Synthesis, crystal structure and spectroscopic studies of a mixed ligand copper (II) complex: trans-bis(succinimidato)-bis(benzylamino)Cu(II)

Article abstract of DOI:10.1515/znb-2006-0809

The molecules of the title compound, [Cu(C₁₁H₁₃N ₂O₂)₂], lie across centres of inversion in space group P2₁/c and are linked by intermolecular N-H?O and C-H?O hydrogen bonds. The central Cu atom has a slightly distorted square-planar coordination comprised of four N atoms. Cu-N bond distances are 1.975(2) and 2.020(2) ?. The interplanar angle between the phenyl and succinimidato ring is 87.34(10)°.

Full text of DOI:10.1515/znb-2006-0809

Synthesis, Crystal Structure and Spectroscopic Studies of a Mixed Ligand
Copper (II) Complex: trans-Bis(succinimidato)-bis(benzylamino)Cu(II)
Murat Tas¸a, Hanife Sarac¸og˘lub, Hu¨meyra Batıc, Nezihe C¸ alıs¸kand, and
Orhan Bu¨yu¨kgu¨ngo¨rd
a Giresun University, Faculty of Art and Sciences, Department of Chemistry,
28049 Giresun, Turkey
b Rize University, Faculty of Art and Sciences, Department of Physics,
53100 Rize, Turkey
c Ondokuz Mayıs University, Faculty of Arts and Sciences, Department of Chemistry,
55139 Kurupelit, Samsun, Turkey
d Ondokuz Mayıs University, Faculty of Arts and Sciences, Department of Physics, 55139 Kurupelit,
Samsun, Turkey
Reprint requests to Dr. M. TAS¸. Fax: +90 0454 2164518. E-mail: murattas@ktu.edu.tr
Z. Naturforsch. 61b, 979 – 982 (2006); received December 28, 2005
The molecules of the title compound, [Cu(C11H13N2O2)2], lie across centres of inversion in space
group P21/c and are linked by intermolecular N-H···O and C-H···O hydrogen bonds. The central
Cu atom has a slightly distorted square-planar coordination comprised of four N atoms. Cu–N bond
˚
distances are 1.975(2) and 2.020(2) A. The interplanar angle between the phenyl and succinimidato
ring is 87.34(10)◦.
Key words: Succinimide, Succinimidato, Mixed Ligand Complex
Introduction
The complexes of transition metals with five-
membered heterocyclic imidate ligands such as
hydantoins or succinimide (pyrrolidine-2,5-diones)
(Scheme 1) possessing more than one donor atom, are
of great interest in the chemistry of coordination com-
pounds, since they can act either as neutral molecules
or deprotonated as monoanions [1]. Imidate ligands are
generally monodentate ligands having a deprotonated
nitrogen atom.
Scheme 2. The structure of the title complex.
of copper(II) having alkyl amine ligands. The au-
thors reported only N-H···O inter- and intra-molecular
hydrogen bonds for these molecules. However, the
complexes of imidates and alkylamines with aro-
matic substituents can also have other hydrogen bond
systems. Therefore, the crystal structure determina-
tion of the title complex (Scheme 2) was carried
out to search for different hydrogen bond interac-
tions. The results are compared with those found in
Scheme 1. Imide ligands.
Various Cu(II) complex having imidate ligands have the related complex trans-bis(succinimidato)-bis(1,2-
been synthesized and their crystal structures have diphenylethylamine) copper(II) [4]. We also studied
been determined [2 – 8]. Especially, Akitsu et al. stud- the IR spectra and the r. t. magnetic susceptibility of
the title complex.
ied succinimide and 5,5-diphenylhydantoin complexes
c
0932–0776 / 06 / 0800–0979 $ 06.00 ꢀ 2006 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
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M. Tas¸ et al. · trans-Bis(succinimidato)-bis(benzylamino)Cu(II)
Table 1. Crystal data and structure refinement for the
[(C22H26N4O4)Cu].
Experimental Section
Materials and measurements
Formula
C22H26N4O4Cu
Molecular weight
Crystal system
Space group
474.01
monoclinic
P21/c
11.6302(10)
5.0138(3)
19.1276(18)
99.020(7)
1101.57(16)
2
1.429
494
0.71073
27.13
Succinimide, benzylamine, and copper(II) acetate mono-
hydrate were commercially available and were reagent grade.
FT-IR spectra (4000 – 200 cm−1) were recorded on a Jasco-
430 FT-IR spectrophotometer with samples prepared as KBr
pellets. The magnetic susceptibility of the complex was mea-
sured using a Sherwood scientific MX1 model Gouy mag-
netic susceptibility balance at r. t.
˚
a [A]
˚
b [A]
˚
c [A]
β [◦]
3
˚
V [A ]
Z
The crystal data were collected using ω-2θ scan tech-
niques on a Stoe IPDS-2 diffractometer with a graphite-
Dcalc [g/cm3]
F(000)
˚
monochromated Mo-Kα radiation (λ = 0.71073 A). Soft-
˚
µ (Mo-Kα ) [A]
θmax [◦]
ware programs used for data collection and cell refine-
ment: X-AREA [9]; for data reduction: X-RED32 [9]; to
solve structure: SHELXS97 [10]; to refinement of structure:
SHELXL97 [10]; for molecular graphics: ORTEPIII [11]; to
prepare material for publication: WinGX [12].
Crystal dimensions [mm]
Temperature [K]
Number of measured reflections
Number of unique reflections
0.400×0.303×0.303
293(2)
12122
9534
Number of reflections used in refinement 2405
Number of parameters
142
1.03
Preparation of the complex
Goodness-of-fit
Final R indices |F| > 2σ(|F| )
R Indices (all data)
2
2
R1 = 0.042; wR2 = 0.103
R1 = 0.060; wR2 = 0.111
To a solution of copper(II) acetate monohydrate (0.499 g,
2.5 mmol) and succinimide (0.495 g, 5 mmol) in water
(30 ml), benzylamine (0.54 g, 5 mmol) was added slowly
and a light reddish-brown solid was precipitated. The mix-
◦
˚
Table 2. Selected interatomic distances (A) and angles ( ) for
the title and related complex.
◦
ture was stirred for 1 h at 50 C. The solid was dissolved
Title complex
Related complex
with the addition of a small amount of absolute ethanol to
give a deep blue solution at 50 ◦C. The solution was slowly
cooled to r. t. Light reddish-brown needles precipitated, were
Bonds:
Cu(1)-N(1)
Cu(1)-N(2)
O(1)-C(1)
O(2)-C(4)
N(1)-C(1)
N(1)-C(4)
N(2)-C(5)
N(2)-H(1N)
N(2)-H(2N)
1.976(2)
2.019(2)
1.222(4)
1.228(4)
1.359(4)
1.361(4)
1.481(4)
0.80 (4)
0.83 (4)
1.961(3)
2.032(4)
1.220(5)
1.225(4)
1.367(5)
1.371(5)
1.485(5)
0.89 (4)
0.89 (4)
¯
filtered and dried on air (Yield: 76.4%). FT-IR (KBr): ν =
3259 – 3157 υ(NH2), 1770 υ(C=O), 1455 υ(C-N), 603 – 572
υ(Cu-N) cm−1. C22H26N4O4Cu (474.01): calcd. C 55.75,
H 5.53, N 11.82; found C 55.79, H 5.48, N 11.78
The complex exhibits an experimental magnetic moment
of 1.82 BM corresponding to one unpaired electron.
Angles:
Results and Discussion
N(1)-Cu(1)-N(2)
N(1)-Cu(1)-N(2)i
N(1)-Cu(1)-N(1)i
N(2)-Cu(1)-N(2)i
90.6(1)
89.4(1)
180.0(2)
180.0(2)
88.5(1)
91.5(1)
180
Molecular structure of the complex
180
Crystallographic data of the title complex
(Scheme 2) are summarized in Table 1. Selected
bond lengths, angles and hydrogen bond geometries
are listed and compared with data of trans-bis(suc-
cinimidato)-bis(1,2-diphenylethylamine)copper(II)
in Table 2. The molecular structure and intra- and
inter-molecular hydrogen bonds are shown in Figs. 1
and 2, respectively.
As the related complex, the title compound
(Scheme 2) consists of benzylamine and succinimide
moieties linked to the Cu atom. The copper ion in the
complex lies in the center of a slightly distorted square-
planar coordination, with N(2) of the benzylamine and
D-H [A] H···A [A] D···A [A] D-H···A [◦]
˚
˚
˚
Hydrogen bonds:
C(5)-H(5B)···O(1)
0.97
2.82
2.75
3.567(4) 134.8
3.615(5) 149.5
3.009(3) 171(3)
3.031(4) 177(3)
3.413(4) 151.80
3.537(5) 159.8
3.511(4) 134.8
iv
C(5)-H(5A)···O(2)i 0.97
N(2)-H(2N)···O(2)ii 0.83(4) 2.19(4)
N(2)-H(1N)···O(1)iii 0.80(4) 2.23(4)
C(2)-H(2B)···O(1)iv 0.97
2.53
2.65
2.79
C(8)-H(8)···O(2)v
0.93
0.93
C(11)-H(11)···Oiii
i
ii
iii
1 − x, −y, −z; 1 − x, 1 − y, −z; x, 1 + y, z; 1 − x, 1/2 + y, 1/2 − z,
1+x, y, z.
v
N(2)i and N(1)i atoms are related by symmetry [code:
(i) 1−x,−y,−z] (Fig. 1).
Succinimidato and benzylamine groups function as
N(1) of the pyrrolidine-2,5-dione (succinimidato). The monodentate ligands, similar to the situation in the re-
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M. Tas¸ et al. · trans-Bis(succinimidato)-bis(benzylamino)Cu(II)
981
Fig. 1. The intramolecular
H-bonds and the Ortep-III
diagram with 30% proba-
bility ellipsoids of the title
complex.
[1.976(2)] bond lengths are slightly longer than this
˚
in the reference complex [2.032(4) and 1.961(3) A,
respectively] [4]. The cis-N-Cu-N bond angles are
89.4(1) and 90.6(1)◦ and the trans-N-Cu-N angles are
180.0(2)◦ for the title complex (Fig. 1). The corre-
sponding bond angles are 88.5(1), 91.5(1) and 180 ◦ for
the related complex [4]. Akitsu et al. reported only one
type of hydrogen bonds which is formed between an
amine hydrogen atom of 1,2-diphenylethylamineand a
carbonyl oxygen atom of the succinimidato ligand for
the related complex [4]. The N(2)-H(2N)···O(2) intra-
molecular hydrogen bond angle was reported as 133◦
˚
and the bond length was reported as 2.966(4) A [4]. No
intermolecular hydrogen bonds have been reported this
reference complex [4].
Fig. 2. Intermolecular hydrogen bonds in the title complex.
lated complex. Cu-N(1) bond distances are 1.976(2)
The possibility of hydrogen bonds was explored for
the title complex by the statistical criterion proposed
by Taylor and Kenrad [13]. Two of four possible N-
H···O and five C-H···O hydrogen bonds have been
detected (Fig. 2, Table 2). The N(2) atom of benzyl-
amine at (x,y,z) acts as a hydrogen bond donor, via the
H(1N) atoms, to an O(1) atom of a succinimidate at
(x,1 + y,z) and via the H(2N) atom to the O(2) atom
of the succinimidate at (1 − x,1 − y,−z), so generat-
ing by translation two different chains running approx-
˚
and Cu-N(2) bond distances are 2.019(2) A. The in-
terplanar angle between the phenyl and the succin-
imidato (pyrrolidine-2,5-dione) ring is 87.34(10) ◦; i.e.
these rings are nearly perpendicular to each other.
The rings have an approximately planar structure,
with the largest deviation from the plane being that
˚
˚
of atom C(3) [−0.027(3) A]. Cu-Namine [2.019(2) A]
bond lengths are slightly shorter and Cu-Nimidate
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M. Tas¸ et al. · trans-Bis(succinimidato)-bis(benzylamino)Cu(II)
imately parallel to the [010] direction. In this way, Ir spectra of the complex
the special position of the Cu(II) ion is centered at
The IR spectrum of succinimide reveals a band at
3450 cm−1, ascribed to the N–H vibrations and a C=O
peaks can be seen at 1770 cm−1
(m+1/2,n+1/2,k) and (m+1/2,n,k+1/2)(where
m, n and k independently take the value zero and
integer). Also, the C(2) atom of the succinimidato
ring acts as a hydrogen bond donor, via the H(2B)
atom to the O(1) atom of the succinimide ligand at
(1 − x,1/2 + y,1/2 − z). The benzene ring acts as a
hydrogen bond donor via C(8)-H(8) to O(2) of the
succinimide at (1 + x,y,z). So, C-H···O bonds re-
sult in the formation of sheets of molecules lying
parallel to the (100) axis, and the N-H···O bonds
link the sheets of molecules to each other. In addi-
tion, C(11) acts as a hydrogen bond donor via H(11)
to O(1) at (x,1 + y,z), and the C(2)-H(2B) atoms at
(1 − x,1/2 + y,1/2 + z) give intermolecular hydro-
gen bonds with an O(1) atom at (x,1 + y,z) (Fig. 2,
Table 2).
.
The N-H stretching vibration of the succinimide has
disappeared in the complex, indicating deprotonation
upon complex formation. Two new sharp peaks ap-
pear for the NH2 group of benzylamine at 3259 and
3157 cm−1. The peak for ν(C=O) remains non-shifted
indicating that the C=O unit is non-coordinated to
the copper(II) ion. The ν(C–N) mode at 1429 cm−1
for the succinimide is shifted to higher wave num-
ber and appears at 1455 cm−1 in the complex indi-
cating thereby imidate formation and coordination to
the metal ion [14]. Metal-nitrogen coordination bands
were seen at 603 – 572 cm−1
.
Supplementary Data
The intramolecular hydrogen bond between N(2)
of 1,2-diphenylethylamine and an oxygen atom of the
succinimide ligand hydrogens occurs between C(5) of
benzylamine and a carbonyl oxygen atom of the suc-
cinimide at (1−x,−y,−z) (Fig. 1, Table 2) as a differ-
ence from the related complex. The results obtained in
this work indicate that there are significant differences
in the molecular packing between the two complexes.
Crystallographic data (excluding structure factors)
have been deposited with the Cambridge Crystallo-
graphic Data Centre as the supplementary publication
No. CCDC 267836. Copies of the data can be ob-
tained, free of charge, on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44-
1223-336033 or e-mail: deposit@ccdc.cam.ac.uk).
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