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Acta Cryst. (2007). E63, m2271    [ doi:10.1107/S1600536807037798 ]

Azido{2,4-dibromo-6-[2-(diethylamino)ethyliminomethyl]phenolato}copper(II)

K. Li, H. Zhang, X.-N. Wang, J.-Y. Peng and Y.-P. Diao

Abstract top

In the title mononuclear copper(II) complex, [Cu(C13H17Br2N2O)(N3)], the CuII atom is four-coordinated by the phenolate O, imine N and amine N atoms of the Schiff base ligand, and by the terminal N atom of the azide ligand, forming a square-planar geometry.

Comment top

Copper(II) complexes with Schiff base ligands have received much attention in recent years (Hatfield & Bunger, 1969; Gray et al., 1986; Ichikawa et al., 1970). Some of the complexes have been found to have pharmacological and antitumor properties (Adsule et al., 2006). We have recently reported a few transition metal complexes (Diao, Huang et al., 2007; Diao, Shu et al., 2007; Diao, 2007a,b). In order to further develop the coordination chemistry of such copper complexes, we report herein the title new copper(II) compound.

The CuII atom in the mononuclear complex is four-coordinate in a square-planar geometry with one phenolate O, one imine N, and one amine N atoms of one Schiff base ligand and one terminal N atom of an azide ligand (Fig. 1). All the bond values (Table 1) subtended at the metal centres are comparable with the values observed in other Schiff base copper(II) complexes (Hebbachi & Benali-Cherif, 2005; Zhu et al., 2006; Butcher et al., 2003).

Related literature top

For related literature, see: Adsule et al. (2006); Butcher et al. (2003); Diao (2007a,b); Diao, Huang et al. (2007); Diao, Shu et al. (2007); Gray et al. (1986); Hatfield & Bunger (1969); Hebbachi & Benali-Cherif (2005); Ichikawa et al. (1970); Zhu et al. (2006).

Experimental top

3,5-Dibromosalicylaldehyde (0.1 mmol, 18.0 mg), N,N-diethylethane-1,2-diamine (0.1 mmol, 11.6 mg), sodium azide (0.1 mmol, 6.5 mg), and Cu(CH3COO)2·H2O (0.1 mmol, 20.0 mg) were dissolved in a methanol solution (10 ml). The mixture was stirred at room temperature for 30 min to give a blue solution. After keeping the solution in air for 5 days, blue block-like crystals were formed.

Refinement top

H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of the complex with 30% probability level.
Azido{2,4-dibromo-6-[2-(diethylamino)ethyliminomethyl]phenolato}copper(II) top
Crystal data top
[Cu(C13H17Br2N2O)(N3)]F000 = 948
Mr = 482.68Dx = 1.913 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3167 reflections
a = 10.996 (2) Åθ = 2.3–24.3º
b = 11.635 (2) ŵ = 6.08 mm−1
c = 13.330 (3) ÅT = 298 (2) K
β = 100.74 (3)ºBlock, blue
V = 1675.5 (6) Å30.27 × 0.25 × 0.24 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3780 independent reflections
Radiation source: fine-focus sealed tube2586 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.063
T = 298(2) Kθmax = 27.5º
ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −14→14
Tmin = 0.291, Tmax = 0.323k = −14→14
13870 measured reflectionsl = −17→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.101  w = 1/[σ2(Fo2) + (0.0453P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
3780 reflectionsΔρmax = 0.88 e Å−3
201 parametersΔρmin = −0.58 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C13H17Br2N2O)(N3)]V = 1675.5 (6) Å3
Mr = 482.68Z = 4
Monoclinic, P21/cMo Kα
a = 10.996 (2) ŵ = 6.08 mm−1
b = 11.635 (2) ÅT = 298 (2) K
c = 13.330 (3) Å0.27 × 0.25 × 0.24 mm
β = 100.74 (3)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3780 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2586 reflections with I > 2σ(I)
Tmin = 0.291, Tmax = 0.323Rint = 0.063
13870 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042201 parameters
wR(F2) = 0.101H-atom parameters constrained
S = 0.99Δρmax = 0.88 e Å−3
3780 reflectionsΔρmin = −0.58 e Å−3
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 > 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
xyzUiso*/Ueq
Cu1−0.04346 (5)0.67672 (4)0.11117 (4)0.03252 (16)
Br10.28932 (4)0.76477 (4)0.39187 (3)0.04188 (15)
Br20.49306 (5)1.06280 (4)0.13495 (4)0.04974 (17)
O10.0942 (3)0.7338 (2)0.2045 (2)0.0356 (7)
N1−0.0162 (3)0.7771 (3)0.0018 (3)0.0336 (8)
N2−0.2078 (3)0.6380 (3)0.0141 (3)0.0340 (8)
N3−0.0613 (4)0.5441 (3)0.1955 (3)0.0509 (11)
N40.0232 (4)0.5031 (3)0.2546 (3)0.0394 (9)
N50.0983 (4)0.4595 (4)0.3123 (3)0.0570 (12)
C10.1712 (4)0.8663 (3)0.0915 (3)0.0309 (9)
C20.1760 (4)0.8075 (3)0.1863 (3)0.0299 (9)
C30.2798 (4)0.8336 (3)0.2621 (3)0.0297 (9)
C40.3719 (4)0.9071 (3)0.2469 (3)0.0357 (10)
H40.43910.92110.29910.043*
C50.3644 (4)0.9606 (4)0.1531 (3)0.0370 (10)
C60.2656 (4)0.9426 (4)0.0766 (3)0.0357 (10)
H60.26050.98050.01460.043*
C70.0728 (4)0.8491 (3)0.0063 (3)0.0326 (10)
H70.07350.8943−0.05120.039*
C8−0.1089 (4)0.7677 (4)−0.0921 (3)0.0439 (12)
H8A−0.08500.7092−0.13660.053*
H8B−0.11770.8403−0.12840.053*
C9−0.2284 (4)0.7352 (4)−0.0596 (4)0.0431 (12)
H9A−0.26060.8009−0.02800.052*
H9B−0.28910.7132−0.11900.052*
C10−0.1847 (4)0.5282 (4)−0.0367 (4)0.0438 (12)
H10A−0.16570.46950.01560.053*
H10B−0.11170.5381−0.06690.053*
C11−0.2884 (5)0.4838 (5)−0.1187 (4)0.0622 (15)
H11A−0.36200.4743−0.09060.093*
H11B−0.26490.4111−0.14330.093*
H11C−0.30390.5378−0.17400.093*
C12−0.3136 (4)0.6258 (4)0.0673 (4)0.0450 (12)
H12A−0.30440.55450.10560.054*
H12B−0.38910.62040.01660.054*
C13−0.3267 (6)0.7227 (5)0.1388 (4)0.0690 (17)
H13A−0.24950.73420.18490.103*
H13B−0.39000.70410.17700.103*
H13C−0.34900.79170.10030.103*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0324 (3)0.0350 (3)0.0295 (3)−0.0053 (2)0.0041 (2)0.0043 (2)
Br10.0420 (3)0.0507 (3)0.0322 (3)0.0050 (2)0.0049 (2)0.0075 (2)
Br20.0383 (3)0.0558 (3)0.0550 (3)−0.0155 (2)0.0085 (2)0.0046 (2)
O10.0371 (18)0.0375 (16)0.0315 (16)−0.0089 (14)0.0046 (14)0.0042 (13)
N10.034 (2)0.038 (2)0.0279 (19)−0.0047 (17)0.0050 (16)0.0013 (15)
N20.031 (2)0.0337 (19)0.036 (2)−0.0026 (16)0.0028 (16)0.0017 (16)
N30.055 (3)0.046 (2)0.048 (2)−0.014 (2)0.001 (2)0.017 (2)
N40.054 (3)0.034 (2)0.030 (2)−0.007 (2)0.009 (2)0.0006 (17)
N50.064 (3)0.056 (3)0.047 (3)0.008 (2)0.002 (2)0.014 (2)
C10.031 (2)0.033 (2)0.029 (2)−0.0037 (19)0.0085 (19)−0.0008 (18)
C20.034 (2)0.026 (2)0.032 (2)0.0034 (19)0.009 (2)−0.0001 (17)
C30.030 (2)0.032 (2)0.027 (2)0.0051 (18)0.0057 (19)−0.0020 (17)
C40.028 (3)0.041 (2)0.038 (3)−0.001 (2)0.004 (2)−0.007 (2)
C50.032 (3)0.035 (2)0.048 (3)−0.0048 (19)0.015 (2)0.001 (2)
C60.040 (3)0.035 (2)0.033 (2)−0.003 (2)0.008 (2)0.0016 (19)
C70.039 (3)0.033 (2)0.026 (2)−0.003 (2)0.0077 (19)0.0026 (17)
C80.042 (3)0.054 (3)0.032 (3)−0.009 (2)−0.003 (2)0.008 (2)
C90.034 (3)0.044 (3)0.048 (3)−0.002 (2)−0.001 (2)0.008 (2)
C100.035 (3)0.044 (3)0.050 (3)0.005 (2)0.001 (2)0.000 (2)
C110.056 (4)0.062 (3)0.062 (4)0.005 (3)−0.005 (3)−0.022 (3)
C120.032 (3)0.055 (3)0.049 (3)−0.004 (2)0.010 (2)−0.002 (2)
C130.067 (4)0.091 (4)0.055 (4)0.005 (3)0.025 (3)−0.008 (3)
Geometric parameters (Å, °) top
Cu1—O11.892 (3)C5—C61.360 (6)
Cu1—N11.934 (3)C6—H60.9300
Cu1—N31.940 (4)C7—H70.9300
Cu1—N22.066 (4)C8—C91.507 (6)
Br1—C31.891 (4)C8—H8A0.9700
Br2—C51.898 (4)C8—H8B0.9700
O1—C21.298 (5)C9—H9A0.9700
N1—C71.281 (5)C9—H9B0.9700
N1—C81.464 (5)C10—C111.515 (6)
N2—C121.478 (5)C10—H10A0.9700
N2—C91.487 (6)C10—H10B0.9700
N2—C101.490 (6)C11—H11A0.9600
N3—N41.199 (5)C11—H11B0.9600
N4—N51.138 (5)C11—H11C0.9600
C1—C61.408 (6)C12—C131.500 (7)
C1—C21.429 (5)C12—H12A0.9700
C1—C71.430 (6)C12—H12B0.9700
C2—C31.410 (6)C13—H13A0.9600
C3—C41.370 (6)C13—H13B0.9600
C4—C51.384 (6)C13—H13C0.9600
C4—H40.9300
O1—Cu1—N193.78 (14)C1—C7—H7117.1
O1—Cu1—N393.04 (15)N1—C8—C9106.2 (4)
N1—Cu1—N3164.42 (16)N1—C8—H8A110.5
O1—Cu1—N2170.90 (14)C9—C8—H8A110.5
N1—Cu1—N284.26 (15)N1—C8—H8B110.5
N3—Cu1—N291.08 (16)C9—C8—H8B110.5
C2—O1—Cu1127.3 (3)H8A—C8—H8B108.7
C7—N1—C8119.5 (4)N2—C9—C8110.3 (4)
C7—N1—Cu1125.8 (3)N2—C9—H9A109.6
C8—N1—Cu1114.7 (3)C8—C9—H9A109.6
C12—N2—C9110.7 (3)N2—C9—H9B109.6
C12—N2—C10110.6 (3)C8—C9—H9B109.6
C9—N2—C10111.7 (3)H9A—C9—H9B108.1
C12—N2—Cu1113.3 (3)N2—C10—C11116.8 (4)
C9—N2—Cu1104.8 (3)N2—C10—H10A108.1
C10—N2—Cu1105.6 (3)C11—C10—H10A108.1
N4—N3—Cu1123.2 (3)N2—C10—H10B108.1
N5—N4—N3175.8 (5)C11—C10—H10B108.1
C6—C1—C2121.3 (4)H10A—C10—H10B107.3
C6—C1—C7116.4 (4)C10—C11—H11A109.5
C2—C1—C7122.3 (4)C10—C11—H11B109.5
O1—C2—C3120.3 (4)H11A—C11—H11B109.5
O1—C2—C1124.7 (4)C10—C11—H11C109.5
C3—C2—C1115.0 (4)H11A—C11—H11C109.5
C4—C3—C2123.4 (4)H11B—C11—H11C109.5
C4—C3—Br1118.9 (3)N2—C12—C13114.2 (4)
C2—C3—Br1117.6 (3)N2—C12—H12A108.7
C3—C4—C5119.5 (4)C13—C12—H12A108.7
C3—C4—H4120.2N2—C12—H12B108.7
C5—C4—H4120.2C13—C12—H12B108.7
C6—C5—C4120.9 (4)H12A—C12—H12B107.6
C6—C5—Br2120.7 (3)C12—C13—H13A109.5
C4—C5—Br2118.4 (3)C12—C13—H13B109.5
C5—C6—C1119.9 (4)H13A—C13—H13B109.5
C5—C6—H6120.1C12—C13—H13C109.5
C1—C6—H6120.1H13A—C13—H13C109.5
N1—C7—C1125.9 (4)H13B—C13—H13C109.5
N1—C7—H7117.1
Selected geometric parameters (Å, °) top
Cu1—O11.892 (3)Cu1—N22.066 (4)
Cu1—N11.934 (3)Br1—C31.891 (4)
Cu1—N31.940 (4)Br2—C51.898 (4)
O1—Cu1—N193.78 (14)O1—Cu1—N2170.90 (14)
O1—Cu1—N393.04 (15)N1—Cu1—N284.26 (15)
N1—Cu1—N3164.42 (16)N3—Cu1—N291.08 (16)
Acknowledgements top

This project was financially supported by a research grant from Liaoning Normal University.

references
References top

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