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

Ma, J.-Y.

doi:10.1107/S1600536808016589

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m878

doi:10.1107/S1600536808016589

Open

access

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

Jun-Ying Ma ^a ^*

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

(Received 5 April 2008; accepted 30 May 2008; online 7 June 2008)

In the title mononuclear copper(II) complex, [Cu(C₁₀H₁₂BrN₂O)(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. In the crystal structure, symmetry-related molecules are linked by an N—H⋯S hydrogen bond.

Related literature

For related literature, see: Diao & Li (2007 ); Diao et al. (2007 ); Ma et al. (2005 ); Ma, Gu et al. (2006 ); Ma, Lv et al. (2006 ); Ma, Wu et al. (2006 ); Wei et al. (2007 ).

Experimental

Crystal data

[Cu(C₁₀H₁₂BrN₂O)(NCS)]
M_r = 377.75
Monoclinic, P 2₁ /n
a = 5.952 (3) Å
b = 19.660 (3) Å
c = 12.718 (2) Å
β = 94.331 (3)°
V = 1484.0 (8) Å³
Z = 4
Mo Kα radiation
μ = 4.30 mm⁻¹
T = 298 (2) K
0.32 × 0.32 × 0.31 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.259, T_max = 0.267
11246 measured reflections
2997 independent reflections
1875 reflections with I > 2σ(I)
R_int = 0.071

Refinement

R[F² > 2σ(F²)] = 0.076
wR(F²) = 0.180
S = 1.11
2997 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 1.68 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S1ⁱ	0.91	2.76	3.635 (9)	162
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); 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/S1600536808016589/su2051sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016589/su2051Isup2.hkl

checkCIF report

Comment top

Recently, we have reported on teh crystal structure alanyses of some metal complexes derived from 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, (I), is reported on here.

In complex (I), 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). All the bond lengths and angles related to the Cu atom in the complex are within normal ranges, and comparable to the values observed in other similar copper(II) complexes (Wei et al., 2007; Diao et al., 2007; Diao & Li, 2007). The four coordinating atoms around the Cu centre are approximately coplanar, giving a square-planar geometry with an average deviation of 0.090 (5) Å; the Cu atom lies 0.095 (2) Å above this plane. The C8—C9—N2—C10 torsion angle is 1.5 (3)°.

In the crystal structure of compound (I) symmetry related molecules are linked by an N—H···S hydrogen bond (Table 1).

Related literature top

For related literature, see: Diao & Li (2007); Diao et al. (2007); Ma et al. (2005); Ma, Gu et al. (2006); Ma, Lv et al. (2006); Ma, Wu et al. (2006); Wei et al. (2007).

Experimental top

N-Methylethane-1,2-diamine (0.5 mmol, 37.0 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 this 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, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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. The molecular structure of compound (I), showing the atomic numbering scheme and the displacement ellipsoids drawn at the 30% probability level.

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

Crystal data top

[Cu(C₁₀H₁₂BrN₂O)(NCS)]	F(000) = 748
M_r = 377.75	D_x = 1.691 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1708 reflections
a = 5.952 (3) Å	θ = 2.5–25.3°
b = 19.660 (3) Å	µ = 4.30 mm⁻¹
c = 12.718 (2) Å	T = 298 K
β = 94.331 (3)°	Block, blue
V = 1484.0 (8) Å³	0.32 × 0.32 × 0.31 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2997 independent reflections
Radiation source: fine-focus sealed tube	1875 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
ω scan	θ_max = 26.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.259, T_max = 0.267	k = −24→24
11246 measured reflections	l = −15→15

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.181	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0672P)² + 4.7203P] where P = (F_o² + 2F_c²)/3
2997 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 1.68 e Å⁻³
0 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

[Cu(C₁₀H₁₂BrN₂O)(NCS)]	V = 1484.0 (8) Å³
M_r = 377.75	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.952 (3) Å	µ = 4.30 mm⁻¹
b = 19.660 (3) Å	T = 298 K
c = 12.718 (2) Å	0.32 × 0.32 × 0.31 mm
β = 94.331 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2997 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1875 reflections with I > 2σ(I)
T_min = 0.259, T_max = 0.267	R_int = 0.071
11246 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	0 restraints
wR(F²) = 0.181	H-atom parameters constrained
S = 1.11	Δρ_max = 1.68 e Å⁻³
2997 reflections	Δρ_min = −0.84 e Å⁻³
164 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	0.77313 (15)	0.20764 (5)	0.04645 (8)	0.0407 (3)
N1	1.0514 (10)	0.1635 (3)	0.0963 (5)	0.0392 (15)
N2	0.8291 (12)	0.2634 (4)	0.1796 (7)	0.058 (2)
H2A	0.7645	0.2393	0.2304	0.070*
N3	0.4927 (12)	0.2539 (4)	0.0002 (6)	0.053 (2)
O1	0.7104 (8)	0.1410 (3)	−0.0588 (4)	0.0460 (14)
S1	0.0695 (4)	0.29376 (15)	−0.0863 (2)	0.0664 (8)
Br1	1.31654 (16)	−0.06412 (5)	−0.23999 (9)	0.0633 (4)
C1	1.1328 (13)	0.0028 (4)	−0.1792 (7)	0.044 (2)
C2	0.9203 (14)	0.0131 (4)	−0.2253 (8)	0.049 (2)
H2	0.8712	−0.0121	−0.2845	0.059*
C3	0.7799 (13)	0.0596 (4)	−0.1860 (7)	0.047 (2)
H3	0.6360	0.0657	−0.2184	0.057*
C4	0.8518 (13)	0.0994 (4)	−0.0946 (6)	0.0367 (18)
C5	1.0688 (12)	0.0860 (4)	−0.0492 (6)	0.0369 (18)
C6	1.2068 (14)	0.0376 (4)	−0.0913 (7)	0.045 (2)
H6	1.3497	0.0291	−0.0592	0.054*
C7	1.1533 (13)	0.1183 (4)	0.0480 (7)	0.042 (2)
H7	1.2941	0.1047	0.0773	0.051*
C8	1.1509 (15)	0.1902 (5)	0.1982 (7)	0.052 (2)
H8A	1.3140	0.1889	0.1997	0.062*
H8B	1.1038	0.1625	0.2557	0.062*
C9	1.0734 (14)	0.2612 (5)	0.2099 (7)	0.051 (2)
H9A	1.1028	0.2760	0.2824	0.061*
H9B	1.1531	0.2912	0.1650	0.061*
C10	0.7370 (17)	0.3305 (6)	0.1855 (10)	0.083 (4)
H10A	0.8001	0.3526	0.2482	0.125*
H10B	0.5763	0.3276	0.1874	0.125*
H10C	0.7728	0.3562	0.1248	0.125*
C11	0.3146 (15)	0.2696 (4)	−0.0378 (7)	0.048 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0271 (5)	0.0511 (6)	0.0429 (6)	0.0011 (4)	−0.0028 (4)	−0.0086 (5)
N1	0.028 (3)	0.047 (4)	0.041 (4)	−0.004 (3)	−0.006 (3)	−0.001 (3)
N2	0.040 (4)	0.062 (5)	0.070 (5)	−0.001 (4)	−0.005 (4)	−0.022 (4)
N3	0.030 (4)	0.069 (5)	0.058 (5)	0.008 (3)	−0.006 (3)	−0.015 (4)
O1	0.025 (3)	0.055 (4)	0.056 (4)	0.006 (3)	−0.009 (2)	−0.012 (3)
S1	0.0412 (13)	0.0813 (18)	0.0744 (18)	0.0000 (13)	−0.0115 (12)	0.0316 (15)
Br1	0.0480 (6)	0.0520 (6)	0.0910 (8)	0.0037 (4)	0.0131 (5)	−0.0149 (5)
C1	0.036 (4)	0.030 (4)	0.068 (6)	0.003 (3)	0.014 (4)	−0.002 (4)
C2	0.035 (5)	0.045 (5)	0.066 (6)	−0.005 (4)	0.001 (4)	−0.009 (4)
C3	0.029 (4)	0.047 (5)	0.064 (6)	0.000 (4)	−0.014 (4)	−0.007 (4)
C4	0.031 (4)	0.033 (4)	0.044 (5)	0.001 (3)	−0.006 (3)	−0.002 (4)
C5	0.029 (4)	0.040 (4)	0.041 (5)	0.004 (3)	0.004 (3)	0.013 (4)
C6	0.042 (5)	0.037 (4)	0.057 (5)	0.000 (4)	−0.002 (4)	0.007 (4)
C7	0.028 (4)	0.043 (5)	0.055 (5)	0.003 (4)	−0.007 (4)	0.015 (4)
C8	0.048 (5)	0.065 (6)	0.039 (5)	−0.011 (4)	−0.017 (4)	−0.003 (4)
C9	0.039 (5)	0.075 (6)	0.038 (5)	−0.006 (4)	−0.002 (4)	−0.022 (5)
C10	0.051 (6)	0.092 (8)	0.106 (9)	0.038 (6)	−0.005 (6)	−0.039 (7)
C11	0.042 (5)	0.051 (5)	0.050 (5)	−0.015 (4)	−0.001 (4)	−0.004 (4)

Geometric parameters (Å, º) top

Cu1—O1	1.890 (5)	C2—H2	0.9300
Cu1—N1	1.934 (6)	C3—C4	1.439 (11)
Cu1—N3	1.952 (7)	C3—H3	0.9300
Cu1—N2	2.024 (7)	C4—C5	1.399 (10)
N1—C7	1.262 (10)	C5—C6	1.390 (11)
N1—C8	1.479 (10)	C5—C7	1.446 (12)
N2—C10	1.432 (12)	C6—H6	0.9300
N2—C9	1.476 (11)	C7—H7	0.9300
N2—H2A	0.9100	C8—C9	1.481 (12)
N3—C11	1.172 (11)	C8—H8A	0.9700
O1—C4	1.282 (9)	C8—H8B	0.9700
S1—C11	1.612 (10)	C9—H9A	0.9700
Br1—C1	1.911 (8)	C9—H9B	0.9700
C1—C6	1.356 (12)	C10—H10A	0.9600
C1—C2	1.368 (12)	C10—H10B	0.9600
C2—C3	1.358 (12)	C10—H10C	0.9600

O1—Cu1—N1	92.3 (3)	C6—C5—C4	121.6 (8)
O1—Cu1—N3	89.5 (3)	C6—C5—C7	116.9 (7)
N1—Cu1—N3	178.1 (3)	C4—C5—C7	121.4 (7)
O1—Cu1—N2	168.3 (3)	C1—C6—C5	119.9 (8)
N1—Cu1—N2	83.4 (3)	C1—C6—H6	120.1
N3—Cu1—N2	94.7 (3)	C5—C6—H6	120.1
C7—N1—C8	120.0 (7)	N1—C7—C5	125.2 (7)
C7—N1—Cu1	126.0 (5)	N1—C7—H7	117.4
C8—N1—Cu1	113.9 (5)	C5—C7—H7	117.4
C10—N2—C9	112.8 (8)	N1—C8—C9	108.4 (7)
C10—N2—Cu1	120.2 (7)	N1—C8—H8A	110.0
C9—N2—Cu1	107.4 (5)	C9—C8—H8A	110.0
C10—N2—H2A	105.0	N1—C8—H8B	110.0
C9—N2—H2A	105.0	C9—C8—H8B	110.0
Cu1—N2—H2A	105.0	H8A—C8—H8B	108.4
C11—N3—Cu1	166.5 (7)	N2—C9—C8	108.1 (7)
C4—O1—Cu1	126.5 (5)	N2—C9—H9A	110.1
C6—C1—C2	120.7 (8)	C8—C9—H9A	110.1
C6—C1—Br1	121.4 (6)	N2—C9—H9B	110.1
C2—C1—Br1	117.9 (7)	C8—C9—H9B	110.1
C3—C2—C1	121.1 (8)	H9A—C9—H9B	108.4
C3—C2—H2	119.4	N2—C10—H10A	109.5
C1—C2—H2	119.4	N2—C10—H10B	109.5
C2—C3—C4	120.6 (7)	H10A—C10—H10B	109.5
C2—C3—H3	119.7	N2—C10—H10C	109.5
C4—C3—H3	119.7	H10A—C10—H10C	109.5
O1—C4—C5	125.7 (7)	H10B—C10—H10C	109.5
O1—C4—C3	118.1 (7)	N3—C11—S1	177.5 (9)
C5—C4—C3	116.1 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.91	2.76	3.635 (9)	162

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₀H₁₂BrN₂O)(NCS)]
M_r	377.75
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	5.952 (3), 19.660 (3), 12.718 (2)
β (°)	94.331 (3)
V (Å³)	1484.0 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.30
Crystal size (mm)	0.32 × 0.32 × 0.31

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.259, 0.267
No. of measured, independent and observed [I > 2σ(I)] reflections	11246, 2997, 1875
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.181, 1.11
No. of reflections	2997
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.68, −0.84

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.91	2.76	3.635 (9)	162

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Acknowledgements

The author acknowledges support from the Scientific Research Foundation of Henan University of Science and Technology (project No. 05-072).

References

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Diao, Y.-P. & Li, K. (2007). Acta Cryst. E63, m2496–m2497. Web of Science CSD CrossRef IUCr Journals Google Scholar
Diao, Y.-P., Shu, X.-H., Zhang, B.-J., Zhen, Y.-H. & Kang, T.-G. (2007). Acta Cryst. E63, m1816. CSD CrossRef IUCr Journals 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
Wei, Y.-J., Wang, F.-W. & Zhu, Q.-Y. (2007). Acta Cryst. E63, m2629. Web of Science CSD CrossRef 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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m878

doi:10.1107/S1600536808016589

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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