Tin(IV) complexes with 2-hydroxybenz(2-hydroxynaphth)aldehyde nicotinoylhydrazones (H2Ns, H2Nnf). Molecular and crystal structures of [SnCl3(HNnf)] · 2DMF

Article abstract of DOI:10.1134/S1070328415050073

The reaction of SnCl₄ with 2-hydroxybenz(2-hydroxynaphth)aldehyde nicotinoylhydrazones (H₂Ns, H₂Nnf) in CH₃OH gave non-electrolyte complexes [SnCl₃(HNs)] (I) and [SnCl₃(HNnf)] (II), which w

Full text of DOI:10.1134/S1070328415050073

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2015, Vol. 41, No. 5, pp. 293–299. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © N.V. Shmatkova, I.I. Seifullina, Z.A. Starikova, 2015, published in Koordinatsionnaya Khimiya, 2015, Vol. 41, No. 5, pp. 259–265.
Tin(IV) Complexes with 2ꢀHydroxybenz(2ꢀ
Hydroxynaphth)aldehyde Nicotinoylhydrazones (H2Ns, H2Nnf).
Molecular and Crystal Structures of [SnCl3(HNnf)] · 2DMF
†
N. V. Shmatkovaa, *, I. I. Seifullinaa, and Z. A. Starikovab,
a Mechnikov National University, ul. Petra Velikogo 2, Odessa, 270100 Ukraine
b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, GSPꢀ1, 117813 Russia
*eꢀmail: nsnmatkova@ukr.net
Received September 24, 2014
Abstract—The reaction of SnCl4 with 2ꢀhydroxybenz(2ꢀhydroxynaphth)aldehyde nicotinoylhydrazones
(H2Ns, H2Nnf) in CH3OH gave nonꢀelectrolyte complexes [SnCl3(HNs)] (I) and [SnCl3(HNnf)] (II),
which were recrystallized to give the solvates [SnCl3(HNs)] · DMF (III) and [SnCl3(HNnf)] · 2DMF (IV).
It was found by IR spectroscopy that the ligands in I–IV are protonated at the N(Py) and coordinated in the
tridentate chelating mode through the azomethine nitrogen atom and oxy and oxyazine oxygen atoms. The
thermolysis of I–IV and electron impactꢀinduced fragmentation of I and II are accompanied by the formaꢀ
tion of the complexes [SnCl2(Ns)] and [SnCl2(Nnf)]. The molecular and crystal structures of IV were deterꢀ
mined by Xꢀray diffraction (CIF file CCDC no. 816105).
DOI: 10.1134/S1070328415050073
INTRODUCTION
the structure of new Sn(IV) coordination compounds
with hydrazones.
Previously, in a study of complexation of GeCl4
with nicotinoylhydrazones of 2ꢀhydroxybenzꢀ (H2Ns)
and 2ꢀhydroxyꢀ1ꢀnaphthaldehydes (H2Nnf) in methꢀ
anol, we found that the composition and structure of
the complexes vary depending on the aldehyde moiꢀ
EXPERIMENTAL
Commercial specialꢀpurity grade SnCl4
,
ρ
=
4.02 g/cm3; reagent grade nicotinic acid hydrazide,
highꢀpurity grade 2ꢀhydroxybenzꢀ and 2ꢀhydroxyꢀ1ꢀ
naphthaldehydes, and analytical grade organic solꢀ
vents (methanol, acetonitrile, DMF, and diethyl
ether) were used.
ety: [GeCl2(Ns
⋅
HCl)CH3OH (Ge : H2Ns molar
ratio of 1 : 1) and [Ge(Ns
⋅
HCl)2] (1 : 2), [Ge(Nnf
⋅
HCl)2] (Ge : H2Nnf = 1 : 2) [1, 2]. In all complexes,
the ligand occurs in the same form protonated at the
pyridine nitrogen and connected to germanium(IV)
via the azomethine nitrogen atom and oxyazine and
oxy oxygen atoms. It was expedient to elucidate how
the composition and structure of the complexes being
formed are affected by the replacement of the central
atoms using the same hydrazones as ligands. This
information is also of interest for elucidating the reguꢀ
larities in the variation of complexing ability in the
series of Lewis acids, tetrachlorides of the electronic
analogues of Ge(IV) and Sn(IV).
Nicotinoylhydrazones were synthesized by conꢀ
densation of nicotinic acid hydrazide with equimolar
amounts of aldehydes in methanol according to the
general procedure of hydrazone synthesis [3] and
recrystallized from acetonitrile. The product purity
was verified by TLC on Silufol UVꢀ254 plates in chloꢀ
roform : acetone = 1 : 10 (H2Ns) and chloroform :
methanol = 20 : 1 (H2Nnf) eluent systems. Yield, %
(mp, °C): H2Ns, 78 (190); H2Nnf, 87 (240).
IR (
(NH), 3050, 2930
1625–1623 (C=N), 1600, 1580, 1490
(NH), 1290–1286 (Ph–O).
complexes [SnCl3(HNs)]
ν
, cm–1): 3380–3370
(CH)ring, 1680–1670
ν
(OH), 3220–3200, 3190
(C=O),
(C=C)ring,
ν
ν
ν
ν
ν
The present study is devoted to the products
formed in the reaction of SnCl4 with 2ꢀhydroxybenzꢀ
and 2ꢀhydroxynaphthaldehyde nicotinoylhydrazones
in methanol. The results of this study can be used to
estimate the complexing properties of SnCl4 with
respect to the considered ligands in comparison with
these properties of GeCl4 and to obtain new data about
1560–1540
The
δ
ν
(
I)
and
were prepared by adding SnCl4
) solutions of
[SnCl3(HNnf)] (II
(0.002 mole, 0.23 mL) to hot (50°С
)
H2Ns and H2Nnf (0.002 moles in 25 mL and in 40 mL
of methanol, respectively) with continuous stirring.
The stirring was continued for additional 10 min at
†
Deceased.
50°С. The precipitates thus formed were immediately
293

294
SHMATKOVA et al.
separated on a glass filter, washed with hot methanol ple injection into the ion source at an ionizing voltage
10 mL), and dried at 80 to a constant weight. of 70 eV and a source temperature of 220
The yields were 85% ( ) and 77% (II).
(
2
×
°
С
°C.
I
Xꢀray diffraction. The experimental set of reflecꢀ
tions for the monoclinic polymorph crystal of IV was
collected on a Bruker SMART CCD diffractometer
For C13H10N3O2Cl3Sn (
anal. C, 33.54; H, 2.15; N, 9.03; Cl, 22.87; Sn, 25.53.
calcd., %:
Found, %: C, 33.58; H, 2.18; N, 9.10; Cl, 22.91; Sn, 25.44.
I)
( МоК radiation). The absorption corrections were
λ
α
applied by the SADABS program [6]. The structure
was solved by the direct method. All nonꢀhydrogen
atoms were located from the difference Fourier maps
2
and refined on
in the anisotropic approximation.
Fhkl
For C17H12N3O2Cl3Sn (II
anal. C, 39.61; H, 2.33; N, 8.15; Cl, 20.65; Sn, 23.05.
calcd., %:
Found, %: C,39.68; H, 2.35; N, 8.21; Cl, 20.69; Sn, 22.89.
)
All hydrogen atoms (except for H(N) found in the difꢀ
ference map) were placed into the geometrically calꢀ
culated positions and included in the refinement in the
riding model with U(H) = 1.2 U(C), where U(C) is the
equivalent thermal factor of the carbon atom bearing
this H atom.
The solvates [SnCl3(HNs)]
[SnCl3(HNnf)] 2DMF (IV) were isolated from satuꢀ
rated (40 ) solutions of and II in a mixed solvent
CH3OH : DMF = 1 : 3) as a result of isothermal evapꢀ
oration for 24–32 h at 20 . After preliminary isolaꢀ
tion of crystals of IV suitable for Xꢀray diffraction, the
precipitates were separated, washed with cold methaꢀ
⋅
DMF (III) and
⋅
Experimental data collection and structure refineꢀ
ment details are summarized in the table. The calculaꢀ
tions were carried out by SHELXTL software [7]. The
atom coordinates, bond lengths. bond angles, and
thermal parameters are deposited with the Cambridge
Crystalloraphic Data Centre (CCDC no. 816105;
www.ccdc.cam.uk/conts/retrieving.html or deposit@
ccdc.cam.ac.uk).
°С
I
(
°С
nol (2
×
5 mL), and dried at 80°С to a constant weight.
The yields were 60% (III) and 52% (IV).
RESULTS AND DISCUSSION
For C16H17N4O3Cl3Sn (III
anal. C, 35.68; H, 3.16; N, 10.41; Cl, 19.77;Sn, 22.06.
calcd., %:
Found, %: C, 35.74;H, 3.13; N, 10.50; Cl, 19.81;Sn, 21.83.
)
The study of the reaction of SnCl4 with nicotinoylꢀ
hydrazones in methanol showed that, irrespective of
the aldehyde moiety (2ꢀhydroxybenzꢀ or 2ꢀhydroxyꢀ
1ꢀnaphthꢀ), complexes with the same Sn : ligand : Cl
molar ratio of 1 : 1 : 3 are formed. They are yellow (I)
and orange (II) compounds readily soluble in DMF
and DMSO and moderately soluble in acetonitrile.
According to electrical conductivity measurements,
For C23H26N5O4Cl3Sn (IV
anal. C, 41.72; H, 3.93; N, 10.58; Cl, 16.08; Sn, 17.94.
calcd., %:
)
the compounds were nonꢀelectrolytic in DMF (
37.6 ( ), 40l.3 (II
–1 cm2 mol–1). Hence, all chlorine
atoms of and II are in the inner sphere and are
λ
=
Found, %: C, 41.78; H, 3.90; N, 10.65; Cl, 15.94; Sn, 17.86.
I
)
Ω
I
Analysis of the complexes for C, H, N was perꢀ
formed on a semiautomatic CHN analyzer; chlorine
was quantified by mercurometry [4], and tin was
determined by inductively coupled plasma atomic
emission spectroscopy (ICP AES) on an Optimaꢀ2100
DV Perkin Elmer instrument. The molar electrical
covalently bonded to tin atoms. Since the complexes
are not charged, they can be described as
[
SnCl3(HNs)
not undergo solvolysis in a DMF solution, as indicated
by invariability of the values with time.
The crystal solvates formed by complexes
namely, [SnCl3(HNs)] DMF III
[SnCl3(HNnf)] 2DMF (IV), were isolated from a
CH3OH–DMF solvent mixture. The thermolysis of
III and IV, unlike the thermolysis of and II, starts
with the endotherm corresponding to desolvation in
the 160–190 temperature range with the TGꢀmass
loss of 14% (for III, 1 mole of DMF) or 22% (for IV
2 moles of DMF) and then continues similarly to
and II
More precisely, one mole of HCl is eliminated at
, which gives rise to an endotherm (Тmax
), the TG mass loss being 8.0 ( ) and 7.5% (II
mtheor, %: , 7.8; II, 7.1). The contents of tin and
were run on an MXꢀ1321 instrument with direct samꢀ chlorine in the products formed upon maintenance of
(I) and [SnCl3(HNnf)] (II). They do
λ
I
and II
,
conductivity
λ
of 10–3 M solutions of I–IV in DMF
·
(
) and
was measured using an Economics Expert digital
instrument and the electrolyte type was determined
according to the tables [5].
Thermogravimetric measurements were carried
out on a Paulik–Paulik–Erdey Qꢀderivatograph. The
⋅
I
°C
samples were heated in air from 20 to 1000°C at a rate
,
of 10°C/min. The sample weight was 100 mg, a platiꢀ
num crucible without a lid served as the sample holder,
and calcined alumina was used as the reference.
The IR absorption spectra (400–4000 cm–1) of 290–360
samples of I–IV as KBr pellets were recorded on a 350
Specord 75 IR spectrophotometer and mass spectra
I
.
°C
=
)
°
C
I
(
Δ
I
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TIN(IV) COMPLEXES
2DMF (IV
295
Crystal data and refinement details for [SnCl3(HNnf)]
Parameter
⋅
)
Value
Formula
M
C17H12N3O2Cl3Sn ⋅ 2(C3H7NO)
661.53
120
Temperature, K
System
Monoclinic
21/
Space group
P
c
a
, Å
, Å
12.3115(8)
17.431(1)
13.6124(9)
114.843(1)
2650.9(3)
4
b
c
, Å
β
V
Z
ρ
, deg
, Å3
(calcd.), g cm–3
1.658
Crystal color; habit
Crystal size, mm
Yellow prism
0.50
×
0.30 × 0.20
μ
, cm–1
min/Tmax
θmax, deg
1.306
T
0.434/0.655
58.0
2
Total number of reflections
28822
Number of independent reflections (Rint
)
6964 (0.0615)
0.0398 (4485)
0.0700
R
1 (on
F
for reflections with I >
2σ(I))
wR2 (on F2 for all reflections)
Number of refined parameters
GOOF
325
0.993
Δρmax/ρmin
,
e
/Å3
0.265/–0.187
the complexes at 290
°
C
confirm this conclusion. The
The IR spectra of complexes exhibit no
(NH), or
hydrazones and, instead, new bands appear at 560–
550 cm–1 432 cm–1
(Sn–O) and 445 (SnN) [8].
The
ν
(OH),
subsequent destruction of complexes and highꢀtemꢀ
perature burning out of the organic part of the moleꢀ
cules is accompanied by several exotherms at
ν
ν
(C=O) bands present in the spectra of
ν
ν
Т
max = 420 (
↑)
(I,
II), 550 (
↑)
(
II), and 610°C (↑)
(
I,
ν
(C=N) band shifts to lower frequency by 10–
12 cm–1 and the bending modes of the pyridine ring
II). The thermolysis ends at 700 (
I) and 640°C
(
II)
with the formation of a solid residue identified as SnO2
according to chemical analysis data and TG calculaꢀ
tions.
shift to higher frequency (~1010, 635, and 415 cm–1 in
the spectra of I–
IV and ~996, 620, and 400 cm–1 in the
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296
SHMATKOVA et al.
spectra of the ligands). The results indicate that in
IV, the ligand is bonded to tin via the azomethine equal to typical С(sp2)–О
nitrogen atom and the oxygen atoms of the oxyazine deprotonated hydroxy group [1, 2, 10].
and hydroxy groups. Since the changes in the (Py)
I
–
dination bonds [9]. The C(11)–O(1) distances are
→
metal bond lengths with
δ
The
H(1 ⋅⋅⋅Cl(2
2.82, H⋅⋅⋅O 1.81
dimeric associates {Sn2Cl6(Me2NCHO)2} (Fig. 2).
Furthermore, weak stacking interaction occurs
strong
and N(3)–H(3N)⋅⋅⋅O(2S) (H⋅⋅⋅Cl
, combine the molecules into
hydrogen
bonds,
C(1)–
region could be caused by both the hydrazone coordiꢀ
nation involving the N(Py) atom and protonation [1,
2], the final conclusion about the structure of the tin
polyhedron in these complexes was based on Xꢀray
A
)
A)
Å
)
π π
–
diffraction study of IV
.
between the parallel aromatic systems, the distance
between the planes of the pyridine and naphthalene
rings being 3.44 Å and the dihedral angle being 7.4
The structure of IV contains two DMF solvent
molecules. The complex molecule is shown in Fig. 1.
The molecule has a zwitterꢀion structure, the pyridine
nitrogen atom being protonated and the negative
charge being delocalized on the O(2)C(11)N(2)
hydrazine moiety. The coordination polyhedron of
tin, {SnCl3O2N}, is a somewhat extended octahedron;
the axial Sn–Cl(2) and Sn–Cl(3) bonds are longer
than the equatorial Sn–Cl(1) bond (Sn–Cl(1),
°
(Fig. 3).
The packing of the dimeric associates in the crystal
(Fig. 4) is determined by hydrogen bonding between
the methyl hydrogens of the solvent molecules and the
chlorine atoms; the Cl⋅⋅⋅
shorter than the sum of the van der Waals radii of Cl
and H (2.97 Å) [11].
Thus, considering the analogy in the composition
and IR spectra, it can be concluded that compounds
Н distances (2.8–2.9 Å) are
2.3574(8);
Sn–Cl(2),
2.4089(8);
Sn–Cl(3),
2.4260(8); Sn–O(1), 2.024(2); Sn–O(2), 2.092(2);
Sn–N(1), 2.152(2) Å). The axial Cl(2) atom is
involved in the Cl(2)⋅⋅⋅Н(1А)–С(1) hydrogen bond,
which results in shortening of the Sn–Cl(2) bond
compared to the other axial bond (Sn–Cl(3)). The
substantial decrease in the Sn–Cl(1) distance is typiꢀ
cal of equatorial bonds and apparently reflects the
transꢀeffect of nitrogen.
I–IV have the same coordination unit: {SnCl3O2N}.
The arising negative charge is counterbalanced by the
hydrazone form protonated at the heterocyclic nitroꢀ
gen atom.
Attention is drawn by the fact that thermolysis of
the complexes is accompanied by dehydrochlorinaꢀ
In the central moiety of the HNnf– ligand, the tion of their molecules (–1 mole HCl) to give species
bond lengths (N(1)–N(2), 1.409(3); C(1)–N(1), stable in the temperature range of 360–420
1.291(4); C(12)–N(2), 1.305(4); C(11)–O(1), of the mass spectra of and II demonstrated that the
1.335(4); C(12)–O(2), 1.305(3) Å) are typical of electron impactꢀinduced fragmentation gives rise to
°C. A study
I
coordinated nicotinoylhydrazones. The negative species with
m
I
/
z
of 36 [HCl]+
II), 429
), and 479 [SnCl2(Nnf)]+
(II). In all
(
I
,
charge is likely to be concentrated on the oxygen atom [SnCl2(Ns)]+ (
of the nicotinoyl residue, because the C(12)=O(2) probability, these are complexes with fiveꢀcoordinate
bond is substantially longer than the C=O
→
Sn coorꢀ Sn(IV) atom, similar to that described in [8]:
N N
N N
Cl
–HCl
O
O
Sn
Sn
O
O
HN
N
Cl
Cl
Cl
Cl
The performed study showed that in the case of ways: by the total negative charge of the tin coordinaꢀ
Sn(IV), unlike Ge(IV), only equimolar complexes are tion unit in and II and by the chloride ion in
HCl)CH3OH] and [Ge(Ns HCl)2].
The initial step of the thermolysis of [Ge(Ns
HCl)2] and [SnCl3(HNs)] (
nation octahedra of different composition, [SnCl3(HNnf)] (II) is dehydrochlorination; however,
SnCl3O2N} and {GeCl2O2N}, with identical tridenꢀ in the case of and II, it occurs at higher temperature,
I
formed regardless of what is the aldehyde moiety in
nicotinoylhydrazone.
[
GeCl2(Ns
⋅
⋅
⋅
The Sn(IV) and Ge(IV) complexes contain coordiꢀ HCl)2], [Ge(Nnf
⋅
I),
{
I
tate chelating form of the ligand protonated at N(Py). which is attributable to stronger binding of the chloꢀ
The positive charge is counterbalanced in different ride ion.
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TIN(IV) COMPLEXES
297
H(3N)
N(3)
C(5)
C(14)
C(6)
C(7)
C(4)
C(3)
C(15)
N(2)
C(13)
N(1)
C(1)
C(8)
C(16)
C(17)
C(12)
C(2)
C(11)
C(10)
Cl(2)
C(9)
O(2)
Sn(1)
O(1)
Cl(3)
Cl(1)
Fig. 1. Structure of the complex molecule [SnCl (HNnf)] in IV; the thermal ellipsoids are shown to 50% probability.
3
C(5S)
C(4S)
O(2S)
N(2S)
C(15)
C(16)
C(6S)
H(3N)
N(3)
C(14)
C(17)
C(13)
Cl(1
Sn(1
A)
Cl(2A)
C(12)
O(2)
C(1
A)
N(2)
N(1)
A
)
Cl(3A)
H(1AA
)
H(1A)
C(1)
Sn(1)
Cl(3)
C(4)
Cl(2)
C(5)
C(6)
C(2)
Cl(1)
O(1)
C(11)
C(3)
C(8)
C(10)
C(9)
C(7)
Fig. 2. Centrosymmetric dimeric associates {Sn Cl (Me NCHO) }.
2
6
2
2
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298
SHMATKOVA et al.
O(1)
Sn(1)
C(10)
C(9)
O(2)
C(5A)
C(11)
C(6
A
)
N(3A)
C(4A)
C(14A)
C(15A)
C(17)
C(12)
N(2)
C(8)
C(7)
C(1)
N(1)
C(2)
C(3)
C(13)
C(16)
C(3
C(8
N(3)
C(13
A
)
C(7A)
N(2A)
A
)
)
C(16
A)
C(1A)
A
C(12A)
C(17
A
)
C(14)
C(15)
C(9
C(2
A)
N(1A)
C(4)
C(6)
C(11
A)
C(5)
A
)
O(2A)
C(10A)
Sn(1A)
O(1A)
Fig. 3.
π
–
π
ꢀStacking interactions of the aromatic moieties in IV.
x
0
z
y
Fig. 4. Packing of molecules in the crystal of IV
.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 41
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TIN(IV) COMPLEXES
5. Gearly, W.J., Coord. Chem. Rev., 1971, no. 7, p. 81.
299
Thus, in relation to the given ligands, it was found
that GeCl4 and SnCl4 differ considerably in the comꢀ
plexing properties, as indicated by the differences
between the compositions and structures of the coorꢀ
dination compounds they form.
6. SADABS. Version 2.01. Bruker/Siemens Area Detector
Absorption Correction Program, Madison, WI: Bruker
AXS, 2001.
7. Sheldrick, G.M., Acta Crystallogr., Sect. A: Found.
Crystallogr., 2008, vol. 64, p. 112.
8. Han Dong Yin, Min Hong, Gang Li, and Da Qi Wang,
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Translated by Z. Svitanko
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2015