{2-[2-(Ethyl­amino)ethyl­imino­meth­yl]-5-methoxy­phenolato}(thio­cyanato-κN)­copper(II)

Zhu, Y.

doi:10.1107/S1600536810009402

metal-organic compounds

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Volume 66| Part 4| April 2010| Page m419

doi:10.1107/S1600536810009402

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{2-[2-(Ethylamino)ethyliminomethyl]-5-methoxyphenolato}(thiocyanato-κN)copper(II)

Yu Zhu ^a ^*

^aDepartment of Chemistry, Baicheng Normal College, Baicheng 137000, People's Republic of China
^*Correspondence e-mail: zhuyu_bcnc@sohu.com

(Received 8 March 2010; accepted 12 March 2010; online 17 March 2010)

In the title mononuclear copper(II) complex, [Cu(C₁₂H₁₇N₂O₂)(NCS)], the Cu^II atom is four-coordinated by an NNO-donor set of the tridentate Schiff base ligand and the N atom of a terminal thiocyanate ligand in a slightly distorted square-planar geometry.

Related literature

For Cu^II complexes with Schiff base ligands, see: Dede et al. (2009 ); Rai (2010 ); Rajasekar et al. (2010 ); Roper et al. (1989 ). For related structures, see: Adams et al. (2003 ); Roy & Manassero (2010 ).

Experimental

Crystal data

[Cu(C₁₂H₁₇N₂O₂)(NCS)]
M_r = 342.90
Monoclinic, P 2₁ /c
a = 12.296 (6) Å
b = 10.582 (5) Å
c = 12.480 (6) Å
β = 113.810 (7)°
V = 1485.7 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.61 mm⁻¹
T = 293 K
0.30 × 0.27 × 0.27 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.643, T_max = 0.670
8523 measured reflections
3282 independent reflections
2123 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.129
S = 1.00
3282 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.817 (3)
Cu1—N1	1.828 (3)
Cu1—N3	1.868 (3)
Cu1—N2	1.912 (4)

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/S1600536810009402/ci5055sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810009402/ci5055Isup2.hkl

checkCIF report

Comment top

Copper(II) complexes with Schiff base ligands have received much attention in coordination chemistry (Rai, 2010; Roy & Manassero, 2010; Rajasekar et al., 2010; Dede et al., 2009). In the present work, we report the the crystal structure of a new copper(II) complex, the title compound, with the Schiff base ligand 2-[(2-ethylaminoethylimino)methyl]-5-methoxyphenolate.

The Cu^II atom in the title complex is four-coordinated by the NNO donor set of the Schiff base ligand, and the N atom of the terminal thiocyanate ligand, in a square-planar geometry. The coordination bond distances (Table 1) are within normal ranges and comparable to those in related complexes (Roper et al., 1989; Adams et al., 2003).

Related literature top

For Cu^II complexes with Schiff base ligands, see: Dede et al. (2009); Rai (2010); Rajasekar et al. (2010); Roper et al. (1989). For related structures, see: Adams et al. (2003); Roy & Manassero (2010).

Experimental top

Equimolar quantities (1 mmol each) of 2-hydroxy-4-methoxybenzaldehyde, N-ethylethylenediamine, ammonium thiocyanate, and copper nitrate were mixed and stirred in a methanol-acetonitrile (2:1 v/v) solution at room temperature for 3 h. The solution was allowed to evaporate slowly to give needle-shaped single crystals.

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 the title compound, showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level.

{2-[2-(Ethylamino)ethyliminomethyl]-5-methoxyphenolato}(thiocyanato-κN) copper(II) top

Crystal data top

[Cu(C₁₂H₁₇N₂O₂)(NCS)]	F(000) = 708
M_r = 342.90	D_x = 1.533 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2310 reflections
a = 12.296 (6) Å	θ = 2.6–25.0°
b = 10.582 (5) Å	µ = 1.61 mm⁻¹
c = 12.480 (6) Å	T = 293 K
β = 113.810 (7)°	Block cut from needle, blue
V = 1485.7 (12) Å³	0.30 × 0.27 × 0.27 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3282 independent reflections
Radiation source: fine-focus sealed tube	2123 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scan	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.643, T_max = 0.670	k = −13→13
8523 measured reflections	l = −16→10

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0551P)² + 1.5145P] where P = (F_o² + 2F_c²)/3
3282 reflections	(Δ/σ)_max = 0.001
183 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Cu(C₁₂H₁₇N₂O₂)(NCS)]	V = 1485.7 (12) Å³
M_r = 342.90	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.296 (6) Å	µ = 1.61 mm⁻¹
b = 10.582 (5) Å	T = 293 K
c = 12.480 (6) Å	0.30 × 0.27 × 0.27 mm
β = 113.810 (7)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3282 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2123 reflections with I > 2σ(I)
T_min = 0.643, T_max = 0.670	R_int = 0.039
8523 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.00	Δρ_max = 0.61 e Å⁻³
3282 reflections	Δρ_min = −0.34 e Å⁻³
183 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.55890 (4)	0.38272 (4)	0.94272 (4)	0.04744 (18)
N1	0.6492 (3)	0.3114 (3)	1.0844 (3)	0.0465 (8)
N2	0.4301 (3)	0.2831 (3)	0.9449 (3)	0.0596 (9)
H2N	0.3686	0.3382	0.9287	0.072*
N3	0.4579 (3)	0.4525 (3)	0.7995 (3)	0.0488 (8)
O1	0.6770 (2)	0.4836 (3)	0.9392 (2)	0.0543 (7)
O2	1.0326 (3)	0.7210 (3)	1.0840 (3)	0.0718 (9)
S1	0.30391 (13)	0.57348 (14)	0.60132 (10)	0.0790 (4)
C1	0.7807 (3)	0.5063 (4)	1.0246 (3)	0.0460 (9)
C2	0.8513 (4)	0.5995 (4)	1.0075 (3)	0.0516 (10)
H2	0.8249	0.6414	0.9360	0.062*
C3	0.9598 (4)	0.6314 (4)	1.0944 (4)	0.0552 (10)
C4	0.9978 (5)	0.7842 (5)	0.9760 (4)	0.0858 (17)
H4A	0.9877	0.7240	0.9152	0.129*
H4B	1.0578	0.8443	0.9801	0.129*
H4C	0.9240	0.8276	0.9590	0.129*
C5	1.0006 (4)	0.5683 (5)	1.2010 (4)	0.0664 (12)
H5	1.0740	0.5885	1.2598	0.080*
C6	0.9326 (4)	0.4776 (4)	1.2183 (4)	0.0629 (12)
H6	0.9605	0.4365	1.2904	0.075*
C7	0.8217 (4)	0.4421 (4)	1.1327 (3)	0.0480 (9)
C8	0.7542 (4)	0.3458 (4)	1.1546 (3)	0.0510 (10)
H8	0.7884	0.3035	1.2258	0.061*
C9	0.5884 (4)	0.2097 (4)	1.1177 (4)	0.0597 (11)
H9A	0.6175	0.2042	1.2023	0.072*
H9B	0.6024	0.1293	1.0880	0.072*
C10	0.4593 (4)	0.2402 (4)	1.0658 (4)	0.0630 (12)
H10A	0.4129	0.1660	1.0658	0.076*
H10B	0.4421	0.3062	1.1106	0.076*
C11	0.3850 (5)	0.1848 (5)	0.8565 (4)	0.0792 (15)
H11A	0.4379	0.1126	0.8819	0.095*
H11B	0.3879	0.2159	0.7845	0.095*
C12	0.2620 (5)	0.1410 (5)	0.8301 (4)	0.0816 (16)
H12A	0.2569	0.1124	0.9009	0.122*
H12B	0.2422	0.0727	0.7748	0.122*
H12C	0.2074	0.2095	0.7976	0.122*
C13	0.3932 (4)	0.5018 (4)	0.7173 (3)	0.0459 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0569 (3)	0.0430 (3)	0.0396 (3)	−0.0019 (2)	0.0166 (2)	0.00224 (19)
N1	0.063 (2)	0.0397 (17)	0.0379 (16)	0.0056 (15)	0.0213 (15)	0.0010 (13)
N2	0.077 (3)	0.0499 (19)	0.0485 (19)	−0.0137 (18)	0.0216 (18)	0.0024 (15)
N3	0.055 (2)	0.0471 (18)	0.0396 (17)	−0.0061 (16)	0.0142 (15)	0.0017 (14)
O1	0.0489 (16)	0.0666 (18)	0.0378 (14)	−0.0067 (14)	0.0073 (12)	0.0121 (12)
O2	0.0598 (19)	0.089 (2)	0.0557 (19)	−0.0252 (18)	0.0123 (15)	−0.0104 (16)
S1	0.0831 (9)	0.1010 (10)	0.0463 (6)	0.0400 (8)	0.0192 (6)	0.0180 (6)
C1	0.046 (2)	0.050 (2)	0.0409 (19)	0.0040 (18)	0.0167 (17)	−0.0023 (17)
C2	0.048 (2)	0.063 (3)	0.040 (2)	−0.002 (2)	0.0142 (17)	−0.0014 (18)
C3	0.052 (2)	0.060 (3)	0.051 (2)	−0.004 (2)	0.0181 (19)	−0.0141 (19)
C4	0.078 (4)	0.106 (4)	0.069 (3)	−0.044 (3)	0.024 (3)	−0.008 (3)
C5	0.051 (3)	0.078 (3)	0.054 (3)	0.002 (2)	0.004 (2)	−0.007 (2)
C6	0.063 (3)	0.068 (3)	0.045 (2)	0.010 (2)	0.008 (2)	0.003 (2)
C7	0.047 (2)	0.050 (2)	0.043 (2)	0.0092 (19)	0.0146 (17)	0.0009 (17)
C8	0.064 (3)	0.048 (2)	0.038 (2)	0.018 (2)	0.0180 (19)	0.0068 (17)
C9	0.087 (3)	0.044 (2)	0.047 (2)	0.001 (2)	0.025 (2)	0.0102 (18)
C10	0.086 (4)	0.052 (2)	0.052 (2)	−0.018 (2)	0.029 (2)	0.002 (2)
C11	0.103 (4)	0.073 (3)	0.065 (3)	−0.030 (3)	0.037 (3)	−0.011 (3)
C12	0.078 (3)	0.093 (4)	0.057 (3)	−0.029 (3)	0.009 (2)	−0.002 (3)
C13	0.054 (2)	0.046 (2)	0.038 (2)	−0.0007 (19)	0.0193 (18)	−0.0025 (17)

Geometric parameters (Å, º) top

Cu1—O1	1.817 (3)	C4—H4B	0.96
Cu1—N1	1.828 (3)	C4—H4C	0.96
Cu1—N3	1.868 (3)	C5—C6	1.346 (6)
Cu1—N2	1.912 (4)	C5—H5	0.93
N1—C8	1.286 (5)	C6—C7	1.402 (6)
N1—C9	1.463 (5)	C6—H6	0.93
N2—C11	1.453 (6)	C7—C8	1.410 (6)
N2—C10	1.474 (5)	C8—H8	0.93
N2—H2N	0.91	C9—C10	1.488 (6)
N3—C13	1.139 (5)	C9—H9A	0.97
O1—C1	1.313 (4)	C9—H9B	0.97
O2—C3	1.346 (5)	C10—H10A	0.97
O2—C4	1.409 (6)	C10—H10B	0.97
S1—C13	1.610 (4)	C11—C12	1.487 (7)
C1—C2	1.386 (6)	C11—H11A	0.97
C1—C7	1.409 (5)	C11—H11B	0.97
C2—C3	1.379 (6)	C12—H12A	0.96
C2—H2	0.93	C12—H12B	0.96
C3—C5	1.389 (6)	C12—H12C	0.96
C4—H4A	0.96

O1—Cu1—N1	94.97 (13)	C3—C5—H5	120.4
O1—Cu1—N3	88.49 (13)	C5—C6—C7	122.9 (4)
N1—Cu1—N3	176.29 (15)	C5—C6—H6	118.5
O1—Cu1—N2	177.40 (14)	C7—C6—H6	118.5
N1—Cu1—N2	86.67 (15)	C6—C7—C1	117.6 (4)
N3—Cu1—N2	89.82 (15)	C6—C7—C8	120.9 (4)
C8—N1—C9	120.1 (3)	C1—C7—C8	121.6 (4)
C8—N1—Cu1	126.4 (3)	N1—C8—C7	125.5 (3)
C9—N1—Cu1	113.4 (3)	N1—C8—H8	117.3
C11—N2—C10	114.7 (3)	C7—C8—H8	117.3
C11—N2—Cu1	116.6 (3)	N1—C9—C10	107.1 (3)
C10—N2—Cu1	108.9 (3)	N1—C9—H9A	110.3
C11—N2—H2N	105.2	C10—C9—H9A	110.3
C10—N2—H2N	105.2	N1—C9—H9B	110.3
Cu1—N2—H2N	105.2	C10—C9—H9B	110.3
C13—N3—Cu1	174.4 (3)	H9A—C9—H9B	108.5
C1—O1—Cu1	127.7 (2)	N2—C10—C9	106.8 (4)
C3—O2—C4	118.0 (3)	N2—C10—H10A	110.4
O1—C1—C2	118.0 (3)	C9—C10—H10A	110.4
O1—C1—C7	122.9 (4)	N2—C10—H10B	110.4
C2—C1—C7	119.1 (4)	C9—C10—H10B	110.4
C3—C2—C1	121.3 (4)	H10A—C10—H10B	108.6
C3—C2—H2	119.3	N2—C11—C12	115.7 (4)
C1—C2—H2	119.3	N2—C11—H11A	108.4
O2—C3—C2	124.5 (4)	C12—C11—H11A	108.4
O2—C3—C5	115.7 (4)	N2—C11—H11B	108.4
C2—C3—C5	119.8 (4)	C12—C11—H11B	108.4
O2—C4—H4A	109.5	H11A—C11—H11B	107.4
O2—C4—H4B	109.5	C11—C12—H12A	109.5
H4A—C4—H4B	109.5	C11—C12—H12B	109.5
O2—C4—H4C	109.5	H12A—C12—H12B	109.5
H4A—C4—H4C	109.5	C11—C12—H12C	109.5
H4B—C4—H4C	109.5	H12A—C12—H12C	109.5
C6—C5—C3	119.3 (4)	H12B—C12—H12C	109.5
C6—C5—H5	120.4	N3—C13—S1	178.8 (4)

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₁₇N₂O₂)(NCS)]
M_r	342.90
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.296 (6), 10.582 (5), 12.480 (6)
β (°)	113.810 (7)
V (Å³)	1485.7 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.61
Crystal size (mm)	0.30 × 0.27 × 0.27

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.643, 0.670
No. of measured, independent and observed [I > 2σ(I)] reflections	8523, 3282, 2123
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.129, 1.00
No. of reflections	3282
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.34

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

Selected bond lengths (Å) top

Cu1—O1	1.817 (3)	Cu1—N3	1.868 (3)
Cu1—N1	1.828 (3)	Cu1—N2	1.912 (4)

References

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