metal-organic compounds

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1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN catena-poly[[bis[aqua(1,10-phenanthroline)lead(ii)]-bis(l 3-2-hydroxy-5-sulfonatobenzoato)] acetic acid monosolvate] Yuan-Zheng Cheng, Wei-Wei Shi, Xue-Dong Wang, Shu-E Deng and Li-Ping Zhang* Department of Chemistry, Weifang Medical University, Weifang , People s Republic of China Correspondence zlpchyzh@163.com Received 18 May 2012; accepted 27 May 2012 Key indicators: single-crystal X-ray study; T = 293 K; mean (C C) = Å; disorder in solvent or counterion; R factor = 0.027; wr factor = 0.064; data-toparameter ratio = Experimental Crystal data [Pb 2 (C 7 H 4 O 6 S) 2 (C 12 H 8 N 2 ) 2 - (H 2 O) 2 ]C 2 H 4 O 2 M r = Triclinic, P1 a = (7) Å b = (5) Å c = (5) Å = (4) Data collection Oxford Xcalibur CCD diffractometer Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2011) T min = 0.309, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 310 parameters = (5) = (5) V = (11) Å 3 Z =1 Mo K radiation = 8.09 mm 1 T = 293 K mm 6374 measured reflections 3745 independent reflections 3438 reflections with I > 2(I) R int = restraints H-atom parameters constrained max = 1.83 e Å 3 min = 0.84 e Å 3 In the title compound, [Pb 2 (C 7 H 4 O 6 S) 2 (C 12 H 8 N 2 ) 2 (H 2 O) 2 ]- CH 3 COOH, the seven-coordinate Pb II atom is chelated by two N atoms of one 1,10-phenanthroline ligand, four O atoms from three 5-sulfosalicylate dianions and one water O atom. Each dianion serves as a bridging ligand, connecting adjacent Pb II atoms into a centrosymmetric polymeric chain extending parallel to [001]. There are interactions between the aromatic systems of neighbouring dianions, with plane-toplane distances of (2) Å, and between phenanthroline ligands, with a centroid-to-centroid distance of (2) Å. O HO hydrogen bonding additionally stabilizes the crystal packing. The acetic acid molecules are incorporated in the voids of this arrangement. They exhibit half-occupancy due to disorder around a centre of inversion. Related literature For background to 5-sulfosalicylic acid and its metal complexes, see: Chen et al. (2003); Du et al. (2006); Fan & Zhu (2005a,b, 2006); Li et al. (2004). Table 1 Selected bond lengths (Å). Pb1 O (3) Pb1 N (3) Pb1 N (3) Pb1 O (3) Symmetry codes: (i) x; y þ 1; z þ 1; (ii) x; y; z þ 1. Table 2 Hydrogen-bond geometry (Å, ). Pb1 O3 i (3) Pb1 O (4) Pb1 O1 ii (1) D HA D H HA DA D HA O4 H4O (4) 141 O7 H7AO2 iii (5) 172 Symmetry code: (iii) x þ 1; y þ 1; z þ 1. Data collection: CrysAlis PRO (Oxford Diffraction, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publcif (Westrip, 2010). The authors gratefully acknowledge financial support from Shandong Provincial Education Department (grant No. J09LB57) Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2635). m878 Cheng et al. doi: /s x

2 metal-organic compounds References Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Chen, Z.-F., Shi, S.-M., Hu, R.-X., Zhang, M., Liang, H. & Zhou, Z.-Y. (2003). Chin. J. Chem. 21, Du, Z.-X., Han, M.-L., Wang, J.-G. & Qin, J.-H. (2006). Acta Cryst. E62, m3047 m3048. Fan, S.-R. & Zhu, L.-G. (2005a). Acta Cryst. E61, m1298 m1300. Fan, S.-R. & Zhu, L.-G. (2005b). Acta Cryst. E61, m1598 m1600. Fan, S.-R. & Zhu, L.-G. (2006). Inorg. Chem. 45, Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Li, J.-F., Zhao, Y.-J., Li, X.-H. & Hu, M.-L. (2004). Acta Cryst. E60, m1210 m1212. Oxford Diffraction (2011). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Sheldrick, G. M. (2008). Acta Cryst. A64, Westrip, S. P. (2010). J. Appl. Cryst. 43, Cheng et al. [Pb 2 (C 7 H 4 O 6 S) 2 (C 12 H 8 N 2 ) 2 (H 2 O) 2 ]C 2 H 4 O 2 m879

3 supplementary materials [doi: /s x] catena-poly[[bis[aqua(1,10-phenanthroline)lead(ii)]-bis(µ 3-2-hydroxy-5- sulfonatobenzoato)] acetic acid monosolvate] Yuan-Zheng Cheng, Wei-Wei Shi, Xue-Dong Wang, Shu-E Deng and Li-Ping Zhang Comment 5-Sulfosalicylic acid (H 3 ssal) has three functional groups, viz -SO 3 H, -COOH and -OH, and can form three kind of ions (H 2 ssal -, Hssal 2- and ssal 3- ) (Fan & Zhu, 2006). Hssal 2- possesses the ability to bridge and chelate metal atoms using the carboxylate O atoms and the sulfonate O atoms (Chen et al., 2003). A few complexes containing Hssal 2- and phen ligands have been reported (Chen et al., 2003; Li et al., 2004; Fan & Zhu, 2005a,b, 2006; Du et al., 2006). Among the aforementioned complexes, there is a polymer (Fan & Zhu, 2006), which contains Pb II atoms and N,N-dimethylformamide ligands. In this paper, we report a new polymeric Pb II complex which contains water ligands instead of N,Ndimethylformamide ligands and acetic acid solvent molecules in the crystal lattice. The Pb II atom is seven-coordinated by two N atoms of one phenanthroline ligand, four O atoms from three Hssal 2- ligands, and one O atom from one H 2 O molecule (Fig. 1). The Pb O distances range from (3) Å to (4) Å, and the Pb N distances from (3) Å to (3) Å (Table 1). The distances of Pb Pb separated by the Hssal 2- ligand are (4) Å and (5) Å, while the Pb Pb separation by sulfonate is (3) Å. In the crystal, there is an intramolecular O4 H4 O6 hydrogen bond in the Hssal 2- ligand. In addition, there are intermolecular O H O hydrogen bonds linking water molecular and Hssal 2- ligands (Table 2 and Fig. 2). Aromatic π π stacking occurs between neighbouring phenanthroline ligands (Fig. 3). The centroid centroid distance between Cg3 (C1/C5 C8/C12) and Cg3 (C1/C5 C8/C12) [symmetry code: 1 - x, -y, 2 - z] is (2) Å. π π interactions between the aromatic systems of neighbouring dianions with plane-to-plane distances of (2) Å also occur. In the voids of this arrangement acetic acid molecules are incorporated. They exhibit half-occupancy due to disorder around a centre of inversion. Experimental A mixture of Pb(CH 3 COO) 2.3H 2 O (0.5 mmol, g) and 1.10-phenanthroline (0.5 mmol, g) in a solution of dimethylacetylamide (DMAC; 20 ml) was stirred for 20 min. Then 5-sulfosalicylic acid dihydrate (0.5 mmol, g) and NaOH (0.5 mmol, g) were dissolved in water (20 ml), which was added dropwise into the previous solution under stirring. The mixed solution was stirred for 1 h and filtered. The resulting solution was set aside for evaporation at room temperature for 11 d, and colorless block-shaped single crystals were obtained. Refinement The H atoms were placed at calculated positions and were allowed to ride on their parent atoms,with C H = 0.93 (aromatic C H), 0.96 (methyl) and O H = 0.82 (hydroxyl), 0.85 (water) Å, with U iso (H) = 1.2U eq (aromatic C), U iso (H)= 1.5U eq (methyl C) and U iso (H) = 1.5U eq (O). The acetic acid molecule is disordered around an inversion centre and was modelled with half-occupancy. sup-1

4 Computing details Data collection: CrysAlis PRO (Oxford Diffraction, 2011); cell refinement: CrysAlis PRO (Oxford Diffraction, 2011); data reduction: CrysAlis PRO (Oxford Diffraction, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publcif (Westrip, 2010). Figure 1 The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. [Symmetry codes: (A) -x, -y + 1, -z + 1; (B) x, y, z + 1]. Only one orientation of the disordered acetic acid molecule is shown. sup-2

5 Figure 2 Part of the crystal structure of the title compound, showing O H O hydrogen bonds as green dashed lines. sup-3

6 Figure 3 The π π stacking of the 1,10-phenanthroline units in the title compound. Only one orientation of the disordered acetic acid molecule is shown. catena-poly[[bis[aqua(1,10-phenanthroline)lead(ii)]-bis(µ 3-2-hydroxy- 5-sulfonatobenzoato)] acetic acid monosolvate] Crystal data [Pb 2 (C 7 H 4 O 6 S) 2 (C 12 H 8 N 2 ) 2 (H 2 O) 2 ] C 2 H 4 O 2 M r = Triclinic, P1 Hall symbol: -P 1 a = (7) Å b = (5) Å c = (5) Å α = (4) β = (5) γ = (5) V = (11) Å 3 Data collection Oxford Xcalibur CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator Detector resolution: pixels mm -1 ω scans Z = 1 F(000) = 624 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 4152 reflections θ = µ = 8.09 mm 1 T = 293 K Block, colourless mm Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2011) T min = 0.309, T max = measured reflections 3745 independent reflections 3438 reflections with I > 2σ(I) sup-4

7 R int = θ max = 25.0, θ min = 3.1 h = 11 9 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 310 parameters 28 restraints Primary atom site location: structure-invariant direct methods k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0245P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 1.83 e Å 3 Δρ min = 0.84 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) Pb (15) (12) (11) (4) S (9) (9) (7) (2) O (3) (3) (2) (8) O (3) (3) (3) (8) O (3) (3) (3) (9) O (3) (3) (2) (7) H * O (3) (3) (2) (7) O (3) (3) (2) (7) O (4) (4) (4) (11) H7B * H7A * N (3) (3) (2) (7) N (3) (3) (3) (8) C (4) (3) (3) (8) C (4) (4) (3) (9) H * C (4) (4) (3) (10) H * C (5) (4) (3) (10) H4A * C (4) (4) (3) (9) C (5) (4) (4) (11) sup-5

8 H * C (5) (4) (4) (11) H * C (4) (4) (3) (9) C (4) (4) (4) (10) H * C (4) (4) (4) (10) H * C (4) (4) (3) (10) H * C (4) (3) (3) (9) C (4) (3) (3) (8) C (4) (4) (3) (9) C (4) (4) (3) (10) H * C (4) (4) (3) (9) H * C (4) (3) (3) (8) C (3) (3) (3) (8) H * C (4) (4) (3) (9) O (15) (5) (3) (17) 0.50 H * 0.50 O (3) (4) (5) (15) 0.50 C (9) (4) (6) (2) 0.50 H20A * 0.50 H20B * 0.50 H20C * 0.50 C (8) (7) (7) (2) 0.50 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Pb (7) (7) (6) (5) (5) (5) S (4) (4) (4) (3) (3) (3) O (19) (14) (13) (14) (12) (11) O (16) (16) (14) (13) (12) (12) O (15) (18) (15) (14) (12) (13) O (15) (15) (13) (12) (11) (11) O (15) (14) (12) (12) (11) (11) O (15) (15) (11) (12) (11) (10) O (2) (19) (3) (17) (19) (18) N (15) (14) (13) (12) (11) (11) N (16) (14) (14) (13) (12) (12) C (18) (16) (16) (14) (14) (13) C (19) (18) (16) (15) (14) (14) C (2) (2) (18) (17) (16) (15) C (2) (19) (19) (17) (17) (15) C (2) (17) (17) (15) (15) (14) sup-6

9 C (2) (18) (2) (17) (18) (16) C (2) (19) (2) (18) (18) (17) C (18) (17) (18) (15) (15) (14) C (19) (2) (2) (17) (16) (17) C (2) (2) (2) (17) (16) (17) C (2) (19) (19) (16) (16) (16) C (18) (16) (17) (14) (14) (13) C (16) (16) (15) (13) (13) (13) C (16) (18) (17) (14) (13) (14) C (2) (18) (19) (16) (16) (15) C (19) (18) (17) (15) (14) (14) C (16) (16) (15) (14) (13) (13) C (16) (16) (15) (13) (13) (12) C (18) (18) (17) (15) (14) (14) O (3) (3) (3) (2) (2) (2) O (2) (3) (2) (2) (2) (2) C (3) (4) (3) (3) (3) (3) C (3) (3) (3) (3) (3) (3) Geometric parameters (Å, º) Pb1 O (3) C5 C (5) Pb1 N (3) C6 C (6) Pb1 N (3) C6 H Pb1 O (3) C7 C (5) Pb1 O3 i (3) C7 H Pb1 O (4) C8 C (5) Pb1 O1 ii (1) C8 C (5) S1 O (3) C9 C (6) S1 O (3) C9 H S1 O (3) C10 C (5) S1 C (3) C10 H O3 Pb1 i (3) C11 H O4 C (4) C13 C (4) O4 H C13 C (5) O5 C (5) C13 C (5) O6 C (4) C14 C (6) O7 H7B C15 C (5) O7 H7A C15 H N1 C (4) C16 C (5) N1 C (4) C16 H N2 C (5) C17 C (5) N2 C (4) C18 H C1 C (5) O8 C (7) C1 C (5) O8 H C2 C (5) O9 C (8) C2 H C20 C (10) C3 C (6) C20 H20A C3 H C20 H20B C4 C (5) C20 H20C sup-7

10 C4 H4A O6 Pb1 N (10) C4 C5 C (3) O6 Pb1 N (9) C6 C5 C (3) N2 Pb1 N (9) C7 C6 C (3) O6 Pb1 O (8) C7 C6 H N2 Pb1 O (9) C5 C6 H N1 Pb1 O (9) C6 C7 C (4) O6 Pb1 O3 i (10) C6 C7 H N2 Pb1 O3 i (10) C8 C7 H N1 Pb1 O3 i (9) C12 C8 C (3) O5 Pb1 O3 i (9) C12 C8 C (3) O6 Pb1 O (10) C9 C8 C (3) N2 Pb1 O (10) C10 C9 C (4) N1 Pb1 O (10) C10 C9 H O5 Pb1 O (10) C8 C9 H O3 i Pb1 O (11) C11 C10 C (4) O2 S1 O (19) C11 C10 H O2 S1 O (19) C9 C10 H O3 S1 O (19) N2 C11 C (3) O2 S1 C (17) N2 C11 H O3 S1 C (16) C10 C11 H O1 S1 C (16) N2 C12 C (3) S1 O3 Pb1 i (15) N2 C12 C (3) C14 O4 H C8 C12 C (3) C19 O5 Pb (2) C18 C13 C (3) C19 O6 Pb (2) C18 C13 C (3) Pb1 O7 H7B C14 C13 C (3) Pb1 O7 H7A O4 C14 C (3) H7B O7 H7A O4 C14 C (3) C2 N1 C (3) C15 C14 C (3) C2 N1 Pb (2) C16 C15 C (4) C1 N1 Pb (2) C16 C15 H C11 N2 C (3) C14 C15 H C11 N2 Pb (2) C15 C16 C (4) C12 N2 Pb (2) C15 C16 H N1 C1 C (3) C17 C16 H N1 C1 C (3) C18 C17 C (3) C5 C1 C (3) C18 C17 S (3) N1 C2 C (3) C16 C17 S (3) N1 C2 H C17 C18 C (3) C3 C2 H C17 C18 H C4 C3 C (3) C13 C18 H C4 C3 H O5 C19 O (3) C2 C3 H O5 C19 C (3) C3 C4 C (3) O6 C19 C (3) C3 C4 H4A O9 C21 O (6) C5 C4 H4A O9 C21 C (5) C4 C5 C (3) O8 C21 C (5) sup-8

11 O2 S1 O3 Pb1 i (2) C5 C6 C7 C8 0.1 (7) O1 S1 O3 Pb1 i (2) C6 C7 C8 C (7) C17 S1 O3 Pb1 i 13.4 (3) C6 C7 C8 C (4) O6 Pb1 O5 C (19) C12 C8 C9 C (6) N2 Pb1 O5 C (2) C7 C8 C9 C (4) N1 Pb1 O5 C (2) C8 C9 C10 C (7) O3 i Pb1 O5 C (2) C12 N2 C11 C (6) O7 Pb1 O5 C (2) Pb1 N2 C11 C (3) N2 Pb1 O6 C (2) C9 C10 C11 N2 0.9 (7) N1 Pb1 O6 C (2) C11 N2 C12 C8 0.8 (6) O5 Pb1 O6 C (19) Pb1 N2 C12 C (3) O3 i Pb1 O6 C (2) C11 N2 C12 C (4) O7 Pb1 O6 C (3) Pb1 N2 C12 C1 0.4 (4) O6 Pb1 N1 C (3) C9 C8 C12 N2 0.3 (6) N2 Pb1 N1 C (3) C7 C8 C12 N (4) O5 Pb1 N1 C (3) C9 C8 C12 C (4) O3 i Pb1 N1 C (3) C7 C8 C12 C1 0.4 (6) O7 Pb1 N1 C (3) N1 C1 C12 N2 1.4 (5) O6 Pb1 N1 C (3) C5 C1 C12 N (3) N2 Pb1 N1 C1 1.1 (3) N1 C1 C12 C (4) O5 Pb1 N1 C (3) C5 C1 C12 C8 1.8 (6) O3 i Pb1 N1 C (3) C18 C13 C14 O (3) O7 Pb1 N1 C (3) C19 C13 C14 O4 1.5 (5) O6 Pb1 N2 C (3) C18 C13 C14 C (5) N1 Pb1 N2 C (3) C19 C13 C14 C (3) O5 Pb1 N2 C (3) O4 C14 C15 C (3) O3 i Pb1 N2 C (3) C13 C14 C15 C (5) O7 Pb1 N2 C (3) C14 C15 C16 C (6) O6 Pb1 N2 C (3) C15 C16 C17 C (5) N1 Pb1 N2 C (3) C15 C16 C17 S (3) O5 Pb1 N2 C (3) O2 S1 C17 C (3) O3 i Pb1 N2 C (3) O3 S1 C17 C (3) O7 Pb1 N2 C (3) O1 S1 C17 C (3) C2 N1 C1 C5 1.0 (5) O2 S1 C17 C (3) Pb1 N1 C1 C (3) O3 S1 C17 C (3) C2 N1 C1 C (3) O1 S1 C17 C (3) Pb1 N1 C1 C (4) C16 C17 C18 C (5) C1 N1 C2 C3 1.2 (6) S1 C17 C18 C (2) Pb1 N1 C2 C (3) C14 C13 C18 C (5) N1 C2 C3 C4 3.1 (6) C19 C13 C18 C (3) C2 C3 C4 C5 2.6 (6) Pb1 O5 C19 O6 2.7 (3) C3 C4 C5 C (4) Pb1 O5 C19 C (3) C3 C4 C5 C1 0.5 (6) Pb1 O6 C19 O5 3.0 (4) N1 C1 C5 C4 1.3 (6) Pb1 O6 C19 C (2) C12 C1 C5 C (4) C18 C13 C19 O5 0.0 (5) N1 C1 C5 C (4) C14 C13 C19 O (3) C12 C1 C5 C6 2.2 (6) C18 C13 C19 O (3) sup-9

12 C4 C5 C6 C (4) C14 C13 C19 O6 0.4 (5) C1 C5 C6 C7 1.3 (6) Symmetry codes: (i) x, y+1, z+1; (ii) x, y, z+1. Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O4 H4 O (4) 141 O7 H7A O2 iii (5) 172 Symmetry code: (iii) x+1, y+1, z+1. sup-10