metal-organic compounds Acta Crystallographica Section E
Structure Reports Online ISSN 1600-5368
Bis{2-[2-(isopropylammonio)ethyliminomethyl]-5-methoxyphenolato}copper(II) bis(perchlorate) Chen-Yi Wang,a* Feng Cao,a Ping Wang,b Xiang Wua and Cai-Jun Yuana a
Department of Chemistry, Huzhou University, Huzhou 313000, People’s Republic of China, and bCollege of Chemical Engineering, Nanjing Forestry University, Nangjing 210037, People’s Republic of China Correspondence e-mail:
[email protected] Received 18 April 2010; accepted 12 May 2010 ˚; Key indicators: single-crystal X-ray study; T = 298 K; mean (C–C) = 0.008 A disorder in solvent or counterion; R factor = 0.059; wR factor = 0.182; data-toparameter ratio = 15.6.
In the title compound, [Cu(C13H20N2O2)2](ClO4)2, the CuII atom in the complex dication is chelated by two phenolate O atoms and two imine N atoms from two zwitterionic 2-[2(isopropylammonio)ethyliminomethyl]-5-methoxyphenolate ligands, forming a distorted square-planar geometry. One of the perchlorate anions is disordered over two sites with occupancies of 0.611 (15) and 0.389 (15). Intramolecular N— H O hydrogen bonds are observed in the complex dication. In the crystal structure, the perchlorate anions are linked to complex dications by intermolecular N—H O hydrogen bonds.
Experimental Crystal data
Data collection
For general background to CuII complexes, see: Collinson & Fenton (1996); Hossain et al. (1996); Tarafder et al. (2002); Musie et al. (2003); Garcı´a-Raso et al. (2003); Reddy et al. (2000); Ray et al. (2003); Arnold et al. (2003); Raptopoulou et al. (1998). For related structures, see: Wang et al. (2009a,b, 2010); Wang (2009). For bond lengths and angles in related CuII complexes, see: Hebbachi & Benali-Cherif (2005); Butcher et al. (2003); Elmali et al. (2000); Warda et al. (1997).
36964 measured reflections 7004 independent reflections 3260 reflections with I > 2(I) Rint = 0.117
Bruker SMART CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.839, Tmax = 0.861
Refinement R[F 2 > 2(F 2)] = 0.059 wR(F 2) = 0.182 S = 1.01 7004 reflections 449 parameters
94 restraints H-atom parameters constrained ˚ 3 max = 0.67 e A ˚ 3 min = 0.39 e A
Table 1 ˚ ). Selected bond lengths (A Cu1—O1 Cu1—O3
Related literature
˚3 V = 6438.2 (8) A Z=8 Mo K radiation = 0.91 mm 1 T = 298 K 0.20 0.18 0.17 mm
[Cu(C13H20N2O2)2](ClO4)2 Mr = 735.06 Orthorhombic, Pbca ˚ a = 17.4415 (13) A ˚ b = 14.009 (1) A ˚ c = 26.350 (2) A
1.925 (3) 1.933 (3)
Cu1—N3 Cu1—N1
1.969 (4) 1.970 (4)
Table 2 ˚ , ). Hydrogen-bond geometry (A D—H A
D—H
H A
D A
D—H A
N4—H4B O1 N4—H4A O12 N2—H2B O3 N2—H2A O6
0.90 0.90 0.90 0.90
1.86 2.04 2.23 2.20
2.705 2.930 2.849 3.070
156 171 125 163
(5) (13) (5) (9)
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
This work was supported financially by the Natural Science Foundation of China (grant No. 30771696), the Zhejiang
Acta Cryst. (2010). E66, m669–m670
doi:10.1107/S1600536810017472
Wang et al.
m669
metal-organic compounds Provincial Natural Science Foundation of China (grant No. Y407318), and the Science and Technology Plan of Huzhou (grant No. 2009 GG06). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI5083).
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[Cu(C13H20N2O2)2](ClO4)2
Hossain, M. E., Alam, M. N., Begum, J., Ali, M. A., Nazimuddin, M., Smith, F. E. & Hynes, R. C. (1996). Inorg. Chim. Acta, 249, 207–213. Musie, G. T., Li, X. & Powell, D. R. (2003). Inorg. Chim. Acta, 348, 69–74. Raptopoulou, C. P., Papadopoulos, A. N., Malamatari, D. A., Ioannidis, E., Moisidis, G., Terzis, A. & Kessissoglou, D. P. (1998). Inorg. Chim. Acta, 272, 283–290. Ray, M. S., Bhattacharya, R. B., Chaudhuri, S., Righi, L., Bocelli, G., Mukhopadhyay, G. & Ghosh, A. (2003). Polyhedron, 22, 617–624. Reddy, P. A. N., Datta, R. & Chakravarty, A. R. (2000). Inorg. Chem. Commun. 3, 322–324. Sheldrick, G. M. (1996). SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Tarafder, M. T. H., Jin, K. T., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2002). Polyhedron, 21, 2547–2554. Wang, C.-Y. (2009). J. Coord. Chem. 62, 2860–2868. Wang, C.-Y., Li, J.-F. & Cao, F. (2010). Acta Cryst. E66, m445–m446. Wang, C.-Y., Wu, X., Tu, S.-J. & Jiang, B. (2009a). Synth. React. Inorg. Met. Org. Nano Met. Chem. 39, 78–82. Wang, C.-Y., Ye, J.-Y., Lv, C.-Y., Lan, W.-Z. & Zhou, J.-B. (2009b). J. Coord. Chem. 62, 2164–2171. Warda, S. A., Friebel, C., Sivy´, J., Plesch, G. & Bla´hova´, M. (1997). Acta Cryst. C53, 50–54.
Acta Cryst. (2010). E66, m669–m670
supplementary materials
supplementary materials Acta Cryst. (2010). E66, m669-m670
[ doi:10.1107/S1600536810017472 ]
Bis{2-[2-(isopropylammonio)ethyliminomethyl]-5-methoxyphenolato}copper(II) bis(perchlorate) C.-Y. Wang, F. Cao, P. Wang, X. Wu and C.-J. Yuan Comment In recent years, copper(II) complexes have received much attention for their interesting biological activities and versatile structures (Collinson & Fenton, 1996; Hossain et al., 1996; Tarafder et al., 2002; Musie et al., 2003; García-Raso et al., 2003). Considerable effort has been made to construct a variety of copper(II) complexes in an attempt to model the physical and chemical behaviour of copper-containing metalloenzymes (Reddy et al., 2000). The peculiarity of copper lies in its ability to form complexes with coordination number four, five, and six (Ray et al., 2003; Arnold et al., 2003; Raptopoulou et al., 1998). As part of our investigations into novel urease inhibitors (Wang et al., 2009a,b,2010; Wang, 2009), the title compound, a new CuII complex, has been synthesized, and its crystal structure is reported here. The asymmetric units contains one mononuclear copper(II) complex dication, and two perchlorate anions (Fig. 1). The CuII atom in the dication is chelated by two phenolate O atoms and two imine N atoms from two 2-[(2isopropylammonioethylimino)methyl]-5-methoxyphenolate ligands, forming a square-planar geometry. The coordinate bond lengths (Table 1) and angles are typical and are comparable with those observed in other related copper(II) complexes (Hebbachi & Benali-Cherif, 2005; Butcher et al., 2003; Elmali et al., 2000; Warda et al., 1997). There are two intramolecular N—H···O hydrogen bonds in the complex dication. In the crystal structure, the perchlorate anions are linked to the complex dications by intermolecular N—H···O hydrogen bonds (Table 2 and Fig. 2). Experimental 4-Methoxysalicylaldehyde (1.0 mmol, 152 mg), N-isopropyl-1,2-diaminoethane (1.0 mmol, 102 mg) and Cu(ClO4)2.6H2O (1.0 mmol, 370 mg) were dissolved in methanol (80 ml). The mixture was stirred at room temperature for about 1 h to give a blue solution. After keeping the solution in air for a few days, blue block-like crystals were formed. Refinement H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C–H distances of 0.93–0.98 Å, N—H distances of 0.90 Å, and with Uiso(H) set at 1.2Ueq(C,N) and 1.5Ueq(Cmethyl). One of the perchlorate anions is disordered over two distinct sites with occupancies of 0.611 (15) and 0.389 (15). The positional and Uij parameters of disordered atoms Cl2 and Cl2' were constrained to be the same. The Cl···O and O···O distances in the disorder components were restrained to 1.42 (1) and 2.35 (2) Å, respectively. The Uij parameters of disordered O atoms were restrained to an approximate isotropic behaviour. The C10—C11 and C10—C12 distances were restrained to 1.540 (8) Å.
sup-1
supplementary materials Figures Fig. 1. The structure of the title complex, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. C-bound H atoms have been omitted for clarity. Only the major disorder component of one of the perchlorate anions is shown.
Fig. 2. The crystal packing of the title compound. Intermolecular N—H···O hydrogen bonds are drawn as dashed lines.
Bis{2-[2-(isopropylammonio)ethyliminomethyl]-5-methoxyphenolato}copper(II) bis(perchlorate) Crystal data [Cu(C13H20N2O2)2](ClO4)2
F(000) = 3064
Mr = 735.06
Dx = 1.517 Mg m−3
Orthorhombic, Pbca Hall symbol: -P 2ac 2ab a = 17.4415 (13) Å
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2387 reflections θ = 2.4–24.5°
b = 14.009 (1) Å
µ = 0.91 mm−1 T = 298 K
c = 26.350 (2) Å V = 6438.2 (8) Å3 Z=8
Block, blue 0.20 × 0.18 × 0.17 mm
Data collection Bruker SMART CCD area-detector diffractometer Radiation source: fine-focus sealed tube
7004 independent reflections
graphite
3260 reflections with I > 2σ(I) Rint = 0.117
ω scan
θmax = 27.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.839, Tmax = 0.861 36964 measured reflections
h = −22→20 k = −17→17 l = −29→33
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.059
sup-2
Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites
supplementary materials wR(F2) = 0.182
H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0802P)2 + 0.2786P]
S = 1.01
where P = (Fo2 + 2Fc2)/3
7004 reflections
(Δ/σ)max = 0.001
449 parameters
Δρmax = 0.67 e Å−3
94 restraints
Δρmin = −0.39 e Å−3
Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 Rfactors(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) Cu1 Cl1 N1 N2 H2A H2B N3 N4 H4A H4B O1 O2 O3 O4 O5 O6 O7 O8 Cl2' O9' O10' O11' O12' Cl2 O9
x
y
z
Uiso*/Ueq
Occ. (
