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Acta Cryst. (2007). E63, m2300    [ doi:10.1107/S1600536807037920 ]

Tetrakis([mu]3-2-{[1,1-bis(hydroxymethyl)-2-oxidoethyl]iminomethyl}phenolato)tetracopper(II)

J.-F. Dong, L.-Z. Li, H.-Y. Xu and D.-Q. Wang

Abstract top

In the title tetranuclear complex, [Cu4(C11H13NO4)4], which has crystallographic \overline{4} symmetry, the CuII ions are coordinated by the tridentate Schiff base ligands, forming a tetranuclear Cu4O4 cubane-like configuration. The CuII ion adopts a CuNO4 distorted square-pyramidal coordination environment. In the crystal structure, intermolecular O-H...O bonds help to form a three-dimensional structure.

Comment top

Considerable efforts have been devoted to the study of polynuclear CuII complexes due to their importance as models for enzymatic systems (Beinert, 1980) and in studying metal-metal interactions. The chemistry of transition metal complexes of hydroxy(aryl-OH and alkyl-OH) rich molecules containing imine/amine group is important in the biomimetic studies of metalloproteins (Mishtu et al., 2002).

A few structurally characterized multinuclear complexes containing Schiff base ligands has been reported (Mishtu et al., 2002). As part of our ongoing studies (Dong et al., 2007) in this area, we report here the synthesis and crystal structure of the title compound, (I), a tetracopper(II) complex with a tridentate Schiff base ligand derived from the condensation of salicylaldehyde and trihydroxymethylaminomethane. Mishtu et al. (2002) reported the same cluster as a hydrate in a different space group.

Compound (I) contains a teranuclear cubane core based on an approximately cubic array of alternating copper and oxygen atoms (Fig. 1). Each CuII atom resides in a distorted square-pyramid coordination environment with one nitrogen and two oxygen atoms from one Schiff base ligand and two oxygen atoms from the neighboring units of the cubane. The Cu atom deviates from the basal plane formed by O1, N1, O2 and O2i (i = y − 1/4, −x + 5/4, −z + 9/4) by 0.0672 (12) Å, with a significantly longer Cu—Oapical bond distance (Table 1).

Within the cluster, the Cu···Cu distances [3.591 (4) Å, 3.154 (3) Å] are similar to the reported values for related structures (Si et al., 2002; Mishtu et al., 2002), indicating no significant bonding interactions between the CuII ions in (I).

In the crystal structure, the intermolecular O—H···O hydrogen bonds help to form a three-dimensional network (Fig. 2, Table 2).

Related literature top

For related literature, see: Beinert (1980); Dong et al. (2007); Mishtu et al. (2002); Si et al. (2002).

Experimental top

Trihydroxymethylaminomethane (1 mmol, 121.14 mg) was dissolved in hot methanol (10 ml) and added in portions to a methanol solution (3 ml) of salicylaldehyde (1 mmol, 0.11 ml). The mixture was then stirred at 323 K for 2 h. Subsequently, an aqueous solution (2 ml) of cupric acetate hydrate (1 mmol, 199.7 mg) was added dropwise and stirred for another 5 h. The solution was held at room temperature for ten days, whereupon blue blocks of (I) were obtained.

Refinement top

All the H atoms were placed in calculated positions (C—H = 0.93–0.97 Å, O—H = 0.82 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl, O).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); 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.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids (arbitrary spheres for the H atoms). The asymmetric atoms are labelled.
[Figure 2] Fig. 2. Packing diagram of (I) with hydrogen bonds shown as dashed lines.
Tetrakis(µ3-2-{[1,1-bis(hydroxymethyl)-2-\ oxidoethyl]iminomethyl}phenolato)tetracopper(II) top
Crystal data top
[Cu4(C11H13NO4)4]Z = 4
Mr = 1147.06F000 = 2352
Tetragonal, I41/aDx = 1.528 Mg m−3
Hall symbol: -I 4adMo Kα radiation
λ = 0.71073 Å
a = 17.209 (3) ÅCell parameters from 5431 reflections
b = 17.209 (3) Åθ = 2.4–28.1º
c = 16.836 (3) ŵ = 1.75 mm−1
α = 90ºT = 298 (2) K
β = 90ºBlock, blue
γ = 90º0.53 × 0.49 × 0.48 mm
V = 4986.0 (13) Å3
Data collection top
Siemens SMART CCD area-detector
diffractometer		2203 independent reflections
Radiation source: fine-focus sealed tube1821 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.050
T = 298(2) Kθmax = 25.0º
ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −20→18
Tmin = 0.457, Tmax = 0.487k = −20→16
12748 measured reflectionsl = −18→20
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)] = 0.028H-atom parameters constrained
wR(F2) = 0.075  w = 1/[σ2(Fo2) + (0.0407P)2 + 3.0697P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
2203 reflectionsΔρmax = 0.32 e Å−3
156 parametersΔρmin = −0.19 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu4(C11H13NO4)4]γ = 90º
Mr = 1147.06V = 4986.0 (13) Å3
Tetragonal, I41/aZ = 4
a = 17.209 (3) ÅMo Kα
b = 17.209 (3) ŵ = 1.75 mm−1
c = 16.836 (3) ÅT = 298 (2) K
α = 90º0.53 × 0.49 × 0.48 mm
β = 90º
Data collection top
Siemens SMART CCD area-detector
diffractometer		2203 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1821 reflections with I > 2σ(I)
Tmin = 0.457, Tmax = 0.487Rint = 0.050
12748 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028Δρmax = 0.32 e Å−3
wR(F2) = 0.075Δρmin = −0.19 e Å−3
S = 1.06Absolute structure: ?
2203 reflectionsFlack parameter: ?
156 parametersRogers parameter: ?
H-atom parameters constrained
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
Cu10.396178 (15)0.739558 (15)1.069439 (16)0.02320 (12)
N10.37415 (11)0.69497 (11)0.96723 (11)0.0261 (4)
O10.31430 (10)0.81400 (10)1.06436 (10)0.0347 (4)
O20.48427 (9)0.66875 (9)1.07064 (8)0.0235 (4)
O30.36321 (12)0.57702 (11)0.82462 (11)0.0452 (5)
H30.35180.53090.82860.068*
O40.32782 (10)0.58053 (12)1.07332 (10)0.0393 (5)
H40.36440.57611.10420.059*
C10.32492 (15)0.72192 (14)0.91698 (15)0.0341 (6)
H10.31920.69510.86940.041*
C20.27757 (15)0.79070 (15)0.92818 (15)0.0343 (6)
C30.27275 (14)0.83153 (14)1.00084 (15)0.0293 (5)
C40.22008 (15)0.89372 (15)1.00520 (17)0.0400 (7)
H4A0.21510.92081.05270.048*
C50.17574 (18)0.91569 (17)0.94118 (18)0.0492 (8)
H5A0.14200.95770.94590.059*
C60.18063 (19)0.87623 (18)0.87002 (19)0.0543 (9)
H60.15080.89140.82670.065*
C70.23011 (18)0.81440 (18)0.86439 (17)0.0497 (8)
H70.23260.78700.81680.060*
C80.40970 (14)0.61676 (13)0.95857 (14)0.0262 (5)
C90.48709 (13)0.61901 (14)1.00416 (14)0.0285 (5)
H9A0.50000.56691.02170.034*
H9B0.52790.63640.96860.034*
C100.42851 (15)0.59321 (15)0.87300 (15)0.0355 (6)
H10A0.45810.63470.84840.043*
H10B0.46140.54750.87430.043*
C110.35195 (14)0.55883 (15)0.99569 (15)0.0328 (6)
H11A0.30660.55490.96170.039*
H11B0.37610.50790.99800.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02486 (18)0.02156 (18)0.02318 (18)0.00370 (11)−0.00404 (12)−0.00364 (11)
N10.0298 (11)0.0224 (10)0.0260 (10)0.0035 (8)−0.0045 (9)−0.0034 (8)
O10.0382 (10)0.0368 (10)0.0291 (9)0.0146 (8)−0.0113 (8)−0.0098 (8)
O20.0288 (9)0.0195 (8)0.0222 (9)0.0043 (6)−0.0045 (7)−0.0024 (6)
O30.0653 (14)0.0341 (11)0.0362 (10)0.0008 (9)−0.0197 (10)−0.0073 (9)
O40.0288 (10)0.0581 (12)0.0310 (10)0.0011 (9)0.0001 (8)0.0036 (9)
C10.0433 (16)0.0315 (14)0.0273 (13)0.0041 (12)−0.0095 (12)−0.0054 (11)
C20.0384 (15)0.0309 (14)0.0336 (14)0.0049 (11)−0.0102 (12)0.0015 (11)
C30.0303 (14)0.0229 (12)0.0346 (14)0.0016 (10)−0.0066 (11)0.0009 (11)
C40.0381 (16)0.0364 (15)0.0456 (16)0.0106 (12)−0.0080 (13)−0.0057 (13)
C50.0496 (18)0.0366 (16)0.061 (2)0.0180 (13)−0.0146 (15)0.0033 (14)
C60.061 (2)0.0534 (19)0.0489 (19)0.0191 (16)−0.0243 (15)0.0073 (15)
C70.064 (2)0.0486 (18)0.0360 (16)0.0164 (15)−0.0187 (14)−0.0041 (14)
C80.0288 (13)0.0239 (12)0.0258 (12)0.0027 (10)−0.0032 (10)−0.0069 (10)
C90.0254 (13)0.0289 (13)0.0312 (14)0.0042 (10)−0.0018 (11)−0.0075 (11)
C100.0441 (16)0.0339 (15)0.0287 (14)0.0027 (12)−0.0008 (12)−0.0082 (11)
C110.0323 (14)0.0298 (14)0.0364 (15)0.0016 (10)−0.0008 (11)−0.0002 (11)
Geometric parameters (Å, °) top
Cu1—O11.9063 (16)C3—C41.404 (3)
Cu1—N11.9218 (19)C4—C51.374 (4)
Cu1—O2i1.9438 (15)C4—H4A0.9300
Cu1—O21.9451 (16)C5—C61.380 (4)
Cu1—O2ii2.5930 (16)C5—H5A0.9300
N1—C11.284 (3)C6—C71.366 (4)
N1—C81.486 (3)C6—H60.9300
O1—C31.321 (3)C7—H70.9300
O2—C91.410 (3)C8—C101.531 (3)
O2—Cu1iii1.9438 (15)C8—C91.538 (3)
O3—C101.416 (3)C8—C111.540 (3)
O3—H30.8200C9—H9A0.9700
O4—C111.421 (3)C9—H9B0.9700
O4—H40.8200C10—H10A0.9700
C1—C21.449 (3)C10—H10B0.9700
C1—H10.9300C11—H11A0.9700
C2—C71.410 (4)C11—H11B0.9700
C2—C31.413 (3)
O1—Cu1—N194.72 (7)C6—C5—H5A119.6
O1—Cu1—O2i91.99 (7)C7—C6—C5118.8 (3)
N1—Cu1—O2i169.85 (7)C7—C6—H6120.6
O1—Cu1—O2176.00 (7)C5—C6—H6120.6
N1—Cu1—O285.00 (7)C6—C7—C2122.3 (3)
O2i—Cu1—O288.83 (7)C6—C7—H7118.9
N1—Cu1—O2ii113.99 (7)C2—C7—H7118.9
O2i—Cu1—O2ii72.12 (6)N1—C8—C10114.8 (2)
O2—Cu1—O2ii76.28 (6)N1—C8—C9106.55 (18)
C1—N1—C8122.3 (2)C10—C8—C9107.05 (19)
C1—N1—Cu1125.16 (17)N1—C8—C11106.31 (19)
C8—N1—Cu1111.62 (14)C10—C8—C11110.29 (19)
C3—O1—Cu1126.14 (15)C9—C8—C11111.9 (2)
C9—O2—Cu1iii128.79 (14)O2—C9—C8112.44 (18)
C9—O2—Cu1113.51 (13)O2—C9—H9A109.1
Cu1iii—O2—Cu1108.40 (7)C8—C9—H9A109.1
C10—O3—H3109.5O2—C9—H9B109.1
C11—O4—H4109.5C8—C9—H9B109.1
N1—C1—C2125.5 (2)H9A—C9—H9B107.8
N1—C1—H1117.3O3—C10—C8115.2 (2)
C2—C1—H1117.3O3—C10—H10A108.5
C7—C2—C3118.8 (2)C8—C10—H10A108.5
C7—C2—C1117.6 (2)O3—C10—H10B108.5
C3—C2—C1123.5 (2)C8—C10—H10B108.5
O1—C3—C4118.7 (2)H10A—C10—H10B107.5
O1—C3—C2123.7 (2)O4—C11—C8113.1 (2)
C4—C3—C2117.5 (2)O4—C11—H11A109.0
C5—C4—C3121.8 (3)C8—C11—H11A109.0
C5—C4—H4A119.1O4—C11—H11B109.0
C3—C4—H4A119.1C8—C11—H11B109.0
C4—C5—C6120.8 (3)H11A—C11—H11B107.8
C4—C5—H5A119.6
N1—Cu1—O2—O186.3 (9)
Symmetry codes: (i) y−1/4, −x+5/4, −z+9/4; (ii) −x+1, −y+3/2, z; (iii) −y+5/4, x+1/4, −z+9/4.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O4iv0.821.912.723 (3)172
O4—H4···O1iii0.821.852.668 (2)171
Symmetry codes: (iv) y−1/4, −x+3/4, z−1/4; (iii) −y+5/4, x+1/4, −z+9/4.
Table 1
Selected geometric parameters (Å) top
Cu1—O11.9063 (16)Cu1—O21.9451 (16)
Cu1—N11.9218 (19)Cu1—O2ii2.5930 (16)
Cu1—O2i1.9438 (15)
Symmetry codes: (i) y−1/4, −x+5/4, −z+9/4; (ii) −x+1, −y+3/2, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O4iii0.821.912.723 (3)172
O4—H4···O1iv0.821.852.668 (2)171
Symmetry codes: (iii) y−1/4, −x+3/4, z−1/4; (iv) −y+5/4, x+1/4, −z+9/4.
Acknowledgements top

The authors thank the Natural Science Foundation of Shandong Province (grant No. Y2004B02) for a research grant.

references
References top

Beinert, H. (1980). Coord. Chem. Rev. 33, 55–85.

Dong, J.-F., Li, L.-Z., Xu, T., Cui, H. & Wang, D.-Q. (2007). Acta Cryst. E63, m1501–m1502.

Mishtu, D., Chebrolu, P. R., Pauli, K. S. & Kari, R. (2002). Inorg. Chem. Commun. 5, 380–383.

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. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-Ray Instruments Inc., Madison, Wisconsin, USA.

Si, S.-F., Tang, J.-K., Liao, D.-Z., Jiang, Z.-H. & Yan, S.-P. (2002). Inorg. Chem. Commun. 5, 76–77.