A novel zinc(II) complex with the ligand 2,20,200-(1,4,7-triazanonane-1,4,7-triyl)- triacetate (NOTA)

A novel zinc(II) complex with the ligand 2,2000,2000000-(1,4,7-triazanonane-1,4,7-triyl)- triacetate (NOTA) Iria Pereira-Garcı ´a, Alejandro Macı ´as,* Rufina Bastida and Laura Valencia Departamento de Quı ´mica Inorga ´nica, Facultade de Quı ´mica, Avd. das Ciencias s/n, Universidade de Santiago de Compostela, 15706-Santiago de Compostela, A Corun ˜a, Galicia, Spain Correspondence e-mail: alejandroalberto.ma[email protected] Received 20 October 2008; accepted 9 December 2008 Key indicators: single-crystal X-ray study; T= 100 K; mean (C–C) = 0.005 A ˚; Rfactor = 0.039; wR factor = 0.084; data-to-parameter ratio = 16.6. The zinc(II) complex with NOTA [2,20,200-(1,4,7-triazanonane1,4,7-triyl)triacetate] has previously been synthesized and studied in solution, but was not isolated. The corresponding title Zn II complex pentasodium(I) bis{[2,20,200-(1,4,7-triazanonane-1,4,7-triyl)triacetato]zinc(II)} tris(perchlorate) methanol solvate, Na 5 [Zn(C 12 H 18 N 3 O 6 )] 2 (ClO 4 ) 3 CH 3 OH, was crystallized as a sodium perchlorate double salt in methanol solution. The asymmetric unit contains two independent [Zn(NOTA)]  complex anion entities, five sodium cations, three perchlorate anions and a methanol solvent molecule. The two Zn II cations exhibit a distorted trigonal-prismatic N 3 O 3 coordination with a bifacial arrangement of the donor atoms. Neither the methanol solvent molecule nor the perchlorate anions appear to be coordinated to the Zn centres. The crystal structure shows a layer arrangement parallel to (001) generated by interactions between the [Zn(NOTA)]  units, the Na + cations, two ClO 4  units and the methanole molecule, leading to an overall layer composition of [Na 5 [Zn(C 12 H 18 N 3 O 6 )] 2 (ClO 4 ) 2. - CH 3 OH] + . The third ClO 4 anion is isolated and situated between the layers without any significant interactions. Related literature Details on the synthesis of NOTA are given by Desreux (1980). For NOTA complexes of Al, Cr, Fe, Co, Ni, Cu, Ga and In characterized by X-ray diffraction studies, see: Boeyens & Van der Merwe (1997); Bossek et al. (1995); Clarke & Martell (1991); Craig et al. (1989); Jyo et al. (1990); Van der Merwe et al. (1983, 1985); Moore et al. (1990); Wieghardt et al. (1982). For general background, see: Geraldes et al. (1985). Experimental Crystal data Na 5 [Zn(C 12 H 18 N 3 O 6 )] 2 (ClO 4 ) 3 - CH 4 O M r = 1176.67 Orthorhombic, Pna21 a= 16.8879 (5) A ˚ b= 9.4723 (3) A ˚ c= 26.4552 (9) A ˚ V= 4232.0 (2) A ˚ 3 Z=4 Mo Kradiation = 1.47 mm 1 T= 100 (2) K 0.22 0.10 0.10 mm Data collection Bruker APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.738, T max = 0.867 31309 measured reflections 9954 independent reflections 8605 reflections with I>2(I) R int = 0.036 Refinement R[F 2 >2(F 2 )] = 0.039 wR(F 2 ) = 0.084 S= 1.07 9954 reflections 601 parameters 1 restraint H atoms treated by a mixture of independent and constrained refinement  max = 0.56 e A ˚ 3  min =0.58 e A ˚ 3 Absolute structure: Flack (1983), 4585 Friedel pairs Flack parameter: 0.383 (7) Table 1 Selected bond lengths (A ˚). Zn1—O5 2.027 (3) Zn1—O1 2.062 (2) Zn1—O3 2.066 (2) Zn1—N2 2.160 (3) Zn1—N3 2.172 (3) Zn1—N1 2.189 (3) Zn2—O23 2.047 (3) Zn2—O21 2.057 (3) Zn2—O25 2.072 (3) Zn2—N22 2.198 (3) Zn2—N21 2.201 (3) Zn2—N23 2.201 (3) Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999). We thank the Xunta de Galicia (Spain; Project PGIDIT07PXIB209039PR) for financial support. The X-ray data were collected at the Unidade de Raios X, RIAIDT, University of Santiago de Compostela, Spain. metal-organic compounds m84 Pereira-Garcı ´aet al. doi:10.1107/S1600536808041895 Acta Cryst. (2009). E65, m84–m85 Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2202). References Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. Boeyens, J. C. A. & Van der Merwe, M. J. (1997). Inorg. Chem. 36, 3779–3780. Bossek, U., Hanke, D., Wieghardt, K. & Nuber, B. (1995). Polyhedron,12, 1–5. Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Clarke, E. T. & Martell, A. E. (1991). Inorg. Chim. Acta,181, 273–280. Craig, A. S., Helps, I. M., Parker, D., Ferguson, G., Bailey, N. A., Smith, J. A. S., Adams, H. & Williams, M. (1989). Polyhedron,8, 2481–2484. Desreux, J. F. (1980). Inorg. Chem. 19, 1319–1324. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. Flack, H. D. (1983). Acta Cryst. A39, 876–881. Geraldes, C. F. G. C., Alpoim, M. C., Marques, M. P. M., Sherry, A. D. & Singh, M. (1985). Inorg. Chem. 24, 3876–3881. Jyo, A., Kohno, Y., Terazono, Y. & Kawano, S. (1990). Anal. Sci. 6, 629–631. Moore, D. A., Fanwick, P. E. & Welch, M. J. (1990). Inorg. Chem. 29, 672–676. Sheldrick, G. M. (1996). SADABS. University of Go ¨ttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Van der Merwe, M. J., Boeyens, J. C. A. & Hancock, R. D. (1983). Inorg. Chem. 22, 3490–3491. Van der Merwe, M. J., Boeyens, J. C. A. & Hancock, R. D. (1985). Inorg. Chem. 24, 1208–1213. Wieghardt, K., Bossek, U., Chaudhuri, P., Herrmann, W., Menke, B. C. & Weiss, J. (1982). Inorg. Chem. 21, 4308–4314. metal-organic compounds Acta Cryst. (2009). E65, m84–m85 Pereira-Garcı ´aet al. Na 5 [Zn(C 12 H 18 N 3 O 6 )] 2 (ClO 4 ) 3 CH 4 Om85 supporting information sup-1 Acta Cryst. (2009). E65, m84–m85 supporting information Acta Cryst. (2009). E65, m84–m85 [doi:10.1107/S1600536808041895] A novel zinc(II) complex with the ligand 2,2′,2′′-(1,4,7-triazanonane-1,4,7triyl)triacetate (NOTA) Iria Pereira-García, Alejandro Macías, Rufina Bastida and Laura Valencia S1. Comment NOTA (1,4,7-triazacyclononane-N, N′, N′′-triacetate) has a well-known preference for small metal ions, and many metal NOTA complexes (M = Al, Cr, Fe, Co, Ni, Cu, Ga and In) have been structurally characterized: (Boeyens & Van der Merwe, 1997; Bossek et al., 1995; Clarke & Martell, 1991; Craig et al., 1989; Jyo et al., 1990; Van der Merwe et al., 1983, 1985; Moore et al., 1990; Wieghardt et al., 1982). Our starting objective was the synthesis of NOTA (1,4,7-triazacyclononane-N,N′,N′′-triacetate) complexes in aqueous solutions and its isolation as salts of the type [X][M(NOTA)], where X+ is a monovalent cation and M is ZnII or Cd(II). We also developed a species distribution diagram for NOTA complexes in aqueous solution based on the experimental data obtained by Geraldes et al. (1985). From these experiments we concluded that the anionic salts [Zn(NOTA)]- and [Cd(NOTA)]-, due to their extreme solubility in aqueous solution, do not precipitate as neither sodium nor the alkylammonium salts. These difficulties for isolating the complexes led us to synthesize the ZnII and Cd(II) NOTA complexes in methanol, a solvent in which the sodium salts are less soluble than in aqueous solution. A ZnII complex with a 1:1 composition was prepared by reaction of the NOTA ligand L with hydrous ZnII perchlorate in a 1:1 molar ratio of metal:ligand. This complex was synthesized by a single-step procedure as described and the reaction revealed a pure product that was also characterized by ESI-MS and 1H-NMR spectroscopy. The molecular structure of the complex entity [Zn(NOTA)]- and selected bond lengths (Å) and angles (°) of the coordination environment of ZnII are given in Fig. 1 and Table 1, respectively. The asymmetric unit contains two independent mononuclear complex [Zn(NOTA)]- entities, five sodium cations, three perchlorate anions and a methanol solvent molecule. The coordination environment, distances and angles of both independent [Zn(NOTA)]- molecules are similar. When the metal centre coordination requirements do not favour an octahedral environment, the metal core geometry in NOTA complexes is trigonal-prismatic (Wieghardt et al., 1982). Thus, the ZnII centres present a sixcoordinated N3O3 core in a distorted trigonal-prismatic arrangement. Each Zn atom is bound to three N atoms from the macrocyclic backbone and three O atoms from the pendant-arms. Like in all the other known structures of NOTA complexes, in the [Zn(NOTA)]- entities the donor atoms are disposed in a bifacial arrangement. Three N atoms occupy one facial plane of the prism, and three O atoms belong to the other plane. The average Zn—N and Zn—O bond lengths are 2.187 Å and 2.055 Å, respectively. These bond lengths are in the range found for M–N and M–O bonds in other NOTA complexes with divalent transition metals. The crystal structure shows a layer arrangement parallel (001) generated by interactions between the [Zn(NOTA)]- units, the Na+ cations, two ClO4units and the methanol molecule, leading to an overall layer composition of [Na5[Zn(C12H18N3O6)]2(ClO4)2.CH3OH]+. The third ClO4 anion is isolated and situated between the layers without any significant interactions (Fig. 2). supporting information sup-2 Acta Cryst. (2009). E65, m84–m85 S2. Experimental Synthesis of the macrocycle NOTAH3: The ligand NOTA was prepared from its triazamacrocycle precursor TACN by alkylation with bromoacetic acid using a modification of a previously reported method (Desreux, 1980). TACN and NaOH were dissolved in water, and to the solution was added a bromoacetic acid/ NaOH aqueous solution at 273 K. The reaction mixture temperature was raised to 323 K, and a NaOH aqueous solution was added. The mixture was maintained at 323 K under stirring for 5 d. Then, concentrated hydrobromic acid was added until a pH of ~ 7 was reached. NOTAH3 does not precipitate from aqueous solutions in a well-defined state, thus a purification stage was needed. After a liquidliquid extraction with n-butanol, a white powder characterized as a salt of the expected ligand was finally obtained. C12H21N3O6.(CH2BrCOOH)3:MS (ESI, m/z) 304 [H(LH3)]+, 326 {Na(LH3)]}+, 348 [Na2(LH2)]+; 1H NMR data: (250 MHz, D2O, SiMe4): d 3.5 (s, 12 H from –CH2– in the ring), d 3.9 (s, 6 H from CH2BrCOOH), d 4.3 (s, 6 H from –CH2– in pendants). Synthesis of the metal complexes: Hydrated zinc perchlorate was added to a solution of the purified ligand NOTAH3 in methanol. The reaction mixture was heated and then cooled. A concentrated NaOH methanolic solution was added until a pH of 7 was reached. Single crystals were obtained by the diffusion vapour-phase crystallization method in a MeOH/Et2O solvent system. The ZnII complex was characterized by ESI-MS, 1HNMR, COSY NMR and X-ray diffraction. Na[ZnL]1.5(NaClO4).0.5MeOH: MS(ESI, m/z) 366 [Zn(LH2)]+, 388 {Na[Zn(LH)]}+. Colour: colourless. The correspondent Cd(II) complex was also obtained in methanolic solution, but it has not been isolated in crystalline form. S3. Refinement The absolute structure parameter was refined (Flack, 1983) and points to racemic twinning, with a ratio of the twin fractions of approximately 3:2. The hydrogen atoms attached to the carbon atoms were located in their calculated positions and refined using a riding model with U(H) equal to 1.2× Ueq (1.5 for methyl groups) of the parent atom and C —H= 0.97 Å. The hydrogen atom attached to the oxygen atom in the methanol molecule was localized in a Fourier map and refined with Uiso constrained to be 1.5 × Ueq of the O atom. supporting information sup-3 Acta Cryst. (2009). E65, m84–m85 Figure 1 The molecular structure of one [Zn(NOTA)]- complex with atom labelling and displacement ellipsoids drawn at the 50% probability level. The structure of the second [Zn(NOTA)]- entity is very similar. supporting information sup-4 Acta Cryst. (2009). E65, m84–m85 Figure 2 The crystal structure of the title compound in a projection along [010], emphasizing the layer arrangement parallel (001) as generated by interactions between the [Zn(NOTA)]- units, the Na+ cations, two ClO4units and the methanol molecule. The third ClO4 anion is isolated and situated between the layers without any significant interactions. pentasodium(I) bis[(1,4,7-triazacyclononane-N,N′,N′′-triacetato)zinc(II)] tris(perchlorate) methanol solvate Crystal data Na5[Zn(C12H18N3O6)]2(ClO4)3·CH4O Mr = 1176.67 Orthorhombic, Pna21 Hall symbol: P 2c -2n a = 16.8879 (5) Å b = 9.4723 (3) Å c = 26.4552 (9) Å V = 4232.0 (2) Å3 Z = 4 F(000) = 2392 Dx = 1.847 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 9827 reflections θ = 2.4–27.7° µ = 1.47 mm−1 T = 100 K Prism, colourless 0.22 × 0.10 × 0.10 mm Data collection Bruker APEXII CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω and φ scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.738, Tmax = 0.867 31309 measured reflections 9954 independent reflections 8605 reflections with I > 2σ(I) Rint = 0.036 θmax = 28.3°, θmin = 1.5° h = −21→22 k = −12→12 l = −35→32 supporting information sup-5 Acta Cryst. (2009). E65, m84–m85 Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.039 wR(F2) = 0.084 S = 1.07 9954 reflections 601 parameters 1 restraint Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0392P)2 + 1.4688P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001 Δρmax = 0.56 e Å−3 Δρmin = −0.58 e Å−3 Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 Extinction coefficient: 0.00024 (8) Absolute structure: Flack (1983), 4585 Friedel pairs Absolute structure parameter: 0.383 (7) 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 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 Rfactors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) xy z U iso*/Ueq Zn1 1.07460 (2) 0.01616 (4) 0.917626 (16) 0.00860 (9) N1 1.12568 (18) −0.1518 (3) 0.96418 (12) 0.0120 (7) N2 1.12185 (18) 0.1482 (3) 0.97696 (12) 0.0118 (7) N3 0.97800 (19) −0.0083 (3) 0.97112 (12) 0.0129 (7) O1 1.16120 (14) −0.0640 (3) 0.87080 (10) 0.0118 (5) O2 1.21023 (15) −0.2696 (3) 0.84582 (10) 0.0149 (6) O3 1.08723 (14) 0.2045 (3) 0.87911 (10) 0.0109 (5) O4 1.14849 (15) 0.4106 (3) 0.88043 (10) 0.0138 (6) O5 0.98658 (14) −0.0531 (3) 0.87180 (10) 0.0127 (6) O6 0.85724 (14) −0.0775 (3) 0.86305 (10) 0.0134 (6) C1 1.1941 (2) −0.0791 (4) 0.98715 (16) 0.0161 (8) H1A 1.2341 −0.0596 0.9607 0.019* H1B 1.2187 −0.1417 1.0127 0.019* C2 1.1699 (2) 0.0601 (4) 1.01240 (15) 0.0174 (8) H2A 1.1386 0.0398 1.0432 0.021* H2B 1.2179 0.1128 1.0226 0.021* C3 1.0484 (2) 0.2058 (4) 1.00086 (15) 0.0134 (8) H3A 1.0233 0.2739 0.9774 0.016* H3B 1.0629 0.2573 1.0321 0.016* C4 0.9891 (2) 0.0898 (4) 1.01387 (15) 0.0169 (9) H4A 1.0082 0.0367 1.0437 0.020* H4B 0.9376 0.1332 1.0227 0.020* supporting information sup-6 Acta Cryst. (2009). E65, m84–m85 C5 0.9838 (2) −0.1590 (4) 0.98620 (15) 0.0157 (8) H5A 0.9663 −0.2188 0.9576 0.019* H5B 0.9474 −0.1764 1.0149 0.019* C6 1.0663 (2) −0.2020 (4) 1.00137 (14) 0.0156 (8) H6A 1.0787 −0.1621 1.0350 0.019* H6B 1.0692 −0.3061 1.0039 0.019* C7 1.1508 (2) −0.2609 (4) 0.92774 (14) 0.0152 (8) H7A 1.1064 −0.3272 0.9217 0.018* H7B 1.1955 −0.3151 0.9421 0.018* C8 1.1760 (2) −0.1946 (4) 0.87764 (14) 0.0095 (7) C9 1.1674 (2) 0.2606 (4) 0.95153 (14) 0.0140 (8) H9A 1.2228 0.2292 0.9470 0.017* H9B 1.1678 0.3460 0.9731 0.017* C10 1.1323 (2) 0.2972 (4) 0.90042 (14) 0.0107 (8) C11 0.9056 (2) 0.0144 (4) 0.94157 (15) 0.0128 (8) H11A 0.8936 0.1166 0.9399 0.015* H11B 0.8605 −0.0336 0.9582 0.015* C12 0.9163 (2) −0.0434 (4) 0.88855 (15) 0.0120 (8) Zn2 0.60272 (2) 0.05820 (4) 0.708125 (16) 0.00988 (9) N21 0.53471 (18) −0.0972 (3) 0.66409 (11) 0.0111 (7) N22 0.68311 (18) 0.0323 (3) 0.64345 (12) 0.0137 (7) N23 0.54514 (19) 0.2003 (3) 0.65352 (12) 0.0141 (7) O21 0.52931 (15) −0.0254 (3) 0.76249 (10) 0.0134 (6) O22 0.45361 (15) −0.2103 (3) 0.78197 (10) 0.0168 (6) O23 0.70301 (16) −0.0144 (3) 0.74292 (10) 0.0160 (6) O24 0.83384 (17) −0.0339 (3) 0.73661 (12) 0.0267 (7) O25 0.60456 (15) 0.2484 (3) 0.74679 (10) 0.0142 (6) O26 0.55583 (15) 0.4664 (3) 0.74935 (10) 0.0145 (6) C21 0.5825 (2) −0.1491 (4) 0.62115 (14) 0.0129 (8) H21A 0.5636 −0.1044 0.5895 0.015* H21B 0.5754 −0.2524 0.6178 0.015* C22 0.6700 (2) −0.1160 (4) 0.62845 (16) 0.0162 (8) H22A 0.6920 −0.1791 0.6548 0.019* H22B 0.6986 −0.1350 0.5965 0.019* C23 0.6640 (2) 0.1362 (4) 0.60296 (15) 0.0161 (8) H23A 0.6354 0.0882 0.5752 0.019* H23B 0.7136 0.1761 0.5891 0.019* C24 0.6130 (2) 0.2540 (4) 0.62434 (16) 0.0160 (8) H24A 0.6460 0.3145 0.6465 0.019* H24B 0.5933 0.3132 0.5962 0.019* C25 0.4863 (2) 0.1230 (4) 0.62259 (15) 0.0151 (8) H25A 0.5090 0.1028 0.5888 0.018* H25B 0.4386 0.1823 0.6179 0.018* C26 0.4633 (2) −0.0149 (4) 0.64821 (15) 0.0132 (8) H26A 0.4303 0.0058 0.6783 0.016* H26B 0.4312 −0.0725 0.6246 0.016* C27 0.5128 (2) −0.2061 (4) 0.70054 (15) 0.0145 (8) H27A 0.5563 −0.2757 0.7034 0.017* supporting information sup-7 Acta Cryst. (2009). E65, m84–m85 H27B 0.4650 −0.2564 0.6884 0.017* C28 0.4961 (2) −0.1420 (4) 0.75278 (14) 0.0121 (8) C29 0.7628 (2) 0.0498 (4) 0.66439 (15) 0.0175 (9) H29A 0.7774 0.1510 0.6637 0.021* H29B 0.8013 −0.0023 0.6432 0.021* C30 0.7672 (2) −0.0043 (4) 0.71825 (16) 0.0165 (9) C31 0.5101 (2) 0.3140 (4) 0.68376 (14) 0.0140 (8) H31A 0.4565 0.2856 0.6950 0.017* H31B 0.5048 0.3998 0.6627 0.017* C32 0.5604 (2) 0.3469 (4) 0.72938 (15) 0.0140 (8) Cl1P 0.90733 (6) 0.49270 (10) 0.94241 (4) 0.0164 (2) Cl2P 0.76010 (6) 0.50986 (10) 0.57365 (4) 0.0207 (2) Cl3P 0.85405 (6) 0.29914 (10) 0.79612 (4) 0.0198 (2) O1P 0.87409 (16) 0.4307 (3) 0.81979 (11) 0.0225 (7) O2P 0.78137 (15) 0.2457 (3) 0.81750 (11) 0.0215 (7) O3P 0.91798 (15) 0.2025 (3) 0.80605 (11) 0.0199 (6) O4P 0.84347 (19) 0.3166 (3) 0.74240 (12) 0.0322 (8) O5P 0.98116 (16) 0.4732 (3) 0.91612 (13) 0.0264 (7) O6P 0.92441 (19) 0.5250 (3) 0.99436 (12) 0.0300 (8) O7P 0.86528 (16) 0.6093 (3) 0.91977 (11) 0.0196 (6) O8P 0.86005 (19) 0.3672 (3) 0.93927 (13) 0.0326 (8) O9P 0.81100 (17) 0.6321 (3) 0.57245 (13) 0.0307 (7) O10P 0.7577 (3) 0.4429 (4) 0.52517 (14) 0.0578 (12) O11P 0.68191 (19) 0.5555 (3) 0.58564 (16) 0.0445 (10) O12P 0.78848 (18) 0.4105 (3) 0.61010 (12) 0.0303 (8) C1S 0.7491 (3) 0.6009 (5) 0.71492 (18) 0.0350 (12) H1S1 0.7719 0.5133 0.7016 0.053* H1S2 0.7837 0.6804 0.7064 0.053* H1S3 0.6967 0.6160 0.6999 0.053* O1S 0.74181 (18) 0.5907 (3) 0.76745 (11) 0.0238 (7) H1S 0.708 (3) 0.650 (5) 0.7779 (19) 0.036* Na1 0.94165 (8) 0.95334 (15) 0.78618 (6) 0.0129 (3) Na2 0.84425 (8) 0.67402 (15) 0.83292 (6) 0.0180 (3) Na3 0.52011 (8) 0.11140 (16) 0.83393 (6) 0.0175 (3) Na4 0.66600 (9) 0.40410 (15) 0.80596 (6) 0.0146 (3) Na5 0.74113 (8) −0.00225 (14) 0.82877 (6) 0.0121 (3) Atomic displacement parameters (Å2) U11 U22 U33 U12 U13 U23 Zn1 0.00958 (19) 0.00826 (19) 0.0080 (2) −0.00044 (15) −0.00002 (19) −0.00020 (19) N1 0.0161 (16) 0.0096 (15) 0.0102 (16) −0.0003 (12) −0.0014 (13) −0.0001 (13) N2 0.0135 (16) 0.0102 (16) 0.0117 (16) −0.0013 (12) −0.0008 (13) −0.0011 (13) N3 0.0172 (18) 0.0110 (16) 0.0106 (16) −0.0007 (12) 0.0024 (14) −0.0027 (13) O1 0.0138 (13) 0.0109 (13) 0.0106 (13) 0.0039 (10) 0.0041 (11) 0.0003 (11) O2 0.0156 (14) 0.0128 (14) 0.0164 (14) 0.0043 (10) 0.0033 (12) −0.0003 (11) O3 0.0119 (13) 0.0117 (13) 0.0092 (13) −0.0018 (10) −0.0016 (11) 0.0001 (11) O4 0.0160 (14) 0.0092 (13) 0.0162 (14) −0.0019 (10) 0.0031 (11) 0.0019 (11) supporting information sup-14 Acta Cryst. (2009). E65, m84–m85 O21—Zn2—N21 78.35 (11) O4iv—Na3—O3Piv 141.14 (10) O25—Zn2—N21 148.30 (11) O1Piv—Na3—O3Piv 53.95 (9) N22—Zn2—N21 80.53 (11) O21—Na3—C10iv 131.52 (12) O23—Zn2—N23 150.03 (12) O3iv—Na3—C10iv 28.26 (9) O21—Zn2—N23 115.34 (11) O5Piv—Na3—C10iv 73.33 (11) O25—Zn2—N23 78.41 (11) O4iv—Na3—C10iv 26.73 (9) N22—Zn2—N23 80.23 (12) O1Piv—Na3—C10iv 145.51 (12) N21—Zn2—N23 80.27 (12) O3Piv—Na3—C10iv 115.66 (11) O23—Zn2—Na3 87.28 (8) O21—Na3—O25 65.18 (9) O21—Zn2—Na3 35.31 (8) O3iv—Na3—O25 81.04 (9) O25—Zn2—Na3 55.57 (8) O5Piv—Na3—O25 164.93 (10) N22—Zn2—Na3 164.36 (9) O4iv—Na3—O25 90.11 (9) N21—Zn2—Na3 112.10 (8) O1Piv—Na3—O25 114.70 (10) N23—Zn2—Na3 110.23 (9) O3Piv—Na3—O25 78.61 (9) C27—N21—C21 114.3 (3) C10iv—Na3—O25 91.59 (10) C27—N21—C26 110.4 (3) O21—Na3—Cl3Piv 87.13 (8) C21—N21—C26 113.4 (3) O3iv—Na3—Cl3Piv 112.97 (8) C27—N21—Zn2 104.8 (2) O5Piv—Na3—Cl3Piv 97.78 (9) C21—N21—Zn2 110.2 (2) O4iv—Na3—Cl3Piv 165.21 (9) C26—N21—Zn2 102.8 (2) O1Piv—Na3—Cl3Piv 27.24 (7) C29—N22—C22 110.3 (3) O3Piv—Na3—Cl3Piv 27.50 (6) C29—N22—C23 113.3 (3) C10iv—Na3—Cl3Piv 138.69 (9) C22—N22—C23 113.7 (3) O25—Na3—Cl3Piv 93.66 (7) C29—N22—Zn2 105.1 (2) O1iv—Na4—O25 152.16 (11) C22—N22—Zn2 102.9 (2) O1iv—Na4—O1S 81.39 (10) C23—N22—Zn2 110.6 (2) O25—Na4—O1S 114.02 (11) C31—N23—C24 110.2 (3) O1iv—Na4—O26 105.71 (10) C31—N23—C25 113.2 (3) O25—Na4—O26 54.58 (9) C24—N23—C25 113.8 (3) O1S—Na4—O26 88.20 (11) C31—N23—Zn2 105.6 (2) O1iv—Na4—O2P 109.63 (11) C24—N23—Zn2 102.2 (2) O25—Na4—O2P 92.77 (10) C25—N23—Zn2 110.9 (2) O1S—Na4—O2P 94.51 (11) C28—O21—Zn2 117.5 (2) O26—Na4—O2P 144.57 (11) C28—O21—Na3 129.0 (2) O1iv—Na4—O3iv 71.43 (9) Zn2—O21—Na3 113.50 (12) O25—Na4—O3iv 91.22 (10) C28—O22—Na2iv 138.5 (2) O1S—Na4—O3iv 152.81 (11) C28—O22—Na1iv 127.0 (2) O26—Na4—O3iv 99.40 (10) Na2iv—O22—Na1iv 92.88 (11) O2P—Na4—O3iv 94.12 (10) C30—O23—Zn2 116.8 (2) O1iv—Na4—C32 131.19 (12) C30—O23—Na5 104.9 (2) O25—Na4—C32 27.70 (10) Zn2—O23—Na5 129.88 (13) O1S—Na4—C32 100.22 (12) C30—O24—Na1iii 164.3 (3) O26—Na4—C32 27.03 (10) C30—O24—Na5 79.6 (2) O2P—Na4—C32 118.75 (12) Na1iii—O24—Na5 87.28 (11) O3iv—Na4—C32 98.08 (11) C32—O25—Zn2 116.6 (2) O1iv—Na4—Cl3P 106.80 (8) C32—O25—Na4 92.2 (2) O25—Na4—Cl3P 100.27 (8) Zn2—O25—Na4 150.14 (13) O1S—Na4—Cl3P 71.34 (8) C32—O25—Na3 108.3 (2) O26—Na4—Cl3P 138.03 (9) supporting information sup-15 Acta Cryst. (2009). E65, m84–m85 Zn2—O25—Na3 89.79 (9) O2P—Na4—Cl3P 23.25 (7) Na4—O25—Na3 88.28 (9) O3iv—Na4—Cl3P 115.65 (7) C32—O26—Na1v122.2 (2) C32—Na4—Cl3P 120.02 (9) C32—O26—Na4 89.6 (2) O4iv—Na5—O2viii 94.98 (11) Na1v—O26—Na4 117.22 (12) O4iv—Na5—O6 118.54 (12) N21—C21—C22 111.3 (3) O2viii—Na5—O6 79.66 (10) N21—C21—H21A 109.4 O4iv—Na5—O23 114.38 (11) C22—C21—H21A 109.4 O2viii—Na5—O23 94.71 (11) N21—C21—H21B 109.4 O6—Na5—O23 127.05 (11) C22—C21—H21B 109.4 O4iv—Na5—O2P 84.12 (10) H21A—C21—H21B 108.0 O2viii—Na5—O2P 174.83 (12) N22—C22—C21 112.1 (3) O6—Na5—O2P 96.27 (10) N22—C22—H22A 109.2 O23—Na5—O2P 90.30 (11) C21—C22—H22A 109.2 O4iv—Na5—O24 157.10 (11) N22—C22—H22B 109.2 O2viii—Na5—O24 101.07 (10) C21—C22—H22B 109.2 O6—Na5—O24 80.68 (10) H22A—C22—H22B 107.9 O23—Na5—O24 48.48 (9) N22—C23—C24 109.9 (3) O2P—Na5—O24 81.29 (10) N22—C23—H23A 109.7 O4iv—Na5—C30 134.93 (12) C24—C23—H23A 109.7 O2viii—Na5—C30 102.99 (11) N22—C23—H23B 109.7 O6—Na5—C30 105.29 (11) C24—C23—H23B 109.7 O23—Na5—C30 24.50 (10) H23A—C23—H23B 108.2 O2P—Na5—C30 81.10 (11) N23—C24—C23 112.5 (3) O24—Na5—C30 24.72 (9) Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x+1/2, −y−1/2, z; (iii) x, y−1, z; (iv) x−1/2, −y+1/2, z; (v) x−1/2, −y+3/2, z; (vi) x, y+1, z; (vii) x+1/2, −y+3/2, z; (viii) x−1/2, −y−1/2, z.