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Acta Cryst. (2007). E63, m3041    [ doi:10.1107/S160053680705773X ]

Di-[mu]-thocyanato-bis{2-bromo-4-chloro-6-[(2-methylaminoethylimino)methyl]phenolatocopper(II)}

P. Zhang

Abstract top

The title compound, [Cu2(C10H11BrClN2O)2(NCS)2], is a centrosymmetric dithiocyanate-bridged binuclear copper(II) complex. The CuII atoms are pentacoordinated by the N,N',O-donor atoms of the Schiff base ligand 2-bromo-4-chloro-6-[(2-methylaminoethylimino)methyl]phenol (HBCP), and by one N and one S atom from two symmetry-related thiocyanate anions, so forming a slightly distorted square-pyramidal coordination configuration. The Cu...Cu distance is 5.480 (2) Å.

Comment top

Recently, we has reported the crystal structure of a mononuclear copper(II) complex derived from the Schiff base ligand 1-[3-(cyclohexylamino)propyliminomethyl]-2-naphthol (Zhang, 2004). As an extension of this work on the structural characterization of Schiff base copper(II) compounds, we report on the crystal structure of the new title binuclear complex.

The title compound is a centrosymmetric dithiocyanato-bridged binuclear copper(II) complex, as shown in Fig. 1. The CuII atoms are pentacoordinated by the NNO donor atoms of the Schiff base ligand, 2-bromo-4-chloro-6-[(2-methylaminoethylimino)methyl]phenol (HBCP), and by one N and one S atom, from symmetry related thiocyanate anions, forming a slightly distorted square pyramidal coordination configuration. The Cu···Cu distance is 5.480 (2) Å. The bond lengths and angles (Table 1) are within normal ranges and comparable to the values found in the complex mentioned above.

Related literature top

For related literature, see: Zhang (2004).

Experimental top

N-Methyl-1,2-diaminoethane (0.1 mmol, 7.4 mg) and 3-bromo-5-chlorosalicylaldehyde (0.1 mmol, 23.5 mg) were dissolved in ethanol (10 cm3). The mixture was stirred for 10 min to give a clear yellow solution. To the solution was added an aqueous solution (2 cm3) of ammonium thiocyanate (0.1 mmol, 7.6 mg) and CuCl2·2H2O (0.1 mmol, 17.1 mg), with stirring. The mixture was stirred at room temperature for 1 h and then filtered. After keeping the brown filtrate in air for seven days, blue block-shaped crystals were formed with high yield (73% based on 3-bromo-5-chlorosalicylaldehyde).

Refinement top

The H2 atom was located in a difference Fourier map and refined isotropically, with the N—H distance restrained to 0.90 (1) Å. The other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The structure of the complex, showing the atom-numbering scheme with displacement ellipsoids drawn at the 30% probability level.
Di-µ-thocyanato-bis{2-bromo-4-chloro-6-[(2- methylaminoethylimino)methyl]phenolatocopper(II)} top
Crystal data top
[Cu2(C10H11Br1Cl1N2O1)2(NCS)2]F000 = 1624
Mr = 824.38Dx = 1.817 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
a = 7.2440 (14) ÅCell parameters from 1694 reflections
b = 19.693 (4) Åθ = 2.4–24.5º
c = 21.128 (4) ŵ = 4.41 mm−1
β = 90.98 (3)ºT = 298 (2) K
V = 3013.6 (10) Å3Block, blue
Z = 40.23 × 0.20 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3443 independent reflections
Radiation source: fine-focus sealed tube2187 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.064
T = 298(2) Kθmax = 27.5º
ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.430, Tmax = 0.472k = −25→25
12868 measured reflectionsl = −27→27
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)] = 0.048H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.0472P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
3443 reflectionsΔρmax = 0.51 e Å−3
176 parametersΔρmin = −0.44 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cu2(C10H11Br1Cl1N2O1)2(NCS)2]V = 3013.6 (10) Å3
Mr = 824.38Z = 4
Monoclinic, C2/cMo Kα
a = 7.2440 (14) ŵ = 4.41 mm−1
b = 19.693 (4) ÅT = 298 (2) K
c = 21.128 (4) Å0.23 × 0.20 × 0.20 mm
β = 90.98 (3)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3443 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2187 reflections with I > 2σ(I)
Tmin = 0.430, Tmax = 0.472Rint = 0.064
12868 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0481 restraint
wR(F2) = 0.115H atoms treated by a mixture of
independent and constrained refinement
S = 0.99Δρmax = 0.51 e Å−3
3443 reflectionsΔρmin = −0.44 e Å−3
176 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
xyzUiso*/Ueq
Cu10.08641 (8)0.23561 (3)0.44417 (3)0.03910 (18)
Br10.10518 (8)0.48082 (3)0.42831 (3)0.0597 (2)
Cl10.30665 (19)0.45169 (8)0.17930 (7)0.0700 (4)
S1−0.2341 (2)0.28910 (9)0.62831 (7)0.0673 (4)
O10.1260 (4)0.32908 (14)0.42352 (13)0.0400 (8)
N10.1986 (5)0.20430 (18)0.36694 (17)0.0404 (9)
N20.1020 (6)0.13676 (19)0.4707 (2)0.0489 (10)
N3−0.0142 (6)0.2635 (2)0.52432 (18)0.0475 (10)
C10.2193 (6)0.3142 (2)0.3153 (2)0.0374 (10)
C20.1652 (6)0.3537 (2)0.3687 (2)0.0363 (10)
C30.1652 (6)0.4246 (2)0.3588 (2)0.0410 (11)
C40.2047 (6)0.4542 (3)0.3019 (2)0.0505 (13)
H40.19920.50110.29720.061*
C50.2524 (6)0.4136 (3)0.2519 (2)0.0495 (13)
C60.2593 (7)0.3449 (3)0.2576 (2)0.0479 (12)
H60.29060.31830.22300.057*
C70.2399 (6)0.2413 (2)0.3195 (2)0.0430 (12)
H70.28770.21930.28450.052*
C80.2424 (8)0.1311 (2)0.3683 (3)0.0628 (15)
H8A0.37040.12470.38120.075*
H8B0.22550.11200.32630.075*
C90.1205 (8)0.0960 (2)0.4131 (2)0.0623 (15)
H9A−0.00020.08910.39360.075*
H9B0.17190.05190.42380.075*
C10−0.0439 (8)0.1095 (3)0.5115 (3)0.0659 (16)
H10A−0.16200.11550.49100.099*
H10B−0.04210.13330.55110.099*
H10C−0.02240.06200.51890.099*
C11−0.1063 (6)0.2737 (2)0.5673 (2)0.0447 (12)
H20.211 (4)0.132 (3)0.491 (2)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0502 (4)0.0315 (3)0.0357 (3)−0.0015 (3)0.0049 (2)0.0000 (2)
Br10.0834 (4)0.0382 (3)0.0574 (4)0.0070 (3)−0.0037 (3)−0.0075 (2)
Cl10.0670 (9)0.0903 (11)0.0529 (8)0.0032 (8)0.0099 (7)0.0358 (8)
S10.0625 (9)0.0938 (12)0.0463 (8)0.0121 (8)0.0181 (7)0.0091 (8)
O10.059 (2)0.0303 (17)0.0310 (17)−0.0028 (15)0.0085 (15)0.0012 (13)
N10.047 (2)0.032 (2)0.043 (2)−0.0035 (17)0.0084 (19)−0.0033 (18)
N20.062 (3)0.037 (2)0.047 (3)−0.002 (2)0.000 (2)0.0011 (19)
N30.059 (3)0.045 (2)0.038 (2)−0.003 (2)0.009 (2)0.0016 (19)
C10.037 (3)0.040 (3)0.036 (3)0.000 (2)0.006 (2)0.002 (2)
C20.031 (2)0.039 (3)0.039 (3)−0.003 (2)−0.004 (2)−0.002 (2)
C30.042 (3)0.039 (3)0.042 (3)0.002 (2)−0.002 (2)−0.003 (2)
C40.043 (3)0.047 (3)0.061 (4)−0.001 (2)−0.003 (3)0.015 (3)
C50.043 (3)0.068 (4)0.037 (3)0.001 (3)0.006 (2)0.018 (3)
C60.044 (3)0.061 (4)0.039 (3)0.000 (2)0.008 (2)0.000 (2)
C70.042 (3)0.043 (3)0.043 (3)−0.001 (2)0.008 (2)−0.015 (2)
C80.080 (4)0.033 (3)0.076 (4)0.002 (3)0.020 (3)−0.007 (3)
C90.093 (4)0.036 (3)0.058 (4)0.003 (3)−0.001 (3)−0.003 (3)
C100.083 (4)0.041 (3)0.074 (4)−0.013 (3)0.003 (3)0.010 (3)
C110.047 (3)0.045 (3)0.043 (3)−0.004 (2)−0.002 (2)0.008 (2)
Geometric parameters (Å, °) top
Cu1—O11.914 (3)C1—C71.445 (6)
Cu1—N31.935 (4)C2—C31.412 (6)
Cu1—N11.936 (4)C3—C41.370 (6)
Cu1—N22.028 (4)C4—C51.374 (7)
Br1—C31.896 (4)C4—H40.9300
Cl1—C51.758 (5)C5—C61.359 (6)
S1—C111.628 (5)C6—H60.9300
O1—C21.291 (5)C7—H70.9300
N1—C71.278 (6)C8—C91.478 (7)
N1—C81.475 (6)C8—H8A0.9700
N2—C91.464 (6)C8—H8B0.9700
N2—C101.476 (6)C9—H9A0.9700
N2—H20.899 (10)C9—H9B0.9700
N3—C111.154 (6)C10—H10A0.9600
C1—C61.397 (6)C10—H10B0.9600
C1—C21.430 (6)C10—H10C0.9600
O1—Cu1—N389.25 (14)C6—C5—C4121.4 (4)
O1—Cu1—N192.72 (14)C6—C5—Cl1119.6 (4)
N3—Cu1—N1176.34 (16)C4—C5—Cl1119.0 (4)
O1—Cu1—N2167.94 (16)C5—C6—C1120.1 (5)
N3—Cu1—N292.91 (17)C5—C6—H6120.0
N1—Cu1—N284.53 (16)C1—C6—H6120.0
C2—O1—Cu1126.9 (3)N1—C7—C1126.1 (4)
C7—N1—C8121.3 (4)N1—C7—H7117.0
C7—N1—Cu1125.9 (3)C1—C7—H7117.0
C8—N1—Cu1112.8 (3)N1—C8—C9109.8 (4)
C9—N2—C10111.2 (4)N1—C8—H8A109.7
C9—N2—Cu1107.6 (3)C9—C8—H8A109.7
C10—N2—Cu1118.2 (3)N1—C8—H8B109.7
C9—N2—H2104 (3)C9—C8—H8B109.7
C10—N2—H2108 (3)H8A—C8—H8B108.2
Cu1—N2—H2106 (3)N2—C9—C8109.9 (4)
C11—N3—Cu1166.0 (4)N2—C9—H9A109.7
C6—C1—C2121.1 (4)C8—C9—H9A109.7
C6—C1—C7117.4 (4)N2—C9—H9B109.7
C2—C1—C7121.4 (4)C8—C9—H9B109.7
O1—C2—C3120.3 (4)H9A—C9—H9B108.2
O1—C2—C1124.8 (4)N2—C10—H10A109.5
C3—C2—C1114.9 (4)N2—C10—H10B109.5
C4—C3—C2123.5 (4)H10A—C10—H10B109.5
C4—C3—Br1119.0 (4)N2—C10—H10C109.5
C2—C3—Br1117.5 (3)H10A—C10—H10C109.5
C3—C4—C5119.1 (5)H10B—C10—H10C109.5
C3—C4—H4120.5N3—C11—S1179.1 (5)
C5—C4—H4120.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Br1i0.899 (10)3.09 (4)3.777 (4)135 (4)
N2—H2···O1i0.899 (10)2.27 (3)3.031 (5)142 (4)
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.914 (3)Cu1—N11.936 (4)
Cu1—N31.935 (4)Cu1—N22.028 (4)
O1—Cu1—N389.25 (14)O1—Cu1—N2167.94 (16)
O1—Cu1—N192.72 (14)N3—Cu1—N292.91 (17)
N3—Cu1—N1176.34 (16)N1—Cu1—N284.53 (16)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Br1i0.899 (10)3.09 (4)3.777 (4)135 (4)
N2—H2···O1i0.899 (10)2.27 (3)3.031 (5)142 (4)
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1.
Acknowledgements top

The author thanks Xianyang Teachers College for a research grant.

references
References top

Bruker (1998). SMART (Version 5.63) and SAINT (Version 6.02). Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.

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

Zhang, P. (2004). Acta Cryst. E60, m1808–m1810.