Bis[2-(cyclo­hexyl­imino­meth­yl)-5-methoxy­phenolato]copper(II)

Miao, J.-Y.

doi:10.1107/S1600536809051629

metal-organic compounds

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Volume 66| Part 1| January 2010| Page m14

doi:10.1107/S1600536809051629

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Bis[2-(cyclohexyliminomethyl)-5-methoxyphenolato]copper(II)

Jian-Ying Miao ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721007, People's Republic of China
^*Correspondence e-mail: jianying_miao@163.com

(Received 30 November 2009; accepted 30 November 2009; online 4 December 2009)

In the title centrosymmetric mononuclear complex, [Cu(C₁₄H₁₈NO₂)₂], the Cu^II ion, lying on an inversion centre, is four-coordinated by two imine N and two phenolate O atoms from two Schiff base ligands, forming a slightly distorted square-planar geometry.

Related literature

For general background to copper complexes, see: Collinson & Fenton (1996 ); Hossain et al. (1996 ); Tarafder et al. (2002 ); Musie et al. (2003 ); García-Raso et al. (2003 ); Reddy et al. (2000 ); Ray et al. (2003 ); Arnold et al. (2003 ); Raptopoulou et al. (1998 ). For related structures, see: Miao (2005 , 2006 ); Wang (2007 ); Zhang (2004 ); Akitsu & Einaga (2004 ); Bluhm et al. (2003 ); Castillo et al. (2003 ); Lacroix et al. (2004 ).

Experimental

Crystal data

[Cu(C₁₄H₁₈NO₂)₂]
M_r = 528.13
Monoclinic, P 2₁ /c
a = 6.4557 (10) Å
b = 11.5170 (17) Å
c = 17.074 (3) Å
β = 99.138 (2)°
V = 1253.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.91 mm⁻¹
T = 298 K
0.23 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.818, T_max = 0.839
6860 measured reflections
2727 independent reflections
2232 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.080
S = 1.04
2727 reflections
161 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); 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/S1600536809051629/ci2979sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051629/ci2979Isup2.hkl

checkCIF report

Comment top

In the last few years there has been a burgeoning effort to identify the biological activities of copper, primarily through techniques associated with the interface of biology/biochemistry/coordination chemistry (Collinson & Fenton, 1996; Hossain et al., 1996; Tarafder et al., 2002). It appears that the biological role of copper is primarily in redox reactions and as a biological catalyst, although much remains to be understood (Musie et al., 2003; García-Raso et al., 2003). An extensive effort has been made to prepare and characterize a variety of copper(II) coordination complexes in an attempt to model the physical and chemical behaviour of copper-containing enzymes (Reddy et al., 2000). The peculiarity of copper lies in its ability to form complexes with coordination number four, five or six (Ray et al., 2003; Arnold et al., 2003; Raptopoulou et al., 1998). As an extension of the work on the structural characterization of such complexes (Miao, 2005, 2006), the crystal structure of the title new mononuclear copper(II) compound, is reported here.

The compound is a centrosymmetric mononuclear copper(II) complex, as shown in Fig. 1. The Cu^II ion, lying on an inversion centre, is four-coordinated by two imine N and two phenolate O atoms from two Schiff base ligands, forming a square-planar geometry. The Cu—O and Cu—N bond lengths are comparable with those reported in similar structures (Wang, 2007; Zhang, 2004; Akitsu & Einaga, 2004; Bluhm et al., 2003; Castillo et al., 2003; Lacroix et al., 2004). Both cyclohexane rings adopt chair conformations.

Related literature top

For general background to copper complexes, see: Collinson & Fenton (1996); Hossain et al. (1996); Tarafder et al. (2002); Musie et al. (2003); García-Raso et al. (2003); Reddy et al. (2000); Ray et al. (2003); Arnold et al. (2003); Raptopoulou et al. (1998). For related structures, see: Miao (2005, 2006); Wang (2007); Zhang (2004); Akitsu & Einaga (2004); Bluhm et al. (2003); Castillo et al. (2003); Lacroix et al. (2004).

Experimental top

4-Methoxysalicylaldehyde (1 mmol, 152 mg), cyclohexylamine (1 mmol, 99 mg) and Cu(CH₃COO)₂.H₂O (0.5 mmol, 100 mg) were dissolved in methanol (50 ml). The mixture was stirred at room temperature for 1 h to give a blue solution. The resulting solution was kept in air for 5 d, and block blue crystals were formed.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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% displacement ellipsoids (arbitrary spheres for the H atoms). Unlabelled atoms are at the symmetry position (-x, -y, -z).

Bis[2-(cyclohexyliminomethyl)-5-methoxyphenolato]copper(II) top

Crystal data top

[Cu(C₁₄H₁₈NO₂)₂]	F(000) = 558
M_r = 528.13	D_x = 1.399 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2706 reflections
a = 6.4557 (10) Å	θ = 2.4–28.7°
b = 11.5170 (17) Å	µ = 0.91 mm⁻¹
c = 17.074 (3) Å	T = 298 K
β = 99.138 (2)°	Block, blue
V = 1253.4 (3) Å³	0.23 × 0.20 × 0.20 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2727 independent reflections
Radiation source: fine-focus sealed tube	2232 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→8
T_min = 0.818, T_max = 0.839	k = −14→14
6860 measured reflections	l = −17→21

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0393P)² + 0.3443P] where P = (F_o² + 2F_c²)/3
2727 reflections	(Δ/σ)_max = 0.001
161 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Cu(C₁₄H₁₈NO₂)₂]	V = 1253.4 (3) Å³
M_r = 528.13	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.4557 (10) Å	µ = 0.91 mm⁻¹
b = 11.5170 (17) Å	T = 298 K
c = 17.074 (3) Å	0.23 × 0.20 × 0.20 mm
β = 99.138 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2727 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2232 reflections with I > 2σ(I)
T_min = 0.818, T_max = 0.839	R_int = 0.021
6860 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.04	Δρ_max = 0.28 e Å⁻³
2727 reflections	Δρ_min = −0.25 e Å⁻³
161 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	0.0000	0.0000	0.0000	0.02741 (11)
N1	0.2825 (2)	−0.05099 (13)	0.05759 (8)	0.0279 (3)
O1	−0.02292 (18)	0.11030 (12)	0.08083 (8)	0.0369 (3)
O2	0.2183 (2)	0.44832 (13)	0.22866 (8)	0.0435 (3)
C1	0.3444 (3)	0.13149 (15)	0.12935 (10)	0.0293 (4)
C2	0.1333 (3)	0.17066 (15)	0.11880 (10)	0.0290 (4)
C3	0.0893 (3)	0.27716 (16)	0.15350 (11)	0.0324 (4)
H3	−0.0488	0.3025	0.1492	0.039*
C4	0.2490 (3)	0.34426 (15)	0.19372 (10)	0.0321 (4)
C5	0.4579 (3)	0.30770 (17)	0.20160 (12)	0.0377 (4)
H5	0.5654	0.3543	0.2271	0.045*
C6	0.5013 (3)	0.20248 (16)	0.17120 (11)	0.0350 (4)
H6	0.6396	0.1769	0.1784	0.042*
C7	0.4013 (3)	0.01873 (15)	0.10362 (11)	0.0314 (4)
H7	0.5373	−0.0064	0.1220	0.038*
C8	0.3570 (3)	−0.17037 (15)	0.04404 (11)	0.0292 (4)
H8	0.3409	−0.1818	−0.0135	0.035*
C9	0.5849 (3)	−0.19822 (16)	0.07803 (12)	0.0344 (4)
H9A	0.6775	−0.1459	0.0555	0.041*
H9B	0.6075	−0.1871	0.1351	0.041*
C10	0.6355 (3)	−0.32350 (17)	0.05889 (14)	0.0425 (5)
H10A	0.7792	−0.3409	0.0820	0.051*
H10B	0.6229	−0.3327	0.0019	0.051*
C11	0.4882 (3)	−0.40877 (17)	0.09089 (14)	0.0448 (5)
H11A	0.5208	−0.4873	0.0763	0.054*
H11B	0.5082	−0.4041	0.1483	0.054*
C12	0.2621 (3)	−0.38098 (17)	0.05739 (14)	0.0455 (5)
H12A	0.1699	−0.4333	0.0801	0.055*
H12B	0.2392	−0.3927	0.0004	0.055*
C13	0.2090 (3)	−0.25579 (16)	0.07562 (13)	0.0389 (4)
H13A	0.2194	−0.2461	0.1325	0.047*
H13B	0.0656	−0.2391	0.0517	0.047*
C14	0.0085 (4)	0.48443 (19)	0.23134 (17)	0.0591 (7)
H14A	−0.0676	0.4892	0.1784	0.089*
H14B	0.0100	0.5592	0.2562	0.089*
H14C	−0.0583	0.4292	0.2612	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02394 (16)	0.02709 (17)	0.02975 (17)	0.00081 (12)	−0.00020 (11)	−0.00354 (12)
N1	0.0262 (7)	0.0262 (7)	0.0306 (8)	0.0021 (6)	0.0025 (6)	0.0001 (6)
O1	0.0262 (6)	0.0415 (7)	0.0409 (7)	0.0005 (5)	−0.0011 (5)	−0.0141 (6)
O2	0.0426 (8)	0.0368 (8)	0.0501 (8)	−0.0028 (6)	0.0043 (6)	−0.0145 (7)
C1	0.0277 (9)	0.0301 (9)	0.0289 (9)	−0.0006 (7)	0.0011 (7)	−0.0003 (7)
C2	0.0281 (9)	0.0321 (9)	0.0260 (8)	−0.0018 (7)	0.0018 (7)	0.0001 (7)
C3	0.0274 (9)	0.0356 (10)	0.0335 (9)	0.0023 (7)	0.0024 (7)	−0.0039 (8)
C4	0.0396 (10)	0.0278 (9)	0.0287 (9)	−0.0018 (8)	0.0045 (8)	−0.0017 (7)
C5	0.0327 (10)	0.0374 (11)	0.0412 (11)	−0.0090 (8)	−0.0001 (8)	−0.0053 (9)
C6	0.0269 (9)	0.0371 (10)	0.0393 (10)	−0.0012 (8)	0.0005 (7)	−0.0015 (8)
C7	0.0251 (9)	0.0355 (10)	0.0325 (9)	0.0015 (7)	0.0014 (7)	0.0025 (7)
C8	0.0275 (9)	0.0278 (9)	0.0322 (9)	0.0027 (7)	0.0040 (7)	0.0009 (7)
C9	0.0280 (9)	0.0311 (10)	0.0439 (11)	0.0013 (7)	0.0047 (8)	0.0026 (8)
C10	0.0333 (10)	0.0361 (11)	0.0592 (13)	0.0076 (8)	0.0107 (9)	0.0050 (9)
C11	0.0474 (12)	0.0291 (10)	0.0588 (13)	0.0049 (9)	0.0115 (10)	0.0069 (9)
C12	0.0433 (11)	0.0317 (10)	0.0634 (14)	−0.0039 (9)	0.0143 (10)	0.0029 (10)
C13	0.0297 (9)	0.0347 (10)	0.0537 (12)	−0.0009 (8)	0.0111 (8)	0.0024 (9)
C14	0.0502 (13)	0.0549 (15)	0.0724 (17)	0.0048 (11)	0.0106 (12)	−0.0306 (12)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.8987 (12)	C8—C9	1.527 (2)
Cu1—O1	1.8987 (12)	C8—C13	1.528 (2)
Cu1—N1ⁱ	2.0169 (14)	C8—H8	0.98
Cu1—N1	2.0169 (14)	C9—C10	1.526 (3)
N1—C7	1.288 (2)	C9—H9A	0.97
N1—C8	1.487 (2)	C9—H9B	0.97
O1—C2	1.309 (2)	C10—C11	1.527 (3)
O2—C4	1.367 (2)	C10—H10A	0.97
O2—C14	1.424 (3)	C10—H10B	0.97
C1—C6	1.406 (2)	C11—C12	1.515 (3)
C1—C2	1.420 (2)	C11—H11A	0.97
C1—C7	1.437 (2)	C11—H11B	0.97
C2—C3	1.411 (2)	C12—C13	1.525 (3)
C3—C4	1.381 (2)	C12—H12A	0.97
C3—H3	0.93	C12—H12B	0.97
C4—C5	1.399 (3)	C13—H13A	0.97
C5—C6	1.365 (3)	C13—H13B	0.97
C5—H5	0.93	C14—H14A	0.96
C6—H6	0.93	C14—H14B	0.96
C7—H7	0.93	C14—H14C	0.96

O1ⁱ—Cu1—O1	180.00 (10)	C13—C8—H8	107.1
O1ⁱ—Cu1—N1ⁱ	90.53 (5)	C10—C9—C8	110.06 (15)
O1—Cu1—N1ⁱ	89.47 (5)	C10—C9—H9A	109.6
O1ⁱ—Cu1—N1	89.47 (5)	C8—C9—H9A	109.6
O1—Cu1—N1	90.53 (5)	C10—C9—H9B	109.6
N1ⁱ—Cu1—N1	180.00 (11)	C8—C9—H9B	109.6
C7—N1—C8	119.69 (15)	H9A—C9—H9B	108.2
C7—N1—Cu1	121.37 (12)	C9—C10—C11	111.40 (16)
C8—N1—Cu1	118.90 (11)	C9—C10—H10A	109.3
C2—O1—Cu1	124.93 (11)	C11—C10—H10A	109.3
C4—O2—C14	118.32 (15)	C9—C10—H10B	109.3
C6—C1—C2	118.65 (16)	C11—C10—H10B	109.3
C6—C1—C7	118.84 (16)	H10A—C10—H10B	108.0
C2—C1—C7	122.36 (16)	C12—C11—C10	110.27 (17)
O1—C2—C3	118.64 (15)	C12—C11—H11A	109.6
O1—C2—C1	122.87 (16)	C10—C11—H11A	109.6
C3—C2—C1	118.44 (16)	C12—C11—H11B	109.6
C4—C3—C2	120.76 (16)	C10—C11—H11B	109.6
C4—C3—H3	119.6	H11A—C11—H11B	108.1
C2—C3—H3	119.6	C11—C12—C13	110.90 (17)
O2—C4—C3	124.00 (17)	C11—C12—H12A	109.5
O2—C4—C5	115.23 (16)	C13—C12—H12A	109.5
C3—C4—C5	120.77 (17)	C11—C12—H12B	109.5
C6—C5—C4	118.93 (17)	C13—C12—H12B	109.5
C6—C5—H5	120.5	H12A—C12—H12B	108.0
C4—C5—H5	120.5	C12—C13—C8	111.31 (15)
C5—C6—C1	122.33 (17)	C12—C13—H13A	109.4
C5—C6—H6	118.8	C8—C13—H13A	109.4
C1—C6—H6	118.8	C12—C13—H13B	109.4
N1—C7—C1	126.40 (17)	C8—C13—H13B	109.4
N1—C7—H7	116.8	H13A—C13—H13B	108.0
C1—C7—H7	116.8	O2—C14—H14A	109.5
N1—C8—C9	116.81 (14)	O2—C14—H14B	109.5
N1—C8—C13	107.74 (13)	H14A—C14—H14B	109.5
C9—C8—C13	110.43 (15)	O2—C14—H14C	109.5
N1—C8—H8	107.1	H14A—C14—H14C	109.5
C9—C8—H8	107.1	H14B—C14—H14C	109.5

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₄H₁₈NO₂)₂]
M_r	528.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	6.4557 (10), 11.5170 (17), 17.074 (3)
β (°)	99.138 (2)
V (Å³)	1253.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.23 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.818, 0.839
No. of measured, independent and observed [I > 2σ(I)] reflections	6860, 2727, 2232
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.080, 1.04
No. of reflections	2727
No. of parameters	161
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.25

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The author acknowledges Baoji University of Arts and Sciences for funding this study (grant No. ZK0831).

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