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Acta Cryst. (2008). E64, m687    [ doi:10.1107/S1600536808010404 ]

{4-Bromo-2-[2-(isopropylamino)ethyliminomethyl]phenolato}thiocyanatocopper(II)

J.-Y. Ma and Y.-T. He

Abstract top

In the title mononuclear Schiff base copper(II) complex, [Cu(C12H16BrN2O)(NCS)], the CuII ion is coordinated by two N atoms and one O atom from a Schiff base ligand, and by one N atom from a thiocyanate anion, giving a square-planar geometry. There are long-range interactions between the Cu atom and S [3.151 (5) Å] and Br [3.929 (5) Å] atoms above and below the square plane.

Comment top

Recently, we have reported some metal complexes derived from the Schiff base ligands (Ma, Lv et al., 2006; Ma, Gu et al., 2006; Ma, Wu et al., 2006; Ma et al., 2005). As part of a further investigation of the structures of such complexes, the title mononuclear copper(II) complex, is reported in this paper.

In the complex the Cu atom is coordinated by two nitrogen atoms and one oxygen atom from a Schiff base ligand, and by one nitrogen atom from a thiocyanate anion, giving a square planar geometry (Fig. 1). There exist long range interactions between the Cu and S (3.151 (5) Å; symmetry code: 1 + x, y, z) and Br (3.929 (5) Å; symmetry code: 1 - x, - y, 1 - z) atoms above and below the square plane. All the bond lengths and angles (Table 1) related to the Cu atom in the complex are within normal ranges. The four coordinating atoms around the Cu centre are approximately coplanar, giving a square-planar geometry with an average deviation of 0.047 (4) Å; the Cu atom lies 0.089 (2) Å above this plane. The C8—C9—N2—C10 torsion angle is 2.0 (3)°.

Related literature top

For related literature, see: Ma et al. (2005); Ma, Gu, Guo et al. (2006); Ma, Lv et al. (2006); Ma, Wu et al. (2006).

Experimental top

N-Isopropylethane-1,2-diamine (0.5 mmol, 51.0 mg) and 5-bromosalicylaldehyde (0.5 mmol, 100.5 mg) were dissolved in methanol (30 ml). The mixture was stirred for 1 h to obtain a clear yellow solution. To the solution was added with stirring a methanol solution (20 ml) of copper(II) acetate (0.5 mmol, 99.6 mg) and a methanol solution (10 ml) of ammonium thiocyanate (0.5 mmol, 38.0 mg). After keeping the resulting solution in air for a few days, blue block-shaped crystals were formed.

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H = 0.93-0.97 Å, N—H = 0.91 Å, and with Uĩso~(H) = 1.2U~eq~(C,N) and 1.5U~eq~(methyl C).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure at the 30% probability level ellipsoids.
{4-Bromo-2-[2-(isopropylamino)ethyliminomethyl]phenolato}thiocyanatocopper(II) top
Crystal data top
[Cu(C12H16BrN2O)(NCS)]F000 = 812
Mr = 405.80Dx = 1.680 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1880 reflections
a = 6.161 (2) Åθ = 2.5–24.3º
b = 20.223 (3) ŵ = 3.98 mm−1
c = 12.930 (3) ÅT = 298 (2) K
β = 95.332 (5)ºBlock, blue
V = 1604.0 (7) Å30.40 × 0.38 × 0.37 mm
Z = 4
Data collection top
Bruker SMART 1000
diffractometer		3474 independent reflections
Radiation source: fine-focus sealed tube2126 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.076
T = 298(2) Kθmax = 27.0º
ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −7→7
Tmin = 0.299, Tmax = 0.321k = −25→25
11914 measured reflectionsl = −16→16
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)] = 0.055H-atom parameters constrained
wR(F2) = 0.153  w = 1/[σ2(Fo2) + (0.0682P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
3474 reflectionsΔρmax = 0.81 e Å−3
183 parametersΔρmin = −0.49 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C12H16BrN2O)(NCS)]V = 1604.0 (7) Å3
Mr = 405.80Z = 4
Monoclinic, P21/nMo Kα
a = 6.161 (2) ŵ = 3.98 mm−1
b = 20.223 (3) ÅT = 298 (2) K
c = 12.930 (3) Å0.40 × 0.38 × 0.37 mm
β = 95.332 (5)º
Data collection top
Bruker SMART 1000
diffractometer		3474 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2126 reflections with I > 2σ(I)
Tmin = 0.299, Tmax = 0.321Rint = 0.076
11914 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.055183 parameters
wR(F2) = 0.153H-atom parameters constrained
S = 1.01Δρmax = 0.81 e Å−3
3474 reflectionsΔρmin = −0.49 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 > 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
Cu10.26493 (10)0.20760 (3)0.47898 (5)0.0450 (2)
N10.5364 (7)0.1721 (2)0.5425 (3)0.0408 (10)
N20.3292 (7)0.2854 (2)0.5819 (4)0.0534 (12)
H2A0.26640.27290.63970.064*
N3−0.0164 (8)0.2425 (3)0.4201 (4)0.0616 (14)
O10.2003 (6)0.1286 (2)0.4022 (3)0.0551 (10)
S1−0.4273 (2)0.25260 (9)0.31058 (11)0.0566 (4)
Br10.80195 (10)−0.08910 (3)0.28530 (5)0.0677 (3)
C10.6219 (9)−0.0194 (3)0.3274 (4)0.0475 (13)
C20.6939 (9)0.0269 (3)0.3994 (4)0.0466 (13)
H20.83640.02450.42990.056*
C30.5578 (8)0.0781 (2)0.4285 (4)0.0382 (12)
C40.3387 (8)0.0829 (3)0.3822 (4)0.0418 (12)
C50.2699 (9)0.0321 (3)0.3099 (4)0.0532 (15)
H50.12700.03260.27950.064*
C60.4065 (10)−0.0175 (3)0.2836 (5)0.0552 (15)
H60.3554−0.04990.23650.066*
C70.6414 (9)0.1221 (3)0.5099 (4)0.0436 (12)
H70.78080.11400.54130.052*
C80.6326 (9)0.2117 (3)0.6316 (4)0.0544 (15)
H8A0.79020.20770.63760.065*
H8B0.58010.19570.69550.065*
C90.5675 (9)0.2829 (3)0.6140 (4)0.0536 (15)
H9A0.60060.30810.67730.064*
H9B0.64780.30190.56020.064*
C100.2371 (15)0.3525 (4)0.5575 (6)0.092 (2)
H100.08180.34470.53760.111*
C110.242 (2)0.3952 (5)0.6475 (9)0.150 (4)
H11A0.21220.36970.70720.225*
H11B0.13280.42900.63540.225*
H11C0.38280.41540.65960.225*
C120.319 (2)0.3811 (5)0.4651 (7)0.152 (5)
H12A0.22460.41650.43960.228*
H12B0.32210.34770.41250.228*
H12C0.46330.39790.48240.228*
C13−0.1851 (9)0.2472 (3)0.3741 (4)0.0457 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0348 (4)0.0592 (5)0.0396 (4)0.0019 (3)−0.0042 (3)−0.0043 (3)
N10.038 (2)0.048 (3)0.035 (2)−0.006 (2)−0.0057 (18)0.002 (2)
N20.051 (3)0.066 (3)0.044 (3)0.010 (2)0.007 (2)−0.005 (2)
N30.042 (3)0.079 (4)0.061 (3)0.011 (3)−0.008 (2)−0.015 (3)
O10.036 (2)0.066 (3)0.061 (3)0.0002 (19)−0.0087 (17)−0.011 (2)
S10.0407 (8)0.0800 (11)0.0466 (8)−0.0024 (8)−0.0086 (6)0.0161 (8)
Br10.0639 (5)0.0571 (4)0.0838 (5)−0.0015 (3)0.0157 (4)−0.0128 (3)
C10.043 (3)0.045 (3)0.055 (3)−0.004 (3)0.007 (3)0.000 (3)
C20.043 (3)0.046 (3)0.050 (3)−0.002 (3)−0.001 (2)0.007 (3)
C30.039 (3)0.038 (3)0.037 (3)−0.004 (2)0.000 (2)0.005 (2)
C40.037 (3)0.046 (3)0.041 (3)−0.006 (2)−0.001 (2)0.004 (2)
C50.040 (3)0.062 (4)0.054 (4)−0.009 (3)−0.011 (3)−0.007 (3)
C60.058 (4)0.052 (4)0.054 (4)−0.013 (3)0.001 (3)−0.007 (3)
C70.038 (3)0.048 (3)0.044 (3)0.001 (3)−0.003 (2)0.015 (3)
C80.049 (3)0.063 (4)0.048 (3)−0.006 (3)−0.013 (3)−0.009 (3)
C90.056 (4)0.057 (4)0.049 (3)−0.002 (3)0.006 (3)−0.014 (3)
C100.121 (7)0.082 (5)0.073 (5)0.032 (5)0.002 (5)−0.017 (4)
C110.248 (14)0.083 (7)0.124 (9)0.029 (7)0.039 (9)−0.018 (6)
C120.280 (15)0.099 (7)0.084 (6)0.089 (9)0.055 (8)0.028 (6)
C130.046 (3)0.049 (3)0.043 (3)0.002 (3)0.007 (3)0.002 (3)
Geometric parameters (Å, °) top
Cu1—O11.903 (4)C4—C51.426 (7)
Cu1—N11.932 (4)C5—C61.372 (8)
Cu1—N31.959 (5)C5—H50.9300
Cu1—N22.075 (5)C6—H60.9300
N1—C71.292 (6)C7—H70.9300
N1—C81.481 (6)C8—C91.507 (8)
N2—C91.489 (7)C8—H8A0.9700
N2—C101.493 (9)C8—H8B0.9700
N2—H2A0.9100C9—H9A0.9700
N3—C131.152 (6)C9—H9B0.9700
O1—C41.300 (6)C10—C111.448 (11)
S1—C131.639 (6)C10—C121.458 (12)
Br1—C11.905 (5)C10—H100.9800
C1—C21.364 (7)C11—H11A0.9600
C1—C61.394 (8)C11—H11B0.9600
C2—C31.406 (7)C11—H11C0.9600
C2—H20.9300C12—H12A0.9600
C3—C41.428 (7)C12—H12B0.9600
C3—C71.436 (7)C12—H12C0.9600
O1—Cu1—N192.32 (17)N1—C7—C3124.6 (5)
O1—Cu1—N387.98 (19)N1—C7—H7117.7
N1—Cu1—N3177.5 (2)C3—C7—H7117.7
O1—Cu1—N2171.59 (18)N1—C8—C9108.5 (5)
N1—Cu1—N284.45 (18)N1—C8—H8A110.0
N3—Cu1—N294.91 (19)C9—C8—H8A110.0
C7—N1—C8120.1 (4)N1—C8—H8B110.0
C7—N1—Cu1126.3 (3)C9—C8—H8B110.0
C8—N1—Cu1113.5 (3)H8A—C8—H8B108.4
C9—N2—C10115.9 (5)N2—C9—C8108.5 (5)
C9—N2—Cu1106.1 (3)N2—C9—H9A110.0
C10—N2—Cu1120.5 (4)C8—C9—H9A110.0
C9—N2—H2A104.2N2—C9—H9B110.0
C10—N2—H2A104.2C8—C9—H9B110.0
Cu1—N2—H2A104.2H9A—C9—H9B108.4
C13—N3—Cu1162.4 (5)C11—C10—C12116.1 (9)
C4—O1—Cu1126.3 (3)C11—C10—N2113.2 (7)
C2—C1—C6119.7 (5)C12—C10—N2112.3 (6)
C2—C1—Br1122.8 (4)C11—C10—H10104.6
C6—C1—Br1117.5 (4)C12—C10—H10104.6
C1—C2—C3121.6 (5)N2—C10—H10104.6
C1—C2—H2119.2C10—C11—H11A109.5
C3—C2—H2119.2C10—C11—H11B109.5
C2—C3—C4120.1 (5)H11A—C11—H11B109.5
C2—C3—C7118.1 (5)C10—C11—H11C109.5
C4—C3—C7121.8 (5)H11A—C11—H11C109.5
O1—C4—C5118.8 (5)H11B—C11—H11C109.5
O1—C4—C3125.2 (5)C10—C12—H12A109.5
C5—C4—C3116.0 (5)C10—C12—H12B109.5
C6—C5—C4122.4 (5)H12A—C12—H12B109.5
C6—C5—H5118.8C10—C12—H12C109.5
C4—C5—H5118.8H12A—C12—H12C109.5
C5—C6—C1120.2 (5)H12B—C12—H12C109.5
C5—C6—H6119.9N3—C13—S1178.7 (6)
C1—C6—H6119.9
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.903 (4)Cu1—N31.959 (5)
Cu1—N11.932 (4)Cu1—N22.075 (5)
O1—Cu1—N192.32 (17)O1—Cu1—N2171.59 (18)
O1—Cu1—N387.98 (19)N1—Cu1—N284.45 (18)
N1—Cu1—N3177.5 (2)N3—Cu1—N294.91 (19)
Acknowledgements top

We acknowledge the Scientific Research Foundation of Henan University of Science and Technology (Project No. 05–072).

references
References top

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Ma, J.-Y., Gu, S.-H., Guo, J.-W., Lv, B.-L. & Yin, W.-P. (2006). Acta Cryst. E62, m1437–m1438.

Ma, J.-Y., Lv, B.-L., Gu, S.-H., Guo, J.-W. & Yin, W.-P. (2006). Acta Cryst. E62, m1322–m1323.

Ma, J.-Y., Wu, T.-X., She, X.-G. & Pan, X.-F. (2005). Acta Cryst. E61, m695–m696.

Ma, J.-Y., Wu, T.-X., She, X.-G. & Pan, X.-F. (2006). Z. Kristallogr. New Cryst. Struct. 221, 53–54.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.