712
LAVRENOVA et al.
ric amount of Ba(NO3)2 (0.13 g, 0.5 mmol) was dis- the analytical laboratory of the Nikolaev Institute of
Inorganic Chemistry (Siberian Branch, Russian
Academy of Sciences).
The X-ray diffraction study of polycrystals of com-
pounds I–IV was carried out on a Shimadzu XRD
7000 diffractometer (CuKα radiation) at room tem-
perature.
solved in water (5 mL) on heating, and a solution of
Ba(NO3)2 was slowly added with stirring to a solution
of FeSO4. The resulting solution with a precipitate was
kept at room temperature for 2 h, and a precipitate of
BaSO4 was filtered and thrown away. For the prepara-
tion of Fe(NCS)2, a threefold excess of KNCS (0.29 g,
3 mmol) was dissolved in a minimum amount of
water, and this solution was added to the obtained
solution of Fe(NO3)2. A weighed sample of HC(3,5-
Me2Pz)3)2 (0.45 g, 1.5 mmol) was dissolved in acetone
(5–7 mL) on heating, and the solution was added to a
hot solution of salt Fe(NCS)2. A white precipitate was
formed on cooling in an ice-cold bath. The precipitate
was filtered off, washed with ethanol and acetone, and
X-ray diffraction analyses of complexes II–IV were
carried out using a standard procedure on a Bruker-
Nonius X8 Apex automated four-circle diffractometer
equipped with a 4K CCD two-coordinate detector
(MoKα radiation, λ = 0.71073 Å, graphite monochro-
mator) at 150(2) K. An absorption correction was
applied empirically by intensities of equivalent reflec-
tions (SADABS) [11]. The structures were solved by a
dried in air. Complexes II and III were washed and direct method and refined by least squares for F2 in the
dried similarly. The yield of compound I was 0.18 g anisotropic approximation for all non-hydrogen
(47%).
atoms (SHELXTL) [11]. The hydrogen atoms of the
organic ligands were localized geometrically and
refined by the riding model, and the hydrogen atoms
of the crystallization water molecules were not local-
ized. The crystallographic characteristics and details
of diffraction experiments for compounds II–IV are
presented in Table 1. Selected bond lengths and bond
angles are given in Table 2. The coordinates of atoms
and thermal parameters were deposited with the Cam-
bridge Crystallographic Data Centre (CIF files
CCDC 1415452 (II), 1415453 (III), 1415454 (IV);
http://www.ccdc.cam.ac.uk/data_request/cif).
The magnetic properties of polycrystalline samples
I–III were studied on a MPMS-XL SQUID magne-
tometer (Quantum Design) in a range of 2–300 K in a
magnetic field of 5 kOe. For the calculation of the
paramagnetic component of the molar magnetic sus-
ceptibility (χ), diamagnetic corrections were applied
according to the Pascal additive scheme. The effective
magnetic moment (μeff) was determined in the para-
For C34H44FeN14S2 (I)
anal. calcd., %:
Found, %:
C, 53.1;
C, 53.4;
H, 5.8;
H, 6.2;
N, 25.5.
N, 25.0.
Synthesis of [Fe(HC(3,5-Me2Pz)3)(Phz)(NCS)2] ⋅
0.5H2O (II). A solution of salt Fe(NCS)2 was obtained
in the same way as that for the synthesis of compound I.
To obtain complex II, an equimolar mixture of the
ligands, HC(3,5-Me2Pz)3)2 (0.5 mmol, 0.15 g) and
Phz (0.5 mmol, 0.065 g), was dissolved in acetone
(10 mL), and the obtained solution was added to a
solution of Fe(NCS)2. An orange precipitate was
formed after a solvent excess was removed and the
solution was cooled down in an ice-cold bath. The
yield of compound II was 40%.
For C26H30FeN10OS2 (II)
magnetic range using the equation μeff
=
anal. calcd., %:
Found, %:
C, 50.4;
C, 49.4;
H, 4.9;
H, 4.9;
N, 22.6.
N, 22.5.
1 2
1 2
3k
⎛
⎜
⎝
⎞
⎟
⎠
(
)
where k is the Boltzmann
,
χT
≈ 8χT
N μ2
A
B
Crystals
of
[Fe(HC(3,5-Me2Pz)3)(3,5-
constant, NA is Avogadro’s number, and μB is the Bohr
Me2Pz)(NCS)2] ⋅ C2H5OH (III) suitable for X-ray dif-
fraction analysis precipitated from an ethanolic solu-
tion of complex I during slow crystallization. Single
crystals of complex II were grown in a U-like tube
upon the reaction of an aqueous solution of Fe(NCS)2
and an acetone solution of a mixture of ligands
HC(3,5-Me2Pz)3 and Рhz. An attempt to use this
method for growing single crystal crystals of the heter-
magneton.
Diffuse reflectance spectra were recorded on a UV-
3101 PC scanning spectrophotometer (Shimadzu) at
room temperature.
IR absorption spectra were measured on a Scimitar
FTS 2000 and a Vertex 80 spectrometers in a range of
100–4000 cm–1. The samples were prepared as sus-
pensions in Nujol, fluorinated oil, and polyethylene.
oligand
complex
[Fe(HC(3,5-
Me2Pz)3)(Аecpz)(NCS)2] ⋅ 0.5H2O (Аecpz is 3-
amino-4-ethoxycarbinolpyrazole), the synthesis pro-
cedure for which was published earlier [9], gave crys-
RESULTS AND DISCUSSION
The iron thiocyanate complexes with tris(3,5-
dimethylpyrazol-1-yl)methane and phthalazine were
isolated from aqueous-acetone solutions upon the
reactions of iron(II) thiocyanate with HC(3,5-
Me2Pz)3 and Рhz. Iron(II) thiocyanate was obtained
tals
of
[Fe(HC(3,5-Me2Pz)3)2][Fe(HC(3,5-
Me2Pz)3(NCS)3]2 (IV).
Elemental analyses to C, H, and N were carried out
on a EURO EA 3000 instrument (EuroVector, Italy) at
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
Vol. 42
No. 11
2016
Lavrenova
