Synthesis and structural characterization of ZnII α-Diimine complexes with chloride and thiocyanate co-ligands

Article abstract of DOI:10.1002/zaac.200801365

The preparation and spectroscopic and structural characterization of three Zn^II complexes with bis[N-(2,6-dimethylphenyl)imine]acenaphthene, L¹, and with bis[N-(2-ethylphenyl)imine]acenaphthene, L², are decribed herein. Tw

Full text of DOI:10.1002/zaac.200801365

ARTICLE
DOI: 10.1002/zaac.200801365
Synthesis and Structural Characterization of ZnII ␣-Diimine Complexes with
Chloride and Thiocyanate Co-Ligands
Leonardo C. Ferreira,[a] Carlos A. L. Filgueiras,*[a] Lorenzo C. Visentin,[a]
[a]†
Jairo Bordinhao, and Manfredo Hörner[b]
˜
Keywords: Zinc complexes; α-Diimines; Crystal structure; πϪπ Interactions; τ-Parameter
Abstract. The preparation and spectroscopic and structural charac-
terization of three ZnII complexes with bis[N-(2,6-dimethyl-
phenyl)imine]acenaphthene, L1, and with bis[N-(2-ethylphenyl)-
imine]acenaphthene, L2, are decribed herein. Two of the complexes
troscopy, and single-crystal X-ray diffraction. The structures of the
complexes are significantly different, with the chloride-containing
species forming distorted tetrahedra around the metal, whereas its
thiocyanate analog is dimeric, with each metal at the center of a
were prepared from ZnCl2 and the third from Zn(NCS)2. One-pot distorted square pyramid, with bridging and terminal [SCN]Ϫ li-
reaction techniques were used, leading to high yields. The com-
gands.
plexes were characterized by microanalysis, IR and 1H NMR spec-
plex only shows a weak interaction between two different
complex molecules, in which the chloride ligands do not
lead to actual dimeric species, in the pseudo-halide case a
true dinuclear complex is formed, as the crystallographic
data clearly show. This is due to the ability of the thiocyan-
ate species to form longer N,S-bonded asymmetric bridges
relative to the chloride ligand. These longer bridges keep
the metal atoms away from each other, decreasing the repul-
sion between the electronic clouds of the diimines, leading
to the formation of stable dimers.
Introduction
The preparation of ZnII complexes containing α-diimines
has been widely studied in the last few years [1Ϫ5]. One-
pot reaction techniques were shown to be quite useful in
these syntheses [6]. When the reagents necessary for the for-
mation of the α-diimine were placed in the presence of a
zinc salt, the metal atom directed the formation of the li-
gand and its subsequent complexation.
However, the interest in zinc complexes with diimines
does not rest solely in this aspect; in several cases the re-
sulting complexes are active as Brookhart pre-catalysts in
olefin polymerization processes [7]. In a recent article [8],
such complexes showed catalytic activity in reactions as di-
verse as hydrogenation, hydrosilylation [9] and borylation
Results and Discussion
The one-pot reaction is often a good means to obtain co-
of alcanes and alkenes [10], as well as the reduction of nitro- ordination complexes with α-diimines. This procedure im-
benzene to aniline [11]. proves the efficiency of many multi-step chemical reactions.
The crystal structures of zinc complexes with α-diimines, The method avoids lengthy separation and purification pro-
thus far investigated, have shown the simplest coordination cesses of intermediates. It saves time and resources whereas
around the metal atom, i.e. tetrahedral [12].
the chemical yields are increased. This work presents such
The present work shows how the replacement of the hal- a case, in which two α-diimines were prepared and com-
ide by a pseudo-halide such as thiocyanate can alter the plexed in a single step. This one-pot technique is the same
situation dramatically. Whereas the chloride diimine com- we described in a previous article [13]. It proved to be a
much better way to get the final complexes, which were ob-
tained in high yields, as shown below. Although complex 1
was prepared previously [14], all crystal structures described
in this work are novel, as well as the preparations of com-
plexes 2 and 3.
The IR spectra of compounds 1, 2 and 3 show typical
CϪN absorptions of α-diimines [15]. In 1 these bands occur
at 1688 and 1636 cmϪ1, whereas in 2 they are seen at 1671
and 1637 cmϪ1; and for complex 3 the signals are observed
in 1689, 1666 and 1632 cmϪ1. Although all these bands
have similar intensities, the higher number of signals in 3
* Prof. Dr. C. A. L. Filgueiras
E-Mail: calf@iq.ufrj.br
´
[a] Instituto de Quımica
Universidade Federal do Rio de Janeiro, C.P. 68563
21945-970 Rio de Janeiro, Brazil
´
[b] Departamento de Quımica
Universidade Federal de Santa Maria
97105-900 Santa Maria, Brazil
†
In memoriam
Supporting information for this article is available on the
WWW under www.zaac.wiley-vch.de or from the author.
Z. Anorg. Allg. Chem. 2009, 635, 1225Ϫ1230
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1225

L. C. Ferreira, C. A. L. Filgueiras, L. C. Visentin, J. Bordinha˜o, M. Hörner
Table 1. Crystal data and structure refinement for complexes 1, 2, and 3.
ARTICLE
1
2
3
Empirical formula
Formula weight
T /K
C28H24Cl2 N2Zn
524.76
295(2)
C28H24N2Cl2Zn
524.76
295(2)
C30H24N4S2Zn
570.02
295(2)
˚
Radiation λ /A
0.71073
0.71073
0.71073
Crystal System, space group
Unit cell dimensions /A, °
monoclinic, P21/m
a ϭ 7.7647(5)
b ϭ 18.3030(13)
c ϭ 8.7398(5)
β ϭ 92.611(5)°
1240.79(14)
2, 1.405
monoclinic, P21/n
a ϭ 11.201(2)
b ϭ 19.841(4)
c ϭ 11.519(2)
β ϭ 97.87(3)°
2536.1(9)
4, 1374
1.197
1080
monoclinic, P21/c
a ϭ 12.4380(8)
b ϭ 18.1071(11)
c ϭ 12.9919(7)
β ϭ 108.130(2)°
2780.7(3)
4, 1.362
1.059
1176
˚
3
˚
Volume /A
Z, Calculated density /g·cmϪ3
Absorption coefficient /mmϪ1
F(000)
1.224
540
Crystal size /mm
Theta range /°
Index range
0.30 ϫ 0.27 ϫ 0.18
2.23 to 25.49
0.14 ϫ 0.09 ϫ 0.08
2.59 to 25.00
0.23 ϫ 0.19 ϫ 0.18
2.79 to 25.50
Ϫ8 Յ h Յ 9, Ϫ19 Յ k Յ 22, Ϫ13 Յ h Յ 13, Ϫ23 Յ k Յ 23, Ϫ14 Յ h Յ 15, Ϫ21 Յ k Յ 21,
Ϫ10 Յ l Յ 10
10015
2391 [R(int) ϭ 0.0564]
99.7 %
Ϫ13 Յ l Յ 12
39485
4463 [R(int) ϭ 0.1195]
99.8 %
Ϫ15 Յ l Յ 15
26147
5171 [R(int) ϭ 0.0489]
99.8 %
Reflections collected
Independent reflections
Completeness to θ max.
Max. and min. transmission
Refinement method
0.8098 and 0.7103
0.9103 and 0.8503
0.8322 and 0.7927
Full-matrix least-squares on F2 Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
2391 / 0 / 159
1.033
R1 ϭ 0.0447, wR2 ϭ 0.1204
R1 ϭ 0.0625, wR2 ϭ 0.1299
0.737 and Ϫ0.611
4463 / 0 / 298
1.043
R1 ϭ 0.0535, wR2 ϭ 0.1005
R1 ϭ 0.0963, wR2 ϭ 0.1140
0.396 and Ϫ0.363
5171 / 0 / 338
1.071
R1 ϭ 0.0375, wR2 ϭ 0.0929
R1 ϭ 0.0607, wR2 ϭ 0.1012
0.258 and Ϫ0.442
Ϫ
Ϫ3
˚
Largest diff. peak and hole /e ·A
˚
suggests that the coordination of zinc in 1 and 2 is different Table 2. Selected bond lengths /A and angles /° for complexes 1, 2
and 3.
from that of 3. Such supposition is corroborated by the
presence of two signals at 2144 and 2080 cmϪ1 in the IR
1
2
3
spectrum of 3 [16]. The presence of the latter two absorp-
tions in 3 indicates the existence of different cyanido groups
Zn1ϪN1
Zn1ϪN2
2.114(2)
2.113(3)
2.1998(19)
2.176(2)
1.956(3)
2.006(2)
in the complex; this could be explained by [SCN]Ϫ existing Zn1ϪN3
Zn1ϪN4Љ
simultaneously in a terminal ZnϪNCS mode (CϪN at
Zn1ϪCl1
2080 cmϪ1) as well as a bridging ZnϪNCSϪZn species
Zn1ϪCl2
2.1967(15)
2.1979(15)
1.280(4)
2.1863(15)
2.2138(14)
1.276(5)
(CϪN at 2144 cmϪ1). It is noteworthy that the X-ray data
C1ϪN1
show only a small difference between the CϪN bonds in
C1ϪN1
Zn1ϪS2
N1ϪC2
N2ϪC1
N3ϪC29
C30ϪN4
1.280(4)
1.276(5)
˚
˚
2.5154(8)
1.274(3)
1.278(3)
1.152(4)
1.143(3)
the terminal [1.151(2) A] and bridging [1.143(1) A] situ-
ations, in contrast with a considerable difference of 64 cmϪ1
in the two IR absorptions. This shows the high sensibility
of the IR analysis for the evaluation of the coordination
modes of the [SCN]Ϫ ligand.
N1ϪZn1ϪCl1
N1ϪZn1ϪCl2
Cl1ϪZn1ϪCl2
N1ЈϪZn1ϪN1
N1ϪZn1ϪN2
N1ϪZn1ϪS2
N4ЉϪZn1ϪN2
N3ϪZn1ϪS2
N2ϪZn1ϪN1
N4ЉϪZn1ϪS2
114.35(8)
112.16(8)
117.67(6)
80.54(13)
119.96(11)
106.93(10)
118.03(6)
Single crystals of 1, 2 and 3 were collected after slow
evaporation of all three complexes in MeOH.
Experimental details for the X-ray data collection, refine-
ment and solution, as well as the crystal parameters of 1, 2
and 3 are given in Table 1.
The bond lengths and angles for the three complexes are
shown in Table 2. The molecular structures of 1, 2 and 3
are depicted in Figure 1, Figure 2 and Figure 3, in a thermal
ellipsoid representation and with an atom-labeling scheme
[17].
79.73(12)
152.29(6)
146.73(10)
101.46(8)
76.35(7)
94.37(7)
Symmetry code for equivalent atoms of (1): (Ј) x, 3/2Ϫy, z; for (2):
(Љ) Ϫx, 1Ϫy, 1Ϫz.
The structure of 1 has site symmetry m, with one
zinc atom in
a
distorted tetrahedral arrangement 3/2Ϫy, z. The complex molecule is characterized by a mirror
[Cl1ϪZn1ϪCl2 117.67°(6) and N1ϪZn1ϪN1Ј 80.54°(13)], plane m including atoms C4 and C3, the midpoint of the
containing two chloride ions as ligands [Zn1ϪCl1 C1ϪC1Ј bond, and atoms Zn1, Cl1 and Cl2, respectively.
2.1967(15) A, Zn1ϪCl2 2.1979(15) A], and one N,N-chelat- The terminal phenyl rings in L1 have a mirror plane ap-
˚
˚
1
˚
ing ligand, L [Zn1ϪN1 2.114(2) A]; symmetry code: (Ј) x, proximately perpendicular to the acenenaphthene plane,
1226
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 1225Ϫ1230

Synthesis and Characterization of ZnII α-Diimine Complexes
Figure 3. View of the molecular projection of [Zn2(L1)2(μ-NCS)2]
with the dimeric structure showing square-pyramidal coordination
and μ-thiocyanate eight-membered ring system [17]. Displacement
ellipsoids at the 50 % level; symmetry code: (Љ) Ϫx, 1Ϫy, 1Ϫz. The
numbering scheme in the asymmetrical unit was omitted for clarity.
Figure 1. View of the molecular projection of [Zn(L1)(Cl)2] showing
tetrahedral coordination [17]. Displacement ellipsoids at the 50 %
level; symmetry code: (Ј) x, 3/2Ϫy, z.
The molecular structures of 1 and 2 are relative to those
of three distorted tetrahedral examples from the literature.
Namely,
ZnCl2(p-OMe-BIAN)·1/2CH2Cl2,
[ZnϪCl
˚
˚
2.2013(6) A and ZnϪN 2.085(2) A] [8], ZnCl2(Cybu-BIAN)
[ZnϪCl 2.218(7) and 2.214(8) A; ZnϪN 2.081(2) and
2.085(2) A] [18], and finally (tert-Butyl-BIAN)ZnCl2,
[ZnϪN 2.083(3) and 2.078(3) A, ZnϪCl 2.219(1) and
˚
˚
˚
˚
2.225(1) A] [19]. The ligands are BIAN ϭ 2,8-bis(arylimi-
no)acenaphthene and Cybu ϭ cyclobutyl, respectively.
On the other hand, the structure of 3 with the N,N-
chelating ligand, L1 [Zn1ϪN2 2.176(2) and Zn1ϪN1
2.1998(19)] and [NCS]Ϫ as well as thiocyanate [N4ϪC30
Figure 2. View of the molecular projection of [Zn(L2)(Cl)2] showing
tetrahedral coordination [17]. Displacement ellipsoids at the 50 %
level.
˚
˚
˚
1.143(1) A and C30ϪS2 1.636(3) A; N3ϪC29 1.151(2) A
˚
and C29ϪS1 1.616(3) A] shows a dimeric centrosymmetric
structure, generated by a 2/m site symmetry. The replace-
with a dihedral angle of 87.9(1)°. The zinc atom deviates ment of chloride for thiocyanate leads to the formation of
slightly from the N1/C1/C1Ј/N1Ј mean equatorial plane by two NCS bridges between the two zinc atoms, whereas the
˚
0.0108 A and the angle between the N1/Zn1/N1Ј and coordination arrangement about the metal atoms is com-
˚
N1/C1/C1Ј/N1Ј planes is 1.9(3)°.
pleted by a terminal NCS ligand [Zn1···Zn1Љ 5.483(3) A,
˚
˚
The structure of 2 with site symmetry 1, is resembling to Zn1ϪN4Љ 2.006(2) A, Zn1ϪN3 1.956(3) A and Zn1ϪS2
that of 1. It shows a zinc atom in a slightly more distorted 2.5154(8) A]; symmetry code: (Љ) x, 1Ϫy, 1Ϫz. Bridge for-
˚
tetrahedral environment [Cl1ϪZn1ϪCl2 118.03(6)° and mation results in an almost planar eight-membered ring
˚
N1ϪZn1ϪN2 79.73(12)°], containing two chloride ions as system [r.m.s. 0.0089 A].
Compound 3 is the first diimine complex with [SCN]Ϫ in
two different binding modes, its closest analog is α-bis-
(ethylenedithio)tetrathiafulvaleniumtetrathiocyanatezinc(II).
˚
co-ligands [Zn1ϪCl1 2.1863(15) A and Zn1ϪCl2
2
˚
2.2138(14) A] and an N,N-bonded chelating ligand, L
[Zn1ϪN1 2.113(3) A and Zn1ϪN2 2.125(3) A].
˚
˚
The main differences from 1 relate to the ethyl substitu- The latter contains two bridging NCS groups between the
ents on the aromatic rings. They are unexpectedly in a cis two zinc atoms and two terminal NCS [μ-(NCS) 1.135 and
˚
˚
arrangement. Since they are bulkier than the methyl groups 1.650 A; terminal (NCS) 1.169 and 1.597 A]. The bond
˚
found in 1, the generated strain leads the zinc atom to devi- lengths around the metal atom are Zn1···Zn1a 5.197 A,
ate from N1/C1/C2/N2 by 0.069 A [0.0108 A for 1], whereas Zn1Ϫμ-NCS 2.005 A, Zn1Ϫμ-SCN 2.412 A, and
the angle between the N1/Zn1/N2 and N1/C1/C2/N2 planes Zn1ϪNCS 1.935 A [20]. These bond lengths are in agree-
˚
˚
˚
˚
˚
becomes 12.17(2)° [only 1.93° for 1]. In addition to these ment with those determined for 3.
modifications, the angle between the planes of the aromatic
rings is now 18.80(2)°.
In 3, the zinc atoms show a distorted square pyramidal
arrangement with the terminal N3ϪC29ϪS1 thiocyanate
Z. Anorg. Allg. Chem. 2009, 1225Ϫ1230
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1227

L. C. Ferreira, C. A. L. Filgueiras, L. C. Visentin, J. Bordinha˜o, M. Hörner
ARTICLE
Figure 4. View of 1D self-arrangement of [Zn(L1)(Cl)2] through π···π stacking of the phenyl rings in the [010] crystallographic direction;
symmetry codes: (Ј) x, 3/2Ϫy, z, (ٞ) 1Ϫx, 1Ϫy, 1Ϫz [17]. Hydrogen atoms were omitted for clarity.
X-ray diffraction data for 1 and 3 were collected at 295 K with a
Bruker APEX II CCD area-detector diffractometer [22] with
graphite monochromatized Mo-Kα radiation. Cell parameters were
obtained and refined using the SAINT [22] program. For com-
ligand in an apical position. The angles on the base of pyra-
mid are N4ЉϪZn1ϪN2 146.73(10)°, N1ϪZn1ϪS2
152.29(6)°,
N4ЉϪZn1ϪS2
94.37(7)°,
N2ϪZn1ϪN1
76.35(7)°, N2ϪZn1ϪS2 87.14(5)° and N4ЉϪZn1ϪN1
87.90(8)°, respectively. The calculated τ-parameter [21], τ ϭ
(βϪα)/60, is 0.09. In this calculation, β represents the
pound
2 the X-ray data were collected at 295 K with an
EnrafϪNonius Kappa-CCD [23] diffractometer with graphite
monochromatized Mo-Kα radiation. Cell parameters were obtained
and refined using PHICHI [24] and EvalCCD [25] programs. Inten-
sities for 1, 2, and 3 were corrected by Lorentz polarization and
absorption with the SADABS [22] program. All structures were
N4ЉϪZn1ϪN2 angle and
Ͱ
corresponds to the
N1ϪZn1ϪS2 angle. The zinc atoms deviate from their
˚
mean N1/N2/S2/N4Љ equatorial plane by 0.2213 A. The me-
tal atoms show an N2/C1/C2/N1 dihedral angle of 12.6(2)° solved by SHELXS-97 Direct Methods [26], and refined with
SHELXL-97 [27], contained within the WinGX-32 crystallography
program [28]. Complex 2 shows a disorder effect at the ethyl group
linked to the phenyl ring.
and an N2ϪC1ϪC2ϪN1 torsion angle of 0.34(1)°.
The C13ϪC18 and C19ϪC24 phenyl rings in 3 form di-
hedral angles with the acenenaphthene plane of 87.9(1)°
and 87.1(1)°, respectively, and a 15.0(1)° dihedral angle be-
For 1, 2, and 3 the positional parameters of the hydrogen atoms
bonded to carbon atoms in the phenyl and acenenaphthene rings
were obtained geometrically, with the CϪH distances fixed at
tween themselves.
Furthermore, the crystal structure of 1 reveals complex
molecules related by a center of inversion building a one-
2
˚
0.93 A for Csp , and refined from their respective carbon atoms,
dimensional infinite chain along the [010] crystallographic with Uiso(H) values set at 1.2UeqCsp2. For 1 and 3 the hydrogen
atoms bonded to carbon atoms in the methyl groups were located
direction, Figure 4. The 1D arrangement results from cen-
3
˚
geometrically and with the CϪH distances fixed at 0.96 A for Csp
and with Uiso(H) values set at 1.5UeqCsp3. For 2 the hydrogen
atoms bonded to the carbon atoms in the ethyl group were located
trosymmetric Cphenyl···Cphenyl π···π interactions [C8···C11ٞ
˚
˚
˚
3.723(4) A, C9···C12ٞ 3.720(4) A, and C13···C10ٞ
3.701(5) A; symmetry code: (ٞ) 1Ϫx, 1Ϫy, 1Ϫz]. The pack-
˚
geometrically and with the CϪH distances fixed at 0.96 A and
ing arrangement through secondary bonds was formed ex-
clusively in 1.
3
0.97 A for Csp and with Uiso(H) values set at 1.5UeqCsp3 and
˚
Uiso(H) values set at 1.2UeqCsp3, respectively. X-ray data are listed
In a previous article [13], we reported how mercury com-
plexes were successfully prepared through one-pot reac-
tions. We showed the formation of two distorted tetrahedral
mercury complexes, with Cl and SCN, respectively. The
SCN species only had terminal ligands bonded to mercury.
On the other hand, in the present case the use of a very
similar ligand led to the formation of zinc complexes, in
which the chlorine species remained tetrahedral, whereas
SCN bonded to zinc in different coordination modes, as
mentioned before.
in Table 1.
CCDC-710022, CCDC-710023, and CCDC-710024 contains the
supplementary crystallographic 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.
Preparation of Bis[N-(2,6-methylphenyl)imine]-
acenaphthenedichloridezincII (1), Bis[N-(2-ethylphenyl)-
imine]acenaphthenedichloridezincII (2), and
Bis[N-(2,6-methylphenyl)imine]acenaphthenedithiocyanate-
μ-dithiocyanatezincII (3)
Experimental Section
Acenaphthenequinone (0.547 g, 3 mmol), 2,6-dimethylaniline
(0.750 mL, 6 mmol) (for 1 and 3) and 2-ethylaniline (for 2) were
added to a 100 mL round-bottomed flask containing MeOH
Melting points were determined, without correction, with a Quimi
Q-40M apparatus. Elemental analyses were obtained with a 2400
PerkinϪElmer instrument, using a PE AD-4 balance. IR spectra (30 mL) and 5 drops of glacial HOAc (see Scheme 1). The flask
1
were collected with a Magna-FTIR Nicolet spectrometer, and H
NMR spectra were run at room temperature with a 200 MHz
Bruker instrument.
was connected to a Liebig condenser and heated whilst stirring.
The temperature was kept 20 °C above the boiling point of the
solvent. The color of the mixture changed from yellow to dark red.
1228
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 1225Ϫ1230

Synthesis and Characterization of ZnII α-Diimine Complexes
Scheme 1. Reaction pathway for preparation of 1, 2 and 3.
1
After 1h 30min, heating was interrupted and the mixture cooled to
room temperature. At this point, the Zn(II) salt (3 mmol, chloride
or thiocyanate, respectively) was added and an orange precipitate
immediately formed. The mixture was then kept under reflux for 2
more hours. The solid was filtered off and washed with cold MeOH
(25 mL). It was dried in vacuo and weighed, giving 1.29 g (82 %)
in the case of 1 and 2 and 1.34 g (79 %) in the case of 3. All three
compounds were recrystallized from MeOH, and after a few days
bright orange crystals formed. These were used in m.p. determi-
nations, elemental analyses, IR and 1H NMR spectroscopy, and X-
ray crystallography.
294s, 284s, 253m, 220w, 194m, 177m, 141s, 121m cmϪ1. H NMR
[200 MHz in CDCl3, relative to TMS]: δ ϭ 2.10 (s, 24 H, methyl
group), 6,80- 8,30 (aromatic hydrogens).
Supporting Information (see footnote on the first page of this
article): Atomic coordinates and isotropic displacement parameters
for 1, 2, and 3.
Acknowledgement
The authors are grateful to their sponsors, CNPq, CAPES and to
Properties of 1: Yield 82 %; m.p. 220Ϫ222 °C. C,H,N analysis:
calcd. for 524.76 g·molϪ1: C 64.07; H 4.57; N 5.34 %; found: C
63.78; H 4.32; N 5.20 %. IR (CsI pellet and nujol film between
polyethylene sheets): ν˜ ϭ 3048w, 3022w, 2978w, 2947w, 2851w,
1668s, 1636s, 1604s, 1585s, 1469m, 1435m, 1419m, 1382m, 1292m,
1242m, 1224m, 1200m, 1126m, 1084m, 951m, 833m, 778s, 561w,
532m, 509w, 425w, 418w, 336w, 313s, 299m, 184m, 130m, 108m
´
˜
Laboratorio de Difrac¸ao de Raios X, (LDRX), Universidade
Federal Fluminense, Brazil, for the diffractometer facility. Bruker
APEX II CCD diffractometer was supported by the Financiadora
de Estudos e Projetos (FINEP, CT-Infra 03/2001-Universidade
Federal de Santa Maria, Brazil).
cmϪ1 1H NMR [200 MHz in CDCl3, relative to TMS]: δ ϭ 2.14
.
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Properties of 2: Yield 82 %; m.p. 227Ϫ229 °C. C,H,N analysis:
calcd. for 524.76 g·molϪ1: C 64.07; H 4.57; N 5.34 %; found C,
64.25; H 4.69; N 5.12 %. IR (CsI pellet and nujol film between
polyethylene sheets): ν˜ ϭ 3057m, 3022m, 2961s, 2930s, 2920w,
2871m, 1671s, 1637vs, 1600s, 1588s, 1485s, 1447m, 1419m, 1291s,
1257m, 1125m, 1050m, 834m, 781s, 767s, 580w, w 533f, 502w, 487w,
1
457w, 434w, 412w, 342w, 316s, 180w, 135w, 108w, 101w cmϪ1. H
NMR [200 MHz in CDCl3, relative to TMS]: δ ϭ 1,20 (t, 6 H,
ethyl), 2,78 (m, 4 H, ethyl), 6,97Ϫ8,45 (aromatic hydrogens).
Properties of 3: Yield 79 %; m.p. 262Ϫ263 °C. C,H,N analysis:
calcd. for 1138.72 g·molϪ1, C 63.22; H 4.22; N 9.84 %; found: C
62.95; H 4.14; N 9.72 %. IR (CsI pellet and nujol film between
polyethylene sheets): ν˜ ϭ 3006s, 3022s, 2981w, 2923w, 2866w, 2144s,
2080s, 1689m, 1666m, 1632s, 1605m, 1586m, 1471m, 1435m,
1420m, 1381w, 1359w, 1291m, 1241m, 1225m, 1123m, 951m, 834s,
780s, 560w, 533m, 500w, 478w, 474w, 464w, 429w, 425w, 337s, 311s,
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Received: November 24, 2008
Published Online: April 17, 2009
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www.zaac.wiley-vch.de
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 1225Ϫ1230