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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037798/at2360sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037798/at2360Isup2.hkl
Contains datablock I

CCDC reference: 660054

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.041
  • wR factor = 0.101
  • Data-to-parameter ratio = 18.8

checkCIF/PLATON results

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Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.72 PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. Br2 .. 3.42 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact Br1 .. C7 .. 3.33 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.719 Tmax scaled 0.232 Tmin scaled 0.209 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.20
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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).

Structure description 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).

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).

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)]F(000) = 948
Mr = 482.68Dx = 1.913 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3167 reflections
a = 10.996 (2) Åθ = 2.3–24.3°
b = 11.635 (2) ŵ = 6.08 mm1
c = 13.330 (3) ÅT = 298 K
β = 100.74 (3)°Block, 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)
Graphite monochromatorRint = 0.063
ω scansθmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1414
Tmin = 0.291, Tmax = 0.323k = 1414
13870 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0453P)2]
where P = (Fo2 + 2Fc2)/3
3780 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.88 e Å3
0 restraintsΔρmin = 0.58 e Å3
Crystal data top
[Cu(C13H17Br2N2O)(N3)]V = 1675.5 (6) Å3
Mr = 482.68Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.996 (2) ŵ = 6.08 mm1
b = 11.635 (2) ÅT = 298 K
c = 13.330 (3) Å0.27 × 0.25 × 0.24 mm
β = 100.74 (3)°
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)] = 0.0420 restraints
wR(F2) = 0.101H-atom parameters constrained
S = 0.99Δρmax = 0.88 e Å3
3780 reflectionsΔρmin = 0.58 e Å3
201 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
xyzUiso*/Ueq
Cu10.04346 (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)
N10.0162 (3)0.7771 (3)0.0018 (3)0.0336 (8)
N20.2078 (3)0.6380 (3)0.0141 (3)0.0340 (8)
N30.0613 (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)
H70.07350.89430.05120.039*
C80.1089 (4)0.7677 (4)0.0921 (3)0.0439 (12)
H8A0.08500.70920.13660.053*
H8B0.11770.84030.12840.053*
C90.2284 (4)0.7352 (4)0.0596 (4)0.0431 (12)
H9A0.26060.80090.02800.052*
H9B0.28910.71320.11900.052*
C100.1847 (4)0.5282 (4)0.0367 (4)0.0438 (12)
H10A0.16570.46950.01560.053*
H10B0.11170.53810.06690.053*
C110.2884 (5)0.4838 (5)0.1187 (4)0.0622 (15)
H11A0.36200.47430.09060.093*
H11B0.26490.41110.14330.093*
H11C0.30390.53780.17400.093*
C120.3136 (4)0.6258 (4)0.0673 (4)0.0450 (12)
H12A0.30440.55450.10560.054*
H12B0.38910.62040.01660.054*
C130.3267 (6)0.7227 (5)0.1388 (4)0.0690 (17)
H13A0.24950.73420.18490.103*
H13B0.39000.70410.17700.103*
H13C0.34900.79170.10030.103*
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, º) 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

Experimental details

Crystal data
Chemical formula[Cu(C13H17Br2N2O)(N3)]
Mr482.68
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)10.996 (2), 11.635 (2), 13.330 (3)
β (°) 100.74 (3)
V3)1675.5 (6)
Z4
Radiation typeMo Kα
µ (mm1)6.08
Crystal size (mm)0.27 × 0.25 × 0.24
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.291, 0.323
No. of measured, independent and
observed [I > 2σ(I)] reflections
13870, 3780, 2586
Rint0.063
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.101, 0.99
No. of reflections3780
No. of parameters201
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.88, 0.58

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.

Selected geometric parameters (Å, º) 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)
 

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