Transition metal complexes of derivatized chiral dihydro-1,2,4-triazin-6-ones. Part III [1]. X-ray crystal structure analysis of N,N'-bis[(1-phenyl-5-isopropyl-4,5-dihydro-6-oxo-1,2,4-triazin-3-yl)ethylidene]- propane-1,3-diamine nickel(II)

Article abstract of DOI:10.1515/znb-2000-1113

Template reaction of L-3-acetyl-1-phenyl-5-isopropyl-4,5-dihydro-1,2,4-triazin-6-one (1b) with 1,3-cliaminopropane and nickel acetate gave the corresponding chiral complex 4 in high yield. X-ray structure determination showed that the nickel complex is sq

Full text of DOI:10.1515/znb-2000-1113

Transition Metal Complexes of Derivatized Chiral Dihydro-1,2,4-triazin-6-ones.
Part III [1]. X-Ray Crystal Structure Analysis of
N,N’-Bis[(l-phenyl-5-isopropyl-4,5-dihydro-6-oxo-l,2,4-triazin-3-yl)ethylidene]-
propane-1,3-diamine Nickel(II)
Ahmad S. Abushamleh3, Mustafa M. El-Abadelahb, and Wolfgang Voelterc
a Chemistry Department, Faculty of Arts and Science, The Hashemite University,
Zarqa, Jordan. Fax: 00962-5-3826613. E-mail: shamleh@hu.edu.jo
b Chemistry Department, Faculty of Science, University of Jordan, Amman, Jordan
c Abteilung für Physikalische Biochemie des Physiologisch-Chemischen Instituts der
Universität Tübingen, Hoppe-Seyler-Straße 4, D-72076 Tübingen, Germany.
Fax: 0049-7071-293348. E-mail: wolfgang.voelter@uni-tuebingen.de
Reprint requests to Dr. A. S. Abushamleh or Prof. W. Voelter
Z. Naturforsch. 55b, 1074-1078 (2000); received July 7, 2000
N,N'-[(6-Oxotriazin-3-yl)ethylidene]-l,3-diaminopropane, Nickel Complex
Template reaction of L-3-acetyl-l-phenyl-5-isopropyl-4,5-dihydro-l,2,4-triazin-6-one (lb)
with 1,3-diaminopropane and nickel acetate gave the corresponding chiral complex 4 in high
yield. X-ray structure determination showed that the nickel complex is square planar, and
the ligand N,N’-bis[(l-phenyl-5-isopropyl-4,5-dihydro-6-oxo-l,2,4-triazin-3-yl)ethylid-ene]-
propane-1,3-diamine is of tetra-aza type where the imine nitrogens and the ring HN(4) nitro-
gens are the coordinating sites. MS-FAB and NMR spectral data are in agreement with the
X-ray structure.
Introduction
formation of 3 [3] (Scheme 1), and the implication
of the chiroptical properties of the resulting com-
plexes as investigated by the CD technique [4], As
we are currently investigating the chelating prop-
Chiral 3-acetyl-4,5-dihydro-l,2,4-triazinones [2]
(exemplified by la) are readily convertible to the
respective oximes (2) via the interaction with hy- erties of other derivatized triazinones with some
transition metal ions, we have strong evidence that
droxylamine (Scheme 1). These oxime derivatives
(e.g. 2a) proved to be a useful class of bidentate
oxime 2b (derived from lb, Scheme 1) behaves in
chelating agents, and their derived transition metal an analogous manner to 2a towards Ni2+ [4],
complexes are of significant interest for two
In an attempt to incorporate the triazinone moi-
reasons, namely, the carbon-carbon coupling reac- ety into a macrocyclic framework by utilizing the
tion that took place during the nickel(II) complex template effect [5], we have reacted the C3-acetyl
Ph
Ph
0
,Ph
phV S
I
Ni(OAc),,
EtOH
N-is^Nv
H N ^N
(2a)-
lb
;ni:
I
I
'N ^C H 3
h3c
I
3
o
1,2
'H
3
la
CH2Ph
O
2a
2b
CHMe2
CHMe2 CH2Ph
R
X
N-OH
N-OH
O
Scheme 1
0932-0776/2000/1100-1074 $06.00 © 2000 Verlag der Zeitschrift für Naturforschung, Tübingen ■www.znaturforsch.com
D
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1075
A. S. Abusham leh et al. • Derivatized Chiral Dihydro-l,2,4-triazin-6-ones
compound (lb) with 1,3-diaminopropane in the
presence of nickel acetate (Scheme 2). However,
ates and the product 4 was obtained in a highly
pure state and in high yield. The complex has a
we obtained compound 4 in which the carbon-car- time-averaged structure with C2 symmetry (i.e.,
bon coupling reaction (noted in 3) did not take only one set of signals) and that, as expected, the
place, and an open-chain tetradentate ligand of diastereotopic Me groups of a CHMe2 group give
tetra-aza type (4) was obtained instead.
rise to separate signals. This is evidenced from the
NMR spectra (see experimental part) which show
one set of signals for each type of hydrogen and
carbon atoms in both triazinone moieties (rings A
and B, Fig. 1). An exception is the two methyl
groups of the isopropyl moiety which appear as
two sets of signals due to their anisochronous
character. This behavior of anisochrony is also ob-
served in compound lb.
O
h
Ph
H i
i 11 1
i2nv n C\ HMe,
L-lb
.
+
Ni(OAc).
EtOH
J^°
\
JlBO
n » ch3
H,N
NH,
The constitution of 4 was confirmed by X-ray
crystal structure determination. The molecular
structure of 4 is displayed in Fig. 1. Selected bond
lengths and angles are given in Table I. Values of
the bond angles around the chelated nickel ion
provide further evidence for the nearly square pla-
nar geometry of the nickel complex 4. In addition,
a solution of 4 in chloroform (103 M) is non-con-
ducting indicating that 4 is neutral. Magnetic mea-
surement shows that the complex is also diamag-
netic which is indicative of a square planar
geometry.
Scheme 2
Results and Discussion
The required L-3-acetyl-l,2,4-triazinone deriva-
tive lb was prepared in one-pot reaction following
reported procedures [2] and was characterized by
EI-MS and NMR spectral data. This synthon
lb was utilized to prepare the N,N'-bis-
[(1-phenyl-5-isopropyl-4,5-dihydro-6-oxo-1,2,4-
triazin-3-yl)ethylid-ene]-propane-l,3-diamine
nickel(II) (4) via direct interaction with 1,3-diami-
nopropane in the presence of nickel acetate. In
this reaction, the so-called template effect oper-
Fig. 1. ORTEP plot of the molecular structure of 4.
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1076
A. S. Abushamleh et al. ■Derivatized Chiral Dihydro-l,2,4-triazin-6-ones
Table I. Selected bond lengths (A) and angles (°) for 4.
Atom
Atom
Distance
Atom
Atom
Distance
N(4)
1.859(7)
1.888(7)
1.416(8)
1.36(1)
1.418(8)
1.34(1)
1.286(9)
1.46(1)
1.48(1)
1.47(1)
1.52(1)
N(14)
N(132)
C(3)
1.876(7)
1.903(7)
1.30(1)
1.45(1)
1.31(1)
1.489(9)
1.51(1)
1.28(1)
1.54(1)
1.50(1)
1.49(1)
Ni(l)
Ni(l)
N(l)
N(4)
N(11)
N(14)
N(32)
N(132)
C(3)
C(13)
C(34)
Ni(l)
Ni(l)
N(2)
N(32)
N(2)
C(5)
C(3)
N(4)
N(12)
C(13)
C(30)
C(35)
C(30)
C(130)
C(35)
N(12)
N(14)
N(32)
N(132)
C(5)
C(15)
C(33)
C(13)
C(15)
C(33)
C(130)
C(6)
C(16)
C(34)
Atom
Atom
Atom
Angle
Atom
Atom
Atom
Angle
N(14)
N(132)
N(132)
C(6)
96.7(2)
169.5(3)
83.1(3)
N(32)
N(32)
N(132)
C(3)
83.5(3)
173.0(3)
98.0(3)
N(4)
N(4)
Ni(l)
Ni(l)
Ni(l)
N(l)
Ni(l)
Ni( 1)
Ni(l)
N(2)
N(4)
N(14)
N(4)
N( 14)
N(2)
N(32)
125.7(7)
114.6(6)
113.6(7)
127.8(5)
116.8(5)
115.5(6)
112.6(7)
114.0(7)
128.5(8)
114.0(8)
113.8(6)
112.4(7)
126.3(8)
114.8(7)
112.4(6)
126.6(5)
121.3(6)
113.6(6)
124.7(6)
123.8(6)
110.0(7)
114.4(6)
117.4(8)
105.7(6)
113.7(7)
127.3(7)
111.9(7)
108.7(7)
112.6(7)
N(l)
N(4)
C(3)
C(5)
Ni(l)
Ni(l)
N(11)
Ni(l)
Ni(l)
Ni(l)
N(4)
N(12)
N(12)
N(14)
N(32)
N(132)
C(3)
C(13)
C(15)
C(30)
C(130)
C(30)
C(50)
N(14)
C(130)
C(150)
C(3)
C(16)
C(13)
C(33)
C(35)
C(6)
N(11)
N(14)
N(32)
N(132)
C(5)
Ni(l)
Ni(l)
Ni(l)
N(4)
N(4)
C(5)
C(6)
C(5)
N(l)
N(12)
N(14)
N(11)
N(32)
N(32)
N(132)
N(132)
N(12)
N(14)
N(14)
N(32)
N(132)
C(33)
C(13)
C(13)
C(15)
C(30)
C(130)
C(34)
C(130)
C(16)
C(15)
C(31)
C(34)
C(34)
C(13)
C( 13)
C(15)
C(16)
C(30)
C(33)
C(35)
C(130)
C(131)
C(35)
Experimental
L-3-Acetyl-1 -phenyl-5-isopropyl-4,5-dihydro-l,2,4-
triazin-6-one (lb)
Melting points (uncorrected) were determined
using a Gallenkamp melting point apparatus in
This compound was prepared via direct interac-
one-end open glass capillaries. The magnetic mo- tion between l-chloro-l-phenylhydrazino-2-pro-
ment was measured for a finely ground solid sam- panone [6,7] with L-valine methyl ester hydro-
ple of 4 at ambient temperature using a Johnson chloride (Aldrich) in the presence of excess
Matthey Magnetic Susceptibility balance. Optical triethylamine according to the general procedure
described for the synthesis of analogous chiral tria-
rotations were measured on a Perkin-Elmer 141
photoelectric spectropolarimeter. NMR spectra zinones [2]. Yield of pure product = 87%, m.p. =
were recorded on a Bruker WM-400 spectrometer
for solutions in CDC13 with TMS as internal refer-
75-77 °C. - ’H NMR (400 MHz, CDC13): (5 =
0.94, 1.01 (2xd, J = 6.8, 7.0 Hz, 6H, CH (C//3)2),
ence. Mass spectra (El) were obtained using a Fin- 2.33 (m, 1H, C //(C H 3)2), 2.45 (s, 3H, C //3CO),
nigan MAT TSQ-70 spectrometer at 70 eV; ion 4.05 (dd, J = 5.3, 3.5 Hz, 1H, H-5), 7.26 (tt, J = 8.8,
source temperature = 200 °C. MS-FAB spectra
1.3 Hz, 1H, H-4'), 7.40 (dd, J = 8.4, 8.8 Hz, 2H, H-
were obtained with a VG Analytical Ltd. ZAB HS 375'), 7.55 (tt, J = 8.4, 1.3 Hz, 2H, H-2'16'). 13C
mass spectrometer, equipped with xenon gun op-
erating at 8 keV and 0.8 mA emission using as the
NMR (100 MHz, CDCL): (3 = 16.6, 18.2
(CH(CH3)^), 23.7 (CH(CH3)2), 32.7 (CH3CO),
sample containing matrix, TG/G, CHC13 (thiogly- 58.9 (C-5), 124.7 (C-276'), 126.9 (C-4'), 128.5 (C-
cerol/glycerol) or NBA (3-nitrobenzyl alcohol).
375'), 140.7 (C3), 141.8 (C-V), 161.4 (C-6), 192.9
Elemental analyses were performed at the (CH3C=0). MS (El, 70 eV): m/z (%) = 259.13047
Laboratories of Quantitative Technologies Inc. (M+, 63, C14H 17N3 0 , requires 259.13208),
(QTI), New Jersey, USA.
216(100), 188(57), 174(4), 146(13), 118(5), 104(6),
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A. S. Abusham leh et al. ■Derivatized Chiral Dihydro-l,2,4-triazin-6-ones
1077
92(13), 77(6). Analysis for C14H 17N30 7 (259.13):
calcd. C 64.85, H 6.61, N 16.20; found C 64.49, H
6.75, N 16.14.
Crystal structure determination o f 4
Deep red prismatic crystals were grown by al-
lowing a hot solution of 4 in the solvent pair
CH2C12/C6H6 (2:3 v/v) to cool slowly to ambient
temperature for 24 h (open flask); crystal dimen-
sions: 0.20 x 0.10 x 0.30 mm.
N,N'-Bis[(l-phenyl-5-isopropyl-4,5-dihydro-6-oxo-
1,2,4-triazin-3-yl)ethylidene]-propane-1,3-diamine
nickel(II) (4)
Crystal data for NiC31H38N80 2: FW = 613.39,
monoclinic, space group P2[ (#4) with a = 7.319(1),
b = 20.429(2), c = 10.2432(6) A, ß = 97.13(6)°; V =
1519.8(2) A3, Z = 2, dcaic = 1.34 g/cm\ Data collec-
tion was made at 23.0 °C, using a Rigaku AFC5R
diffractometer operating in the omega scan mode.
2558 independent reflections were measured
within the range 6 = 6.0-60.1° using Cu-KHradia-
tion (A = 1.54178 A). The cell parameters and ori-
entation matrix for the data collection were ob-
tained using the setting angles of 25 reflections
(6 = 13.3-23.6°). The structure was solved by di-
rect methods using the program SIR 92 [8] and
expanded using Fourier techniques (DIRDIF 94)
[9]. The non-hydrogen atoms were refined aniso-
tropically by full-matrix least-squares on F2 [10].
This resulted in R-values R x/wR2 = 0.0757/0.0520
for all data and 0.0640/0.050 for the 2221 observed
reflections and 379 variable parameters; GOF =
1.90, residual electron density between 0.47 and
-0.37 e/A3. The hydrogen atoms in the structure
were generated except for the methyl groups in
which case at least one hydrogen was found on the
difference Fourier maps and used to calculate the
positions of the others. The hydrogens were in-
cluded in the calculations, but were not refined.
The acetyl compound lb, (1.56 g, 6 mmol),
nickel acetate tetrahydrate (0.75 g, 3 mmol) and
absolute ethanol (80 ml) were stirred at rt for few
minutes. 1,3-Diaminopropane (0.24 g, 3.25 mmol)
in absolute ethanol (20 ml) was then added drop-
wise over a period of 10 min. The reaction mixture
was brought to reflux under constant stirring for
15 h. During the first hour of the reflux time the
reaction mixture assumed a blue color, then green
during the second and third hours and finally a
deep-red color persisted for the rest of the reflux
time. The solvent was removed in vacuo and an
oily residue was obtained. This was dissolved in
40 ml of dichloromethane and the solution was fil-
tered off. To the filtrate was added 60 ml of hot
benzene and the solution was heated for few min-
utes then set aside overnight. Deep-red crystals
were separated. These were filtered off, washed
with little benzene and dried in vacuo. Yield =
1.93 g (65%), m.p. > 300 °C. - 'H NMR (400
MHz, CDC13): (3 = 1.15, 1.49 (2xd, J = 6.8, 6.7 Hz,
12H, CH (C//3)2), 1.92 (m, 2H, C//(CH 3)2), 2.08
(quintet, J = 6.8 Hz, 2H, CH2C //2CH2), 2.96 (d,
J
= 6.7 Hz, 2H, H-5), 3.22 (br m, 4H,
C //2C H ,C //,), 7.15 (t, J = 7.5 Hz, 2H, H-4’), 7.32
(dd, J = 7.5, 7.7 Hz, 4H, H-3'15'), 7.61 (d, , J = 7.7
Hz, 4H, H-2'16'). 13C NMR (100 MHz, CDC13):
(3 - 15.6 (CH3C=N), 19.0, 20.5 (CH(CH3)2),
27.9 (CH,CH2CH2), 33.2 (CH(CH3)2), 48.2
(NCH2CH^CH2), 62.8 (C-5/15), 123.7 (C-276'),
125.7 (C-4'), 128.2 (C-375'), 141.3 (C l'), 156.1 (C-
Acknowledgments
A. S. A. gratefully acknowledges financial sup-
port from the Hashemite University, Jordan.
Supplementary materials
Tables of positional parameters, interatomic an-
3/13), 160.5 (C-6/16), 176.4 (CH3C=N). MS: pos. gles and distances, structural factor amplitudes and
FAB in TG/G, CH2C12 = 613 corresponding to thermal parameters and packing diagrams for the
[M+H]+, pos. FAB exact mass = 613.2559, and structure of compound 4 are available from the
these are consistent with NiC31H38N80 2. - Analy- Cambridge Crystallographic Data Center under
sis for NiC31H38N80? (613.41): calcd. C 60.70, H the depository number CCDC 149840.
E-mail: deposit@ccdc.cam.ac.uk
6.24, N 18.27; found C 60.43, H 6.13, N 18.21.
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A. S. Abusham leh et al. • Derivatized Chiral Dihydro-l,2,4-triazin-6-ones
1078
b) P. W. Neber, H. Wörner, Liebigs Ann. Chem. 526,
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c) W. Dieckmann, O. Platz, Ber. Dtsch. Chem. Ges.
38, 2986 (1905);
d) R. Fusco. R. Romani, Gazz. Chim. Ital. 76, 419
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[3] A. S. Abushamleh, M. M. El-Abadelah, C. Maichle-
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[4] A. S. Abushamleh, M. M. El-Abadelah, W. Voelter,
in preparation.
[5] M. C. Thompson, D. H. Busch, J. Am. Chem. Soc.
86, 213 (1964).
[6] a) R. R. Phillips, Org. React. 10, 143 (1959);
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(1962);
c) G. C. Barrett, M. M. El-Abadelah, M. K. Har-
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[7] a) N. F. Eweiss, A. Osman, J. Heterocycl. Chem. 17,
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[10] Least squares function minimized: 'Zw(\F0\- IFCI)2,
were:
tv = il{o2{F0)] = [o1c(F0)+p2F llA ]-\ oc(F0] = e.s.d.
based on counting statistics, p = /?-factor.
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