metal-organic compounds

Transcription

1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN (Acetato-jO)bis(2,2 0 -bipyridyl-j 2 N,N 0 )- copper(ii) ethyl sulfate methyl sulfate (1/0.5/0.5) Zhi-Gang Wen a * and Mao-Lian Li b a Department of Chemistry and Chemical Engineering, Qiannan Normal College for Nationalities, Duyun, Guizhou , People s Republic of China, and b Department of Chemistry and Biology, Qinzhou University, Qinzhou, Guangxi , People s Republic of China Correspondence marise @163.com Received 4 November 2008; accepted 11 November 2008 Key indicators: single-crystal X-ray study; T = 291 K; mean (C C) = Å; disorder in main residue; R factor = 0.029; wr factor = 0.076; data-to-parameter ratio = Experimental Crystal data [Cu(C 2 H 3 O 2 )(C 10 H 8 N 2 ) 2 ]- (C 2 H 5 O 4 S) 0.5 (CH 3 O 4 S) 0.5 M r = Triclinic, P1 a = (7) Å b = (13) Å c = (14) Å = (1) Data collection Bruker SMART CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.703, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 331 parameters = (1) = (1) V = (2) Å 3 Z =2 Mo K radiation = 1.07 mm 1 T = 291 (2) K mm 8803 measured reflections 4347 independent reflections 3848 reflections with I > 2(I) R int = restraints H-atom parameters constrained max = 0.55 e Å 3 min = 0.25 e Å 3 In the title complex, [Cu(C 2 H 3 O 2 )(C 10 H 8 N 2 ) 2 ](CH 3 CH 2 - OSO 3 ) 0.5 (CH 3 OSO 3 ) 0.5, the Cu II ion is bis-chelated by two 2,2 0 -bipyridine lignds and coordinated by an O atom of an acetate ligand in a CuN 4 O disorted square-pyramidal environment. In the structure, equal amounts of methyl sulfate and ethyl sulfate anions are disordered on the same crystallographic sites. The crystal structure is stabilized by weak intermolecular C HO interactions. Table 1 Selected geometric parameters (Å, ). Cu1 O (15) Cu1 N (17) Cu1 N (17) O1 Cu1 N (7) O1 Cu1 N (6) N2 Cu1 N (7) O1 Cu1 N (7) N2 Cu1 N (7) Cu1 N (17) Cu1 N (18) N1 Cu1 N (7) O1 Cu1 N (7) N2 Cu1 N (7) N1 Cu1 N (7) N4 Cu1 N (7) Related literature For genernal background to supramolecular assembly and crystal engineering, see: Aakeröy et al. (1998); Batten & Robson (1998); Yaghi et al. (1998); Kitagawa et al. (2004); Lu et al. (2006). For related strutures, see: Akrivos et al. (1994); Blake et al. (2000); Belokon et al. (2002); Lopez-Sandoval et al. (2004). Table 2 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA C16 H16AO5 i (3) 151 C12 H12BO (3) 174 C8 H8AO6 ii (3) 133 C7 H7AO2 ii (3) 162 C4 H4AO2 ii (3) 163 C2 H2AO (3) 162 C1 H1AO (3) 114 Symmetry codes: (i) x þ 2; y þ 1; z þ 2; (ii) x þ 1; y þ 1; z þ 1. Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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 by a key grant from the Qiannan Normal College for Nationalities Foundation of Guizhou Province (grant No. 2007z15) and the Qinzhou University Foundation of Guangxi Zhuang Autonomous Region of the People s Republic of China (grant No. 2008XJKY-10B). doi: /s Wen and Li m1563

2 metal-organic compounds Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2732). References Aakeröy, C. B. & Beatty, A. M. (1998). Chem. Commun. pp Akrivos, P. D., Hadjikakou, S. K., Karagiannidis, P., Luic, M. & Kojic-Prodic, B. (1994). J. Coord. Chem. 31, Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, Belokon, Y. N., Carta, P., Gutnov, A. V., Maleev, V., Moskalenko, M. A., Yashkina, L. V., Ikonnikov, N. S., Voskoboev, N. V., Khrustalev, V. N. & North, M. (2002). Helv. Chim. Acta, 85, Blake, A. J., Hubberstey, P., Suksangpanya, U. & Wilson, C. L. (2000). J. Chem. Soc. Dalton Trans. pp Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, Lopez-Sandoval, H., Richaud, A., Contreras, R., Leigh, G. J., Hitchcock, P. B., Flores-Parra, A., Galvez-Ruiz, J. C., Cruz, A., Noth, H. & Barba-Behrens, N. (2004). Polyhedron, 23, Lu, W.-J., Zhu, Y.-M. & Zhong, K.-L. (2006). Acta Cryst. C62, m448 m450. Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, Yaghi, O. M., Li, H., Davis, C., Richardson, D. & Groy, T. L. (1998). Acc. Chem. Res. 31, m1564 Wen and Li [Cu(C 2 H 3 O 2 )(C 10 H 8 N 2 ) 2 ](C 2 H 5 O 4 S) 0.5 (CH 3 O 4 S) 0.5

3 [doi: /s ] (Acetato-κO)bis(2,2 -bipyridyl-κ 2 N,N )copper(ii) ethyl sulfate methyl sulfate (1/0.5/0.5) Zhi-Gang Wen and Mao-Lian Li S1. Comment The field of supramolecular assembly and crystal engineering in which transition metal cationic centres are linked through anions via hydrogen-bonded supramolecular synthons is receiving growing attention (Yaghi et al., 1998; Kitagawa et al., 2004; Lu et al., 2006). This work is driven by the elegant multi-dimensional architectures which can be fabricated by bringing together the rapidly maturing fields of hydrogen-bonded crystal engineering inorganic coordination polymer construction (Aakeröy et al., 1998; Batten et al., 1998). In the synthethis of the title compound, methylsulfate and ethylsulfate are produced in two two stages (Blake et al., 2000). Herein, we report the synthesis and crystal structure of the title compound, (I), containing a discrete copper(ii) complex cation and a disordered mixture of equal amounts of ethyl sulfate and methyl sulfate anions. The molecular structure of (I) is shown in Fig. 1. The Cu II ion is chelated by two 2,2 -bipyridine ligands and is bonded to one oxygen of acetate moiety ion forming a CuN 4 O distorted square-pyramidal coordination environment. In the crystal structure weak C-H O hydrogen bonds link complex cations and sulfonate anions to form a three-dimensional network (Fig.2 and Table 2). Some crystal structures which are closely related to the title compound have already been studied (Blake et al., 2000; Lopez-Sandoval et al., 2004; Belokon et al., 2002; Akrivos et al., 1994). S2. Experimental Reagents and solvents used were of commercially available quality. To an aqueous solution (10 ml) of aminomethanesulfonic acid (0.11 g,1 mmol) and NaOH (0.04 g,1.0 mmol), Cu(CH 3 COO) 2.H 2 O (0.20 g, 1.0 mmol) in methanol (10 ml) was added slowly. The solution was stirred for 30 min and then 2,2 -bipyridine (0.156 g, 1 mmol) in ethanol (10 ml) was added slowly. The mixture was refluxed overnight to give a green solution. After filtration, the solution was allowed to stand in air and after several days, green block-shaped crystal were collected in 20% yield. Analysis found: C 50.72, 30, H 4.22, N 10.16, S 5.72%; calculated for C 47 H 46 Cu 2 N 8 O 12 S 2 : C 50.90, H 4.16, N 10.12, S 5.78%. S3. Refinement H atoms were positioned geometrically and refined using a riding model, with C H = Å and with U iso (H) = 1.2U eq (C) or 1.5U eq (C) for methyl H atoms. From an initial solution irregular bond lengths, large displacement parameters in the C atoms of the anion and the presence of large peaks in difference Fourier maps which were close to the terminal (C 2 H 5 ) group, led us to suspect the presence of the disorder. The initially refined ratio of the site-occupany factors for the disorder components were eventually fixed at 0.5/0.5. sup-1

4 Figure 1 The molecular structure with displacement ellipsoids at the 30% probability level. The disorder is shown as open bonds. sup-2

5 Figure 2 Part of the crystal structure showing hydrogen bonds as dashed lines. H atoms, except for those involved in hydrogen bonds, are not included. (Acetato-κO)bis(2,2 -bipyridyl-κ 2 N,N )copper(ii) ethyl sulfate methyl sulfate (1/0.5/0.5) Crystal data [Cu(C 2 H 3 O 2 )(C 10 H 8 N 2 ) 2 ](C 2 H 5 O 4 S) 0.5 (CH 3 O 4 S) 0.5 M r = Triclinic, P1 Hall symbol: -P 1 a = (7) Å b = (13) Å c = (14) Å α = (1) β = (1) γ = (1) V = (2) Å 3 Data collection Bruker SMART CCD area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.703, T max = Z = 2 F(000) = 570 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 4397 reflections θ = µ = 1.07 mm 1 T = 291 K Block, green mm 8803 measured reflections 4347 independent reflections 3848 reflections with I > 2σ(I) R int = θ max = 25.5, θ min = 2.3 h = 8 8 k = l = sup-3

6 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 331 parameters 2 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/[σ 2 (F o2 ) + (0.0354P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.55 e Å 3 Δρ min = 0.25 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 F 2 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 F 2. 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 F 2 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 (Å 2 ) x y z U iso */U eq Occ. (<1) Cu (4) (18) (18) (9) O (2) (12) (12) (4) O (3) (14) (14) (4) N (2) (13) (13) (4) N (2) (13) (13) (4) N (3) (15) (14) (4) N (2) (13) (13) (4) C (3) (17) (18) (5) H1A * C (3) (18) (2) (6) H2A * C (3) (17) (19) (5) H3A * C (3) (16) (17) (5) H4A * C (3) (15) (15) (4) C (3) (15) (15) (4) C (3) (17) (16) (5) H7A * C (3) (18) (18) (5) H8A * C (4) (18) (19) (6) H9A * C (3) (16) (18) (5) H10A * sup-4

7 C (3) (17) (19) (5) C (4) (2) (3) (8) H12A * H12B * H12C * C (3) (18) (18) (5) H13A * C (4) (19) (2) (6) H14A * C (4) (19) (2) (7) H15A * C (4) (18) (19) (6) H16A * C (3) (16) (15) (5) C (3) (16) (16) (5) C (4) (2) (18) (6) H19A * C (5) (3) (2) (8) H20A * C (5) (3) (2) (8) H21A * C (4) (2) (2) (6) H22A * S (9) (4) (4) (14) O (3) (13) (16) (5) O (3) (16) (18) (6) O (3) (14) (14) (5) O (3) (14) (13) (4) C23A (16) (5) (4) (4) 0.50 H23A * 0.50 H23B * 0.50 H23C * 0.50 C23B (17) (5) (4) (4) 0.50 H23D * 0.50 H23E * 0.50 C24B (9) (6) (5) (19) 0.50 H24A * 0.50 H24B * 0.50 H24C * 0.50 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Cu (15) (14) (14) (10) (10) (10) O (9) (9) (9) (7) (7) (7) O (11) (11) (10) (9) (9) (8) N (9) (9) (9) (7) (7) (7) N (9) (9) (9) (7) (7) (7) sup-5

8 N (10) (11) (10) (8) (8) (8) N (9) (9) (9) (7) (7) (7) C (12) (12) (13) (10) (10) (10) C (13) (12) (16) (10) (12) (11) C (12) (12) (14) (9) (11) (10) C (11) (11) (12) (9) (9) (9) C (10) (10) (10) (8) (8) (8) C (10) (10) (10) (8) (8) (8) C (11) (12) (11) (9) (9) (9) C (13) (13) (13) (10) (10) (10) C (14) (12) (15) (10) (12) (10) C (12) (11) (13) (9) (10) (9) C (12) (11) (14) (9) (10) (10) C (15) (15) (2) (12) (15) (15) C (13) (12) (13) (10) (10) (10) C (13) (14) (17) (11) (12) (12) C (13) (13) (18) (10) (12) (12) C (14) (12) (13) (10) (11) (10) C (11) (11) (10) (9) (9) (8) C (13) (11) (10) (10) (9) (8) C (18) (15) (13) (13) (13) (11) C (2) (2) (15) (19) (16) (14) C (18) (2) (17) (18) (15) (17) C (14) (18) (15) (12) (12) (13) S (3) (3) (3) (2) (3) (2) O (13) (10) (13) (9) (11) (9) O (11) (13) (16) (10) (11) (11) O (14) (11) (10) (10) (9) (9) O (11) (10) (9) (9) (8) (8) C23A (18) (7) (10) (2) (18) (7) C23B (18) (7) (10) (2) (18) (7) C24B (4) (5) (4) (3) (3) (4) Geometric parameters (Å, º) Cu1 O (15) C12 H12B Cu1 N (17) C12 H12C Cu1 N (17) C13 C (3) Cu1 N (17) C13 H13A Cu1 N (18) C14 C (4) O1 C (3) C14 H14A O2 C (3) C15 C (4) N1 C (3) C15 H15A N1 C (2) C16 C (3) N2 C (3) C16 H16A N2 C (3) C17 C (3) N3 C (3) C18 C (3) N3 C (3) C19 C (4) sup-6

9 N4 C (3) C19 H19A N4 C (3) C20 C (4) C1 C (3) C20 H20A C1 H1A C21 C (4) C2 C (3) C21 H21A C2 H2A C22 H22A C3 C (3) S1 O (18) C3 H3A S1 O (18) C4 C (3) S1 O (2) C4 H4A S1 O (17) C5 C (3) O6 C23A (7) C6 C (3) O6 C23B (7) C7 C (3) C23A H23A C7 H7A C23A H23B C8 C (3) C23A H23C C8 H8A C23B C24B 1.46 (5) C9 C (3) C23B H23D C9 H9A C23B H23E C10 H10A C24B H24A C11 C (3) C24B H24B C12 H12A C24B H24C O1 Cu1 N (7) H12A C12 H12B O1 Cu1 N (6) C11 C12 H12C N2 Cu1 N (7) H12A C12 H12C O1 Cu1 N (7) H12B C12 H12C N2 Cu1 N (7) N4 C13 C (2) N1 Cu1 N (7) N4 C13 H13A O1 Cu1 N (7) C14 C13 H13A N2 Cu1 N (7) C15 C14 C (2) N1 Cu1 N (7) C15 C14 H14A N4 Cu1 N (7) C13 C14 H14A C11 O1 Cu (15) C14 C15 C (2) C10 N1 C (18) C14 C15 H15A C10 N1 Cu (14) C16 C15 H15A C6 N1 Cu (13) C15 C16 C (2) C1 N2 C (18) C15 C16 H16A C1 N2 Cu (15) C17 C16 H16A C5 N2 Cu (13) N4 C17 C (2) C18 N3 C (2) N4 C17 C (18) C18 N3 Cu (14) C16 C17 C (2) C22 N3 Cu (17) N3 C18 C (2) C13 N4 C (18) N3 C18 C (18) C13 N4 Cu (14) C19 C18 C (2) C17 N4 Cu (14) C20 C19 C (3) N2 C1 C (2) C20 C19 H19A N2 C1 H1A C18 C19 H19A C2 C1 H1A C19 C20 C (3) sup-7

10 C3 C2 C (2) C19 C20 H20A C3 C2 H2A C21 C20 H20A C1 C2 H2A C20 C21 C (3) C2 C3 C (2) C20 C21 H21A C2 C3 H3A C22 C21 H21A C4 C3 H3A N3 C22 C (3) C3 C4 C (2) N3 C22 H22A C3 C4 H4A C21 C22 H22A C5 C4 H4A O3 S1 O (12) N2 C5 C (18) O3 S1 O (13) N2 C5 C (17) O5 S1 O (12) C4 C5 C (18) O3 S1 O (11) N1 C6 C (18) O5 S1 O (11) N1 C6 C (17) O4 S1 O (12) C7 C6 C (18) C23A O6 S (19) C6 C7 C (2) C23B O6 S (18) C6 C7 H7A O6 C23A H23A C8 C7 H7A O6 C23A H23B C9 C8 C (2) O6 C23A H23C C9 C8 H8A O6 C23B C24B 107 (2) C7 C8 H8A O6 C23B H23D C10 C9 C (2) C24B C23B H23D C10 C9 H9A O6 C23B H23E C8 C9 H9A C24B C23B H23E N1 C10 C (2) H23D C23B H23E N1 C10 H10A C23B C24B H24A C9 C10 H10A C23B C24B H24B O2 C11 O (2) H24A C24B H24B O2 C11 C (2) C23B C24B H24C O1 C11 C (2) H24A C24B H24C C11 C12 H12A H24B C24B H24C C11 C12 H12B N2 Cu1 O1 C (15) C10 N1 C6 C (18) N1 Cu1 O1 C (4) Cu1 N1 C6 C5 3.6 (2) N4 Cu1 O1 C (15) N2 C5 C6 N1 0.6 (2) N3 Cu1 O1 C (15) C4 C5 C6 N (18) O1 Cu1 N1 C (3) N2 C5 C6 C (18) N2 Cu1 N1 C (19) C4 C5 C6 C7 1.0 (3) N4 Cu1 N1 C (18) N1 C6 C7 C8 0.6 (3) N3 Cu1 N1 C (18) C5 C6 C7 C (19) O1 Cu1 N1 C (4) C6 C7 C8 C9 1.4 (3) N2 Cu1 N1 C (13) C7 C8 C9 C (4) N4 Cu1 N1 C (14) C6 N1 C10 C9 1.7 (3) N3 Cu1 N1 C (14) Cu1 N1 C10 C (17) O1 Cu1 N2 C (18) C8 C9 C10 N1 0.2 (4) N1 Cu1 N2 C (18) Cu1 O1 C11 O2 5.2 (3) N4 Cu1 N2 C (3) Cu1 O1 C11 C (16) sup-8

11 N3 Cu1 N2 C (18) C17 N4 C13 C (3) O1 Cu1 N2 C (14) Cu1 N4 C13 C (17) N1 Cu1 N2 C (14) N4 C13 C14 C (4) N4 Cu1 N2 C (3) C13 C14 C15 C (4) N3 Cu1 N2 C (14) C14 C15 C16 C (4) O1 Cu1 N3 C (15) C13 N4 C17 C (3) N2 Cu1 N3 C (13) Cu1 N4 C17 C (15) N1 Cu1 N3 C (14) C13 N4 C17 C (18) N4 Cu1 N3 C (14) Cu1 N4 C17 C (2) O1 Cu1 N3 C (2) C15 C16 C17 N4 1.7 (3) N2 Cu1 N3 C (2) C15 C16 C17 C (2) N1 Cu1 N3 C (2) C22 N3 C18 C (3) N4 Cu1 N3 C (2) Cu1 N3 C18 C (17) O1 Cu1 N4 C (17) C22 N3 C18 C (19) N2 Cu1 N4 C (4) Cu1 N3 C18 C (2) N1 Cu1 N4 C (17) N4 C17 C18 N3 1.3 (3) N3 Cu1 N4 C (18) C16 C17 C18 N (19) O1 Cu1 N4 C (15) N4 C17 C18 C (19) N2 Cu1 N4 C (2) C16 C17 C18 C (3) N1 Cu1 N4 C (15) N3 C18 C19 C (4) N3 Cu1 N4 C (14) C17 C18 C19 C (2) C5 N2 C1 C2 0.1 (3) C18 C19 C20 C (4) Cu1 N2 C1 C (17) C19 C20 C21 C (4) N2 C1 C2 C3 0.2 (4) C18 N3 C22 C (4) C1 C2 C3 C4 0.2 (3) Cu1 N3 C22 C (18) C2 C3 C4 C5 0.6 (3) C20 C21 C22 N3 0.1 (4) C1 N2 C5 C4 0.3 (3) O3 S1 O6 C23A 60 (3) Cu1 N2 C5 C (15) O5 S1 O6 C23A 62 (3) C1 N2 C5 C (17) O4 S1 O6 C23A 179 (3) Cu1 N2 C5 C6 4.6 (2) O3 S1 O6 C23B 62 (3) C3 C4 C5 N2 0.6 (3) O5 S1 O6 C23B 61 (3) C3 C4 C5 C (19) O4 S1 O6 C23B 179 (3) C10 N1 C6 C7 2.1 (3) S1 O6 C23B C24B 175 (2) Cu1 N1 C6 C (15) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C16 H16A O5 i (3) 151 C12 H12B O (3) 174 C8 H8A O6 ii (3) 133 C7 H7A O2 ii (3) 162 C4 H4A O2 ii (3) 163 C2 H2A O (3) 162 C1 H1A O (3) 114 Symmetry codes: (i) x+2, y+1, z+2; (ii) x+1, y+1, z+1. sup-9