Transition metal complexes with 2,6-Di-tert-butyl-p-quinone 1′-phthalazinylhydrazone

Article abstract of DOI:10.1134/S1070363213100216

2,6-Di-tert-butyl-p-quinone 1′-phthalazinylhydrazone (HL) was synthesized. Quantum-chemical calculations of the energy of possible tautomeric forms of the hydrazone were performed. The complexes of Zn(II), Hg(II), Ni(II), and Cu(II) of ML₂ comp

Full text of DOI:10.1134/S1070363213100216

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 10, pp. 1928–1936. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © S.I. Levchenkov, I.N. Shcherbakov, L.D. Popov, S.N. Lyubchenko, K.Yu. Suponitskii, A.A. Tsaturyan, S.S. Beloborodov, V.A. Kogan,
2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 10, pp. 1722–1730.
Transition Metal Complexes
with 2,6-Di-tert-butyl-p-quinone 1'-Phthalazinylhydrazone
S. I. Levchenkova, I. N. Shcherbakovb, L. D. Popovb, S. N. Lyubchenkob, K. Yu. Suponitskiic,
A. A. Tsaturyanb, S. S. Beloborodovb, and V. A. Koganb
a Southern Scientific Center of the Russian Academy of Sciences, ul. Chekhova 41, Rostov-on-Don, 344022 Russia
e-mail: s.levchenkov@gmail.com
b Southern Federal University, Department of Chemistry, Rostov-on-Don, Russia
c Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow, Russia
Received November 1, 2012
Abstract—2,6-Di-tert-butyl-p-quinone 1'-phthalazinylhydrazone (HL) was synthesized. Quantum-chemical
calculations of the energy of possible tautomeric forms of the hydrazone were performed. The complexes of
Zn(II), Hg(II), Ni(II), and Cu(II) of ML2 composition were obtained and studied. The structure of the NiL2
complex was established by XRD. It was shown by DFT-D3 calculations that the cis-structure of the complex
is stabilized due to the interligand dispersion interaction.
DOI: 10.1134/S1070363213100216
Hydrazones of carbonyl compounds belong to one
of the most popular types of ligand systems, as the
easily form coordination compounds with the majority
of the transition metals [1–6]. The interest in the 1-
hydrazino-phthalazine (hydralazine), its derivatives,
and their complexes with transition metals is due to the
biological activity inherent to these compounds [6–12].
The study of the hydrazones based on hydrazine-
phthalazine is stimulated by the fact that the meta-
bolism of hydralazine includes its interaction with the
carbonyl compounds formed in the Krebs cycle [11–
17]. A number of hydralazine hydrazones with some
mono- and dicarbonyl compounds were described [17–
20], as well as their mono- and binuclear coordination
compounds with transition metals [21–30].
This paper presents the results of studies of the
physical and chemical properties of 2,6-di-tert-butyl-p-
quinone 1'-phthalazinylhydrazone (I) and the transition
metal complexes II–V based on it.
O
O
М(CH3COO)2
N
N
N
N
H
N
М
/
2
N
N
N
I (HL)
М = Zn (II), Hg (III), Cu (IV), Ni (V)
1
Hydrazone I was identified by elemental analysis,
IR and H NMR spectroscopy. Compound I can exist
in several tautomeric forms: phthalazone Ia, hydrazone
Ib, and azophenol Ic.
The presence in the H NMR spectrum of com-
1
pound I of two proton signals from the tert-butyl
groups indicates the presence of one of the quinoid
forms, Ia or Ib. In the azophenol form Ic a fast (in the
1928

TRANSITION METAL COMPLEXES WITH 2,6-DI-tert-BUTYL-p-QUINONE
1929
O
OH
O
N
N
N
HN
N
N
H
N
N
N
N
N
N
Ib
Ia
Ic
NMR time scale) rotation of the phenolic moiety
around the single N–C bond should be expected, that
should result in the appearance in the 1H NMR spectra
of the signals of two t-Bu groups in the form of 18-
proton singlet.
ε 33 500 L cm–1 mol–1). In an alkaline environment
there is a significant red shift of the absorption band to
555 nm (ε 31 300 L cm–1 mol–1), which is associated
with the formation of the deprotonated form of the
hydrazone. In the acidic environment in the spectrum
of the hydrazone I there are two absorption bands at
385 nm (ε 17,600 L cm–1 mol–1) and 399 nm
(ε 18500 L cm–1 mol–1), which can be attributed to
various protonated forms of the hydrazone.
In accordance with the available data it is
presumable that, as in the case of other hydrazine-
phthalazine hydrazones [6, 19, 29–33], compound I
exists primarily as phthalazonehydrazone tautomer Ia.
Hydrazone I forms with Zn(II), Hg(II), Cu(II), and
Ni(II) acetates the complexes of the type II–V of ML2
composition. The disappearance of the absorption band
ν(NH) and low-frequency shift of the band ν(C=N) in
the IR spectra of complexes indicates the bidentate
ligand coordination of the monodeprotonated form. In
the 1H NMR spectra of compounds II, III, and V there
are no signals from the protons of NH-group, and there
are two signals from the protons of tert-butyl groups,
which also confirms the coordination of the ligand in
monodeprotonated quinoid form.
To confirm this assumption we performed
quantum-chemical calculations of the electronic and
steric structure of the tautomers Ia–Ic within the
density functional theory (DFT). We used a hybrid
exchange-correlation functional B3LYP [34] with the
exchange part in the form proposed in the work of
Becke [35], and the correlation part of the Lee–Yang–
Parr [36]. The geometric structure of the molecules
was initially optimized over all the natural variables
without restrictions on symmetry. Minima on the
potential energy surface for each structure were
identified by calculation of the matrix of force
constants and frequencies of normal vibrations. As the
basis set we used the extended valence-split basis
6311+G(d,p).
In the electronic spectra of complexes II–V in
toluene a red shift of the absorption band maximum is
observed by 62, 56, 58, and 57 nm, respectively, as
compared with its positions in the spectrum of the
hydrazone I, due to the partial charge transfer from the
anionic ligand on the metal ion.
The most stable form of the tautomers Ia–Ic and
their relative energies are shown in Fig. 1.
The effective magnetic moment of the copper
complex IV at room temperature (1.79 MB) is typical
of copper(II) with a planar environment of the central
ion [37, 38]. At lowering the temperature to 77.4 K the
value of μeff remains practically unchanged, indicating
the absence of intermolecular magnetic exchange
interaction between the copper(II) ions.
According to calculations, the most stable form of
compound I is phthalazonehydrazone tautomer Ia,
stabilized by an intramolecular hydrogen bond. Hyd-
razone Ib and azophenol Ic tautomers are destabilized
relative to Ia by 9.3 and 15.1 kcal mol–1, respectively.
The electron absorption spectrum of the hydrazone
I in toluene contains an absorption band at 471 nm
(ε 34 500 L cm–1 mol–1). In aqueous ethanol the
position of the band is almost unchanged (470 nm,
According to the available data it is presumable that
mercury and zinc complexes are tetrahedral, and
copper and nickel complexes have planar structure.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013

1930
LEVCHENKOV et al.
Ia (–1148.4858213 a. u.)
ΔE 0.00 kcal mol–1
Ib (–1148.47009370 a. u.)
ΔE 9.34 kcal mol–1
Ic (–1148.4617141 a. u.)
ΔE 15.13 kcal mol–1
Fig. 1. The total energies (a. u. ) and relative stability ΔE (kcal mol–1) of tautomeric forms of the compounds I in a vacuum.
Fig. 2. The structure of complex V; ellipsoids of thermal vibrations are given for the 50% probability.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013

TRANSITION METAL COMPLEXES WITH 2,6-DI-tert-BUTYL-p-QUINONE
1931
Table 1. Selected interatomic distances and angles in the
structure of complex V according to XRD data
The latter complex can have cis- or trans-molecular
structure. Given the presence in the ligand molecule of
the bulky tert-butyl groups at the donor nitrogen
atoms, it might be expected that the complexes should
have trans-structure, in which the steric hindrance is
minimal [39, 40]. However, the results of X-ray
studies of the nickel complex V showed that the
complex has an unusual cis-structure (Fig. 2).
Bond
d, Ǻ
Angle
ω, deg
Ni1–N7
Ni1–N3
Ni1–N5
Ni1–N1
N1–N2
N1–C9
N2–C1
N3–C1
N3–N4
N5–N6
N7–N8
N5–C31
N6–C23
N7–C23
O1–C12
O2–C34
1.8624
1.8594
1.9244
1.9454
1.3615
1.3316
1.3276
1.3646
1.3576
1.3575
1.3585
1.3406
1.3296
1.3636
1.2276
1.2186
N7Ni1N3
N7Ni1N5
N3Ni1N5
N7Ni1N1
N3Ni1N1
N5Ni1N1
C9N1N2
C9N1Ni1
N2N1Ni1
C1N2N1
N4N3C1
N4N3Ni1
C1N3Ni1
C31N5N6
C31N5Ni1
N6N5Ni1
N8N7Ni1
99.8719
81.2917
154.3617
155.0017
82.4418
107.3517
115.14
Formula unit in the crystalline state is a mono-
nuclear complex NiL2. Complex molecule is not
symmetric, the geometric characteristics of the ligands
are somewhat different from each other (Table 1). The
five-membered metallocycles are essentially flat, with
little distortion of the envelope type with nickel as the
top atom. The inflection of the plane of chelate rings at
the line connecting the donor nitrogen atoms in one
ring (NiN1N2C1N3) is 4.2°, and in the second ring
(NiN5N6C23N7) it is 8.9°. The two ligand molecules in
general are also almost flat, the dihedral angle between
the mean planes of quinonimine fragments and
phthalazine rings are –2.94(19)° and 6.09(18)°,
respectively.
131.03
113.73
111.74
122.84
124.13
112.23
116.14
127.73
115.53
124.13
Waals radii], C42–H42B···C29ii , d = 2.68 Å (δ = 0.22 Å)
[symmetry code (ii): 1 + x, y, z].
The coordination polyhedron of the nickel ion in
complex V can be described as a highly distorted
square or strongly flattened tetrahedron (Fig. 2), the
dihedral angle between the mean square planes of five-
membered chelate rings of two ligands is 38.84 (19)°.
This significant tetrahedral distortion is a consequence
of steric repulsion of bulky tert-butyl groups of the cis-
oriented ligands and of the mutual repulsion of the
lone electron pairs of nitrogen atoms N4 and N8.
In order to assess the relative stability of the
possible isomeric forms of the complex V we carried
out quantum-chemical calculation of the total energy
of the cis,trans-isomers (singlet spin state) and high-
spin (triplet spin state) isomers. Table 2 shows the total
and relative energies of the isomers obtained in the
framework of density functional theory (functional
B3LYP) with the basis set 6-311G(d) (B3LYP
column), Fig. 4, shows the optimal structures, Table 3
lists some of the geometric parameters.
It is known that the tetrahedral ligand environment
of nickel ion in the coordination compounds deter-
mines its high-spin state (S = 1), while the square-
planar configuration corresponds to low-spin state (S = 0)
[37]. It is interesting that with such a large value of the
tetrahedral distortion the low-spin state of the nickel
ion (S = 0) is realized as evidenced by its dia-
magnetism.
The trans-isomer, as well as cis-isomer is not flat
due to steric repulsion of quinonimine fragment of one
ligand and phthalazine moiety of the second ligand.
The angle between the least-mean-square planes of
five-membered chelate rings is even more than in the
cis-isomer, 42.7°.
Complex V crystals have a very interesting struc-
ture. The molecules are packed in layers, parallel to the
a0b crystallographic plane, so that the t-butyl groups
are located on the surface of each layer. The areas of
hydrophobic interaction are formed between the layers
(Fig. 3, shaded area).
In the high-spin isomer the ligand planes are turned
by 73.4°, and the structure of coordination unit is close
to the heavily distorted pseudotetrahedron, the N–Ni–N
angles for the equivalent nitrogen atoms of the ligands
are very different: 117.4° for N3–Ni1–N7 and 160.3°
for N1–Ni1– N5.
Within the layers, the molecules are connected
through π-π and CH···π contacts, the shortest of which
is C2···C10i, d = 3.289(7) Å [symmetry code (i) is 1 – x,
1 – y, –z, by δ = 0.11 Å less than the sum of van der
The calculated optimal structure of the cis-isomer is
close to the X-ray data, but there is a strong steric
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013

1932
LEVCHENKOV et al.
Fig. 3. The crystal packing of complex V, view along the crystallographic b axis. Darkened area corresponds to the hydrophobic
interactions of t-butyl groups.
repulsion of the ligands, which is seen in the increased
distances between atoms of quinonimine fragments of
ligands in comparison with the data of X-ray
diffraction (Table 3). Thus, the distance between the
carbon atoms of quinonimine fragments C12–C34 is
overestimated by more than 1 Å.
molecular structure of the crystal. To account for the
dispersion interaction between the ligands, we used the
method of DFT-D3 proposed by Grimme and
coworkers [41], in which the energy of the dispersion
interaction is calculated as correction to the energy
calculated by density functional theory (DFT)
As a result of the overestimation of the steric repul-
sion, the calculations with the B3LYP functional show
that the cis-isomer of complex V is by 4.39 kcal mol–1
less stable than the trans-isomer. Furthermore, the cis-
isomer is even less favourable than the high-spin iso-
mers. This discrepancy between the results of
calculations and experimental data can be explained by
insufficient accounting for the nonbonded dispersion
interaction between the ligands in the complex in the
framework of DFT method. From the analysis of the
crystal structure, however, the significant role of these
interactions is obvious in the formation of supra-
EDFT-D3 = EDFT – Edisp
,
(1)
where Edisp is the sum of two-center contributions to
the dispersion interaction. At short distances the
Becke–Johnson damping function was applied [42–44].
Table 2 shows the results of calculation of the
energy of isomers, Table 3 lists the optimum geometric
parameters in the columns marked B3LYP-D3. Addi-
tional accounting for the dispersion correction has
almost no effect on the bond lengths in the complex,
but significantly improves the theoretical description
of the equilibrium geometry of the interligand contacts
Table 2. Full (E, au) and relative (ΔE, kcal mol–1) energies of isomers calculated using the methods of DFT (functional
B3LYP) and B3LYp-D3
B3LYP
B3LYP-D3
Isomer
E, au
ΔE, kcal mol–1
E, au
ΔE, kcal mol–1
cis-
–3802.506037
4.33
–3802.783145
0.00
trans-
–3802.512937
–3802.509056
0.00
2.43
–3802.782642
–3802.776231
0.32
4.34
Tetrahedral
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013

TRANSITION METAL COMPLEXES WITH 2,6-DI-tert-BUTYL-p-QUINONE
1933
cis- (S = 0)
trans- (S = 0)
S = 1
Fig. 4. Optimized low-spin cis,trans-structures (S = 0) and high-spin structure (S = 1) of complex V isomers.
in the complex, as can be seen by comparing the
distances between the quinonimine substituents C34–C12,
C9–C31, and C14–C36 of the ligands (Table 3). The
improvement of description of steric repulsion between
the ligands affects the decrease of the inflection angle
in the five-membered chelate rings. Similar changes in
the equilibrium geometry can be noted in the trans-
isomer, but the relative stabilization of this isomer in
the framework of DFT-D3 is much smaller. When
taking into account the dispersion interaction, the cis-
isomer becomes the most stable, by 0.3 kcal mol–1
more stable than the trans-isomer.
EXPERIMENTAL
1H NMR spectra were taken from solutions in
DMSO-d6 on a Varian Unity 300 (300 MHz) spec-
trometer, internal reference HMDS. IR spectra were
recorded on a Varian Scimitar spectrophotometer
within 400–4000 cm–1, samples were prepared as a
suspension in mineral oil. The absorption spectra in the
visible and ultraviolet regions were recorded on a
Varian Cary 5000 spectrophotometer, solutions were
investigated with a concentration of 10–3 M in toluene
in cells 1 cm thick. Magnetic susceptibility was
measured by Faraday method in the temperature range
of 77.4–300 K.
Thus, the results of quantum chemical-calculations sug-
gest that a key role in the stabilization of the cis-isomer
of the complex V is the interligand dispersion interaction.
Quantum-chemical calculations were performed in
EC YUGINFO SFU cluster using Gaussian'03
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013

1934
LEVCHENKOV et al.
Table 3. Selected geometric parameters (d, Å; angles, deg) for the optimal structures of cis-and trans-isomers of the complex
V in the framework of B3LYP and B3LYp-D3 calculation compared to the XRD data for complex V
B3LYP
B3LYP-D3
Parameter
XRDа
cis
trans
1.918
1.891
1.347
1.331
1.328
1.366
1.345
42.7
cis
trans
1.911
1.882
1.347
1.329
1.327
1.365
1.344
39.0
d(Ni1–N1), Å
d(Ni1–N3), Å
d(N1–N2), Å
d(N1–C9), Å
d(N2–C1), Å
d(N3–C1), Å
d(N3–N4), Å
1.935
1.860
1.359
1.335
1.328
1.364
1.357
38.8
1.947
1.875
1.347
1.338
1.331
1.361
1.340
38.3
1.946
1.874
1.346
1.336
1.331
1.362
1.341
36.0
Angle between the five-membered
ring, deg
Inflection of the chelate ring at N···N,
deg
4.2 and 8.9
12.8
17.6
10.8
13.2
d(N1–N5), Å
d(C9–C31), Å
d(С12–С34), Å
d(С14–С36), Å
3.117
3.764
5.470
3.119
3.133
3.887
6.601
3.542
–
–
–
–
3.111
3.705
5.304
3.187
–
–
–
–
a The mean values of the geometrical parameters for the two ligands in the complex are reported.
software [45]. To prepare the data, the presentation
graphics, visualization of results of calculations we
used the program Chemcraft [46].
was added a solution of 0.25 mmol of a metal acetate
in 10 mL of methanol. The reaction mixture was refluxed
for 30 min, the formed precipitate was filtered off,
washed with methanol, and recrystallized from DMF.
Hydrazone (I). To a hot suspension of 0.391 g
(2 mmol) of 1-hydrazinophthalazine hydrochloride in
20 mL of ethanol was added 0.164 g (2 mmol) of
sodium acetate. The mixture was boiled for 10 min,
0.44 g (2 mmol) of 2,6-di-tert-butyl-p-quinone was
added, and the reaction mixture was refluxed for 4 h.
Then 50 mL of water was added and the mixture was
left overnight. The orange precipitate was filtered off,
washed with water and ethanol, and recrystallized from
hexane. Yield 0.396 g (55%), mp 207°C. IR spectrum
(ν, cm–1): 3371 (NH), 1684 s (C=O), 1636 s, 1597
Complex II. Yield 0.180 g (90%), mp > 250°C. IR
spectrum (ν, cm–1): 1672 s (C=O), 1619 s, 1594
(C=N). 1H NMR spectrum (CDCl3, δ, ppm): 8.61–8.68
m (1H, CHarom), 8.602 s (1H, CHarom), 7.81-7.90 m
(2H, CHarom), 7.70–7.78 m (1H, CHarom), 8.329 d (1H,
CHarom, J = 2.6 Hz), 6.584 d (1H, CHarom, J = 2.6 Hz),
1.349 s (9H, t-Bu); 0.879 s (9H, t-Bu). EAS in toluene
(λ, nm): 533 (ε 55,000 L cm–1 mol–1). Found, %: C
67.25, H 6.30, N 14.03. C44H50N8O2Zn. Calculated, %:
C 67.04, H 6.39, N 14.21.
1
(C=N). H NMR spectrum (CDCl3, δ, ppm): 10.928 s
Complex III. Yield 0.198 g (86%), mp > 250°C.
IR spectrum (ν, cm–1): 1677 s (C=O), 1622 s, 1592
(C=N). 1H NMR spectrum (CDCl3, δ, ppm): 8.63–8.69
m (1H, CHarom), 8.531 (1H, CHarom), 7.78–7.89 m (2H,
CHarom), 7.65–7.73 m (1H, CHarom), 8.178 d (1H,
CHarom, J = 2.6 Hz), 6.769 d (1H, CHarom, J = 2.6 Hz),
1.318 s (9H, t-Bu); 0.869 s (9H, t-Bu). EAS in toluene
(λ, nm): 527 (ε 67,000 L cm–1 mol–1). Found, %: C
57.39, H 5.32, N 12.04. C44H50HgN8O2. Calculated, %:
C 57.22, H 5.46, N 12.13.
(1H, NH); 8.50–8.60 m (1H, CHarom), 8.044 (1H,
CHarom), 7.70–7.80 m (2H, CHarom), 7.56-7.67 m (1H,
CHarom) 8.094 d (1H, CHarom, J = 2.5 Hz), 7.101 d (1H,
CHarom, J = 2.5 Hz), 1.328 s (9H, t-Bu); 1.356 s (9H,
t-Bu). EAS in toluene (λ, nm): 471 (ε 34.500 L cm–1 mol–1).
Found, %: C 72.65, H 7.39, N 15.62. C22H26N4O.
Calculated, %: C 72.90, H 7.23, N 15.46.
Complexes II–V (general procedure). To a hot solu-
tion of 0.5 mmol of hydrazone I in 25 mL of methanol
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013

TRANSITION METAL COMPLEXES WITH 2,6-DI-tert-BUTYL-p-QUINONE
1935
(Transition Metal Complexes with Hydrazones.
Physical and Chemical Properties and Structure),
Moscow: Nauka, 1990.
Complex IV. Yield 0.177 g (90%), mp > 250°C. IR
spectrum (ν, cm–1): 1673 s (C=O), 1615 s, 1595 (C=N).
EAS in toluene (λ, nm): 529 (ε 52,000 L cm–1 mol–1).
μeff (MB): 1.79 (300 K), 1.77 (77.4 K). Found, %: C
67.36, H 6.49, N 14.11. C44H50CuN8O2. Calculated, %:
C 67.20, H 6.41, N 14.25.
3. Parpiev, N.A., Yusupov, V.G., Yakimovich, S.I., and
Sharipov, Kh.G., Atsilgidrazony i ikh kompleksy s
perekhodnymi metallami (Acylhydrazones and Their
Complexes with Transition Metals), Tashkent: Fan,
1988.
Complex (V). Yield 0.176 g (90%), mp > 250°C.
IR spectrum (ν, cm–1): 1670 s (C=O), 1609 s, 1591 (C=N).
ESP in toluene (nm): 474, 528 (ε 6200 L cm–1 mol–1),
657.1H NMR spectrum (CDCl3, δ, ppm): 8.734 s (1H,
CHarom), 8.48-8.56 m (1H, CHarom), 7.73-7.90 m (3H,
CHarom), 7.630 d (1H, CHarom, J = 2.8 Hz), 7,373 d (1H,
CHarom, J = 2.8 Hz), 1.369 s (9H, t-Bu); 1.118 s (9H, t-
Bu). Found, %: C 67.85, H 6.38, N 14.52.
C44H50N8NiO2. Calculated, %: C 67.61, H 6.45, N
14.34.
4. Stadler, A.-M. and Harrowfild, J., Inorg. Chim. Acta.,
2009, vol. 362, no. 12, p. 4298.
5. Popov, L.D., Morozov, A.N., Shcherbakov, I.N., Tupo-
lova, Yu.P., Lukov, V.V., and Kogan, V.A., Russ.
Chem. Rev., 2009, vol. 78, no. 7, p. 643.
6. Kogan, V.A., Levchenkov, S.I., Popov, L.D., and
Shcherbakov, I.N., Russ. J. Gen. Chem., 2009, vol. 79,
no. 12, p. 2767.
7. Zelenin, K.N., Khorseeva, L.A., and Alekseev, V.V.,
Khim. Farm. Zh., 1992, vol. 26, no. 5, p. 30.
A single crystal of the complex V for XRD was
obtained by slow cooling of a solution in DMF. Dark
green prismatic crystals (M = 781.63), triclinic at 100 K,
a = 9.696(5) Å, b = 11.977(6) Å, c = 17.393(9) Å, α =
100.654 (10)°, β = 91.963(10)°, γ = 95.964 (9)°, V =
1971.4(17) Å3, space group P1, Z = 2, ρcalc = 1.317 g cm–3.
The intensities of 12,588 reflections were measured on
a Bruker SMART APEX2 CCD diffractometer (λMo-
Kα = 0.71073 Е, graphite monochromator, ω-scanning,
2θ < 56°) for the single crystal of the size
0.21×0.17×0.14 mm. Processing of the array of
measured intensities was carried out by the program
SAINT [47], SADABS [48]. The structure was solved
by the direct method and refined (509 parameters) by
full-matrix anisotropic approximation for non-
hydrogen atoms with respect to F2hkl. Hydrogen atoms
were placed in geometrically calculated positions and
refined using a rider model [Uiso(H) = nUeq(C), where
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