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Acta Cryst. (2007). E63, m1824-m1825    [ doi:10.1107/S1600536807026967 ]

Di-[mu]-acetato-[kappa]4O:O-bis{2-[(2-aminoethyl)iminomethyl]phenolato-[kappa]3N,N',O}copper(II)

C.-C. Zhao, Y.-B. Jiang, A.-L. Cui and H.-Z. Kou

Abstract top

The title complex, [Cu2(C9H11N2O)2(C2H3O2)2] or Cu2L2OAc2 [L is (salicylideneimino)ethylamine and OAc is acetate], has a centrosymmetric acetate-bridged dinuclear structure with each CuII ion in a distorted square-pyramidal coordination geometry, the angles at the CuII ion deviating from ideal values. The basal plane is occupied by two N atoms, one phenoxy O atom and one O atom from an OAc ligand, with an O atom of a bridging OAc ligand in the apical position. The apical Cu-O bond distance is longer than the equatorial Cu-N or Cu-O bond distances. In the crystal structure, intermolecular hydrogen bonds involving the amino N atom and the uncoordinated acetate ligand O atom connect the dinuclear units into a two-dimensional network.

Comment top

Schiff bases play a significant role in coordination chemistry as a widely used ligand (Green et al., 1973; Dey, 1974). Not only the nitrogen atoms but also other high electronegativity atoms like oxygen and sulfur exist in the molecular structure lead to various chelation modes (Dutta & Das, 1988; Chattopadhyay et al., 2006; Mikuriya et al., 2001; Nakajima et al., 1998). In this contribution, we report the tridentate Schiff base 2-(Salicylideneimino)ethylamine, which is not saturated and then other donors may be accepted in the coordination environment giving the bridged structures. Several mono- and di-nuclear complexes have been reported (Gardner et al., 1968; Saridha et al., 2005; Mandal & Nag, 1984). Carboxylate is another interesting bridging group because it exhibits several coordination modes (Sessler et al., 1991; Boyle et al., 1998; Turner et al., 1992; Rettig et al., 1999; Wang et al., 2004). We focus our interest in the carboxylate and tridentate Schiff base groups and obtain the title acetate-bridged dinuclear copper(II) complex Cu2L2Ac2 (I).

Fig. 1 shows the dimeric structure of (I). The two Cu(II) atoms are inversion-center related and are doubly bridged by two oxygen atoms of two acetate ligands. The Cu(1) atom reveals a CuN2O3 coordination environment with the two nitrogen atoms and one oxygen atom of the L− ligand and one oxygen atom of the acetate occupying the basal plane [Cu(1)—O(1) 1.916 (2) Å, Cu(1)—N(1) 1.946 (2) Å, Cu(1)—N(2) 2.011 (2) Å]. Each acetate group bridges two copper(II) ions through O(2) and O(2 A) oxygen atoms involving axial and equatorial positions in the copper(II) coordination polyhedra, respectively. The axial Cu—O bond distance [Cu(1)—O(2 A) 2.454 (3) Å] is significantly longer than the equatorial one [Cu(1)—O(2) 1.970 (2) Å]. Since many five-coordinate structures with intermediate geometries between regular trigonal bipyramidal (TBP) and square pyramidal (SP), the τ value has been used to evaluate the distortion (Addison et al., 1984). In the present complex, τ values is calculated to be 0.08 which indicates that it is very close to a SP geometry. The Cu(II) centers and bridged oxygen atoms form a rhombic plane with the angles O(2)—Cu(1)—O(2 A) and Cu(1)—O(2)—Cu(1 A) of 85.60 ° and 94.40 °, respectively.

A supramolecular network through weak intermolecular N—H···O hydrogen bonds was displayed in Fig. 2. The intramolecular hydrogen bonds exist through N—H···O (phenol) with a distance of 3.203 Å (N···O), which help to stabilize each of the dinuclear unit. The intermolecular hydrogen bonds exist through N—H···O (acetate) of the adjacent molecules with the N···O distance of 3.009 Å. As a result, the crystal structure can be described as a two-dimensional network.

Related literature top

For related literature, see: Addison et al. (1984); Boyle et al. (1998); Chattopadhyay et al. (2006); Dey (1974); Dutta & Das (1988); Gardner et al. (1968); Green et al. (1973); Mandal & Nag (1984); Mikuriya et al. (2001); Nakajima et al. (1998); Rettig et al. (1999); Saridha et al. (2005); Sessler et al. (1991); Turner et al. (1992); Wang et al. (2004).

For related literature, see: Benelli et al. (1990).

Experimental top

Cu2L2Ac2 was synthesized as previously reported with a slight modification (Cristiano et al., 1990). A solution of salicylaldehyde (2.45 g, 20 mmol) was slowly added to a water-ethanol solution (1: 1, v/v) of copper (II) acetate (4.00 g, 20 mmol) of 100 ml. After adding NaOH (0.10 g, 2.5 mmol) and heating for 10 min, we carefully add ethylenediamine (1.25 g, 20 mmol) to the resulting black-green solution, which gradually changed to black-blue. After the addition was completed, the solution was heated for half an hour. After evaporation of the excess solvent and cooling in the refrigerator, a dark blue precipitate was formed and collected by filtration. Yield: 65%.

A small quantity of the precipitate (50 mg, 0.2 mmol) was dissolved in a water-methanol solution (1: 4, v/v) of 15 ml approximately. After slow evaporation for two weeks, single crystals sutiable for X-ray diffraction analysis were obtained as light-blue rhombic slices.

Refinement top

H atoms bound to C and N atoms were placed in caculated positions with C—H = 0.93–0.77Å and N—H = 0.90Å and included in the refinement with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(C) for methyl H atoms.

Computing details top

Data collection: CrystalStructure (Rigaku/MSC, 2004); cell refinement: CrystalStructure; data reduction: CrystalStructure; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHEXLTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of complex (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. [symmetry code: (A) −x + 1, −y + 2, −z]
[Figure 2] Fig. 2. A hydrogen bonded (dashed lines) layer within the crystal structure of the title compound.
Di-µ-acetato-κ4<it>O</it>:<it>O</it>-bis{2-[(2-\ aminoethyl)iminomethyl]phenolato-\ κ3<it>N</it>,<it>N</it>',<it>O</it>}copper(II) top
Crystal data top
[Cu2(C9H11N2O)2(C2H3O2)2]F000 = 588
Mr = 571.56Dx = 1.622 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2675 reflections
a = 11.099 (2) Åθ = 3.2–27.5º
b = 14.745 (3) ŵ = 1.86 mm−1
c = 7.4660 (15) ÅT = 293 K
β = 106.68 (3)ºRhomb, blue
V = 1170.4 (4) Å30.28 × 0.20 × 0.12 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		2675 independent reflections
Radiation source: fine-focus sealed tube2159 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.065
Detector resolution: 100x100 microns pixels mm-1θmax = 27.5º
T = 293 Kθmin = 3.2º
ω scansh = −14→14
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −19→19
Tmin = 0.652, Tmax = 0.795l = −8→9
10843 measured reflections
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)] = 0.039H-atom parameters constrained
wR(F2) = 0.088  w = 1/[σ2(Fo2) + (0.010P)2 + 1.P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.007
2675 reflectionsΔρmax = 0.39 e Å−3
154 parametersΔρmin = −0.40 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2(C9H11N2O)2(C2H3O2)2]V = 1170.4 (4) Å3
Mr = 571.56Z = 2
Monoclinic, P21/cMo Kα
a = 11.099 (2) ŵ = 1.86 mm−1
b = 14.745 (3) ÅT = 293 K
c = 7.4660 (15) Å0.28 × 0.20 × 0.12 mm
β = 106.68 (3)º
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		2675 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2159 reflections with I > 2σ(I)
Tmin = 0.652, Tmax = 0.795Rint = 0.065
10843 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039154 parameters
wR(F2) = 0.088H-atom parameters constrained
S = 1.07Δρmax = 0.39 e Å−3
2675 reflectionsΔρmin = −0.40 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
Cu10.42654 (3)1.09572 (2)−0.06380 (4)0.03275 (12)
O10.31409 (19)1.07381 (13)0.0841 (3)0.0416 (5)
O20.57032 (18)1.06438 (13)0.1520 (3)0.0380 (4)
N10.2959 (2)1.14930 (14)−0.2682 (3)0.0363 (5)
N20.5350 (2)1.10879 (15)−0.2366 (3)0.0383 (5)
H2B0.58281.1590−0.20810.046*
H2C0.58601.0604−0.22630.046*
C10.1953 (3)1.09581 (18)0.0429 (4)0.0373 (6)
C70.1813 (3)1.16371 (18)−0.2704 (4)0.0392 (7)
H7A0.12921.1917−0.37620.047*
C60.1268 (3)1.14059 (18)−0.1248 (4)0.0388 (6)
C80.3441 (3)1.17848 (19)−0.4217 (4)0.0439 (7)
H8A0.37511.2402−0.40100.053*
H8B0.27771.1764−0.53900.053*
C30.0044 (3)1.0980 (2)0.1428 (5)0.0578 (9)
H3A−0.03631.08270.23140.069*
C5−0.0006 (3)1.1638 (2)−0.1492 (5)0.0509 (8)
H5A−0.04471.1935−0.25810.061*
C20.1283 (3)1.0751 (2)0.1724 (5)0.0492 (8)
H2A0.16971.04480.28200.059*
C4−0.0610 (3)1.1440 (3)−0.0189 (6)0.0620 (10)
H4A−0.14451.1608−0.03750.074*
C90.4492 (3)1.1152 (2)−0.4288 (4)0.0444 (7)
H9A0.41591.0559−0.47270.053*
H9B0.49381.1387−0.51320.053*
O30.6197 (3)1.20989 (15)0.1595 (3)0.0636 (7)
C100.6400 (3)1.13237 (19)0.2222 (4)0.0364 (6)
C110.7492 (3)1.1133 (3)0.3916 (5)0.0594 (9)
H11A0.79481.16840.43250.089*
H11B0.80391.06960.36010.089*
H11C0.71851.08980.49010.089*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0409 (2)0.02722 (18)0.02902 (19)0.00513 (14)0.00822 (13)0.00394 (12)
O10.0430 (12)0.0456 (12)0.0369 (11)0.0091 (9)0.0123 (9)0.0104 (8)
O20.0418 (11)0.0312 (10)0.0364 (10)0.0011 (9)0.0040 (8)0.0037 (8)
N10.0495 (15)0.0265 (11)0.0302 (12)0.0032 (10)0.0071 (10)0.0011 (8)
N20.0458 (14)0.0304 (12)0.0388 (13)0.0013 (10)0.0122 (10)0.0022 (9)
C10.0442 (16)0.0276 (13)0.0391 (15)−0.0010 (12)0.0104 (12)−0.0035 (10)
C70.0451 (17)0.0274 (14)0.0354 (15)0.0030 (12)−0.0038 (12)−0.0002 (10)
C60.0402 (16)0.0273 (14)0.0455 (16)0.0009 (12)0.0069 (12)−0.0044 (11)
C80.064 (2)0.0328 (15)0.0321 (15)0.0041 (14)0.0101 (13)0.0082 (11)
C30.054 (2)0.055 (2)0.075 (3)−0.0083 (17)0.0350 (19)−0.0121 (17)
C50.0393 (17)0.0391 (17)0.067 (2)−0.0020 (14)0.0038 (15)−0.0044 (14)
C20.055 (2)0.0421 (17)0.0540 (19)−0.0056 (15)0.0211 (15)−0.0042 (14)
C40.0373 (18)0.051 (2)0.097 (3)−0.0039 (16)0.0182 (19)−0.0133 (19)
C90.064 (2)0.0398 (16)0.0321 (15)0.0013 (15)0.0176 (14)0.0010 (11)
O30.0890 (19)0.0327 (12)0.0596 (15)0.0009 (12)0.0063 (13)−0.0027 (10)
C100.0409 (16)0.0351 (15)0.0350 (14)0.0035 (13)0.0137 (12)−0.0014 (11)
C110.0465 (19)0.071 (2)0.054 (2)−0.0057 (17)0.0034 (15)0.0008 (16)
Geometric parameters (Å, °) top
Cu1—O11.916 (2)C8—C91.506 (4)
Cu1—N11.946 (2)C8—H8A0.9700
Cu1—O21.970 (2)C8—H8B0.9700
Cu1—N22.011 (2)C3—C21.370 (5)
Cu1—O2i2.454 (3)C3—C41.393 (5)
O1—C11.306 (3)C3—H3A0.9300
O2—C101.283 (3)C5—C41.362 (5)
N1—C71.285 (4)C5—H5A0.9300
N1—C81.462 (4)C2—H2A0.9300
N2—C91.480 (4)C4—H4A0.9300
N2—H2B0.9000C9—H9A0.9700
N2—H2C0.9000C9—H9B0.9700
C1—C21.413 (4)O3—C101.231 (3)
C1—C61.426 (4)C10—C111.506 (4)
C7—C61.429 (4)C11—H11A0.9600
C7—H7A0.9300C11—H11B0.9600
C6—C51.415 (4)C11—H11C0.9600
O1—Cu1—N193.33 (9)C9—C8—H8A110.1
O1—Cu1—O289.89 (8)N1—C8—H8B110.1
N1—Cu1—O2169.50 (8)C9—C8—H8B110.1
O1—Cu1—N2174.17 (9)H8A—C8—H8B108.4
N1—Cu1—N284.65 (10)C2—C3—C4120.6 (3)
O2—Cu1—N293.06 (9)C2—C3—H3A119.7
O2i—Cu1—O193.10 (8)C4—C3—H3A119.7
O2—Cu1—O2i85.59 (7)C4—C5—C6122.3 (3)
O2i—Cu1—N1104.19 (8)C4—C5—H5A118.8
O2i—Cu1—N282.12 (8)C6—C5—H5A118.8
C1—O1—Cu1127.10 (17)C3—C2—C1122.5 (3)
C10—O2—Cu1113.76 (17)C3—C2—H2A118.8
C7—N1—C8121.7 (2)C1—C2—H2A118.8
C7—N1—Cu1126.14 (19)C5—C4—C3118.8 (3)
C8—N1—Cu1112.09 (19)C5—C4—H4A120.6
C9—N2—Cu1106.92 (18)C3—C4—H4A120.6
C9—N2—H2B110.3N2—C9—C8107.2 (2)
Cu1—N2—H2B110.3N2—C9—H9A110.3
C9—N2—H2C110.3C8—C9—H9A110.3
Cu1—N2—H2C110.3N2—C9—H9B110.3
H2B—N2—H2C108.6C8—C9—H9B110.3
O1—C1—C2118.7 (3)H9A—C9—H9B108.5
O1—C1—C6124.7 (3)O3—C10—O2123.2 (3)
C2—C1—C6116.6 (3)O3—C10—C11120.5 (3)
N1—C7—C6125.7 (2)O2—C10—C11116.3 (3)
N1—C7—H7A117.1C10—C11—H11A109.5
C6—C7—H7A117.1C10—C11—H11B109.5
C5—C6—C1119.1 (3)H11A—C11—H11B109.5
C5—C6—C7118.0 (3)C10—C11—H11C109.5
C1—C6—C7122.9 (3)H11A—C11—H11C109.5
N1—C8—C9107.9 (2)H11B—C11—H11C109.5
N1—C8—H8A110.1
Symmetry codes: (i) −x+1, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O3ii0.902.263.009 (6)140
N2—H2C···O1i0.902.373.203 (3)155
Symmetry codes: (ii) x, −y+5/2, z−1/2; (i) −x+1, −y+2, −z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.916 (2)Cu1—N22.011 (2)
Cu1—N11.946 (2)Cu1—O2i2.454 (3)
Cu1—O21.970 (2)
O1—Cu1—N193.33 (9)O2—Cu1—N293.06 (9)
O1—Cu1—O289.89 (8)O2i—Cu1—O193.10 (8)
N1—Cu1—O2169.50 (8)O2—Cu1—O2i85.59 (7)
O1—Cu1—N2174.17 (9)O2i—Cu1—N1104.19 (8)
N1—Cu1—N284.65 (10)O2i—Cu1—N282.12 (8)
Symmetry codes: (i) −x+1, −y+2, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O3ii0.902.263.009 (6)140
N2—H2C···O1i0.902.373.203 (3)155
Symmetry codes: (ii) x, −y+5/2, z−1/2; (i) −x+1, −y+2, −z.
Acknowledgements top

This work was supported by the Natural Science Foundation of China (No. 20671055).

references
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