109.48(5) C(8)-C(7)-C(6) 115.9(4)
by an atom is equal to the valence of the atom. The com-
puted valence of Fe is slightly larger than the formal oxi-
dation state of the iron but only the violation of the valence-
sum rule larger than 0.25⫺0.30 [14] can indicate mistakes Table 3 Atomic coordinates ( x 104) and equivalent isotropic dis-
in the interpretation of the structure by omission or ad- placement parameters (A2 x 103) for [(C4H9)4N][FeCl4]. U(eq) is de-
dition of the weak hydrogen bonds, can show that bonds fined as one third of the trace of the orthogonalized Uij tensor.
are strained as the result of the crystallographic constraints
that prevent the bonds from attaining their ideal lengths x y z U(eq)

[15]. Fe(4) 917(1) 2500 2500 86(1)

In the structure can be found only one short intramolecu- Cl(1) 1587(1) 3922(1) 1853(1) 113(1)
Cl(2) 256(1) 3184(2) 3930(1) 181(1)
lar interaction which can be considered as weak hydrogen N(2) 4356(2) 2500 2500 58(1)
bonds [16, 17] linking C(1)⫺H(1A)···Cl(2# x⫹1/2, ⫺y⫹1/2, C(1) 4821(2) 3282(2) 1734(2) 68(1)
C(2) 5395(2) 3982(3) 2328(3) 87(1)
z⫺1/2) atoms (D···A distance equal to 3.713(3) Å D⫺H···A C(3) 5803(3) 4709(5) 1426(4) 117(2)
C(4) 6421(3) 5345(6) 1887(6) 167(3)
angle equal 156.4° and H···A distance equal 2.80 Å). The C(5) 3895(2) 3256(2) 3288(2) 66(1)
cations and anions are alternately packed in the crystal net C(6) 3382(2) 2659(3) 4107(3) 77(1)
C(7) 2942(3) 3525(4) 4775(4) 109(1)
(Fig. 2). There are no unusually intermolecular short con- C(8) 2414(3) 3037(5) 5637(4) 123(2)
tacts between ions existing in the structure. All
[(C4H9)4N][FeBr4⫺nCln] (n⫽0-4) compounds are isostructu-
ral in solid state. With increasing of bromide atoms amount
in the complex, the unit cell dimensions and volume slightly fractions patterns shows 98.6 % overlapping after taking
increases (Table 4). The superimposition of the powder dif- into considerations the peak positions shifts and intensity

Z. Anorg. Allg. Chem. 2006, 624⫺628  2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim zaac.wiley-vch.de 625
 D. Wyrzykowski, R. Kruszyński, U. Kucharsaka, Z. Warnke

Fig. 2 A part of the molecular packing of the [(C4H9)4N][FeCl4] Fig. 3 Dependence of molar conductivity on the square root of
showing arrangement of cations and anions in the crystal net. concentration for [(C4H9)4N][FeCl4].

Table 5 Molar conductivities at infinite dilution (Λ0) and corre-

lation coefficients (r) for the systems studied.
Table 4 [(C4H9)4N][FeBr4⫺nCln] (n⫽0-4) samples powder dif-
fractometry data and unit cell refinements in orthorhombic space Compound MeOH DMSO AC AN CH2Cl2
group Pnna (No. 52) with Z ⫽ 4. Λ0 r Λ0 r Λ0 r Λ0 r Λ0 r

[(C4H9)4N][FeCl4] 267.7 0.998 88.9 0.997 170.1 0.998 155.4 0.999 66 0.994
N 0 1 2 3 4
[(C4H9)4N][FeBrCl3] 263.5 0.997 99.8 0.998 170.6 0.991 153.2 0.990 64.6 0.996
[(C4H9)4N][FeBr2Cl2] 281.2 0.998 106.8 0.999 169.8 0.995 152.9 0.992 64.8 0.995
Unit Cell: [(C4H9)4N][FeBr3Cl] 365 0.999 ⫺a) ⫺ 171.1 0.993 151.8 0.979 64.7 0.997
a /Å 18.441(2) 18.474(3) 18.509(4) 18.532(3) 18.567(5) [(C4H9)4N][FeBr4] 474 0.999 ⫺ ⫺ 170.6 0.994 154.8 0.99 64.2 0.997
b /Å 11.552(2) 11.565(2) 11.586(2) 11.626(2) 11.652(3)
c /Å 11.437(2) 11.449(2) 11.466(2) 11.480(2) 11.496(3)
Volume /Å3 2436.4(7) 2446.1(8) 2458.8(9) 2473.4(8) 2487.1(9) a)
⫺ sparingly soluble compound
Formula weight 440.11 484.57 529.03 573.49 617.95
Calculated density /Mg/m3 1.200 1.316 1.429 1.540 1.650
Absorption coefficient /mm⫺1 1.055 2.576 4.079 5.562 7.031
F(000) 932 1004 1076 1148 1220 Example results of investigations of a selected com-
Unit cell refinement results
No. Unindexed / indexed lines 0 / 78 0 / 117 0 / 101 0 / 90 0 / 115
pound, [(C4H9)4N][FeCl4] are shown in Figure 3.
Total No. Calculated lines, 2607 2715 2665 2682 2653 The linear relationship between Λ and c1/2 reveals differ-
χ2 2.992·10⫺6 7.436·10⫺6 9.456·10⫺6 6.994·10⫺6 2.904·10⫺5
Snyder’s FOM 3.969 5.467 3.926 4.323 2.8761
ences in the dissociation of the compound in various sol-
vents. Similar relationships were obtained for remaining
complexes. On the basis of these results, molar conductivit-
ies at infinite dilution, Λ0, and correlation coefficients, r,
using linear regression, for all of the systems studied were
changes coupled with unit cell dimensions increasing and determined (Table 5).
changes in compounds compositions. As seen, the molar conductivities at infinite dilution of
the complexes in methanol and dimethyl sulfoxide are dis-
tinctly higher than those of 1:1 electrolytes in these solvents
2.2 Conductometric measurements [18⫺20]. In methanol, the molar conductivities at infinite
dilution are usually approx. 100 [S cm2 mol⫺1], while those
The crystal data show that there are distinctly separated of our compounds are approx. (2.5⫺4.5)-fold as high. Also
[FeBr4⫺nCln] coordination units in the studied compounds. in DMSO, instead of the expected values oscillating around
Hence, the next step in this contribution was to investigate 40 [S cm2 mol⫺1], the conductivities are more than twice as
the behaviour of the complexed anions in non-aqueous me- high. This indicates the presence of a larger number of ions
dia. In particular, it seemed worthwhile to estimate the sta- in these systems than can be expected from the dissociation
bility of the tetrahalogenoferrate(III) anions in such organic of a complex salt into a cation and an anion.
solvents as methanol (MeOH), dimethyl sulfoxide (DMSO), With aprotic polar solvents (AC and AN) and non-polar
acetone (AC), acetonitrile (AN) and dichloromethane solvent (CH2Cl2), the molar conductivities at infinite di-
(CH2Cl2) representing both polar (including amphiprotic lution are consistent with conductivities of binary electro-
and aprotic) and non-polar solvents. To do this, con- lytes [21, 22] and decrease beginning from AC over AN to
ductometric measurements were carried out. To rule out the CH2Cl2. In amphiprotic polar solvents the anions are labile.
influence of cation on the progress of dissociation, a tetra- This notwithstanding, in methanol there is a regularity. Na-
butylammonium cation was used as a stabilizing ion. mely, with increasing number of Br⫺ ions in the tetrahalog-

626 zaac.wiley-vch.de  2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2006, 624⫺628
Tetrabutylammonium Tetrahalogenoferrates(III)

enoferrate(III) ion, Λ0 values distinctly increase culminating with increasing number of the more polar bromide ligands
with [FeBr4]⫺. Accordingly, decomposition of the complex in the anion, the dissociation constants of the salts increase
ions in methanol is influenced by bromide ions as also only slightly. Because the differences among the dissociation
shown by comparison of the conductivities of [FeCl4]⫺ constants of the tetrahalogenoferrates(III) in CH2Cl2 are
(Λ0 ⫽ 267.7) and [FeBr4]⫺1 (Λ0 ⫽ 474). These regularities small, this finding cannot be regarded as a rule, and studies
are not seen in DMSO, where the solubility of the tetrahal- on this issue deserve continuation.
ogenoferrates(III) declines with increasing the number of Generally, the tetrahalogenoferrate(III) anions are un-
Br⫺ ions. stable in amphiprotic solvents due to the propensity of the
The decomposition of the [FeBr4⫺nCln]⫺ ions in DMSO solvents to form hydrogen bonds. In consequence amphip-
and MeOH is also seen in their electronic spectra. In ace- rotic solvents solvate anions more strongly than aprotic sol-
tone, acetonitrile and dichloromethane, the salts obey vents, and they cause tetrahalogenoferrate(III) anions dis-
closely the Lambert-Beer’s laws and characteristic absorp- sociation.
tion bands appear for [FeCl4]⫺ at approx. 533, 607, 620,
685 and 722 nm; for [FeBrCl3]⫺ at approx. 565, 584, 645,
666, 729 and 754 nm; for [FeBr2Cl2]⫺ at approx. 584, 602, 3 Experimental Part
645, 666, 692, 729 and 752 nm; for [FeBr3Cl]⫺ at approx. 3.1 Synthesis
604, 625, 668, 690, 715, 752 and 777 nm; and for [FeBr4]⫺
at approx. 610, 628, 697, 718, 760, 786 and 840 nm. All Preparation of [(C4H9)4N][FeCl4]: Ethanolic solution of ferric chlo-
ride was prepared by dissolving 0.03 mol of FeCl3 in ethanol
these bands are missing in the spectra taken in DMSO
(96 %). To this solution, a stoichiometric quantity of ethanolic
and MeOH. solution of tetrabutylammonium chloride was added. Upon mix-
Due to the instability of the compounds in MeOH ing, an amorphous precipitate of [(C4H9)4N][FeCl4] fell out instan-
and DMSO, dissociation constants, K d⫽ taneously.
{[(C4H9)4N]⫹}{[FeBr4⫺nCln]⫺}/[(C4H9)4N][FeBr4⫺nCln],
could only be determined in acetone, acetonitrile and di- Preparation of [(C4H9)4N][FeBr4]: A similar procedure was used
chloromethane. The determinations were accomplished using stoichiometric quantities of FeBr3 and tetrabutylammonium
using a computer program based on the Pitt’s method [23, bromide.
24]. The following constants were obtained (Table 6): Preparation of [(C4H9)4N][FeBr3Cl] and [(C4H9)4N][FeBrCl3]: To
ethanolic solution of FeBr3 (or FeCl3) a stoichiometric quantity
Table 6 Dissociation constants Kd (standard deviations in par- (0.03 mol) of tetrabutylammonium bromide (or chloride) was ad-
entheses) for the systems studied ded to afford amorphous precipitates of [(C4H9)4N][FeBr3Cl] (or
[(C4H9)4N][FeBrCl3]).
Compound Kd
AC AN CH2Cl2
Preparation of [(C4H9)4N][FeBr2Cl2]: To ethanolic solution of
⫺3 ⫺2
[(C4H9)4N][FeCl4] 7.19·10 1.41·10 1.07·10⫺4 FeCl2 (0.03 mol) Br2 was added (0.03 mol) followed by a stoichio-
(0.28·10⫺3) (0.05·10⫺2) (0.17·10⫺4)
[(C4H9)4N][FeBrCl3] 6.29·10⫺3 1.19·10⫺2 1.11·10⫺4
metric quantity of ethanolic solution of tetrabutylammonium bro-
(0.26·10⫺3) (0.06·10⫺2) (0.10·10⫺4) mide. A precipitate of [(C4H9)4N][FeBr2Cl2] fell out instan-
[(C4H9)4N][FeBr2Cl2] 6.42·10⫺3 1.52·10⫺2 1.17·10⫺4 taneously.
(0.30·10⫺3) (0.19·10⫺2) (0.11·10⫺4)
[(C4H9)4N][FeBr3Cl] 5.32·10⫺3 1.57·10⫺2 1.21·10⫺4
(0.24·10⫺3) (0.12·10⫺2) (0.15·10⫺4) All the compounds were recrystallized from ethanol and dried over
[(C4H9)4N][FeBr4] 5.81·10⫺3 1.04·10⫺2 1.43·10⫺4 P4O10 in a vacuum desiccator. The composition of the compounds
(0.32·10⫺3) (0.06·10⫺2) (0.36·10⫺4)
was established on the basis of elemental analysis (C, H, N) and
potentiometric determination of the chloride and bromide ions by
titration with a 0.1 M AgNO3 solution.
These values show that the strength of the salts increases
with increasing dielectric constants of aprotic solvents in [(C4H9)4N][FeCl4] specimens for crystallographic investigations
the following rank order: CH2Cl2 < AC < AN. were obtained by recrystallization from an ethanol ⫺ acetone (1:1)
In aprotic polar solvents (AC and AN), tetrabutylam- mixture of solvents. The crystals were grown in this medium for
approx. 6 days at ambient temperature.
monium cations are more strongly solvated than anions.
This is mostly due either to a stronger interaction of the
cations with a negative pole of solvent’s dipole or to forma- 3.2 Structure determination
tion of co-ordination bonds with the lone electron pair of
oxygen (AC) or nitrogen (AN). Hence, the dissociation con- A yellow rectangular prism shape crystal (cut from the large needle)
stants determined in these solvents are by 1 to 2 orders of was mounted on a KM-4-CCD automatic diffractometer equipped
with CCD detector, and used for data collection. X-ray intensity
magnitude larger that that determined in CH2Cl2.
data were collected with graphite monochromated MoKα radiation
Another picture is seen with dichloromethane, where a (λ ⫽ 0.71073 Å) at temperature 290.0(2) K, with ω scan mode. A
correlation exists between the number of bromide ions in 15 seconds exposure time was used. The unit cell parameters were
the tetrahalogenoferrate(III) and the dissociation constant. determined from least-squares refinement of the setting angles of
In this case the solvation is possible owing to mutual polar- 5593 strongest reflections. Details concerning crystal data and re-
ization of the ion and a solvent molecule. Consequently, finement are given in Table 1. Examination of two reference frames

Z. Anorg. Allg. Chem. 2006, 624⫺628  2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim zaac.wiley-vch.de 627

monitored after each 40 frames measured showed 4.7 % loss of the
intensity. During the data reduction above decay correction coef-
ficient was taken into account. Lorentz, polarization, and numeri-
cal absorption [25] corrections were applied. The structure was
solved by direct methods. All the non-hydrogen atoms were refined
anisotropically using full-matrix, least-squares technique on F2. All
the hydrogen atoms were found from difference Fourier synthesis
after four cycles of anisotropic refinement, and refined as “riding”
on the adjacent atom with individual isotropic temperature factor
equal 1.2 or 1.5 (for methyl group) times the value of equivalent
temperature factor of the parent atom. The methyl groups were
allowed to rotate about their local three-fold axis. SHELXS97 [26],
SHELXL97 [27] and SHELXTL [28] programs were used for all
the calculations. Atomic scattering factors were those incorporated
in the computer programs. Interatomic bond distances and angles
are listed in Table 2. The atomic coordinates are given in Table 3.
3.3 Powder diffractometry
The X-ray powder diffraction patterns were measured in reflection
mode on an XPert PRO X-ray powder diffraction system equipped
with a Bragg-Brentano PW 3050/65 high resolution goniometer
and PW 3011/20 proportional point detector. The Cu K움1 radiation
was used. The patterns were measured at 291.0(2) K in the range
2-90° with the narrowest beam attenuator. A diamond powder was
used as an internal reference. The samples were sprinkled onto the
sample holders using a small sieve, to avoid a preferred orientation.
The thicknesses of the samples were no more than 0.1 mm. During
the measurements each specimen was spun in the specimen plane
to improve particle statistics. The unit-cell dimensions were deter-
mined with the indexing program TREOR [29], and were refined
with the program LSPAID [30] in orthorhombic space group Pnna
(No.52) with Z ⫽ 4. Details concerning samples data and unit cell
refinements are given in Table 4.
3.4 Conductometric measurements
Conductometric measurements were accomplished on a PW 9526
(PHILIPS) conductometer equipped with a PW 7551/60 con-
ductometric cell with a constant k ⫽ 0.840 cm⫺1. The measure-
ments were carried out at 298±0.2 K controlled by a UT-2/77 ultra-
thermostat. Acetone (Aldrich), acetonitrile (Aldrich), dichloro-
methane (Merck) and dimethyl sulfoxide (Merck) were of spectral
purity. Methanol was purified as described elsewhere [31].
The Vis spectra were recorded on a Perkin Elmer Lambda 18 in-
strument.
4 Supplementary data
Tables of crystal data and structure refinement, anisotropic dis-
placement coefficients, atomic coordinates and equivalent isotropic
displacement parameters for non-hydrogen atoms, H-atom coordi-
nates and isotropic displacement parameters, bond lengths and in-
terbond angles have been deposited with the Cambridge Crystallo-
graphic Data Centre under No. CCDC278703.
Acknowledgements. This research was supported by the Polish State
Committee for Scientific Research under grant DS/8230-4-0088-5
and European Social Fund project no. ZPORR/2.22/II/2.6/ARP/
U/2/05. Crystallographic part was financed by funds allocated by
the Ministry of Scientific Research and Information Technology
628 zaac.wiley-vch.de  2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
D. Wyrzykowski, R. Kruszyński, U. Kucharsaka, Z. Warnke
to the Institute of General and Ecological Chemistry, Technical
University of Łódź.
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