Bis[4-bromo-2-(cyclo­pentyl­imino­meth­yl)phenolato]copper(II)

Cai, B.-H.

doi:10.1107/S1600536809006606

metal-organic compounds

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Volume 65| Part 3| March 2009| Page m339

doi:10.1107/S1600536809006606

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Bis[4-bromo-2-(cyclopentyliminomethyl)phenolato]copper(II)

Bang-Hong Cai ^a ^*

^aDepartment of Chemistry, Jiaying University, Meizhou Guangdong 514015, People's Republic of China
^*Correspondence e-mail: banghong_cai@163.com

(Received 20 February 2009; accepted 23 February 2009; online 28 February 2009)

The title compound, [Cu(C₁₂H₁₃BrNO)₂], was prepared by the reaction of 5-bromosalicylaldehyde, cyclopentylamine and copper(II) acetate in an ethanol solution. The Cu^II atom lies on an inversion center and is four-coordinated in a square-planar geometry by two N and two O atoms from two 4-bromo-2-(cyclopentyliminomethyl)phenolate Schiff base ligands.

Related literature

For background on Schiff base complexes, see: Costes et al. (2002 ); Erxleben (2001 ); Lacroix et al. (1996 ); Odoko et al. (2006 ); Ali et al. (2006 ). For related copper(II) complexes, see: Wang et al. (2007 ); Datta et al. (2008 ); Yusnita et al. (2008 ); Wang & Zheng (2007 ). For a related zinc(II) complex, see: Cai (2009 ).

Experimental

Crystal data

[Cu(C₁₂H₁₃BrNO)₂]
M_r = 597.83
Monoclinic, P 2₁ /c
a = 9.190 (2) Å
b = 10.960 (2) Å
c = 12.166 (2) Å
β = 109.73 (3)°
V = 1153.5 (4) Å³
Z = 2
Mo Kα radiation
μ = 4.44 mm⁻¹
T = 298 K
0.27 × 0.23 × 0.23 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.381, T_max = 0.429 (expected range = 0.320–0.361)
9709 measured reflections
2636 independent reflections
2003 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.098
S = 1.02
2636 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006606/su2099sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006606/su2099Isup2.hkl

checkCIF report

Comment top

Schiff bases are interesting ligands which form a large number of complexes with metal atoms (Costes et al., 2002; Erxleben, 2001; Lacroix et al., 1996; Odoko et al., 2006; Ali et al., 2006). The author has recently reported on the crystal structure of a zinc(II) complex with the Schiff base (2-morpholin-4-ylethyl)-(1-pyridin-2-ylmethylidene)amine (Cai, 2009). As a continuous of our work in this area, we report here on the crystal structure of the title copper(II) complex (Fig. 1), derived from the Schiff base 4-bromo-2-(cyclopentyliminomethyl)phenol.

In the centrosymmetric title complex the Cu^II atom, is located on an inversion center, and is four-coordinate in a square planar geometry with two nitrogen and two oxygen atoms from two Schiff base ligands. All the coordinate bond lengths are typical and comparable with those in similar copper(II) complexes (Wang et al., 2007; Datta et al., 2008; Yusnita et al., 2008; Wang & Zheng, 2007).

Related literature top

For background on Schiff base complexes, see: Costes et al. (2002); Erxleben (2001); Lacroix et al. (1996); Odoko et al. (2006); Ali et al. (2006). For related copper(II) complexes, see: Wang et al. (2007); Datta et al. (2008); Yusnita et al. (2008); Wang & Zheng (2007). For a related zinc(II) complex, see: Cai (2009).

Experimental top

5-Bromosalicylaldehyde (0.2 mmol, 40.3 mg), cyclopentylamine (0.2 mmol, 17.0 mg), and copper(II) acetate monohydrate (0.1 mmol, 20.0 mg) were mixed in 20 ml of ethanol. The mixture was stirred for 2 h at rt, giving a blue solution. Single-crystals were formed by gradual evaporation of the solution in air after several days.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids [unlabelled atoms are related to the labelled atoms by the symmetry operation -x, 2-y, -z].

Bis[4-bromo-2-(cyclopentyliminomethyl)phenolato]copper(II) top

Crystal data top

[Cu(C₁₂H₁₃BrNO)₂]	F(000) = 598
M_r = 597.83	D_x = 1.721 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.190 (2) Å	Cell parameters from 2505 reflections
b = 10.960 (2) Å	θ = 2.3–25.0°
c = 12.166 (2) Å	µ = 4.44 mm⁻¹
β = 109.73 (3)°	T = 298 K
V = 1153.5 (4) Å³	Block, blue
Z = 2	0.27 × 0.23 × 0.23 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2636 independent reflections
Radiation source: fine-focus sealed tube	2003 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.381, T_max = 0.429	k = −14→14
9709 measured reflections	l = −15→15

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0427P)² + 0.9221P] where P = (F_o² + 2F_c²)/3
2636 reflections	(Δ/σ)_max = 0.001
142 parameters	Δρ_max = 0.93 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Cu(C₁₂H₁₃BrNO)₂]	V = 1153.5 (4) Å³
M_r = 597.83	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.190 (2) Å	µ = 4.44 mm⁻¹
b = 10.960 (2) Å	T = 298 K
c = 12.166 (2) Å	0.27 × 0.23 × 0.23 mm
β = 109.73 (3)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2636 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2003 reflections with I > 2σ(I)
T_min = 0.381, T_max = 0.429	R_int = 0.035
9709 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.02	Δρ_max = 0.93 e Å⁻³
2636 reflections	Δρ_min = −0.42 e Å⁻³
142 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.0000	1.0000	0.0000	0.03400 (16)
Br1	−0.34783 (5)	0.60773 (4)	0.33661 (4)	0.06123 (17)
O1	−0.0883 (3)	1.00623 (19)	0.1197 (2)	0.0446 (6)
N1	0.0534 (3)	0.8203 (2)	0.0328 (2)	0.0341 (6)
C1	−0.1071 (4)	0.7941 (3)	0.1548 (3)	0.0344 (7)
C2	−0.1456 (4)	0.9175 (3)	0.1630 (3)	0.0348 (7)
C3	−0.2475 (4)	0.9435 (3)	0.2236 (3)	0.0435 (8)
H3	−0.2753	1.0242	0.2294	0.052*
C4	−0.3073 (4)	0.8541 (3)	0.2744 (3)	0.0465 (9)
H4	−0.3752	0.8741	0.3136	0.056*
C5	−0.2659 (4)	0.7337 (3)	0.2671 (3)	0.0422 (8)
C6	−0.1676 (4)	0.7034 (3)	0.2090 (3)	0.0391 (7)
H6	−0.1404	0.6222	0.2052	0.047*
C7	−0.0063 (4)	0.7551 (3)	0.0935 (3)	0.0374 (7)
H7	0.0184	0.6726	0.0987	0.045*
C8	0.1560 (4)	0.7602 (3)	−0.0219 (3)	0.0386 (7)
H8	0.1265	0.7915	−0.1019	0.046*
C9	0.3252 (4)	0.7923 (4)	0.0374 (4)	0.0603 (11)
H9A	0.3467	0.8740	0.0163	0.072*
H9B	0.3536	0.7874	0.1216	0.072*
C10	0.4115 (5)	0.6976 (5)	−0.0078 (6)	0.0901 (18)
H10A	0.4543	0.7346	−0.0626	0.108*
H10B	0.4955	0.6632	0.0563	0.108*
C11	0.2977 (5)	0.6002 (4)	−0.0671 (4)	0.0642 (12)
H11A	0.3412	0.5199	−0.0429	0.077*
H11B	0.2696	0.6065	−0.1512	0.077*
C12	0.1586 (5)	0.6206 (3)	−0.0307 (4)	0.0507 (9)
H12A	0.1713	0.5824	0.0438	0.061*
H12B	0.0651	0.5900	−0.0889	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0412 (3)	0.0242 (3)	0.0424 (3)	0.0024 (2)	0.0218 (3)	0.0028 (2)
Br1	0.0702 (3)	0.0547 (3)	0.0720 (3)	−0.0114 (2)	0.0414 (2)	0.0125 (2)
O1	0.0659 (16)	0.0251 (11)	0.0570 (15)	0.0009 (11)	0.0395 (13)	0.0012 (10)
N1	0.0374 (14)	0.0263 (13)	0.0425 (15)	0.0034 (11)	0.0185 (12)	0.0018 (11)
C1	0.0377 (17)	0.0294 (16)	0.0387 (17)	0.0018 (13)	0.0163 (14)	0.0037 (13)
C2	0.0401 (18)	0.0290 (15)	0.0373 (17)	0.0023 (13)	0.0159 (14)	0.0031 (13)
C3	0.056 (2)	0.0336 (17)	0.050 (2)	0.0058 (16)	0.0300 (18)	−0.0006 (16)
C4	0.050 (2)	0.049 (2)	0.049 (2)	0.0019 (17)	0.0287 (18)	0.0009 (17)
C5	0.0443 (19)	0.0424 (19)	0.0442 (19)	−0.0079 (15)	0.0205 (16)	0.0070 (15)
C6	0.0461 (19)	0.0289 (16)	0.0441 (19)	−0.0008 (14)	0.0175 (15)	0.0036 (14)
C7	0.0406 (17)	0.0270 (16)	0.0470 (19)	0.0064 (13)	0.0177 (15)	0.0040 (14)
C8	0.0421 (18)	0.0292 (16)	0.0489 (19)	0.0060 (14)	0.0212 (16)	0.0012 (14)
C9	0.043 (2)	0.056 (2)	0.085 (3)	−0.0012 (19)	0.026 (2)	−0.024 (2)
C10	0.051 (3)	0.082 (3)	0.147 (5)	−0.006 (2)	0.046 (3)	−0.051 (4)
C11	0.066 (3)	0.049 (2)	0.085 (3)	0.012 (2)	0.036 (2)	−0.010 (2)
C12	0.059 (2)	0.0349 (19)	0.064 (2)	0.0030 (17)	0.028 (2)	−0.0058 (17)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.892 (2)	C6—H6	0.9300
Cu1—O1	1.892 (2)	C7—H7	0.9300
Cu1—N1	2.036 (2)	C8—C9	1.518 (5)
Cu1—N1ⁱ	2.036 (2)	C8—C12	1.534 (4)
Br1—C5	1.902 (3)	C8—H8	0.9800
O1—C2	1.299 (4)	C9—C10	1.518 (5)
N1—C7	1.278 (4)	C9—H9A	0.9700
N1—C8	1.480 (4)	C9—H9B	0.9700
C1—C6	1.407 (4)	C10—C11	1.498 (6)
C1—C2	1.411 (4)	C10—H10A	0.9700
C1—C7	1.436 (4)	C10—H10B	0.9700
C2—C3	1.403 (4)	C11—C12	1.504 (6)
C3—C4	1.369 (5)	C11—H11A	0.9700
C3—H3	0.9300	C11—H11B	0.9700
C4—C5	1.385 (5)	C12—H12A	0.9700
C4—H4	0.9300	C12—H12B	0.9700
C5—C6	1.362 (5)

O1ⁱ—Cu1—O1	180.0	N1—C8—C9	112.9 (3)
O1ⁱ—Cu1—N1	88.74 (10)	N1—C8—C12	120.2 (3)
O1—Cu1—N1	91.26 (10)	C9—C8—C12	103.1 (3)
O1ⁱ—Cu1—N1ⁱ	91.26 (10)	N1—C8—H8	106.6
O1—Cu1—N1ⁱ	88.74 (10)	C9—C8—H8	106.6
N1—Cu1—N1ⁱ	180.0	C12—C8—H8	106.6
C2—O1—Cu1	128.5 (2)	C10—C9—C8	104.2 (3)
C7—N1—C8	118.3 (3)	C10—C9—H9A	110.9
C7—N1—Cu1	122.1 (2)	C8—C9—H9A	110.9
C8—N1—Cu1	119.42 (19)	C10—C9—H9B	110.9
C6—C1—C2	119.7 (3)	C8—C9—H9B	110.9
C6—C1—C7	117.4 (3)	H9A—C9—H9B	108.9
C2—C1—C7	122.9 (3)	C11—C10—C9	107.3 (3)
O1—C2—C3	119.7 (3)	C11—C10—H10A	110.3
O1—C2—C1	122.9 (3)	C9—C10—H10A	110.3
C3—C2—C1	117.3 (3)	C11—C10—H10B	110.3
C4—C3—C2	122.3 (3)	C9—C10—H10B	110.3
C4—C3—H3	118.9	H10A—C10—H10B	108.5
C2—C3—H3	118.9	C10—C11—C12	106.1 (3)
C3—C4—C5	119.5 (3)	C10—C11—H11A	110.5
C3—C4—H4	120.3	C12—C11—H11A	110.5
C5—C4—H4	120.3	C10—C11—H11B	110.5
C6—C5—C4	120.7 (3)	C12—C11—H11B	110.5
C6—C5—Br1	119.0 (3)	H11A—C11—H11B	108.7
C4—C5—Br1	120.3 (3)	C11—C12—C8	101.8 (3)
C5—C6—C1	120.5 (3)	C11—C12—H12A	111.4
C5—C6—H6	119.7	C8—C12—H12A	111.4
C1—C6—H6	119.7	C11—C12—H12B	111.4
N1—C7—C1	127.8 (3)	C8—C12—H12B	111.4
N1—C7—H7	116.1	H12A—C12—H12B	109.3
C1—C7—H7	116.1

Symmetry code: (i) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₁₃BrNO)₂]
M_r	597.83
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.190 (2), 10.960 (2), 12.166 (2)
β (°)	109.73 (3)
V (Å³)	1153.5 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.44
Crystal size (mm)	0.27 × 0.23 × 0.23

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.381, 0.429
No. of measured, independent and observed [I > 2σ(I)] reflections	9709, 2636, 2003
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.098, 1.02
No. of reflections	2636
No. of parameters	142
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.42

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The author acknowledges financial support from Jiaying University.

References

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