J Chem Crystallogr (2010) 40:169172

DOI 10.1007/s10870-009-9629-6

ORIGINAL PAPER

Crystal Structure of Cuprate (II) Complex of Tetradentate ONNO

Ligand: 4-[(2-{[(1E)-1-Methyl-3-oxobutylidene]amino}ethyl)
imino]pentan-2-one
. Yldrm
Latifa Mouni Mehmet Akkurt S. O
Taibi Ben Hadda Zahid H. Chohan

Received: 30 May 2009 / Accepted: 29 August 2009 / Published online: 16 September 2009
Springer Science+Business Media, LLC 2009

Abstract The title copper complex, Cu[CH3COCH=C

(CH3)N(CH2CH2)N(CH3)C=CHCO CH3], has been synthesized by the reaction of ligand, 4-[2-(1-methyl-3-oxo-but-1enylamino)-ethylamino]-pent-3-en-2-one (ONNO) and
copper chloride. The structure of the synthesized complex was
determined by IR, NMR, mass spectroscopic data and
X-ray crystallography. The structure was solved in monoclinic,
space group P21/n with a = 10.971 (4), b = 8.988 (3), c =
, b = 93.512 (5), V = 1,262.7 (6) A
3, Z = 4 and
12.830 (5) A
with Rint = 0.047. The geometry around the copper atom displays a distorted square-planner structure by coordinating with
two oxygen atoms from carbonyl moiety and two nitrogen
heteroatom from the central moiety of the ligands and thus
established two 6-membered rings and one 5-membered ring.
The two nitrogen atoms form two anioniccationic bonds to
complete the coordination sphere around the copper metal
atom.
Keywords Crystal structure
4-[2-(1-Methyl-3-oxobut-1-enylamino)-ethylamino]-pent-3-en-2-one

Copper (II) chloride

L. Mouni
T. B. Hadda
Laboratoire de Chimie des Materiaux,
Universite Mohammed Premier, Oujda, Morocco
. Yldrm
M. Akkurt
S. O
Department of Physics, F.A.S., Erciyes University,
38039 Kayseri, Turkey
Z. H. Chohan (&)
Department of Chemistry, Bahauddin Zakariya University,
Multan, Pakistan
e-mail: dr.zahidchohan@gmail.com

Introduction
Metallo-organic complexes containing conjugated nitrogen
ligands represent an important class of nonlinear optical
chromophores [1]. Efficient systems involving organometallic and coordination compounds with pyridine [2], diimine [3], salen-type [46] or Schiff-base ligands have been
described [7]. We have also demonstrated the direct impact
of dipolar in drug design of functionalised bis-armed quinoxaline [8] and pyrimidine ligands [9, 10]. In connection
with our research aimed at developing new pharmacophore
site(s) lead us to efficient and selective anti-tubercular [11],
antitumoral [12] or anti-HIV drugs [13], we therefore,
became interested in the pharmaco-modulation of parent
drugs like ethambutol, a clinical anti-tubercular agent.
The ligand, 4-[(2-{[(1E)-1-methyl-3-oxobutylidene]amino}
ethyl)imino] pentan-2-one was prepared since a long time
[14] by condensation of ethylenediamine with pentan-2,4dione or acetylacetone in absolute ethanol (100 mL) at room
temperature. The Tautomerism of which was clarified
recently by our group [15] by studying its crystal structure.
Now we report the coordination behaviour of this polydentate ligand, 4-[(2-{[(1E)-1-methyl-3-oxobutylidene]
amino}ethyl)imino]pentan-2-one with copper dichloride in
a mixture of ethanol/NaOH.

Results and Discussion

Chemistry
The reaction of ethylenediamine with acetylacetone (1:2
molar ratio) in ethanol at room temperature after stirring
48 h gave 4-[(2-{[(1E)-1-methyl-3-oxobutylidene]amino}
ethyl)imino]pentan-2-one (3). An equimolar amount of the

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J Chem Crystallogr (2010) 40:169172

Scheme 1 General protocol

leading to cuprate complex (4)

CH3

CH3
CH3

CH3

NH

HN

H 2N

2
O

NH 2

CH3

O
CH3

CH3

CH3
N

CuCl 2
NaOH/ EtOH/

Cu

O
CH3

CH3

copper (II) chloride and (3) in ethanol was refluxed for

3 h, which lead to the formation of a solid product,
Cu[CH3COCH=C(CH3)N(CH2CH2)N(CH3)C=CHCOCH3]
(4). It was crystalized in ethanol to afford crystals of the
desired copper complex (Scheme 1).
The molecular structure of (4) (Figs. 1, 2) shows the
expected bond lengths and bond angles [16]. The metaldiaminoethane ring of central unit is far away to be perfectly planarity. The structure also shows that oxygen
atoms of carbonyl groups (C2=O1 and C11=O2) and
nitrogen atoms of ethylenediamine moiety (N1C6 and
N2C7), adopts a cis-configuration around the copper atom
Cu1. Small torsion angles in N2Cu1O2C11 = -3.3(3) and
in O1Cu1N1C4 = -13.3(3) also support the cis-configuration of oxygen and nitrogen atoms around copper atom.

Few structures containing the 4-[(2-{[(1E)-1-methyl3-oxobutylidene]amino} ethyl)imino] pentan-2-one (3)

moiety has been reported such as 3,10-bis[2-(2-pyridinyl)
ethyl]-4,9-dimethyl-5,8-diazadodeca-4,8-diene-2,11-dione
tetrahydrate [17]. It was observed that the bond lengths of (4)
have been changed after coordination with copper atom. The
bond distances N1C4 (1.308 (6)) and N2C8 (1.314 (5))
in (4) have been reduced as compared to reported moiety
N1C3 (1.335 (4) and N1aC3a (1.322 (4). While the bond
lengths O1C2 (1.292 (5) and O2C11 (1.292 (5) in (4) has
been enlarged than O1C5 (1.265 (4) and O1aC5a (1.272
(4) in reported moiety of ligand (3).
The tetradentate ligand (3) adopts a meridional conformation with oxygen atoms in cisoidal coordinative geometry. The dihedral angle between the N1/C6/C7 and C6/C7/

Fig. 1 The molecular structure of (4) with the atom-numbering

scheme and 50% probability displacement ellipsoids

Fig. 2 View of the packing diagram of compound (4) in the unitcell

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J Chem Crystallogr (2010) 40:169172

171

Table 1 Crystal data and refinement information

, )
Table 2 Selected geometric parameters (A

Crystal data

Cu1O1

1.917(2)

N1C4

1.308(6)

Cu1O2

1.927(3)

N1C6

1.471(5)

Cu1N1

1.941(3)

N2C7

1.468(5)

Cu1N2
O1C2

1.935(3)
1.292(5)

N2C8
O2C11

1.314(5)
1.292(4)

C12H18CuN2O2

Z=4
-3

Mr = 285.83

Dx = 1.503 Mg m

Monoclinic, P21/n

a = 10.971 (4) A

Mo Ka radiation

O1Cu1O2

87.7(1)

Cu1N2C8

126.9(2)

b = 8.988 (3) A

c = 12.830 (5) A

h = 2.7723.35

O1Cu1N1

93.2(1)

C7N2C8

119.0(3)

l = 1.721 mm-1

O1Cu1N2

178.4(1)

O1C2C1

114.5(4)

b = 93.512 (5)

T = 150 (2) K

O2Cu1N1

175.9(1)

O1C2C3

126.1(4)

3
V = 1,262.7 (6) A

Lath, blue

O2Cu1N2

93.7(1)

N1C4C3

122.0(4)

N1Cu1N2

85.4(1)

N1C4C5

120.8(4)

Cu1O1C2

124.6(3)

N1C6C7

109.1(3)

Cu1O2C11

125.2(2)

N2C7C6

109.4(3)

Cu1N1C4

126.2(3)

N2C8C9

120.7(3)

Cu1N1C6

112.2(2)

N2C8C10

121.4(3)

C4N1C6

121.6(3)

O2C11C10

125.7(3)

Cu1N2C7

113.1(2)

O2C11C12

115.1(3)

Cu1 O2 C11 C12

176.7(2)

Cell parameters from 1,749

reflections

Data collection
Bruker APEX-II CCD
diffractomer

2,643 Reflections with I [ 2r(I)

/ and x scans

Rint = 0.047

Absorption correction: none

hmax = 28.4

12,832 Measured reflections

h = -12 ? 12

3,224 Independent reflections

k = -10 ? 10
l = -18 ? 18

Refinement
Refinement on F2

H atoms constrained to parent site

R[F2 [ 2r(F2)] = 0.071

Calculated weights w =
1/
[r2(F2o) ? (0.0795P)2 ? 2.2377P]
where P = (F2o ? 2F2c )/3

wR(F2) = 0.176

O2 Cu1 O1 C2

-169.2(3)

N1 Cu1 O1 C2
N2 Cu1 O1 C2

14.9(3)
32(4)

O1 Cu1 O2 C11

177.3(3)

Cu1 N1 C6 C7

30.4(4)

N1 Cu1 O2 C11

-81(2)

Cu1 N2 C7 C6

25.3(3)

N2 Cu1 O2 C11

-3.3(3)

Cu1 N2 C8 C9

172.6(3)

O1 Cu1 N1 C4

-13.3(3)

Cu1 N2 C8 C10

-8.3(5)

O1 Cu1 N1 C6

165.9(2)

Cu1 O2 C11 C12

176.7(2)

Cu1 N1 C4 C3
Cu1 N1 C4 C5

5.3(5)
-174.8(3)

S = 1.02

(D/r)max \ 0.0001
-1
Dqmax = 0.77 e A

3,224 reflections

-1
Dqmin = -0.33 e A

O2 Cu1 N1 C4

-115(2)

O2 Cu1 N2 C8

8.4(3)

182 parameters

Extinction correction: none

O2 Cu1 N1 C6

64(2)

N1 Cu1 N2 C7

-7.1(2)

N2 Cu1 N1 C4

167.2(3)

N1 Cu1 N2 C8

-175.6(3)

N2 Cu1 N1 C6

-13.6(2)

Cu1 O1 C2 C1

172.9(3)

O1 Cu1 N2 C7

-25(4)

Cu1 O1 C2 C3

-8.9(6)

O1 Cu1 N2 C8

167(4)

Cu1 O2 C11 C10

-1.8(5)

O2 Cu1 N2 C7

176.9(2)

CCDC number: 732373

N2 planes is calculated as -35.5(4), while the dihedral

angle between the two parallel bonds (O1C2C3) and
(N1C4C3) is 14.15 (17). In the structure, there are no
classic hydrogen bonds, but only short contact CH


p
intramolecular interactions, as detailed in Tables 1 and 2.
Further, the interaction between the Cg3 rings [Cg3


Cg3
] and a ring-metal
(1 - x, 1/2 ? y, 1/2 - z) = 3.511(2) A
] stainteraction [Cg3


Cu1(1 - x, 1 - y, -z) = 3.409 A
bilize the crystal structure.

Experimental
Synthesis of 4-[(2-{[(1E)-1-Methyl-3oxobutylidene]amino}ethyl)imino]pentan-2-one (3)
A mixture of 6.3 g (105 mmoles) of ethylenediamine (1)
and 21 g (210 mmoles) of acetylacetone (2) was stirred in
absolute ethanol (100 mL) at room temperature. The mixture was stirred at room temperature for 48 h until TLC
indicated complete disappearance of substrates. After
removing ethanol, the crude product was filtered and washed

, )
Hydrogen-bond parameters (A
DH


A
DH H


A D


A
C6 H6B Cg3

0.97

2.67

DH


A

3.397(5) 133

Symmetry codes: (i) 1 - x, 1/2 ? y, 1/2 - z. Cg3 is a centroid of the

(Cu1/O2/C11/C10/C8/N2) ring

with water and then with hexane. The solid product thus
obtained was dissolved completely in ethanol and filtered
and thus fine crystals were grown from dichloromethane/
hexane (3) in good yield of 73%. M.p. = 114115. Rf = 0.5
(hexane/dichloromethane = 1/2). IR (KBr, cm-1): 3,470
(NH), 3,015 (C=CH), 2,920 (CH3), 1,710 (C=O), 1,190
(CN); NMR 1H (300 MHz, CDCl3) d ppm: 10.8 (s, 2H,
NH); 5.1 (s, 2H, CH); 3.43.4 (m, 4H, CH2); 2 (s, 6H,
CH3CO); 1.91 (s, 6H, CH3C (N)=C). 13C NMR (300 MHz,
CDCl3) d ppm: 195.6; 162.8; 96.1; 43.5; 28.9; 18.7. SM(IC,
CH4): m/z: (MH)? = 224.

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Synthesis of Cu[4-[(2-{[(1E)-1-Methyl-3oxobutylidene]amino} ethyl)imino]pentan-2-one] (4)

An ethanol solution (30 mL) of ligand (3) (22.42 g,
100 mmol) was stirred with (17.05 g, 100 mmol)
CuCl2.2H2O in ethanol (50 mL). Then NaOH solution
(0.1 M, 10 mL) was added to increase the pH of the
solution. The mixture was refluxed for 2 h. The completion
of reaction was monitored by TLC. The obtained solution
was filtered and reduced to half of its volume by evaporation. The concentrated solution was allowed to stand for
6 days at room temperature, which led to the formation of a
crystalized product. It was filtered, washed with small
amount of ethanol and then dried.
H atoms were geometrically located in calculated positions and treated as riding on their parent atoms, with C
, and with Uiso(H) = 1.2Ueq(C) and
H = 0.930.97 A
Uiso(H) = 1.5Ueq(C) for methyl group.
Data collection: APEX2 [18]. Cell refinement: APEX2.
Data reduction: SAINT (Bruker, 2005). Program(s) used to
solve structure: SIR97 [19]. Program(s) used to refine
structure: SHELXL97 [20]. Molecular graphics: ORTEP-3
for Windows [21]. Software used to prepare material for
publication: WinGX [22].

Supplementary Information
Crystallographic data for the structural analysis has been
deposited with the Cambridge crystallographic Data Centre, CCDC No. 732373 for complex Cu[CH3CO
CH=C(CH3)N (CH2CH2)N(CH3)C=CHCO CH3]. Copies
of this information can be obtained from the Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax:
?44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk).
Acknowledgment This work was supported by the Program du
Projet Global de Recherche de lUniversite Mohamed Premier

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J Chem Crystallogr (2010) 40:169172

dOujda PGR-BH-20050 and PARS CO4 Grants from the Ministry
of National Education of Morocco.

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