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J Chem Crystallogr (2010) 40:169–172 DOI 10.1007/s10870-009-9629-6

ORIGINAL PAPER

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

¨

Latifa Mouni Æ Mehmet Akkurt Æ S. O . Y ıld ı r ım Æ

Taibi Ben Hadda Æ 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[CH 3 CO–CH=C (CH 3 )N(CH 2 –CH 2 )N(CH 3 )C=CHCO CH 3 ], has been synthe- sized by the reaction of ligand, 4-[2-(1-methyl-3-oxo-but-1- enylamino)-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 P2 1 /n with a = 10.971 (4), b = 8.988 (3), c =

12.830 (5) A , b = 93.512 (5), V = 1,262.7 (6) A 3 , Z = 4 and with R int = 0.047. The geometry around the copper atom dis- plays 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 anionic–cationic bonds to complete the coordination sphere around the copper metal atom.

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Keywords

but-1-enylamino)-ethylamino]-pent-3-en-2-one

Copper (II) chloride

Crystal structure 4-[2-(1-Methyl-3-oxo-

L. Mouni T. B. Hadda

Laboratoire de Chimie des Mate´riaux, Universite´ Mohammed Premier, Oujda, Morocco

¨

M. Akkurt S. O . Yı ldı r ım 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 organome- tallic and coordination compounds with pyridine [2], dii- mine [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 quin- oxaline [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-2,4- dione 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 poly- dentate 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) 40:169–172

Scheme 1 General protocol leading to cuprate complex (4)

H 2 N

CH CH 3 3 CH 3 CH 3 NH HN + 2 O O O
CH
CH
3
3
CH 3
CH 3
NH
HN
+
2
O
O
O
O
NH 2
3
CH
CH
1
2
3
3
CH
CH
3
3
N
N
CuCl
2
Cu
NaOH/ EtOH/
O
O
CH
4 CH
3
3

copper (II) chloride and (3) in ethanol was refluxed for 3 h, which lead to the formation of a solid product, Cu[CH 3 CO–CH=C(CH 3 )N(CH 2 –CH 2 )N(CH 3 )C=CHCOCH 3 ] (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 metal- diaminoethane ring of central unit is far away to be per- fectly planarity. The structure also shows that oxygen atoms of carbonyl groups (C2=O1 and C11=O2) and nitrogen atoms of ethylenediamine moiety (N1–C6 and N2–C7), 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-configu- ration of oxygen and nitrogen atoms around copper atom.

Few structures containing the ‘4-[(2-{[(1E)-1-methyl- 3-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 N1–C4 (1.308 (6)) and N2–C8 (1.314 (5)) in (4) have been reduced as compared to reported moiety N1–C3 (1.335 (4) and N1a–C3a (1.322 (4). While the bond lengths O1–C2 (1.292 (5) and O2–C11 (1.292 (5) in (4) has been enlarged than O1–C5 (1.265 (4) and O1a–C5a (1.272 (4) in reported moiety of ligand (3). The tetradentate ligand (3) adopts a meridional confor- mation with oxygen atoms in cisoidal coordinative geom- etry. The dihedral angle between the N1/C6/C7 and C6/C7/

etry. The dihedral angle between the N1/C6/C7 and C6/C7/ Fig. 1 The molecular structure of (
etry. The dihedral angle between the N1/C6/C7 and C6/C7/ Fig. 1 The molecular structure of (

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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Chem Crystallogr (2010) 40:169–172

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Table 1 Crystal data and refinement information

Crystal data

C 12 H 18 CuN 2 O 2

M r = 285.83

Monoclinic, P2 1 /n

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a = 10.971 (4) A

Z = 4

D x = 1.503 Mg m -3 Mo Ka radiation

Cell parameters from 1,749 reflections

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b = 8.988 (3) A

h

= 2.77–23.35

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= 1.721 mm -1

c = 12.830 (5) A

l

b = 93.512 (5)

T = 150 (2) K

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V = 1,262.7 (6) A 3

Lath, blue

Data collection

Bruker APEX-II CCD diffractomer

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

/ and x scans

R int = 0.047

Absorption correction: none

h max = 28.4

12,832 Measured reflections

h = -12 ? 12

3,224 Independent reflections

k = -10 ? 10

l = -18 ? 18

Refinement

Refinement on F 2

H atoms constrained to parent site

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

Calculated weights w =

wR(F 2 ) = 0.176

S = 1.02

3,224 reflections

182 parameters

CCDC number: 732373

1/

[r 2 (F 2 o ) ? (0.0795P) 2 ? 2.2377P] where P = (F o 2 ? 2F 2 c )/3

(D/r) max \ 0.0001

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Dq max = 0.77 e A

Dq min = -0.33 e A

Extinction correction: none

-1

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-1

N2 planes is calculated as -35.5(4) , while the dihedral angle between the two parallel bonds (O1–C2–C3) and (N1–C4–C3) is 14.15 (17) . In the structure, there are no

classic hydrogen bonds, but only short contact C–H p intramolecular interactions, as detailed in Tables 1 and 2. Further, the interaction between the Cg3 rings [Cg3 Cg3

(1 - x,

interaction [Cg3 Cu1(1 - x, 1 - y, -z) = 3.409 A ] sta-

bilize the crystal structure.

and a ring-metal

1 / 2 ? y,

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1 / 2 - z) = 3.511(2) A ]

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Experimental

Synthesis of 4-[(2-{[(1E)-1-Methyl-3- oxobutylidene]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 mix- ture 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

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Table 2 Selected geometric parameters (A , )

Cu1–O1

 

1.917(2)

N1–C4

1.308(6)

Cu1–O2

 

1.927(3)

N1–C6

1.471(5)

Cu1–N1

 

1.941(3)

N2–C7

1.468(5)

Cu1–N2

 

1.935(3)

N2–C8

1.314(5)

O1–C2

 

1.292(5)

O2–C11

1.292(4)

O1–Cu1–O2

 

87.7(1)

Cu1–N2–C8

126.9(2)

O1–Cu1–N1

93.2(1)

C7–N2–C8

119.0(3)

O1–Cu1–N2

178.4(1)

O1–C2–C1

114.5(4)

O2–Cu1–N1

175.9(1)

O1–C2–C3

126.1(4)

O2–Cu1–N2

93.7(1)

N1–C4–C3

122.0(4)

N1–Cu1–N2

85.4(1)

N1–C4–C5

120.8(4)

Cu1–O1–C2

124.6(3)

N1–C6–C7

109.1(3)

Cu1–O2–C11

125.2(2)

N2–C7–C6

109.4(3)

Cu1–N1–C4

 

126.2(3)

N2–C8–C9

120.7(3)

Cu1–N1–C6

112.2(2)

N2–C8–C10

121.4(3)

C4–N1–C6

121.6(3)

O2–C11–C10

125.7(3)

Cu1–N2–C7

113.1(2)

O2–C11–C12

115.1(3)

O2

Cu1

O1

C2

-169.2(3)

Cu1 O2 C11 C12

176.7(2)

N1 Cu1 O1 C2

14.9(3)

Cu1 N1 C4 C3

5.3(5)

N2 Cu1 O1 C2

32(4)

Cu1 N1 C4 C5

-174.8(3)

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)

O2 Cu1 N1 C4

-115(2)

O2 Cu1 N2 C8

8.4(3)

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)

 

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Hydrogen-bond parameters (A , )

 

D–H A

 

D–H H A D A

D–H A

C6 H6B Cg3 i

 

0.97

2.67

3.397(5)

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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. = 114–115. Rf = 0.5 (hexane/dichloromethane = 1/2). IR (KBr, cm -1 ): 3,470 (N–H), 3,015 (C=CH), 2,920 (CH 3 ), 1,710 (C=O), 1,190 (C–N); NMR 1 H (300 MHz, CDCl 3 ) d ppm: 10.8 (s, 2H, NH); 5.1 (s, 2H, CH); 3.4–3.4 (m, 4H, CH 2 ); 2 (s, 6H, CH 3 CO–); 1.91 (s, 6H, CH 3 C (N)=C). 13 C NMR (300 MHz, CDCl 3 ) d ppm: 195.6; 162.8; 96.1; 43.5; 28.9; 18.7. SM(IC, CH 4 ): m/z: (MH) ? = 224.

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Synthesis of Cu[4-[(2-{[(1E)-1-Methyl-3- oxobutylidene]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) CuCl 2 .2H 2 O 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 evapo- ration. 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 posi- tions and treated as riding on their parent atoms, with C–

and with U iso (H) = 1.2U eq (C) and

H = 0.93–0.97 A ,

U iso (H) = 1.5U eq (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].

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Supplementary Information

Crystallographic data for the structural analysis has been deposited with the Cambridge crystallographic Data Cen- tre, CCDC No. 732373 for complex Cu[CH 3 CO– CH=C(CH 3 )N (CH 2 –CH 2 )N(CH 3 )C=CHCO CH 3 ]. 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 l’Universite’ Mohamed Premier

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d’Oujda ‘PGR-BH-20050 and PARS CO4 Grants from the Ministry of National Education of Morocco.

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