{4,4′-Dibromo-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}copper(II)

Xie, Q.-F.; Chen, Y.-M.; Huang, M.-L.

doi:10.1107/S1600536809024015

metal-organic compounds

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Volume 65| Part 8| August 2009| Page m903

doi:10.1107/S1600536809024015

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{4,4′-Dibromo-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}copper(II)

Qing-Fan Xie,^a Yan-Min Chen ^a and Miao-Ling Huang ^a ^*

^aDepartment of Chemistry and Science of Life, Quanzhou Normal University, Fujian 362000, People's Republic of China
^*Correspondence e-mail: hml301@163.com

(Received 13 June 2009; accepted 23 June 2009; online 11 July 2009)

In the title compound, [Cu(C₁₆H₁₂Br₂N₂O₂)], the Cu^II atom is coordinated in a slightly distorted square-planar geometry by two O and two N atoms of the tetradentate dianionic 4,4′-dibromo-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolate Schiff base ligand.

Related literature

For background to complexes of Schiff bases, see: Arnold et al. (1998 ); Jabri et al. (1995 ); Jiang et al. (2003 ). For a related structure, see: Feng et al. (2007 ).

Experimental

Crystal data

[Cu(C₁₆H₁₂Br₂N₂O₂)]
M_r = 487.68
Triclinic, $[P \overline 1]$
a = 8.2848 (4) Å
b = 9.6302 (5) Å
c = 10.9984 (6) Å
α = 115.601 (6)°
β = 92.866 (4)°
γ = 101.527 (5)°
V = 766.10 (7) Å³
Z = 2
Mo Kα radiation
μ = 6.65 mm⁻¹
T = 173 K
0.4 × 0.1 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.715, T_max = 1 (expected range = 0.368–0.514)
6303 measured reflections
2641 independent reflections
2128 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.060
S = 1.01
2641 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2003 ); 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/S1600536809024015/tk2481sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024015/tk2481Isup2.hkl

checkCIF report

Comment top

Schiff base complexes continue to attract attention owing to their anti-bacterial, anti-viral and other biological activities (Arnold et al., 1998; Jabri et al., 1995; Jiang et al., 2003). In order to extend the study of these compounds, the title complex (I) was synthesized and its crystal structure determined.

The copper atom in the mononuclear complex, Fig. 1, assumes a N₂O₂ coordination geometry provided by the dinegative, tetradentate Schiff base ligand. The coordination geometry approximates a square planar arrangement. The structure of (I) resembles that of N,N'-ethylene-bis(salicylaldiminato)nickel(II) (Feng et al., 2007).

Related literature top

For background to complexes of Schiff bases, see: Arnold et al. (1998); Jabri et al. (1995); Jiang et al. (2003). For a related structure, see: Feng et al. (2007).

Experimental top

A mixture of N,N'-ethylene-bis(5-bromosalicylaldimine) (0.1 mmol), Cu(NO₃)₂ (0.1 mmol), DMF (10.0 ml), and ethanol (5.0 ml) was sealed in a 40 mL Teflon-lined stainless steel reactor, heated in an oven at 353 K for 72 h, and then slowly cooled to room temperature. The blue crystals were collected.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2003); 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. Molecular structure of (I) showing atom labelling and displacement ellipsoids at the 30% probability level.

{4,4'-Dibromo-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}copper(II) top

Crystal data top

[Cu(C₁₆H₁₂Br₂N₂O₂)]	Z = 2
M_r = 487.68	F(000) = 474
Triclinic, P1	D_x = 2.114 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2848 (4) Å	Cell parameters from 3643 reflections
b = 9.6302 (5) Å	θ = 2.4–32.6°
c = 10.9984 (6) Å	µ = 6.65 mm⁻¹
α = 115.601 (6)°	T = 173 K
β = 92.866 (4)°	Block, blue
γ = 101.527 (5)°	0.4 × 0.1 × 0.1 mm
V = 766.10 (7) Å³

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2641 independent reflections
Radiation source: fine-focus sealed tube	2128 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Rotation method data acquisition using ω and ϕ scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.715, T_max = 1	k = −11→11
6303 measured reflections	l = −13→13

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0298P)²] where P = (F_o² + 2F_c²)/3
2641 reflections	(Δ/σ)_max = 0.005
208 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Cu(C₁₆H₁₂Br₂N₂O₂)]	γ = 101.527 (5)°
M_r = 487.68	V = 766.10 (7) Å³
Triclinic, P1	Z = 2
a = 8.2848 (4) Å	Mo Kα radiation
b = 9.6302 (5) Å	µ = 6.65 mm⁻¹
c = 10.9984 (6) Å	T = 173 K
α = 115.601 (6)°	0.4 × 0.1 × 0.1 mm
β = 92.866 (4)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2641 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2128 reflections with I > 2σ(I)
T_min = 0.715, T_max = 1	R_int = 0.030
6303 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.01	Δρ_max = 0.50 e Å⁻³
2641 reflections	Δρ_min = −0.35 e Å⁻³
208 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	0.98239 (6)	1.20034 (5)	0.06363 (4)	0.02426 (13)
Br1	0.55269 (5)	0.80260 (4)	0.44272 (4)	0.03477 (13)
Br2	1.24837 (5)	1.57593 (5)	−0.37940 (4)	0.03793 (13)
O2	0.9055 (3)	1.2075 (3)	−0.1004 (2)	0.0258 (6)
O1	0.7760 (3)	1.0630 (3)	0.0529 (2)	0.0332 (6)
N2	1.1879 (4)	1.3606 (3)	0.1009 (3)	0.0241 (7)
N1	1.0890 (4)	1.1769 (3)	0.2128 (3)	0.0241 (7)
C16	0.9859 (5)	1.2886 (4)	−0.1568 (4)	0.0250 (8)
C15	0.9173 (5)	1.2616 (4)	−0.2887 (4)	0.0273 (8)
H15A	0.8176	1.1854	−0.3323	0.033*
C14	0.9942 (5)	1.3449 (4)	−0.3533 (4)	0.0272 (9)
H14A	0.9469	1.3238	−0.4399	0.033*
C13	1.1434 (5)	1.4613 (4)	−0.2894 (4)	0.0280 (9)
C12	1.2146 (5)	1.4889 (4)	−0.1645 (4)	0.0278 (9)
H12A	1.3138	1.5666	−0.1229	0.033*
C11	1.1425 (5)	1.4034 (4)	−0.0966 (4)	0.0246 (8)
C10	1.2328 (5)	1.4321 (4)	0.0297 (4)	0.0257 (8)
H10A	1.3328	1.5096	0.0626	0.031*
C5	0.7334 (5)	1.0083 (4)	0.1394 (4)	0.0266 (8)
C4	0.5657 (5)	0.9251 (4)	0.1244 (4)	0.0295 (9)
H4A	0.4890	0.9111	0.0529	0.035*
C3	0.5139 (5)	0.8652 (4)	0.2115 (4)	0.0281 (9)
H3A	0.4029	0.8122	0.1992	0.034*
C2	0.6253 (5)	0.8827 (4)	0.3184 (4)	0.0257 (8)
C1	0.7877 (5)	0.9614 (4)	0.3382 (4)	0.0248 (8)
H1A	0.8613	0.9728	0.4105	0.030*
C6	0.8457 (5)	1.0256 (4)	0.2511 (4)	0.0246 (8)
C7	1.0206 (5)	1.1058 (4)	0.2782 (4)	0.0254 (8)
H7A	1.0876	1.1053	0.3483	0.030*
C8	1.2681 (5)	1.2481 (4)	0.2451 (4)	0.0290 (9)
H8A	1.3272	1.1760	0.1838	0.035*
H8B	1.3095	1.2730	0.3381	0.035*
C9	1.2922 (5)	1.3988 (4)	0.2276 (4)	0.0279 (8)
H9A	1.2599	1.4812	0.3043	0.033*
H9B	1.4083	1.4368	0.2233	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0249 (3)	0.0287 (3)	0.0179 (2)	0.00328 (19)	0.00093 (18)	0.0109 (2)
Br1	0.0388 (3)	0.0389 (2)	0.0343 (2)	0.00736 (19)	0.00758 (18)	0.0242 (2)
Br2	0.0462 (3)	0.0443 (3)	0.0355 (2)	0.0127 (2)	0.00954 (19)	0.0280 (2)
O2	0.0260 (15)	0.0306 (14)	0.0192 (13)	0.0036 (11)	0.0022 (11)	0.0112 (12)
O1	0.0318 (17)	0.0439 (16)	0.0214 (14)	−0.0038 (12)	−0.0038 (11)	0.0190 (13)
N2	0.0292 (18)	0.0242 (16)	0.0174 (16)	0.0055 (13)	0.0008 (13)	0.0087 (14)
N1	0.0229 (18)	0.0279 (17)	0.0207 (17)	0.0058 (13)	0.0009 (13)	0.0107 (14)
C16	0.028 (2)	0.026 (2)	0.022 (2)	0.0113 (17)	0.0062 (16)	0.0087 (17)
C15	0.029 (2)	0.029 (2)	0.022 (2)	0.0089 (17)	0.0008 (16)	0.0101 (17)
C14	0.031 (2)	0.033 (2)	0.021 (2)	0.0151 (18)	0.0038 (16)	0.0125 (18)
C13	0.037 (2)	0.032 (2)	0.027 (2)	0.0167 (18)	0.0134 (18)	0.0190 (18)
C12	0.025 (2)	0.031 (2)	0.025 (2)	0.0058 (17)	0.0052 (16)	0.0112 (18)
C11	0.027 (2)	0.028 (2)	0.0213 (19)	0.0092 (17)	0.0042 (16)	0.0120 (16)
C10	0.027 (2)	0.0228 (19)	0.024 (2)	0.0049 (16)	0.0027 (16)	0.0076 (17)
C5	0.030 (2)	0.026 (2)	0.020 (2)	0.0083 (17)	0.0018 (16)	0.0072 (17)
C4	0.025 (2)	0.038 (2)	0.024 (2)	0.0031 (17)	−0.0012 (16)	0.0156 (18)
C3	0.024 (2)	0.029 (2)	0.028 (2)	0.0043 (17)	0.0057 (17)	0.0107 (18)
C2	0.031 (2)	0.025 (2)	0.023 (2)	0.0081 (17)	0.0071 (17)	0.0116 (17)
C1	0.028 (2)	0.024 (2)	0.021 (2)	0.0073 (16)	0.0009 (16)	0.0083 (16)
C6	0.030 (2)	0.0209 (19)	0.020 (2)	0.0088 (16)	−0.0004 (16)	0.0063 (16)
C7	0.028 (2)	0.028 (2)	0.0187 (19)	0.0094 (17)	−0.0007 (16)	0.0084 (17)
C8	0.022 (2)	0.038 (2)	0.027 (2)	0.0051 (17)	−0.0025 (16)	0.0165 (18)
C9	0.024 (2)	0.032 (2)	0.022 (2)	0.0023 (17)	−0.0020 (16)	0.0096 (17)

Geometric parameters (Å, º) top

Cu1—O1	1.905 (2)	C12—H12A	0.9300
Cu1—O2	1.917 (2)	C11—C10	1.431 (5)
Cu1—N1	1.943 (3)	C10—H10A	0.9300
Cu1—N2	1.945 (3)	C5—C4	1.420 (5)
Br1—C2	1.907 (3)	C5—C6	1.432 (5)
Br2—C13	1.898 (3)	C4—C3	1.362 (5)
O2—C16	1.301 (4)	C4—H4A	0.9300
O1—C5	1.302 (4)	C3—C2	1.385 (5)
N2—C10	1.272 (4)	C3—H3A	0.9300
N2—C9	1.461 (4)	C2—C1	1.361 (5)
N1—C7	1.273 (4)	C1—C6	1.404 (5)
N1—C8	1.459 (4)	C1—H1A	0.9300
C16—C15	1.423 (5)	C6—C7	1.447 (5)
C16—C11	1.432 (5)	C7—H7A	0.9300
C15—C14	1.374 (5)	C8—C9	1.521 (5)
C15—H15A	0.9300	C8—H8A	0.9700
C14—C13	1.399 (5)	C8—H8B	0.9700
C14—H14A	0.9300	C9—H9A	0.9700
C13—C12	1.358 (5)	C9—H9B	0.9700
C12—C11	1.404 (5)

O1—Cu1—O2	91.88 (10)	C11—C10—H10A	117.2
O1—Cu1—N1	92.75 (11)	O1—C5—C4	119.4 (3)
O2—Cu1—N1	170.19 (12)	O1—C5—C6	124.3 (3)
O1—Cu1—N2	171.68 (11)	C4—C5—C6	116.3 (3)
O2—Cu1—N2	92.89 (11)	C3—C4—C5	122.0 (4)
N1—Cu1—N2	83.60 (12)	C3—C4—H4A	119.0
C16—O2—Cu1	127.2 (2)	C5—C4—H4A	119.0
C5—O1—Cu1	127.5 (2)	C4—C3—C2	120.5 (4)
C10—N2—C9	120.6 (3)	C4—C3—H3A	119.8
C10—N2—Cu1	126.9 (3)	C2—C3—H3A	119.8
C9—N2—Cu1	112.5 (2)	C1—C2—C3	120.3 (3)
C7—N1—C8	119.9 (3)	C1—C2—Br1	119.0 (3)
C7—N1—Cu1	127.3 (3)	C3—C2—Br1	120.7 (3)
C8—N1—Cu1	112.8 (2)	C2—C1—C6	120.9 (3)
O2—C16—C15	118.8 (3)	C2—C1—H1A	119.5
O2—C16—C11	124.6 (3)	C6—C1—H1A	119.5
C15—C16—C11	116.6 (3)	C1—C6—C5	119.9 (3)
C14—C15—C16	121.9 (3)	C1—C6—C7	117.5 (3)
C14—C15—H15A	119.1	C5—C6—C7	122.6 (3)
C16—C15—H15A	119.1	N1—C7—C6	124.6 (3)
C15—C14—C13	120.2 (3)	N1—C7—H7A	117.7
C15—C14—H14A	119.9	C6—C7—H7A	117.7
C13—C14—H14A	119.9	N1—C8—C9	105.9 (3)
C12—C13—C14	119.8 (3)	N1—C8—H8A	110.6
C12—C13—Br2	120.3 (3)	C9—C8—H8A	110.6
C14—C13—Br2	119.9 (3)	N1—C8—H8B	110.6
C13—C12—C11	121.8 (3)	C9—C8—H8B	110.6
C13—C12—H12A	119.1	H8A—C8—H8B	108.7
C11—C12—H12A	119.1	N2—C9—C8	107.7 (3)
C12—C11—C16	119.6 (3)	N2—C9—H9A	110.2
C12—C11—C10	117.8 (3)	C8—C9—H9A	110.2
C16—C11—C10	122.5 (3)	N2—C9—H9B	110.2
N2—C10—C11	125.6 (3)	C8—C9—H9B	110.2
N2—C10—H10A	117.2	H9A—C9—H9B	108.5

Experimental details

Crystal data
Chemical formula	[Cu(C₁₆H₁₂Br₂N₂O₂)]
M_r	487.68
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.2848 (4), 9.6302 (5), 10.9984 (6)
α, β, γ (°)	115.601 (6), 92.866 (4), 101.527 (5)
V (Å³)	766.10 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.65
Crystal size (mm)	0.4 × 0.1 × 0.1

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.715, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	6303, 2641, 2128
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.060, 1.01
No. of reflections	2641
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.35

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Education Department Foundation of Fujian Province of China (grant Nos. JA08212 and 2008 F5053).

References

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