Di-μ-thio­cyanato-bis­({2,4-dichloro-6-[2-(diethyl­amino)ethyl­imino­meth­yl]phenolato}copper(II))

Li, X.-W.; Qiu, Y.

doi:10.1107/S1600536807063325

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m218

https://doi.org/10.1107/S1600536807063325

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Di-μ-thiocyanato-bis({2,4-dichloro-6-[2-(diethylamino)ethyliminomethyl]phenolato}copper(II))

Xian-Wen Li ^a ^* and Yang Qiu ^b

^aDepartment of Chemistry and Chemical Engineering, Minjiang University, Fuzhou 350108, People's Republic of China, and ^bDepartment of Chemistry and Physics, University of Science and Technology of China, Hefei 230026, People's Republic of China
^*Correspondence e-mail: xianwenfz@163.com

(Received 17 November 2007; accepted 26 November 2007; online 18 December 2007)

The title compound, [Cu₂(NCS)₂(C₁₃H₁₇Cl₂N₂O)₂], was obtained by the reaction of 3,5-dichlorosalicylaldehyde, N,N-diethylethane-1,2-diamine, sodium thiocyanate, and copper(II) acetate in an ethanol solution. It crystallizes as a centrosymmetric dimer with a very long Cu⋯S axial bond [2.972 (3) Å]. The Cu atom is five-coordinated by the three donor atoms of the Schiff base ligand, 2,4-dichloro-6-[(2-diethylaminoethylimino)methyl]phenol, one N atom of a thiocyanate group, and one S atom of a symmetry-related thiocyanate group, forming a slightly distorted square-pyramidal geometry.

Related literature

For the biological activity of Schiff base compounds, see: Panneerselvam et al. (2005 ); Shi et al. (2007 ); Singh et al. (2006 , 2007 ); Zhong et al. (2006 ). For related literature, see: Allen et al. (1987 ).

Experimental

Crystal data

[Cu₂(NCS)₂(C₁₃H₁₇Cl₂N₂O)₂]
M_r = 409.81
Monoclinic, P 2₁ /c
a = 8.632 (2) Å
b = 14.115 (3) Å
c = 14.002 (3) Å
β = 90.491 (4)°
V = 1706.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.72 mm⁻¹
T = 293 (2) K
0.20 × 0.17 × 0.16 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.725, T_max = 0.771
13451 measured reflections
3516 independent reflections
3046 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.118
S = 1.06
3516 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 1.34 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807063325/su2031sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063325/su2031Isup2.hkl

checkCIF report

Comment top

Schiff base compounds have been reported to have excellent biological activity (Shi et al., 2007; Panneerselvam et al., 2005). Metal complexes derived from the Schiff bases have also been shown to have excellent biological activity (Singh et al., 2006, 2007; Zhong et al., 2006). As part of our investigations of the structures of metal complexes derived from Schiff bases, we report herein the crystal structure of the title copper complex, (I).

Compound (I) is a centrosymmetric dinuclear copper(II) complex (Fig. 1). The Cu atom is five-coordinated by the three donor atoms (O1, N1 and N2) of the Schiff base ligand 2,4-dichloro-6-[(2-diethylaminoethylimino)methyl]phenol, one N atom of a thiocyanate group, and one S atom of the centrosymmetrically related thiocyanate group, so forming a slightly distorted square-pyramidal geometry. The Cu atom is displaced out of the best least-squares plane defined by the four basal donor atoms by 0.123 (2) Å. Apart from the long Cu···S axial bond [2.972 (3) Å], the other coordination bond distances and angles are within normal ranges (Allen et al., 1987).

Related literature top

For the biological activity of Schiff base compounds, see: Panneerselvam et al. (2005); Shi et al. (2007); Singh et al. (2006, 2007); Zhong et al. (2006). For related literature, see: Allen et al. (1987).

Experimental top

The title compound was obtained by the reaction of equimolar amounts of 3,5-dichlorosalicylaldehyde, N,N-diethylethane-1,2-diamine, sodium thiocyanate, and copper acetate in an ethanol solution. Blue block-like single crystals were obtained by slow evaporation of the filtrate in air.

Structure description top

For the biological activity of Schiff base compounds, see: Panneerselvam et al. (2005); Shi et al. (2007); Singh et al. (2006, 2007); Zhong et al. (2006). For related literature, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top

Fig. 1. The molecular structure of complex (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.

Di-µ-thiocyanato-bis({2,4-dichloro-6-[2- (diethylamino)ethyliminomethyl]phenolato}copper(II)) top

Crystal data top

[Cu₂(NCS)₂(C₁₃H₁₇Cl₂N₂O)₂]	F(000) = 836
M_r = 409.81	D_x = 1.596 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.632 (2) Å	Cell parameters from 6502 reflections
b = 14.115 (3) Å	θ = 2.4–27.7°
c = 14.002 (3) Å	µ = 1.72 mm⁻¹
β = 90.491 (4)°	T = 293 K
V = 1706.0 (6) Å³	Block, blue
Z = 4	0.20 × 0.17 × 0.16 mm

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	3516 independent reflections
Radiation source: fine-focus sealed tube	3046 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 26.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→10
T_min = 0.725, T_max = 0.771	k = −17→17
13451 measured reflections	l = −17→17

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) = 0.118	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.058P)² + 2.2599P] where P = (F_o² + 2F_c²)/3
3516 reflections	(Δ/σ)_max = 0.001
201 parameters	Δρ_max = 1.34 e Å⁻³
0 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

[Cu₂(NCS)₂(C₁₃H₁₇Cl₂N₂O)₂]	V = 1706.0 (6) Å³
M_r = 409.81	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.632 (2) Å	µ = 1.72 mm⁻¹
b = 14.115 (3) Å	T = 293 K
c = 14.002 (3) Å	0.20 × 0.17 × 0.16 mm
β = 90.491 (4)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	3516 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	3046 reflections with I > 2σ(I)
T_min = 0.725, T_max = 0.771	R_int = 0.024
13451 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.06	Δρ_max = 1.34 e Å⁻³
3516 reflections	Δρ_min = −0.67 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cu1	0.13607 (4)	0.16622 (3)	0.06969 (3)	0.03794 (14)
O1	−0.0063 (3)	0.22330 (17)	−0.01736 (16)	0.0489 (6)
N1	0.1165 (3)	0.2683 (2)	0.16144 (18)	0.0410 (6)
N2	0.3213 (3)	0.1254 (2)	0.1558 (2)	0.0444 (6)
N3	0.1658 (4)	0.0673 (2)	−0.0253 (2)	0.0477 (7)
Cl1	−0.21684 (12)	0.25400 (7)	−0.17482 (6)	0.0585 (3)
Cl2	−0.33491 (14)	0.58481 (8)	−0.00046 (9)	0.0716 (3)
S1	0.10771 (10)	−0.05935 (7)	−0.17261 (6)	0.0476 (2)
C1	−0.0792 (4)	0.3018 (2)	−0.0076 (2)	0.0396 (7)
C2	−0.0634 (4)	0.3643 (2)	0.0713 (2)	0.0419 (7)
C3	−0.1427 (4)	0.4516 (3)	0.0723 (3)	0.0498 (8)
H3	−0.1293	0.4927	0.1236	0.060*
C4	−0.2389 (4)	0.4760 (3)	−0.0013 (3)	0.0510 (9)
C5	−0.2616 (4)	0.4157 (3)	−0.0785 (3)	0.0490 (8)
H5	−0.3279	0.4327	−0.1283	0.059*
C6	−0.1850 (4)	0.3311 (2)	−0.0802 (2)	0.0435 (7)
C7	0.0343 (4)	0.3430 (2)	0.1518 (2)	0.0450 (8)
H7	0.0382	0.3872	0.2010	0.054*
C8	0.2109 (5)	0.2585 (3)	0.2480 (3)	0.0621 (11)
H8A	0.2939	0.3048	0.2477	0.075*
H8B	0.1477	0.2698	0.3038	0.075*
C9	0.2742 (7)	0.1654 (3)	0.2521 (3)	0.0741 (14)
H9A	0.1983	0.1234	0.2803	0.089*
H9B	0.3644	0.1662	0.2939	0.089*
C10	0.4629 (6)	0.1738 (4)	0.1273 (4)	0.0883 (17)
H10A	0.4497	0.2409	0.1395	0.106*
H10B	0.5466	0.1518	0.1683	0.106*
C11	0.5099 (6)	0.1626 (5)	0.0307 (4)	0.114 (3)
H11A	0.5219	0.0964	0.0168	0.171*
H11B	0.6069	0.1945	0.0214	0.171*
H11C	0.4328	0.1893	−0.0111	0.171*
C12	0.3232 (5)	0.0217 (3)	0.1662 (3)	0.0581 (10)
H12A	0.3370	−0.0057	0.1034	0.070*
H12B	0.2221	0.0020	0.1886	0.070*
C13	0.4448 (5)	−0.0206 (3)	0.2326 (3)	0.0661 (11)
H13A	0.5456	0.0009	0.2140	0.099*
H13B	0.4406	−0.0884	0.2288	0.099*
H13C	0.4249	−0.0010	0.2970	0.099*
C14	0.1388 (3)	0.0159 (2)	−0.0861 (2)	0.0361 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0441 (2)	0.0384 (2)	0.0312 (2)	−0.00149 (16)	−0.00774 (16)	−0.00402 (15)
O1	0.0670 (16)	0.0426 (13)	0.0368 (12)	0.0082 (11)	−0.0161 (11)	−0.0057 (10)
N1	0.0423 (15)	0.0514 (16)	0.0293 (13)	−0.0062 (12)	−0.0044 (11)	−0.0049 (11)
N2	0.0438 (15)	0.0452 (16)	0.0441 (15)	−0.0062 (12)	−0.0110 (12)	0.0016 (12)
N3	0.0522 (17)	0.0497 (17)	0.0410 (15)	0.0019 (13)	−0.0060 (13)	−0.0096 (13)
Cl1	0.0706 (6)	0.0653 (6)	0.0392 (5)	0.0004 (5)	−0.0145 (4)	0.0011 (4)
Cl2	0.0714 (7)	0.0571 (6)	0.0867 (8)	0.0217 (5)	0.0217 (6)	0.0136 (5)
S1	0.0468 (5)	0.0543 (5)	0.0417 (5)	−0.0034 (4)	0.0008 (4)	−0.0165 (4)
C1	0.0425 (17)	0.0404 (17)	0.0358 (16)	−0.0053 (14)	0.0011 (13)	0.0028 (13)
C2	0.0423 (17)	0.0428 (17)	0.0406 (17)	−0.0016 (14)	0.0037 (13)	0.0003 (14)
C3	0.052 (2)	0.048 (2)	0.050 (2)	0.0001 (16)	0.0146 (16)	−0.0041 (16)
C4	0.0471 (19)	0.047 (2)	0.059 (2)	0.0088 (15)	0.0167 (17)	0.0094 (17)
C5	0.0420 (18)	0.056 (2)	0.049 (2)	0.0045 (15)	0.0060 (15)	0.0153 (16)
C6	0.0444 (17)	0.050 (2)	0.0359 (16)	−0.0046 (14)	0.0023 (13)	0.0064 (14)
C7	0.0479 (19)	0.049 (2)	0.0379 (17)	−0.0054 (15)	0.0026 (14)	−0.0117 (14)
C8	0.056 (2)	0.094 (3)	0.0361 (18)	0.006 (2)	−0.0135 (16)	−0.0129 (19)
C9	0.111 (4)	0.066 (3)	0.045 (2)	0.014 (2)	−0.031 (2)	−0.0106 (19)
C10	0.057 (3)	0.117 (5)	0.091 (4)	−0.022 (3)	−0.014 (3)	0.028 (3)
C11	0.057 (3)	0.187 (7)	0.100 (5)	−0.016 (4)	0.020 (3)	−0.061 (5)
C12	0.052 (2)	0.045 (2)	0.077 (3)	0.0055 (16)	−0.0224 (19)	−0.0060 (19)
C13	0.058 (2)	0.061 (2)	0.079 (3)	0.015 (2)	−0.020 (2)	0.000 (2)
C14	0.0315 (15)	0.0419 (17)	0.0350 (15)	0.0029 (12)	−0.0002 (12)	−0.0001 (13)

Geometric parameters (Å, º) top

Cu1—O1	1.903 (2)	C4—C5	1.389 (6)
Cu1—N1	1.939 (3)	C5—C6	1.365 (5)
Cu1—N3	1.947 (3)	C5—H5	0.9300
Cu1—N2	2.076 (3)	C7—H7	0.9300
Cu1—S1ⁱ	2.972 (3)	C8—C9	1.423 (6)
O1—C1	1.282 (4)	C8—H8A	0.9700
N1—C7	1.278 (4)	C8—H8B	0.9700
N1—C8	1.461 (4)	C9—H9A	0.9700
N2—C10	1.459 (5)	C9—H9B	0.9700
N2—C12	1.470 (5)	C10—C11	1.424 (8)
N2—C9	1.520 (5)	C10—H10A	0.9700
N3—C14	1.141 (4)	C10—H10B	0.9700
Cl1—C6	1.734 (4)	C11—H11A	0.9600
Cl2—C4	1.745 (4)	C11—H11B	0.9600
S1—C14	1.632 (3)	C11—H11C	0.9600
C1—C2	1.420 (5)	C12—C13	1.518 (5)
C1—C6	1.422 (5)	C12—H12A	0.9700
C2—C3	1.410 (5)	C12—H12B	0.9700
C2—C7	1.434 (5)	C13—H13A	0.9600
C3—C4	1.362 (5)	C13—H13B	0.9600
C3—H3	0.9300	C13—H13C	0.9600

O1—Cu1—N1	92.89 (11)	N1—C7—H7	117.3
O1—Cu1—N3	87.38 (11)	C2—C7—H7	117.3
N1—Cu1—N3	176.78 (12)	C9—C8—N1	109.4 (3)
O1—Cu1—N2	168.48 (11)	C9—C8—H8A	109.8
N1—Cu1—N2	83.82 (12)	N1—C8—H8A	109.8
N3—Cu1—N2	95.29 (12)	C9—C8—H8B	109.8
O1—Cu1—S1ⁱ	93.98 (12)	N1—C8—H8B	109.8
N1—Cu1—S1ⁱ	89.43 (12)	H8A—C8—H8B	108.2
N2—Cu1—S1ⁱ	97.02 (12)	C8—C9—N2	114.4 (4)
N3—Cu1—S1ⁱ	93.75 (12)	C8—C9—H9A	108.7
C1—O1—Cu1	127.8 (2)	N2—C9—H9A	108.7
C7—N1—C8	118.1 (3)	C8—C9—H9B	108.7
C7—N1—Cu1	126.5 (2)	N2—C9—H9B	108.7
C8—N1—Cu1	115.4 (2)	H9A—C9—H9B	107.6
C10—N2—C12	119.0 (4)	C11—C10—N2	117.0 (5)
C10—N2—C9	107.4 (4)	C11—C10—H10A	108.0
C12—N2—C9	106.6 (3)	N2—C10—H10A	108.0
C10—N2—Cu1	110.7 (3)	C11—C10—H10B	108.0
C12—N2—Cu1	110.0 (2)	N2—C10—H10B	108.0
C9—N2—Cu1	101.6 (2)	H10A—C10—H10B	107.3
C14—N3—Cu1	159.8 (3)	C10—C11—H11A	109.5
O1—C1—C2	125.2 (3)	C10—C11—H11B	109.5
O1—C1—C6	119.2 (3)	H11A—C11—H11B	109.5
C2—C1—C6	115.6 (3)	C10—C11—H11C	109.5
C3—C2—C1	120.5 (3)	H11A—C11—H11C	109.5
C3—C2—C7	117.2 (3)	H11B—C11—H11C	109.5
C1—C2—C7	122.3 (3)	N2—C12—C13	117.3 (3)
C4—C3—C2	120.4 (3)	N2—C12—H12A	108.0
C4—C3—H3	119.8	C13—C12—H12A	108.0
C2—C3—H3	119.8	N2—C12—H12B	108.0
C3—C4—C5	121.0 (3)	C13—C12—H12B	108.0
C3—C4—Cl2	120.3 (3)	H12A—C12—H12B	107.2
C5—C4—Cl2	118.7 (3)	C12—C13—H13A	109.5
C6—C5—C4	119.0 (3)	C12—C13—H13B	109.5
C6—C5—H5	120.5	H13A—C13—H13B	109.5
C4—C5—H5	120.5	C12—C13—H13C	109.5
C5—C6—C1	123.4 (3)	H13A—C13—H13C	109.5
C5—C6—Cl1	119.2 (3)	H13B—C13—H13C	109.5
C1—C6—Cl1	117.4 (3)	N3—C14—S1	177.6 (3)
N1—C7—C2	125.3 (3)

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	[Cu₂(NCS)₂(C₁₃H₁₇Cl₂N₂O)₂]
M_r	409.81
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.632 (2), 14.115 (3), 14.002 (3)
β (°)	90.491 (4)
V (Å³)	1706.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.72
Crystal size (mm)	0.20 × 0.17 × 0.16

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.725, 0.771
No. of measured, independent and observed [I > 2σ(I)] reflections	13451, 3516, 3046
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.118, 1.06
No. of reflections	3516
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.34, −0.67

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2001), SHELXTL (Bruker, 2001).

Acknowledgements

The authors thank Minjiang University for financial support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Panneerselvam, P., Nair, R. R., Vijayalakshmi, G., Subramanian, E. H. & Krishnan, S. (2005). Eur. J. Med. Chem. 40, 225–229. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Shi, L., Ge, H.-M., Tan, S.-H., Li, H.-Q., Song, Y.-C., Zhu, H.-L. & Tan, R.-X. (2007). Eur. J. Med. Chem. 42, 558–564. Web of Science CrossRef PubMed CAS Google Scholar
Singh, K., Barwa, M. S. & Tyagi, P. (2006). Eur. J. Med. Chem. 41, 147–153. Web of Science CrossRef PubMed Google Scholar
Singh, K., Barwa, M. S. & Tyagi, P. (2007). Eur. J. Med. Chem. 42, 394–402. Web of Science CrossRef PubMed CAS Google Scholar
Zhong, X., Yi, J., Sun, J., Wei, H.-L., Liu, W.-S. & Yu, K.-B. (2006). Eur. J. Med. Chem. 41, 1090–1092. Web of Science CSD CrossRef PubMed CAS Google Scholar

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