{4 Bromo 2 [(2 di­ethyl­amino­ethyl­imino)methyl]phenolato}thio­cyanato­copper(II)

metal-organic papers

Acta Cryst.(2006). E62, m45–m46 doi:10.1107/S1600536805040249 Zhong-Lu You _[Cu(C

13H18BrN2O)(NCS)]

m45

Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

{4-Bromo-2-[(2-diethylaminoethylimino)methyl]-phenolato}thiocyanatocopper(II)

Zhong-Lu You

Department of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, People’s Republic of China

Correspondence e-mail: youzhonglu@yahoo.com.cn

Key indicators

Single-crystal X-ray study

T= 298 K

Mean(C–C) = 0.004 A˚

Rfactor = 0.036

wRfactor = 0.091

Data-to-parameter ratio = 18.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2006 International Union of Crystallography Printed in Great Britain – all rights reserved

The title compound, [Cu(C13H18BrN2O)(NCS)], is a

mono-nuclear Schiff base copper(II) complex. The CuII atom is coordinated by one O and two N atoms of the Schiff base ligand, and by one N atom of the thiocyanate ligand, forming a square-planar coordination.

Comment

Recently, we have reported a series of Schiff base complexes (You, 2005a,b,c). As an extension of this work on the struc-tural characterization of Schiff base complexes, we describe here the synthesis and structure of the title new copper(II) compound, (I).

The molecular structure of compound (I) is illustrated in Fig. 1, and selected bond distances and angles are given in Table 1. Compound (I) is structurally similar to the copper(II) compounds reported recently (You, 2005d,e). The CuIIatom is four-coordinated, in a square-planar arrangement, by one O and two N atoms of the Schiff base ligand, and by one N atom of the thiocyanate anion. The values of thetransangles in the CuON3 square plane are 176.48 (12) and 176.09 (10),

indi-cating a slightly distorted square-planar coordination. The Cu—O and Cu—N bond lengths (Table 1) are comparable with the corresponding values observed in other Schiff base copper(II) complexes (You & Zhu, 2004) and, as expected, the

Received 30 November 2005 Accepted 2 December 2005 Online 7 December 2005

Figure 1

bond involving amine atom N2 is longer than that involving imine atom N1 (Mondalet al., 2001).

In the crystal structure, the molecules stack along theaaxis; the crystal packing is shown in Fig. 2.

Experimental

5-Bromosalicylaldehyde (0.1 mmol, 20.1 mg) and N,N0 -diethyl-ethane-1,2-diamine (0.1 mmol, 11.6 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 20 min to give a yellow solution. To this solution were added an aqueous solution (2 ml) of NH4NCS (0.1 mmol, 6.5 mg) and a MeOH solution (3 ml) of Cu(CH3COO)2H2O (0.1 mmol, 19.9 mg), with stirring. The mixture was stirred for a further 20 min at room temperature and then filtered. The filtrate was kept in air for 5 d, during which time blue block-shaped crystals of (I) were formed.

Crystal data

[Cu(C13H18BrN2O)(NCS)]

Mr= 419.82 Monoclinic,P2₁=c a= 7.052 (1) A˚

b= 16.688 (2) A˚

c= 13.775 (2) A˚

= 94.79 (1) V= 1615.4 (4) A˚3

Z= 4

Dx= 1.726 Mg m

3 MoKradiation Cell parameters from 3328

reflections

= 2.4–24.6

= 3.96 mm1

T= 298 (2) K Block, blue

0.250.180.17 mm

Bruker SMART CCD area-detector diffractometer

!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.404,Tmax= 0.510 11427 measured reflections

3564 independent reflections 2787 reflections withI> 2(I)

Rint= 0.031

max= 27.5

h=8!9

k=21!21

l=16!17

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.036

wR(F2_{) = 0.091}

S= 1.03 3564 reflections 192 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0453P)2 + 0.4325P]

whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.54 e A˚

3

min=0.41 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

Cu1—O1 1.902 (2)

Cu1—N1 1.928 (3)

Cu1—N3 1.938 (3)

Cu1—N2 2.103 (2)

O1—Cu1—N1 92.93 (9)

O1—Cu1—N3 89.52 (11)

N1—Cu1—N3 176.48 (12)

O1—Cu1—N2 176.09 (10)

N1—Cu1—N2 84.27 (10)

N3—Cu1—N2 93.41 (11)

The H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93– 0.97 A˚ , and withUiso(H) = 1.2 or 1.5Ueq(C).

Data collection:SMART(Bruker, 1998); cell refinement:SAINT (Bruker, 1998); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL(Sheldrick, 1997b); software used to prepare material for publication:SHELXTL.

The author thanks Liaoning Normal University, People’s Republic of China, for funding this study.

References

Bruker (1998).SMART(Version 5.628) andSAINT(Version 6.02). Bruker AXS Inc., Madison, Wisconsin, USA.

Mondal, N., Mitra, S., Gramilich, V., Ghodsi, S. O. & Malik, K. M. A. (2001).

Polyhedron,20, 135–141.

Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of

Go¨ttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.

You, Z.-L. (2005a).Acta Cryst.E61, m1571–m1573. You, Z.-L. (2005b).Acta Cryst.E61, m1601–m1603. You, Z.-L. (2005c).Acta Cryst.E61, m1637–m1638. You, Z.-L. (2005d).Acta Cryst.E61, m2226–m2227. You, Z.-L. (2005e).Acta Cryst.E61, m1963–m1964.

You, Z.-L. & Zhu, H.-L. (2004).Z. Anorg. Allg. Chem.630, 2754–2760. Figure 2

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Acta Cryst. (2006). E62, m45–m46 [doi:10.1107/S1600536805040249]

{4-Bromo-2-[(2-diethylaminoethylimino)methyl]phenolato}thiocyanato-copper(II)

Zhong-Lu You

S1. Comment

Recently, we have reported a series of Schiff base complexes (You, 2005a,b,c). As an extension of this work on the

structural characterization of Schiff base complexes, we describe here the synthesis and structure of the title new

copper(II) compound, (I).

The molecular structure of compound (I) is illustrated in Fig. 1, and selected bond distances and angles are given in

Table 1. Compound (I) is structurally similar to the copper(II) compounds reported recently (You, 2005d,e). The CuII

atom is four-coordinated, in a square-planar arrangement, by one O and two N atoms of the Schiff base ligand, and by

one N atom of the thiocyanate anion. The values of the trans angles in the CuON3 square plane are 176.48 (12) and

176.09 (10)°, indicating a slightly distorted square-planar coordination. The Cu—O and Cu—N bond lengths (Table 1)

are comparable with the corresponding values observed in other Schiff base copper(II) complexes (You & Zhu, 2004)

and, as expected, the bond involving amine atom N2 [2.071 (3) Å] is longer than that involving imine atom N1 [1.925 (3)

Å] (Mondal et al., 2001).

In the crystal strucrure, the molecules stack along the a axis; the crystal packing is shown in Fig. 2.

S2. Experimental

5-Bromosalicylaldehy (0.1 mmol, 20.1 mg) and N,N′-diethylethane-1,2-diamine (0.1 mmol, 11.6 mg) were dissolved in

MeOH (10 ml). The mixture was stirred at room temperature for 20 min to give a yellow solution. To this solution were

added an aqueous solution (2 ml) of NH4NCS (0.1 mmol, 6.5 mg) and a MeOH solution (3 ml) of Cu(CH3COO)2·H2O

(0.1 mmol, 19.9 mg), with stirring. The mixture was stirred for a further 20 min at room temperature and then filtered.

The filtrate was kept in air for 5 d, during which time blue block-shaped crystals of (I) were formed.

S3. Refinement

The H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the

Figure 1

The molecular structure of compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the

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Figure 2

The crystal packing of compound (I), viewed along the a axis.

{4-Bromo-2-[(2-diethylaminoethylimino)methyl]phenolato}thiocyanatocopper(II)

Crystal data

[Cu(C13H18BrN2O)(NCS)] Mr = 419.82

Monoclinic, P21/c Hall symbol: -P 2ybc

a = 7.052 (1) Å

b = 16.688 (2) Å

c = 13.775 (2) Å

β = 94.79 (1)°

V = 1615.4 (4) Å3 Z = 4

F(000) = 844

Dx = 1.726 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3328 reflections

θ = 2.4–24.6°

µ = 3.96 mm−1 T = 298 K Block, blue

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.404, Tmax = 0.510

11427 measured reflections 3564 independent reflections 2787 reflections with I > 2σ(I)

Rint = 0.031

θmax = 27.5°, θmin = 1.9° h = −8→9

k = −21→21

l = −16→17

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.036} wR(F2_{) = 0.091} S = 1.03 3564 reflections 192 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0453P)2 + 0.4325P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.54 e Å−3 Δρmin = −0.41 e Å−3

Special details

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 F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

Cu1 0.24192 (5) 0.72498 (2) 1.01867 (3) 0.03673 (12)

Br1 0.93758 (5) 0.40802 (2) 1.16694 (3) 0.05364 (13)

S1 −0.29725 (14) 0.82260 (8) 1.15452 (8) 0.0719 (3)

O1 0.2750 (3) 0.63306 (12) 1.09990 (15) 0.0410 (5)

N1 0.4757 (4) 0.70606 (14) 0.95910 (17) 0.0352 (5)

N2 0.2110 (4) 0.82183 (15) 0.92092 (18) 0.0390 (6)

N3 0.0115 (4) 0.75086 (19) 1.0795 (2) 0.0588 (8)

C1 0.5849 (4) 0.59285 (16) 1.0572 (2) 0.0324 (6)

C2 0.4214 (4) 0.58535 (16) 1.1096 (2) 0.0323 (6)

C3 0.4193 (4) 0.52132 (18) 1.1767 (2) 0.0375 (7)

H3 0.3135 0.5145 1.2119 0.045*

C4 0.5687 (4) 0.46902 (17) 1.1913 (2) 0.0382 (7)

H4 0.5629 0.4271 1.2355 0.046*

C5 0.7289 (4) 0.47863 (17) 1.1403 (2) 0.0359 (7)

C6 0.7373 (4) 0.53849 (17) 1.0741 (2) 0.0358 (6)

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C7 0.6001 (4) 0.65218 (17) 0.9838 (2) 0.0348 (6)

H7 0.7099 0.6517 0.9508 0.042*

C8 0.5146 (5) 0.7638 (2) 0.8834 (3) 0.0514 (9)

H8A 0.5804 0.7376 0.8330 0.062*

H8B 0.5946 0.8067 0.9111 0.062*

C9 0.3304 (5) 0.7965 (2) 0.8414 (2) 0.0501 (8)

H9A 0.2633 0.7561 0.8013 0.060*

H9B 0.3531 0.8422 0.8004 0.060*

C10 0.2880 (6) 0.8978 (2) 0.9632 (3) 0.0696 (12)

H10A 0.4241 0.8914 0.9776 0.083*

H10B 0.2692 0.9392 0.9139 0.083*

C11 0.2081 (8) 0.9266 (3) 1.0516 (4) 0.1023 (18)

H11A 0.0741 0.9358 1.0382 0.153*

H11B 0.2695 0.9757 1.0724 0.153*

H11C 0.2283 0.8871 1.1021 0.153*

C12 0.0093 (5) 0.8275 (2) 0.8795 (3) 0.0513 (9)

H12A −0.0680 0.8425 0.9316 0.062*

H12B −0.0314 0.7745 0.8575 0.062*

C13 −0.0328 (5) 0.8853 (2) 0.7963 (3) 0.0573 (10)

H13A −0.0020 0.9388 0.8179 0.086*

H13B −0.1655 0.8825 0.7743 0.086*

H13C 0.0421 0.8714 0.7437 0.086*

C14 −0.1159 (5) 0.7801 (2) 1.1115 (2) 0.0465 (8)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Cu1 0.0362 (2) 0.0425 (2) 0.0329 (2) 0.00864 (15) 0.01138 (15) 0.00463 (15)

Br1 0.0387 (2) 0.0456 (2) 0.0759 (3) 0.00827 (14) 0.00099 (17) 0.00703 (16)

S1 0.0446 (5) 0.1075 (9) 0.0651 (7) 0.0174 (5) 0.0135 (5) −0.0313 (6)

O1 0.0387 (12) 0.0458 (12) 0.0412 (12) 0.0094 (9) 0.0189 (10) 0.0113 (9)

N1 0.0358 (13) 0.0378 (12) 0.0333 (13) 0.0006 (10) 0.0106 (11) 0.0022 (10)

N2 0.0379 (14) 0.0433 (14) 0.0358 (14) 0.0047 (11) 0.0037 (11) 0.0045 (11)

N3 0.0573 (19) 0.0691 (19) 0.0540 (19) 0.0265 (16) 0.0284 (15) 0.0197 (16)

C1 0.0330 (15) 0.0321 (14) 0.0323 (15) 0.0012 (11) 0.0030 (12) −0.0046 (12)

C2 0.0326 (15) 0.0356 (14) 0.0291 (15) −0.0005 (12) 0.0052 (12) −0.0038 (12)

C3 0.0373 (16) 0.0409 (16) 0.0354 (16) −0.0037 (13) 0.0091 (13) 0.0000 (13)

C4 0.0409 (17) 0.0346 (15) 0.0389 (17) −0.0021 (13) 0.0018 (14) 0.0010 (12)

C5 0.0295 (15) 0.0360 (15) 0.0414 (17) 0.0037 (12) −0.0026 (13) −0.0063 (13)

C6 0.0284 (14) 0.0397 (15) 0.0400 (17) −0.0002 (12) 0.0065 (12) −0.0064 (13)

C7 0.0291 (14) 0.0386 (15) 0.0383 (16) −0.0027 (12) 0.0115 (12) −0.0039 (12)

C8 0.052 (2) 0.0501 (19) 0.056 (2) 0.0058 (16) 0.0244 (17) 0.0156 (16)

C9 0.050 (2) 0.060 (2) 0.0425 (19) 0.0082 (16) 0.0150 (16) 0.0133 (16)

C10 0.068 (3) 0.064 (2) 0.073 (3) 0.007 (2) −0.011 (2) −0.009 (2)

C11 0.127 (5) 0.089 (3) 0.095 (4) 0.002 (3) 0.032 (4) −0.037 (3)

C12 0.0409 (19) 0.060 (2) 0.053 (2) 0.0056 (16) 0.0010 (16) 0.0171 (17)

C13 0.049 (2) 0.074 (2) 0.048 (2) 0.0158 (18) 0.0028 (17) 0.0182 (18)

Cu1—O1 1.902 (2) C5—C6 1.357 (4)

Cu1—N1 1.928 (3) C6—H6 0.9300

Cu1—N3 1.938 (3) C7—H7 0.9300

Cu1—N2 2.103 (2) C8—C9 1.482 (5)

Br1—C5 1.897 (3) C8—H8A 0.9700

S1—C14 1.617 (4) C8—H8B 0.9700

O1—C2 1.302 (3) C9—H9A 0.9700

N1—C7 1.282 (4) C9—H9B 0.9700

N1—C8 1.463 (4) C10—C11 1.464 (6)

N2—C10 1.480 (5) C10—H10A 0.9700

N2—C12 1.490 (4) C10—H10B 0.9700

N2—C9 1.497 (4) C11—H11A 0.9600

N3—C14 1.143 (4) C11—H11B 0.9600

C1—C6 1.411 (4) C11—H11C 0.9600

C1—C2 1.416 (4) C12—C13 1.509 (4)

C1—C7 1.426 (4) C12—H12A 0.9700

C2—C3 1.414 (4) C12—H12B 0.9700

C3—C4 1.370 (4) C13—H13A 0.9600

C3—H3 0.9300 C13—H13B 0.9600

C4—C5 1.389 (4) C13—H13C 0.9600

C4—H4 0.9300

O1—Cu1—N1 92.93 (9) N1—C8—C9 108.1 (3)

O1—Cu1—N3 89.52 (11) N1—C8—H8A 110.1

N1—Cu1—N3 176.48 (12) C9—C8—H8A 110.1

O1—Cu1—N2 176.09 (10) N1—C8—H8B 110.1

N1—Cu1—N2 84.27 (10) C9—C8—H8B 110.1

N3—Cu1—N2 93.41 (11) H8A—C8—H8B 108.4

C2—O1—Cu1 127.65 (19) C8—C9—N2 110.3 (3)

C7—N1—C8 119.1 (3) C8—C9—H9A 109.6

C7—N1—Cu1 126.3 (2) N2—C9—H9A 109.6

C8—N1—Cu1 114.43 (19) C8—C9—H9B 109.6

C10—N2—C12 113.8 (3) N2—C9—H9B 109.6

C10—N2—C9 108.6 (3) H9A—C9—H9B 108.1

C12—N2—C9 108.3 (3) C11—C10—N2 117.0 (4)

C10—N2—Cu1 113.0 (2) C11—C10—H10A 108.0

C12—N2—Cu1 109.78 (19) N2—C10—H10A 108.0

C9—N2—Cu1 102.55 (18) C11—C10—H10B 108.0

C14—N3—Cu1 167.6 (3) N2—C10—H10B 108.0

C6—C1—C2 120.0 (3) H10A—C10—H10B 107.3

C6—C1—C7 117.5 (3) C10—C11—H11A 109.5

C2—C1—C7 122.4 (3) C10—C11—H11B 109.5

O1—C2—C3 118.5 (3) H11A—C11—H11B 109.5

O1—C2—C1 124.5 (3) C10—C11—H11C 109.5

C3—C2—C1 117.0 (3) H11A—C11—H11C 109.5

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C4—C3—H3 119.1 N2—C12—C13 116.9 (3)

C2—C3—H3 119.1 N2—C12—H12A 108.1

C3—C4—C5 120.0 (3) C13—C12—H12A 108.1

C3—C4—H4 120.0 N2—C12—H12B 108.1

C5—C4—H4 120.0 C13—C12—H12B 108.1

C6—C5—C4 120.5 (3) H12A—C12—H12B 107.3

C6—C5—Br1 120.7 (2) C12—C13—H13A 109.5

C4—C5—Br1 118.7 (2) C12—C13—H13B 109.5

C5—C6—C1 120.6 (3) H13A—C13—H13B 109.5

C5—C6—H6 119.7 C12—C13—H13C 109.5

C1—C6—H6 119.7 H13A—C13—H13C 109.5

N1—C7—C1 125.8 (3) H13B—C13—H13C 109.5

N1—C7—H7 117.1 N3—C14—S1 178.6 (3)