Crystal structure of bis­(2-{[(3-bromo­prop­yl)imino]­meth­yl}phenolato-κ2N,O)copper(II)

Ourari, A.; Zoubeidi, C.; Bouacida, S.; Derafa, W.; Merazig, H.

doi:10.1107/S2056989015001309

metal-organic compounds

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doi:10.1107/S2056989015001309

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Crystal structure of bis(2-{[(3-bromopropyl)imino]methyl}phenolato-κ²N,O)copper(II)

Ali Ourari,^a Chahinaz Zoubeidi,^a Sofiane Bouacida,^b,^c ^* Wassila Derafa ^a and Hocine Merazig ^c

^aLaboratoire d'Electrochimie, d'Ingénierie Moléculaire et de Catalyse Redox (LEIMCR), Faculté des Sciences de l'Ingénieur, Université Farhat Abbas, Sétif 19000, Algeria, ^bDépartement Sciences de la Matière, Faculté des sciences Exactes et Sciences de la Nature et de la Vie, Université Oum El Bouaghi, Algeria, and ^cUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Université Constantine 1, 25000 , Algeria
^*Correspondence e-mail: bouacida_sofiane@yahoo.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 16 January 2015; accepted 21 January 2015; online 24 January 2015)

In the title compound, [Cu(C₁₀H₁₁BrNO)₂], the asymmetric unit consists of one-half of the molecule, the other half being generated by an inversion centre. Hence the Cu^II cation is symmetrically coordinated by two bidentate Schiff base anions in a slightly distorted square-planar environment with Cu—O and Cu—N bond lengths of 1.8786 (19) and 2.009 (2) Å, respectively. In the crystal, individual molecules are packed in alternating zigzag layers parallel to (001). Weak C—H⋯π interactions exist between the molecules.

Keywords: crystal structure; copper(II) complex; C—H⋯π interactions.

CCDC reference: 1044698

1. Related literature

For synthesis and applications of similar complexes derived from salicylaldehyde, see: Ghelenji et al. (2011 ); Kia et al. (2010 ); Zhang et al. (2013 ). For the importance of copper in biological systems, see: Siegel (1973 ); Mohan et al. (1998 ). For isotypic structures, see: Floyd et al. (2005 ); Ourari et al. (2015 ).

2. Experimental

2.1. Crystal data

[Cu(C₁₀H₁₁BrNO)₂]
M_r = 545.75
Monoclinic, P 2₁ /n
a = 10.6478 (4) Å
b = 7.1990 (3) Å
c = 13.9283 (5) Å
β = 104.900 (2)°
V = 1031.75 (7) Å³
Z = 2
Mo Kα radiation
μ = 4.95 mm⁻¹
T = 295 K
0.19 × 0.18 × 0.15 mm

2.2. Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2011 ) T_min = 0.677, T_max = 0.796
8212 measured reflections
2594 independent reflections
2088 reflections with I > 2σ(I)
R_int = 0.020

2.3. Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.04
2594 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cg1ⁱ	0.97	2.74	3.645 (4)	155
C4—H4⋯Cg1ⁱⁱ	0.93	2.90	3.805 (3)	164
Symmetry codes: (i) -x+2, -y-1, -z+2; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 1044698

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015001309/wm5116sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015001309/wm5116Isup2.hkl

checkCIF report

Related literature top

For synthesis and applications of similar complexes derived from salicylaldehyde, see: Ghelenji et al. (2011); Kia et al. (2010); Zhang et al. (2013). For the importance of copper in biological systems, see: Siegel (1973); Mohan et al. (1998). For isotypic structures, see: Floyd et al. (2005); Ourari et al. (2015).

Experimental top

Ligand (HL) synthesis: 331.5 mg (1.5 mmol) of 2-bromopropyl ammonium hydrobromide were dissolved in absolute ethanol (15 ml). First, 756 mg (1.5 mmol; excess of 5%) and then 183 mg salicylaldehyde, each dissolved in 10 ml of absolute ethanol, were added and the resulting solution was refluxed under nitrogen atmosphere for 2 h at 333 K. The solvent was removed under reduced pressure and 15 ml of dichloromethane were added to the residue obtained. The mixture was stirred for 15 min, filtered and the solvent evaporated, resulting in a yellow viscous oil (yield: 82%).

Synthesis of the copper complex (I): 215 mg ligand HL (1 mmol) were placed in 10 ml of absolute ethanol. 99.8 mg of copper acetate monohydrate (0.5 mmol), dissolved in 5 ml of absolute ethanol, were added to this solution. The content of the flask was refluxed under stirring and nitrogen atmosphere for 2 h at 333 K. The precipitate obtained was filtered, washed with ethanol and then dried in an oven at moderate temperature (yield 70%; m. p. 393 K). Suitable single crystals were obtained from acetone solution by slow evaporation yielding green single crystals.

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of the title compound with the atomic labelling scheme. Displacement are drawn at the 50% probability level. Non-labelled atoms are generated by symmetry code -x+2, -y, -z+2.
	Fig. 2. Formation of alternating zigzag layers parallel to (001).
	Fig. 3. A view of the layers along [010].

Bis(2-{[(3-bromopropyl)imino]methyl}phenolato-κ²N,O)copper(II) top

Crystal data top

[Cu(C₁₀H₁₁BrNO)₂]	F(000) = 542.0
M_r = 545.75	D_x = 1.757 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.6478 (4) Å	Cell parameters from 3645 reflections
b = 7.1990 (3) Å	θ = 3.2–27.7°
c = 13.9283 (5) Å	µ = 4.95 mm⁻¹
β = 104.900 (2)°	T = 295 K
V = 1031.75 (7) Å³	Prism, green
Z = 2	0.19 × 0.18 × 0.15 mm

Data collection top

Bruker APEXII diffractometer	2088 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
CCD rotation images, thin slices scans	θ_max = 28.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2011)	h = −12→14
T_min = 0.677, T_max = 0.796	k = −9→6
8212 measured reflections	l = −18→18
2594 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0419P)² + 0.8205P] where P = (F_o² + 2F_c²)/3
2594 reflections	(Δ/σ)_max = 0.001
124 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Cu(C₁₀H₁₁BrNO)₂]	V = 1031.75 (7) Å³
M_r = 545.75	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.6478 (4) Å	µ = 4.95 mm⁻¹
b = 7.1990 (3) Å	T = 295 K
c = 13.9283 (5) Å	0.19 × 0.18 × 0.15 mm
β = 104.900 (2)°

Data collection top

Bruker APEXII diffractometer	2594 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2011)	2088 reflections with I > 2σ(I)
T_min = 0.677, T_max = 0.796	R_int = 0.020
8212 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.04	Δρ_max = 0.62 e Å⁻³
2594 reflections	Δρ_min = −0.58 e Å⁻³
124 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	1	0	1	0.03472 (12)
Br1	1.32859 (3)	−0.62235 (6)	0.86101 (3)	0.06803 (14)
O1	0.81891 (18)	−0.0114 (3)	0.98050 (16)	0.0559 (6)
N1	0.99577 (19)	−0.2004 (3)	0.89887 (15)	0.0350 (4)
C5	0.7594 (2)	−0.2139 (3)	0.84019 (19)	0.0368 (5)
C8	0.5014 (3)	−0.1335 (4)	0.8310 (2)	0.0476 (7)
H8	0.4152	−0.1059	0.8282	0.057*
C4	0.8909 (2)	−0.2635 (4)	0.84046 (19)	0.0382 (5)
H4	0.9006	−0.3503	0.7934	0.046*
C9	0.5984 (3)	−0.0546 (4)	0.9037 (2)	0.0468 (6)
H9	0.5767	0.0251	0.9494	0.056*
C6	0.6576 (3)	−0.2913 (4)	0.7663 (2)	0.0492 (7)
H6	0.677	−0.3702	0.7192	0.059*
C3	1.1185 (2)	−0.2808 (4)	0.88563 (19)	0.0394 (5)
H3A	1.1795	−0.1817	0.8837	0.047*
H3B	1.1011	−0.3469	0.8229	0.047*
C10	0.7306 (2)	−0.0917 (4)	0.91054 (19)	0.0392 (5)
C2	1.1783 (3)	−0.4136 (4)	0.9701 (2)	0.0471 (6)
H2A	1.1776	−0.3551	1.0326	0.056*
H2B	1.1249	−0.5245	0.9633	0.056*
C7	0.5294 (3)	−0.2529 (5)	0.7621 (2)	0.0522 (7)
H7	0.4628	−0.3068	0.7134	0.063*
C1	1.3158 (3)	−0.4696 (4)	0.9730 (2)	0.0493 (7)
H1A	1.3521	−0.5375	1.034	0.059*
H1B	1.3676	−0.3584	0.9742	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0302 (2)	0.0403 (2)	0.0355 (2)	−0.00058 (17)	0.01176 (16)	−0.00451 (17)
Br1	0.0490 (2)	0.0798 (3)	0.0742 (2)	0.01763 (16)	0.01380 (16)	−0.01284 (18)
O1	0.0347 (9)	0.0754 (15)	0.0616 (12)	−0.0084 (9)	0.0195 (9)	−0.0318 (11)
N1	0.0324 (10)	0.0359 (11)	0.0380 (10)	0.0046 (8)	0.0115 (8)	0.0000 (8)
C5	0.0342 (12)	0.0326 (12)	0.0428 (13)	0.0009 (10)	0.0083 (10)	0.0000 (10)
C8	0.0324 (12)	0.0529 (17)	0.0582 (16)	0.0005 (12)	0.0129 (12)	0.0067 (13)
C4	0.0403 (12)	0.0333 (12)	0.0416 (13)	0.0047 (10)	0.0118 (10)	−0.0034 (10)
C9	0.0382 (13)	0.0504 (15)	0.0570 (16)	−0.0021 (12)	0.0213 (12)	−0.0063 (13)
C6	0.0428 (14)	0.0445 (15)	0.0576 (17)	0.0020 (12)	0.0082 (12)	−0.0117 (13)
C3	0.0372 (12)	0.0427 (14)	0.0405 (13)	0.0073 (11)	0.0141 (10)	−0.0014 (11)
C10	0.0344 (12)	0.0411 (14)	0.0443 (13)	−0.0041 (10)	0.0140 (10)	−0.0024 (11)
C2	0.0452 (15)	0.0470 (16)	0.0515 (15)	0.0099 (12)	0.0172 (12)	0.0093 (13)
C7	0.0359 (13)	0.0553 (17)	0.0590 (17)	−0.0034 (13)	0.0008 (12)	−0.0053 (14)
C1	0.0411 (14)	0.0502 (17)	0.0534 (16)	0.0057 (12)	0.0062 (12)	0.0030 (13)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.8786 (19)	C4—H4	0.93
Cu1—O1	1.8786 (19)	C9—C10	1.412 (4)
Cu1—N1	2.009 (2)	C9—H9	0.93
Cu1—N1ⁱ	2.009 (2)	C6—C7	1.380 (4)
Br1—C1	1.942 (3)	C6—H6	0.93
O1—C10	1.302 (3)	C3—C2	1.522 (4)
N1—C4	1.284 (3)	C3—H3A	0.97
N1—C3	1.484 (3)	C3—H3B	0.97
C5—C6	1.404 (4)	C2—C1	1.509 (4)
C5—C10	1.408 (4)	C2—H2A	0.97
C5—C4	1.444 (3)	C2—H2B	0.97
C8—C9	1.369 (4)	C7—H7	0.93
C8—C7	1.377 (4)	C1—H1A	0.97
C8—H8	0.93	C1—H1B	0.97

O1ⁱ—Cu1—O1	180.0000 (10)	N1—C3—C2	110.9 (2)
O1ⁱ—Cu1—N1	88.28 (8)	N1—C3—H3A	109.5
O1—Cu1—N1	91.72 (8)	C2—C3—H3A	109.5
O1ⁱ—Cu1—N1ⁱ	91.72 (8)	N1—C3—H3B	109.5
O1—Cu1—N1ⁱ	88.28 (8)	C2—C3—H3B	109.5
N1—Cu1—N1ⁱ	180.0000 (10)	H3A—C3—H3B	108.1
C10—O1—Cu1	130.10 (17)	O1—C10—C5	123.6 (2)
C4—N1—C3	115.7 (2)	O1—C10—C9	118.8 (2)
C4—N1—Cu1	123.89 (16)	C5—C10—C9	117.6 (2)
C3—N1—Cu1	120.39 (16)	C1—C2—C3	113.5 (2)
C6—C5—C10	119.5 (2)	C1—C2—H2A	108.9
C6—C5—C4	118.0 (2)	C3—C2—H2A	108.9
C10—C5—C4	122.5 (2)	C1—C2—H2B	108.9
C9—C8—C7	121.1 (3)	C3—C2—H2B	108.9
C9—C8—H8	119.4	H2A—C2—H2B	107.7
C7—C8—H8	119.4	C8—C7—C6	118.9 (3)
N1—C4—C5	126.8 (2)	C8—C7—H7	120.5
N1—C4—H4	116.6	C6—C7—H7	120.5
C5—C4—H4	116.6	C2—C1—Br1	113.4 (2)
C8—C9—C10	121.4 (3)	C2—C1—H1A	108.9
C8—C9—H9	119.3	Br1—C1—H1A	108.9
C10—C9—H9	119.3	C2—C1—H1B	108.9
C7—C6—C5	121.4 (3)	Br1—C1—H1B	108.9
C7—C6—H6	119.3	H1A—C1—H1B	107.7
C5—C6—H6	119.3

N1—Cu1—O1—C10	−13.1 (3)	Cu1—N1—C3—C2	75.6 (3)
N1ⁱ—Cu1—O1—C10	166.9 (3)	Cu1—O1—C10—C5	9.8 (4)
O1ⁱ—Cu1—N1—C4	−170.0 (2)	Cu1—O1—C10—C9	−169.8 (2)
O1—Cu1—N1—C4	10.0 (2)	C6—C5—C10—O1	−178.9 (3)
O1ⁱ—Cu1—N1—C3	7.98 (19)	C4—C5—C10—O1	1.0 (4)
O1—Cu1—N1—C3	−172.02 (19)	C6—C5—C10—C9	0.8 (4)
C3—N1—C4—C5	177.6 (2)	C4—C5—C10—C9	−179.4 (3)
Cu1—N1—C4—C5	−4.3 (4)	C8—C9—C10—O1	179.3 (3)
C6—C5—C4—N1	176.5 (3)	C8—C9—C10—C5	−0.3 (4)
C10—C5—C4—N1	−3.3 (4)	N1—C3—C2—C1	−168.0 (2)
C7—C8—C9—C10	0.3 (5)	C9—C8—C7—C6	−0.7 (5)
C10—C5—C6—C7	−1.2 (4)	C5—C6—C7—C8	1.1 (5)
C4—C5—C6—C7	179.0 (3)	C3—C2—C1—Br1	−67.5 (3)
C4—N1—C3—C2	−106.3 (3)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cg1ⁱⁱ	0.97	2.74	3.645 (4)	155
C4—H4···Cg1ⁱⁱⁱ	0.93	2.90	3.805 (3)	164

Symmetry codes: (ii) −x+2, −y−1, −z+2; (iii) −x+3/2, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cg1ⁱ	0.97	2.74	3.645 (4)	155
C4—H4···Cg1ⁱⁱ	0.93	2.90	3.805 (3)	164

Symmetry codes: (i) −x+2, −y−1, −z+2; (ii) −x+3/2, y−1/2, −z+3/2.

Acknowledgements

We acknowledge the MESRS and DG–RSDT (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique et la Direction Générale de la Recherche - Algérie) for financial support.

References

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