Inorganic Chemistry Communications 2 (1999) 184187

Synthesis and molecular structure of bis(2-benzoylimino-

benzimidazolinato)copper(II)-dimethylformamide a metal-containing
guanidine derivative 1
Lothar Beyer a,*, Rainer Richter a, Robert Wolf a, Jana Zaumseil a, Maria Lino-Pacheco b,
Jorge Angulo-Cornejo b
a
University of Leipzig, Department of Inorganic Chemistry, Talstrasse 35, D-04103 Leipzig, Germany
b

Universidad Nacional Mayor de San Marcos Lima, Facultad de Qumica Qumica,
e Ingeniera Av. Venezuela s/n, Lima, Peru

Received 26 February 1999

Abstract

Bis(2-benzoylimino-benzimidazolinato)copper(II) (1) as the first neutral chelate of an acylimino-benzimidazoline contains guanidine

and amide moieties directly coordinated to a metal atom. The ligands are arranged in trans position. The synthesis of cis-bis(pyridine)bis(N-
benzoyl-O-ethyl-N9-m-nitrophenyl-isoureato)nickel(II) (2) is described. The molecular structures of both complexes were determined by
X-ray crystal structure analysis. q 1999 Elsevier Science S.A. All rights reserved.

Keywords: Guanidine derivative complexes; Copper(II) complexes; Nickel(II) complexes; Acylisourea complexes; Crystal structures

1. Introduction coordinated guanidine moieties. It offers even greater varia-

Acylimino(benz)imidazolines which act as ligands in 1
exhibit hypotensive [1], cardiovasculeric [2] as well as her-
bicidic [3] activities. They are prepared either by conden-
sation of N-dichloromethylene acid amides with diamines
[4,5] or by acylation of 2-amino-benzimidazoles [6] with
acid chlorides [1,2,7]. Apart from cationic mixed ligand
ruthenium(II) complexes of 1a [RuL2(1a)2]Cl2 (Lsdmso;
PPh3) [8] and a recently published stepped cubane type
complex [Cu4I4(ImNAc)2] with neutral 2-acetylimino-1,3-
dimethylimidazoline (ImNAc) [9], no metal complexes are
known up to now.
In this paper we report for the first time on the isolation
and X-ray structural characterization of the neutral cop-
per(II) complex 1, formed by deprotonation of 1a. Com-
plexes of this type are interesting because they contain the
guanidine fragment and simultaneously coordinate through
the amide group.
In this respect, complex 2 obtained from the same educt as
1 by reaction with m-nitroaniline is a predecessor for metal-
* Corresponding author. Tel.: q49-341-9736161; Fax: q49-341-
9604600.
1
Dedicated to Professor Dr. Joachim Sieler on the occasion of his 60th
birthday.
bility by the possibility of replacing the ethoxy group in the
coordinated ligands by different amino groups. Though acy-
lisoureas have been known for a long time [1016] their
behavior as ligands was ignored with the exception of our
own recent investigation of copper(II) complexes [17].
Thus compound 2 containing two stabilizing pyridine ligands
and also characterized by its crystal structure is in fact the
first nickel(II) chelate of this type.
2. Results and discussion
To synthesize the ligands of the above-mentioned com-
plexes 1 and 2 the same educt N-benzoyl-thiocarbamic acid-
O,S-diethylester [18] was reacted either with o-phenylene-
diamine obtaining 1a or with m-nitroaniline obtaining 2a in
good yields. 1a and 2a are characterized by elemental anal-
yses, mass spectra (see Section 3) and 1H NMR and 13C
NMR spectra (see Fig. 1).
The reaction of 1a with copper(II) acetate-monohydrate
in ethanol yields 1 as a dark green crystalline precipitate (see
Fig. 1). It is very soluble in DMF, DMSO and THF, but
insoluble in methylene chloride, i-propanol or ethylacetate.
The FAB mass spectrum of the crude material shows the

1387-7003/99/$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.
PII S 1 3 8 7 - 7 0 0 3 ( 9 9 ) 0 0 0 4 3 - X

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 L. Beyer et al. / Inorganic Chemistry Communications 2 (1999) 184187 185

Fig. 1. Synthesis and chemical shifts (1H: s (ppm) (399.95 MHz), solvent DMSO-d6; 13
C: s (ppm) (100.58 MHz), solvent DMSO-d6; UNITY 400
spectrometer) of the ligands 1a and 2a. Synthesis of complexes 1 and 2.

molecular peak. The complete elemental analysis agrees well
with the calculated values. Crystals suited for X-ray structure
analysis were obtained by dissolving 1 in DMF and subse-
quent slow evaporation of the solvent at room temperature.
The molecular structure 2 of 1 is shown in Fig. 2. The
complex is a chelate with two bidentate ligands bonding
through N and O. The coordination geometry is tetrahedrally
distorted square-planar (Cu1O1N1/Cu1O2N4 25.8(3)8)
with trans arrangement of the ligands. The central N atoms
N2 and N5 in the ligands are deprotonated. The angles
between the phenyl rings and the chelate rings are 39.8(3)8
and 3.0(5)8. The crystal structure contains molecules of the
solvent dimethylformamide. Between all chelate molecules
related by translation in x direction two hydrogen bonds exist
2
X-ray crystallographic data: C28H20N6O2CuPC3H7NO, Ms609.14, green
plates, as9.875(1), bs23.956(3), cs12.190(1) A , bs106.721(2)8,
Vs2761.7(5) A 3, Zs4, monoclinic, space group P21/c, Dcalcs1.465 g
cmy3, m(MoKa)s0.838 mmy1. Crystal dimensions 0.12=0.08=0.04
mm, Siemens SMART CCD diffractometer, MoKa radiation (ls0.71073
), v scans, 4.3-2u-55.38, room temperature, 14229 reflections measured
A delocalization. In the ultra high vacuum of the XPS experi-
(5676 independent, 1431 observed with IG2s(I)), extinction correction.
Structure solution: Patterson (SHELXS 97) [19], full-matrix least-squares
on F2 (SHELXL 97) [19], H positions calculated, 382 parameters,
R1s0.0871 for 1431 observed reflections, wR2s0.1791 for 5676 independ-
ent reflections, largest difference peak and hole 0.45 and y0.69 e A y3.
which lead to infinite chains of molecules in this direction
(N3H3NN5 [x-1, y, z] with N3N5 3.031 A , H3NN5
2.18 A , N3H3NN5 1698 and N6H6NN2 [xq1, y, z]
with N6N2 2.860 A , H6NN2 2.00 A , N6H6NN2
1738).
Complex 2 precipitates from the emerald-green solution
obtained by addition of nickel(II) acetate-tetrahydrate to
N-benzoyl-O-ethyl-N9-m-nitrophenyl-isourea, dissolved in
warm ethanol which contains additional pyridine (see Fig.
1). The yield is about 50%. The TGA/DTA analysis of 2
shows thermic degradation of pyridine between 1708C and
2308C with two maxima at 189.78C and 188.18C. The weight
loss (18.7%) up to the melting temperature (2338C, brown
melting) corresponds to two pyridine molecules. The Vis
NIR solution spectrum (acetonitrile or pyridine) as well as
the remission spectrum show nearly equal band maxima.
The N1s signals of the XPS spectrum (398.9 and 406.2
eV (NO2)) have an intensity ratio of 2:1, thus proving
deprotonation of the ligand and coordination with electronic
ment the pyridine ligands of the complex are not detected.
This is also shown by the intensity ratio of EbNi2p3/2 855.5
eV:EbN1s 398.9 eVs1:4. The value of the Ni signal corre-
sponds to coordinated nickel(II).

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186 L. Beyer et al. / Inorganic Chemistry Communications 2 (1999) 184187
Fig. 2. ORTEP drawing of the molecular structure of bis(2-benzoylimino-
benzimidazolinato)copper(II) (1). Selected bond lengths (A ) and angles
(8): Cu1O1 1.952(6), Cu1O2 1.918(6), Cu1N1 1.948(6), Cu1N4
1.915(6), O1C1 1.251(9), O2C15 1.252(9), N1C2 1.331(10), N1C4
1.405(10), N2C1 1.347(9), N2C2 1.348(10), N3C2 1.362(9), N3C3
1.395(10), N4C16 1.334(10), N4C18 1.411(10), N5C15 1.349(10),
N5C16 1.382(10), N6C16 1.370(9), N6C17 1.356(10), O1Cu1N1
88.2(3), O2Cu1N4 88.7(3), Cu1O1C1 128.5(6), Cu1O2C15
131.4(6), Cu1N1C2 122.4(6), C1N2C2 119.2(7), Cu1N4C16
124.3(6), C15N5C16 117.6(8), O1C1N2 126.8(8), N1C2N2
130.8(8), O2C15N5 126.9(9), N4C16N5 130.6(8).
The molecular structure 3 of 2 is shown in Fig. 3. The
complex is a chelate with two N,O-coordinating bidentate
ligands and two pyridine ligands. The molecular symmetry
is C2. The coordination polyhedron is an octahedron with cis
arrangement of the pyridine ligands. The central atom N2 of
the chelate ligand is deprotonated. The angles of the phenyl
ring C3C8 and the m-nitrophenyl ring C11C16 to the che-
late ring are 11.7(2) and 62.5(1)8, respectively. The chelate
molecules are chiral but the compound has crystallized as
racemate.
3. Experimental
3.1. 2-Benzoylimino-benzimidazoline (1a)
23.7 g (0.1 mol) N-benzoyl-thiocarbamic acid-O,S-di-
ethylester [18] were refluxed with the same molar amount
3
X-ray crystallographic data: C42H38N8O8Ni, Ms841.51, light-green
prisms, as21.9063(6), bs9.1828(2), cs20.5690(1) A , bs92.126(1)8,
Vs4134.8(2) A 3, Zs4, monoclinic, space group C2/c, Dcalcs1.352 g
cmy3, m(MoKa)s0.531 mmy1. Crystal dimensions 0.32=0.22=0.10
mm, Siemens SMART CCD diffractometer, MoKa radiation (ls0.71073
), v scans, 3.7-2u-55.88, room temperature, 10993 reflections measured
A To 6.1 g (0.025 mol) of N-benzoylimino-thiocarbamic
(4405 independent, 2617 observed with IG2s(I)), extinction correction.
Structure solution: Patterson (SHELXS 97) [19], full-matrix least-squares
on F2 (SHELXL 97) [19], H positions calculated, 269 parameters,
R1s0.0532 for 2617 observed reflections, wR2s0.1106 for 4405 independ-
ent reflections, largest difference peak and hole 0.31 and y0.58 e A y3.
Tuesday Apr 27 10:37 AM StyleTag -- Journal: INOCHE (Inorganic Chemistry Communications)
Fig. 3. ORTEP drawing of the molecular structure of cis-bis-
(pyridine)bis(N-benzoyl-O-ethyl-N9-m-nitrophenyl-isoureato)nickel(II)
(2). The pyridine molecules are plotted with dashed-line bonds and without
labeling of C atoms. Selected bond lengths (A ) and angles (8): Ni1O1
2.021(2), Ni1N1 2.097(2), Ni1N4 2.150(2), O1C2 1.266(3), O2C1
1.361(3), N1C1 1.307(3), N1C11 1.427(3), N2C1 1.337(3), N2C2
1.329(3), O1Ni1N1 87.1(1), Ni1O1C2 127.3(2), C1O2C9
118.8(2), Ni1N1C1 121.8(2), C1N2C2 123.7(2), N1C1N2
128.8(3), O1C2N2 128.2(2).
of o-phenylenediamine (10.8 g) in 100 ml ethanol. After this
the solution was stirred 24 h at room temperature and left
overnight in the refrigerator. The precipitate was filtered and
recrystallized from methanol. Colorless crystals. m.p.: 242
2438C (lit.: 2412438C [4]); yield: 7.1 g (30%). Anal. Calc.
for C14H11N3O (237.25 g/mol): C, 70.87; H, 4.67; N, 17.71;
O, 6.74. Found: C, 70.72; H, 4.81; N, 17.62; O, 6.37%. MS
[m/z]: 237 (Mxq, 54% rel. int.); 105 (C6H5COq, 100% rel.
int.).
3.2. Bis(2-benzoylimino-benzimidazolinato)copper(II) (1)
0.47 g (0.002 mol) 1a was dissolved in 150 ml ethanol.
To this solution 0.20 g (0.001 mol) Cu(OAc)2PH2O in 40
ml ethanol was added. The dark green precipitate was filtered
and washed with cold ethanol. Yield: 0.5 g (93%); no melting
up to 3608C. Anal. Calc. for C28H20N6O2Cu (535.99 g/mol):
C, 62.74; H, 3.76; N, 15.67; O, 5.97; Cu, 11.86. Found: C,
62.81; H, 3.89; N, 15.65; O, 5.64; Cu, 11.14%. FAB-MS:
[m/z]: 537 (Mxqq2H), matrix: 3-nitrobenzylalcohol.
3.3. N-Benzoyl-O-ethyl-N9-m-nitrophenyl-isourea (2a)
acid-O,S-diethylester [18] 3.52 g (0.025 mol) m-nitroani-
line were added. To this solution 70 ml of hot ethanol were
added. The mixture was refluxed for about 5 h. 2a crystallized
in the form of pale yellow needles. m.p.: 86888C [lit.: 87
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 L. Beyer et al. / Inorganic Chemistry Communications 2 (1999) 184187
898C [10]); yield: 5.7 g (70%). Anal. Calc. for C16H15N3O4
(313.3 g/mol): C, 61.33; H, 4.83; N, 13.41. Found: C, 60.94;
H, 4.82; N, 13.22%. MS [m/z]: 313 (Mxq, 12.1% rel. int.),
105 (C6H5COq 100% rel. int.) XPS [eV]: N1s 398.7
(_N), 400.5 (NH), 406.3 (NO2).
3.4. Cis-bis(pyridine)-bis(N-benzoyl-O-ethyl-N9-m-
nitrophenyl-isoureato)nickel(II) (2)
0.78 g (0.0025 mol) 2a was dissolved in a mixture of 100
ml ethanol and 1.5 g pyridine. A hot solution of 0.31 g
(0.00125 mol) nickel(II)acetate-tetrahydrate in 30 ml eth-
anol was added to the ligand solution. 2 crystallized overnight
from the emerald-green solution in the refrigerator. The pre-
cipitate was filtered, washed with a few milliliters of cold
ethanol and stored in a desiccator over pyridine. 2 is stable
in air. Yield: 0.54 g (51.5%). Anal. Calc. for C42H38N8O8Ni
(841.4 g/mol): C, 59.95; H, 4.64; N, 13.31; O, 15.21; Ni,
6.97. Found: C, 59.44; H, 4.65; N, 13.26; O, 15.3; Ni, 6.89%.
XPS [eV]: N1s 398.9 (chelate ring), 406.2 (NO2);
Ni2p3/2 855.5 (NiII coord.). VisNIR [nm(lg e)]aceto-
nitrile: 601.56(0.076); 786.77(0.026); 968.16(0.085);
1403.6(0.016). VisNIR [nm(lg e)] pyridine: 593.10-
(0.069); 786.77(0.026); 965.27(0.096); 1141.7(0.036);
1399.0(0.003).
4. Supplementary material
Further details of the structure determinations are available
on request from Fachinformationszentrum Karlsruhe, D-
76344 Eggenstein-Leopoldshafen, Germany, on quoting the
depository numbers CSD-380217 (1) and CSD-380218 (2).
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187
Acknowledgements
L.B. would like to thank the Fond der Chemischen Indus-
trie for financial support. M.L. thanks the DAAD Bonn for a
grant. We thank Dr. K.H. Hallmeier for recording and dis-
cussion of the XPS spectra and Dr. L. Hennig for recording
and discussion of the NMR spectra.
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