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Acta Cryst. (2008). E64, m218    [ doi:10.1107/S1600536807063325 ]

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

X.-W. Li and Y. Qiu

Abstract top

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.

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.

Refinement top

H atoms were positioned geometrically and treated as riding atoms, with C—H = 0.93–0.97Å and Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

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
[Figure 1] 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]F000 = 836
Mr = 409.81Dx = 1.596 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
a = 8.632 (2) ÅCell parameters from 6502 reflections
b = 14.115 (3) Åθ = 2.4–27.7º
c = 14.002 (3) ŵ = 1.72 mm−1
β = 90.491 (4)ºT = 293 (2) K
V = 1706.0 (6) Å3Block, blue
Z = 40.20 × 0.17 × 0.16 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		3516 independent reflections
Radiation source: fine-focus sealed tube3046 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 293(2) Kθmax = 26.5º
ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −10→10
Tmin = 0.725, Tmax = 0.771k = −17→17
13451 measured reflectionsl = −17→17
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)] = 0.044H-atom parameters constrained
wR(F2) = 0.118  w = 1/[σ2(Fo2) + (0.058P)2 + 2.2599P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
3516 reflectionsΔρmax = 1.34 e Å−3
201 parametersΔρmin = −0.67 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2(NCS)2(C13H17Cl2N2O)2]V = 1706.0 (6) Å3
Mr = 409.81Z = 4
Monoclinic, P21/cMo Kα
a = 8.632 (2) ŵ = 1.72 mm−1
b = 14.115 (3) ÅT = 293 (2) K
c = 14.002 (3) Å0.20 × 0.17 × 0.16 mm
β = 90.491 (4)º
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)
Tmin = 0.725, Tmax = 0.771Rint = 0.024
13451 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044201 parameters
wR(F2) = 0.118H-atom parameters constrained
S = 1.06Δρmax = 1.34 e Å−3
3516 reflectionsΔρmin = −0.67 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
Cu10.13607 (4)0.16622 (3)0.06969 (3)0.03794 (14)
O1−0.0063 (3)0.22330 (17)−0.01736 (16)0.0489 (6)
N10.1165 (3)0.2683 (2)0.16144 (18)0.0410 (6)
N20.3213 (3)0.1254 (2)0.1558 (2)0.0444 (6)
N30.1658 (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)
S10.10771 (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)
H3−0.12930.49270.12360.060*
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)
H5−0.32790.4327−0.12830.059*
C6−0.1850 (4)0.3311 (2)−0.0802 (2)0.0435 (7)
C70.0343 (4)0.3430 (2)0.1518 (2)0.0450 (8)
H70.03820.38720.20100.054*
C80.2109 (5)0.2585 (3)0.2480 (3)0.0621 (11)
H8A0.29390.30480.24770.075*
H8B0.14770.26980.30380.075*
C90.2742 (7)0.1654 (3)0.2521 (3)0.0741 (14)
H9A0.19830.12340.28030.089*
H9B0.36440.16620.29390.089*
C100.4629 (6)0.1738 (4)0.1273 (4)0.0883 (17)
H10A0.44970.24090.13950.106*
H10B0.54660.15180.16830.106*
C110.5099 (6)0.1626 (5)0.0307 (4)0.114 (3)
H11A0.52190.09640.01680.171*
H11B0.60690.19450.02140.171*
H11C0.43280.1893−0.01110.171*
C120.3232 (5)0.0217 (3)0.1662 (3)0.0581 (10)
H12A0.3370−0.00570.10340.070*
H12B0.22210.00200.18860.070*
C130.4448 (5)−0.0206 (3)0.2326 (3)0.0661 (11)
H13A0.54560.00090.21400.099*
H13B0.4406−0.08840.22880.099*
H13C0.4249−0.00100.29700.099*
C140.1388 (3)0.0159 (2)−0.0861 (2)0.0361 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0441 (2)0.0384 (2)0.0312 (2)−0.00149 (16)−0.00774 (16)−0.00402 (15)
O10.0670 (16)0.0426 (13)0.0368 (12)0.0082 (11)−0.0161 (11)−0.0057 (10)
N10.0423 (15)0.0514 (16)0.0293 (13)−0.0062 (12)−0.0044 (11)−0.0049 (11)
N20.0438 (15)0.0452 (16)0.0441 (15)−0.0062 (12)−0.0110 (12)0.0016 (12)
N30.0522 (17)0.0497 (17)0.0410 (15)0.0019 (13)−0.0060 (13)−0.0096 (13)
Cl10.0706 (6)0.0653 (6)0.0392 (5)0.0004 (5)−0.0145 (4)0.0011 (4)
Cl20.0714 (7)0.0571 (6)0.0867 (8)0.0217 (5)0.0217 (6)0.0136 (5)
S10.0468 (5)0.0543 (5)0.0417 (5)−0.0034 (4)0.0008 (4)−0.0165 (4)
C10.0425 (17)0.0404 (17)0.0358 (16)−0.0053 (14)0.0011 (13)0.0028 (13)
C20.0423 (17)0.0428 (17)0.0406 (17)−0.0016 (14)0.0037 (13)0.0003 (14)
C30.052 (2)0.048 (2)0.050 (2)0.0001 (16)0.0146 (16)−0.0041 (16)
C40.0471 (19)0.047 (2)0.059 (2)0.0088 (15)0.0167 (17)0.0094 (17)
C50.0420 (18)0.056 (2)0.049 (2)0.0045 (15)0.0060 (15)0.0153 (16)
C60.0444 (17)0.050 (2)0.0359 (16)−0.0046 (14)0.0023 (13)0.0064 (14)
C70.0479 (19)0.049 (2)0.0379 (17)−0.0054 (15)0.0026 (14)−0.0117 (14)
C80.056 (2)0.094 (3)0.0361 (18)0.006 (2)−0.0135 (16)−0.0129 (19)
C90.111 (4)0.066 (3)0.045 (2)0.014 (2)−0.031 (2)−0.0106 (19)
C100.057 (3)0.117 (5)0.091 (4)−0.022 (3)−0.014 (3)0.028 (3)
C110.057 (3)0.187 (7)0.100 (5)−0.016 (4)0.020 (3)−0.061 (5)
C120.052 (2)0.045 (2)0.077 (3)0.0055 (16)−0.0224 (19)−0.0060 (19)
C130.058 (2)0.061 (2)0.079 (3)0.015 (2)−0.020 (2)0.000 (2)
C140.0315 (15)0.0419 (17)0.0350 (15)0.0029 (12)−0.0002 (12)−0.0001 (13)
Geometric parameters (Å, °) top
Cu1—O11.903 (2)C4—C51.389 (6)
Cu1—N11.939 (3)C5—C61.365 (5)
Cu1—N31.947 (3)C5—H50.9300
Cu1—N22.076 (3)C7—H70.9300
Cu1—S1i2.972 (3)C8—C91.423 (6)
O1—C11.282 (4)C8—H8A0.9700
N1—C71.278 (4)C8—H8B0.9700
N1—C81.461 (4)C9—H9A0.9700
N2—C101.459 (5)C9—H9B0.9700
N2—C121.470 (5)C10—C111.424 (8)
N2—C91.520 (5)C10—H10A0.9700
N3—C141.141 (4)C10—H10B0.9700
Cl1—C61.734 (4)C11—H11A0.9600
Cl2—C41.745 (4)C11—H11B0.9600
S1—C141.632 (3)C11—H11C0.9600
C1—C21.420 (5)C12—C131.518 (5)
C1—C61.422 (5)C12—H12A0.9700
C2—C31.410 (5)C12—H12B0.9700
C2—C71.434 (5)C13—H13A0.9600
C3—C41.362 (5)C13—H13B0.9600
C3—H30.9300C13—H13C0.9600
O1—Cu1—N192.89 (11)N1—C7—H7117.3
O1—Cu1—N387.38 (11)C2—C7—H7117.3
N1—Cu1—N3176.78 (12)C9—C8—N1109.4 (3)
O1—Cu1—N2168.48 (11)C9—C8—H8A109.8
N1—Cu1—N283.82 (12)N1—C8—H8A109.8
N3—Cu1—N295.29 (12)C9—C8—H8B109.8
O1—Cu1—S1i93.98 (12)N1—C8—H8B109.8
N1—Cu1—S1i89.43 (12)H8A—C8—H8B108.2
N2—Cu1—S1i97.02 (12)C8—C9—N2114.4 (4)
N3—Cu1—S1i93.75 (12)C8—C9—H9A108.7
C1—O1—Cu1127.8 (2)N2—C9—H9A108.7
C7—N1—C8118.1 (3)C8—C9—H9B108.7
C7—N1—Cu1126.5 (2)N2—C9—H9B108.7
C8—N1—Cu1115.4 (2)H9A—C9—H9B107.6
C10—N2—C12119.0 (4)C11—C10—N2117.0 (5)
C10—N2—C9107.4 (4)C11—C10—H10A108.0
C12—N2—C9106.6 (3)N2—C10—H10A108.0
C10—N2—Cu1110.7 (3)C11—C10—H10B108.0
C12—N2—Cu1110.0 (2)N2—C10—H10B108.0
C9—N2—Cu1101.6 (2)H10A—C10—H10B107.3
C14—N3—Cu1159.8 (3)C10—C11—H11A109.5
O1—C1—C2125.2 (3)C10—C11—H11B109.5
O1—C1—C6119.2 (3)H11A—C11—H11B109.5
C2—C1—C6115.6 (3)C10—C11—H11C109.5
C3—C2—C1120.5 (3)H11A—C11—H11C109.5
C3—C2—C7117.2 (3)H11B—C11—H11C109.5
C1—C2—C7122.3 (3)N2—C12—C13117.3 (3)
C4—C3—C2120.4 (3)N2—C12—H12A108.0
C4—C3—H3119.8C13—C12—H12A108.0
C2—C3—H3119.8N2—C12—H12B108.0
C3—C4—C5121.0 (3)C13—C12—H12B108.0
C3—C4—Cl2120.3 (3)H12A—C12—H12B107.2
C5—C4—Cl2118.7 (3)C12—C13—H13A109.5
C6—C5—C4119.0 (3)C12—C13—H13B109.5
C6—C5—H5120.5H13A—C13—H13B109.5
C4—C5—H5120.5C12—C13—H13C109.5
C5—C6—C1123.4 (3)H13A—C13—H13C109.5
C5—C6—Cl1119.2 (3)H13B—C13—H13C109.5
C1—C6—Cl1117.4 (3)N3—C14—S1177.6 (3)
N1—C7—C2125.3 (3)
Symmetry codes: (i) −x, −y, −z.
Acknowledgements top

The authors thank Minjiang University for financial support.

references
References top

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