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

Ma, J.-Y.; He, Y.-T.

doi:10.1107/S1600536808010404

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m687

doi:10.1107/S1600536808010404

Open

access

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

Jun-Ying Ma ^a ^* and Yin-Ting He ^b

^aChemical Engineering & Pharmaceutics College, Henan University of Science and Technology, Luoyang Henan 471003, People's Republic of China, and, Department of Chemistry, Pingdingshan University, Pingdingshan Henan 467000, People's Republic of China, and ^bZhoukou Vocational and Technical College, Zhoukou Henan 466600, People's Republic of China
^*Correspondence e-mail: junying-ma@163.com

(Received 5 April 2008; accepted 15 April 2008; online 18 April 2008)

In the title mononuclear Schiff base copper(II) complex, [Cu(C₁₂H₁₆BrN₂O)(NCS)], the Cu^II 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.

Related literature

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

Experimental

Crystal data

[Cu(C₁₂H₁₆BrN₂O)(NCS)]
M_r = 405.80
Monoclinic, P 2₁ /n
a = 6.161 (2) Å
b = 20.223 (3) Å
c = 12.930 (3) Å
β = 95.332 (5)°
V = 1604.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 3.98 mm⁻¹
T = 298 (2) K
0.40 × 0.38 × 0.37 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.299, T_max = 0.321 (expected range = 0.214–0.229)
11914 measured reflections
3474 independent reflections
2126 reflections with I > 2σ(I)
R_int = 0.076

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.153
S = 1.01
3474 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.903 (4)
Cu1—N1	1.932 (4)
Cu1—N3	1.959 (5)
Cu1—N2	2.075 (5)

O1—Cu1—N1	92.32 (17)
O1—Cu1—N3	87.98 (19)
N1—Cu1—N3	177.5 (2)
O1—Cu1—N2	171.59 (18)
N1—Cu1—N2	84.45 (18)
N3—Cu1—N2	94.91 (19)

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808010404/om2226sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010404/om2226Isup2.hkl

checkCIF report

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.

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

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)]	F(000) = 812
M_r = 405.80	D_x = 1.680 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1880 reflections
a = 6.161 (2) Å	θ = 2.5–24.3°
b = 20.223 (3) Å	µ = 3.98 mm⁻¹
c = 12.930 (3) Å	T = 298 K
β = 95.332 (5)°	Block, blue
V = 1604.0 (7) Å³	0.40 × 0.38 × 0.37 mm
Z = 4

Data collection top

Bruker SMART 1000 diffractometer	3474 independent reflections
Radiation source: fine-focus sealed tube	2126 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
ω scans	θ_max = 27.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.299, T_max = 0.321	k = −25→25
11914 measured reflections	l = −16→16

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0682P)²] where P = (F_o² + 2F_c²)/3
3474 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

[Cu(C₁₂H₁₆BrN₂O)(NCS)]	V = 1604.0 (7) Å³
M_r = 405.80	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.161 (2) Å	µ = 3.98 mm⁻¹
b = 20.223 (3) Å	T = 298 K
c = 12.930 (3) Å	0.40 × 0.38 × 0.37 mm
β = 95.332 (5)°

Data collection top

Bruker SMART 1000 diffractometer	3474 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2126 reflections with I > 2σ(I)
T_min = 0.299, T_max = 0.321	R_int = 0.076
11914 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.01	Δρ_max = 0.81 e Å⁻³
3474 reflections	Δρ_min = −0.49 e Å⁻³
183 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	0.26493 (10)	0.20760 (3)	0.47898 (5)	0.0450 (2)
N1	0.5364 (7)	0.1721 (2)	0.5425 (3)	0.0408 (10)
N2	0.3292 (7)	0.2854 (2)	0.5819 (4)	0.0534 (12)
H2A	0.2664	0.2729	0.6397	0.064*
N3	−0.0164 (8)	0.2425 (3)	0.4201 (4)	0.0616 (14)
O1	0.2003 (6)	0.1286 (2)	0.4022 (3)	0.0551 (10)
S1	−0.4273 (2)	0.25260 (9)	0.31058 (11)	0.0566 (4)
Br1	0.80195 (10)	−0.08910 (3)	0.28530 (5)	0.0677 (3)
C1	0.6219 (9)	−0.0194 (3)	0.3274 (4)	0.0475 (13)
C2	0.6939 (9)	0.0269 (3)	0.3994 (4)	0.0466 (13)
H2	0.8364	0.0245	0.4299	0.056*
C3	0.5578 (8)	0.0781 (2)	0.4285 (4)	0.0382 (12)
C4	0.3387 (8)	0.0829 (3)	0.3822 (4)	0.0418 (12)
C5	0.2699 (9)	0.0321 (3)	0.3099 (4)	0.0532 (15)
H5	0.1270	0.0326	0.2795	0.064*
C6	0.4065 (10)	−0.0175 (3)	0.2836 (5)	0.0552 (15)
H6	0.3554	−0.0499	0.2365	0.066*
C7	0.6414 (9)	0.1221 (3)	0.5099 (4)	0.0436 (12)
H7	0.7808	0.1140	0.5413	0.052*
C8	0.6326 (9)	0.2117 (3)	0.6316 (4)	0.0544 (15)
H8A	0.7902	0.2077	0.6376	0.065*
H8B	0.5801	0.1957	0.6955	0.065*
C9	0.5675 (9)	0.2829 (3)	0.6140 (4)	0.0536 (15)
H9A	0.6006	0.3081	0.6773	0.064*
H9B	0.6478	0.3019	0.5602	0.064*
C10	0.2371 (15)	0.3525 (4)	0.5575 (6)	0.092 (2)
H10	0.0818	0.3447	0.5376	0.111*
C11	0.242 (2)	0.3952 (5)	0.6475 (9)	0.150 (4)
H11A	0.2122	0.3697	0.7072	0.225*
H11B	0.1328	0.4290	0.6354	0.225*
H11C	0.3828	0.4154	0.6596	0.225*
C12	0.319 (2)	0.3811 (5)	0.4651 (7)	0.152 (5)
H12A	0.2246	0.4165	0.4396	0.228*
H12B	0.3221	0.3477	0.4125	0.228*
H12C	0.4633	0.3979	0.4824	0.228*
C13	−0.1851 (9)	0.2472 (3)	0.3741 (4)	0.0457 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0348 (4)	0.0592 (5)	0.0396 (4)	0.0019 (3)	−0.0042 (3)	−0.0043 (3)
N1	0.038 (2)	0.048 (3)	0.035 (2)	−0.006 (2)	−0.0057 (18)	0.002 (2)
N2	0.051 (3)	0.066 (3)	0.044 (3)	0.010 (2)	0.007 (2)	−0.005 (2)
N3	0.042 (3)	0.079 (4)	0.061 (3)	0.011 (3)	−0.008 (2)	−0.015 (3)
O1	0.036 (2)	0.066 (3)	0.061 (3)	0.0002 (19)	−0.0087 (17)	−0.011 (2)
S1	0.0407 (8)	0.0800 (11)	0.0466 (8)	−0.0024 (8)	−0.0086 (6)	0.0161 (8)
Br1	0.0639 (5)	0.0571 (4)	0.0838 (5)	−0.0015 (3)	0.0157 (4)	−0.0128 (3)
C1	0.043 (3)	0.045 (3)	0.055 (3)	−0.004 (3)	0.007 (3)	0.000 (3)
C2	0.043 (3)	0.046 (3)	0.050 (3)	−0.002 (3)	−0.001 (2)	0.007 (3)
C3	0.039 (3)	0.038 (3)	0.037 (3)	−0.004 (2)	0.000 (2)	0.005 (2)
C4	0.037 (3)	0.046 (3)	0.041 (3)	−0.006 (2)	−0.001 (2)	0.004 (2)
C5	0.040 (3)	0.062 (4)	0.054 (4)	−0.009 (3)	−0.011 (3)	−0.007 (3)
C6	0.058 (4)	0.052 (4)	0.054 (4)	−0.013 (3)	0.001 (3)	−0.007 (3)
C7	0.038 (3)	0.048 (3)	0.044 (3)	0.001 (3)	−0.003 (2)	0.015 (3)
C8	0.049 (3)	0.063 (4)	0.048 (3)	−0.006 (3)	−0.013 (3)	−0.009 (3)
C9	0.056 (4)	0.057 (4)	0.049 (3)	−0.002 (3)	0.006 (3)	−0.014 (3)
C10	0.121 (7)	0.082 (5)	0.073 (5)	0.032 (5)	0.002 (5)	−0.017 (4)
C11	0.248 (14)	0.083 (7)	0.124 (9)	0.029 (7)	0.039 (9)	−0.018 (6)
C12	0.280 (15)	0.099 (7)	0.084 (6)	0.089 (9)	0.055 (8)	0.028 (6)
C13	0.046 (3)	0.049 (3)	0.043 (3)	0.002 (3)	0.007 (3)	0.002 (3)

Geometric parameters (Å, º) top

Cu1—O1	1.903 (4)	C4—C5	1.426 (7)
Cu1—N1	1.932 (4)	C5—C6	1.372 (8)
Cu1—N3	1.959 (5)	C5—H5	0.9300
Cu1—N2	2.075 (5)	C6—H6	0.9300
N1—C7	1.292 (6)	C7—H7	0.9300
N1—C8	1.481 (6)	C8—C9	1.507 (8)
N2—C9	1.489 (7)	C8—H8A	0.9700
N2—C10	1.493 (9)	C8—H8B	0.9700
N2—H2A	0.9100	C9—H9A	0.9700
N3—C13	1.152 (6)	C9—H9B	0.9700
O1—C4	1.300 (6)	C10—C11	1.448 (11)
S1—C13	1.639 (6)	C10—C12	1.458 (12)
Br1—C1	1.905 (5)	C10—H10	0.9800
C1—C2	1.364 (7)	C11—H11A	0.9600
C1—C6	1.394 (8)	C11—H11B	0.9600
C2—C3	1.406 (7)	C11—H11C	0.9600
C2—H2	0.9300	C12—H12A	0.9600
C3—C4	1.428 (7)	C12—H12B	0.9600
C3—C7	1.436 (7)	C12—H12C	0.9600

O1—Cu1—N1	92.32 (17)	N1—C7—C3	124.6 (5)
O1—Cu1—N3	87.98 (19)	N1—C7—H7	117.7
N1—Cu1—N3	177.5 (2)	C3—C7—H7	117.7
O1—Cu1—N2	171.59 (18)	N1—C8—C9	108.5 (5)
N1—Cu1—N2	84.45 (18)	N1—C8—H8A	110.0
N3—Cu1—N2	94.91 (19)	C9—C8—H8A	110.0
C7—N1—C8	120.1 (4)	N1—C8—H8B	110.0
C7—N1—Cu1	126.3 (3)	C9—C8—H8B	110.0
C8—N1—Cu1	113.5 (3)	H8A—C8—H8B	108.4
C9—N2—C10	115.9 (5)	N2—C9—C8	108.5 (5)
C9—N2—Cu1	106.1 (3)	N2—C9—H9A	110.0
C10—N2—Cu1	120.5 (4)	C8—C9—H9A	110.0
C9—N2—H2A	104.2	N2—C9—H9B	110.0
C10—N2—H2A	104.2	C8—C9—H9B	110.0
Cu1—N2—H2A	104.2	H9A—C9—H9B	108.4
C13—N3—Cu1	162.4 (5)	C11—C10—C12	116.1 (9)
C4—O1—Cu1	126.3 (3)	C11—C10—N2	113.2 (7)
C2—C1—C6	119.7 (5)	C12—C10—N2	112.3 (6)
C2—C1—Br1	122.8 (4)	C11—C10—H10	104.6
C6—C1—Br1	117.5 (4)	C12—C10—H10	104.6
C1—C2—C3	121.6 (5)	N2—C10—H10	104.6
C1—C2—H2	119.2	C10—C11—H11A	109.5
C3—C2—H2	119.2	C10—C11—H11B	109.5
C2—C3—C4	120.1 (5)	H11A—C11—H11B	109.5
C2—C3—C7	118.1 (5)	C10—C11—H11C	109.5
C4—C3—C7	121.8 (5)	H11A—C11—H11C	109.5
O1—C4—C5	118.8 (5)	H11B—C11—H11C	109.5
O1—C4—C3	125.2 (5)	C10—C12—H12A	109.5
C5—C4—C3	116.0 (5)	C10—C12—H12B	109.5
C6—C5—C4	122.4 (5)	H12A—C12—H12B	109.5
C6—C5—H5	118.8	C10—C12—H12C	109.5
C4—C5—H5	118.8	H12A—C12—H12C	109.5
C5—C6—C1	120.2 (5)	H12B—C12—H12C	109.5
C5—C6—H6	119.9	N3—C13—S1	178.7 (6)
C1—C6—H6	119.9

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₁₆BrN₂O)(NCS)]
M_r	405.80
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	6.161 (2), 20.223 (3), 12.930 (3)
β (°)	95.332 (5)
V (Å³)	1604.0 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.98
Crystal size (mm)	0.40 × 0.38 × 0.37

Data collection
Diffractometer	Bruker SMART 1000 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.299, 0.321
No. of measured, independent and observed [I > 2σ(I)] reflections	11914, 3474, 2126
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.153, 1.01
No. of reflections	3474
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.49

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—O1	1.903 (4)	Cu1—N3	1.959 (5)
Cu1—N1	1.932 (4)	Cu1—N2	2.075 (5)

O1—Cu1—N1	92.32 (17)	O1—Cu1—N2	171.59 (18)
O1—Cu1—N3	87.98 (19)	N1—Cu1—N2	84.45 (18)
N1—Cu1—N3	177.5 (2)	N3—Cu1—N2	94.91 (19)

Acknowledgements

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

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ma, J.-Y., Gu, S.-H., Guo, J.-W., Lv, B.-L. & Yin, W.-P. (2006). Acta Cryst. E62, m1437–m1438. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, J.-Y., Lv, B.-L., Gu, S.-H., Guo, J.-W. & Yin, W.-P. (2006). Acta Cryst. E62, m1322–m1323. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, J.-Y., Wu, T.-X., She, X.-G. & Pan, X.-F. (2005). Acta Cryst. E61, m695–m696. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, J.-Y., Wu, T.-X., She, X.-G. & Pan, X.-F. (2006). Z. Kristallogr. New Cryst. Struct. 221, 53–54. CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.