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1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Poly[[hexaaquabis(l 3 -benzene-1,3,5- tricarboxylato-j 3 O 1 :O 3 :O 5 )bis(5,5 0 - dimethyl-2,2 0 -bipyridine-j 2 N,N 0 )trizinc] hexahydrate] Wen-Wen Shan,* Han-Lin Xiong and Chong-Zhen Mei North China University of Water Conservancy and Electric Power, Zhengzhou , People s Republic of China Correspondence hbsysww@163.com Received 1 June 2011; accepted 8 June 2011 Key indicators: single-crystal X-ray study; T = 296 K; mean (C C) = Å; disorder in solvent or counterion; R factor = 0.045; wr factor = 0.124; data-toparameter ratio = Experimental Crystal data [Zn 3 (C 9 H 3 O 6 ) 2 (C 12 H 12 N 2 ) 2 - (H 2 O) 6 ]6H 2 O M r = Triclinic, P1 a = (10) Å b = (10) Å c = (1) Å = (8) = (8) = (8) V = (19) Å 3 Z =1 Mo K radiation = 1.54 mm 1 T = 296 K mm In the title compound, {[Zn 3 (C 9 H 3 O 6 ) 2 (C 12 H 12 N 2 ) 2 (H 2 O) 6 ]- 6H 2 O} n, one Zn II atom, lying on an inversion center, is sixcoordinated by two O atoms from two benzene-1,3,5- tricarboxylate (btc) ligands and four water molecules in a distorted octahedral geometry. The other Zn II atom is fivecoordinated by two N atoms from a 5,5 0 -dimethyl-2,2 0 - bipyridine (dmbpy) ligand, two O atoms from two btc ligands and one water molecule in a distorted trigonal bipyramidal geometry. The compound features a one-dimensional ladder structure, with windows of ca (1) (2) Å. The ladders are linked together by intermolecular O HO hydrogen bonds and interactions between the benzene rings and between the pyridine rings [centroid-to-centroid distances (2) and (3) Å, respectively] to form a three-dimensional supramolecular structure. One of the lattice water molecules is disordered over two positions in a 0.592:0.408 ratio. Related literature For background to network topologies and the applications of coordination polymers, see: Maspoch et al. (2007); Ockwig et al. (2005). For background to effective methods for the construction of coordination polymers, see: Du et al. (2007); Zang et al. (2006, 2010). For O HO hydrogen bonds, see: Desiraju (2004). Data collection Bruker APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2001) T min = 0.739, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 336 parameters Table 1 Hydrogen-bond geometry (Å, ) measured reflections 4330 independent reflections 3426 reflections with I > 2(I) R int = restraints H-atom parameters constrained max = 0.74 e Å 3 min = 0.59 e Å 3 D HA D H HA DA D HA O1W H1WAO5 i (4) 166 O1W H1WBO6W (5) 176 O2W H2WAO2 i (4) 162 O2W H2WBO5W i (6) 135 O3W H3WBO3 i (4) 125 O3W H3WCO (4) 113 O4W H4WAO5W (19) 173 O4W 0 H4WDO (11) 177 O5W H5WAO6W (9) 179 O5W H5WCO6 iv (7) 164 O6W H6WBO1 iv (5) 154 O6W H6WDO4 v (6) 154 Symmetry codes: (i) x þ 1; y; z þ 1; () x; y þ 1; z þ 1; (i) x; y 1; z; (iv) x; y þ 1; z; (v) x 1; y þ 1; z. Data collection: APEX2 (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: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008). Acta Cryst. (2011). E67, m921 m922 doi: /s Shan et al. m921

2 metal-organic compounds This work was supported financially by the Natural Science Foundation of Henan Province (grant No. 2010A140009) and the International Technology Cooperation Project of the Science and Technology Department of Henan Province of China (grant No ). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2439). References Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Desiraju, G. R. (2004). Hydrogen Bonding. Encyclopedia of Supramolecular Chemistry, edited by J. L. Atwood & J. W. Steed, pp New York: Marcel Dekker Inc. Du, M., Jiang, X.-J. & Zhao, X.-J. (2007). Inorg. Chem. 46, Maspoch, D., Ruiz-Molina, D. & Veciana, J. (2007). Chem. Soc. Rev. 36, Ockwig, N. W., Delgado-Friedrichs, O., O Keefee, M. & Yaghi, O. M. (2005). Acc. Chem. Res. 38, Sheldrick, G. M. (2008). Acta Cryst. A64, Zang, S.-Q., Liang, R., Fan, Y.-J., Hou, H.-W. & Mak, T. C. W. (2010). Dalton Trans. pp Zang, S.-Q., Su, Y., Li, Y.-Z., Ni, Z.-P. & Meng, Q.-J. (2006). Inorg. Chem. 45, m922 Shan et al. [Zn 3 (C 9 H 3 O 6 ) 2 (C 12 H 12 N 2 ) 2 (H 2 O) 6 ]6H 2 O Acta Cryst. (2011). E67, m921 m922

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4 Acta Cryst. (2011). E67, m921-m922 [ doi: /s ] Poly[[hexaaquabis( 3-benzene-1,3,5-tricarboxylato- 3O1:O3:O5)bis(5,5'-dimethyl-2,2'-bipyridine2 N,N')trizinc] hexahydrate] W.-W. Shan, H.-L. Xiong and C.-Z. Mei Comment In recent years, supramolecular coordination assemblies have received much attention not only for their variety of architectures but also for the potential applications as functional materials (Maspoch et al., 2007; Ockwig et al., 2005). According to literature, carboxylate-based ligands are good bridging ligands to construct coordination polymers, in which many supramolecular structures have been furnished (Zang et al., 2006, 2010). The rational assembly of target metal organic networks depends on deliberate designs of the ligands with adjustable connectivity and a reasonable choice of metal ions with specific coordination nature. Additionally, the use of auxiliary ligands is also an effective method for the construction of coordination polymers (Du et al., 2007). To further explore the influence of multicarboxylates and N-donor ligands on the properties and construction of coordination compounds, we undertake synthetic and structural studies on the title compound, a Zn(II) complex based on benzene-1,3,5-tricarboxylic acid (H3btc) and 5,5'-dimethyl-2,2'-bipyridine (dmbpy). As shown in Fig. 1, the asymmetric unit of the title compound consists of one and a half ZnII atoms, one btc ligand, one dmbpy ligand, three coordinated and three uncoordinated water molecules. Zn2 atom is located on an inversion center. Zn1 atom is coordinated by two O atoms from two btc ligands, one water molecule and two N atoms from one chelating dmbpy ligand, completing a distorted trigonal bipyramidal geometry. N2, O1 and O4i [symmetry code: (i) x - 1, y, z] comprise the equatorial plane, while O1W and N1 occupy the axial positions. Zn2 atom is in a distorted octahedral coordination environment and coordinated by two O atoms from a pair of symmetry-related btc ligands and four O atoms from two pairs of coordinated water molecules. O2W, O2W, O3W and O3W [symmetry code: () -x + 1, -y - 1, -z + 1] comprise the equatorial plane, while O6 and O6 occupy the axial positions. As depicted in Fig. 2, adjacent Zn1 atoms are linked together through btc ligands, forming a chain running along the a axis with the dmbpy ligands hanging from the chain. A pair of symmetry-related chains are connected by Zn2 atoms, resulting in a one-dimensional ladder structure containing large windows [ca (1) (2) Å2]. The ladders are extended into a three-dimensional supramolecular structure through hydrogen bonds (Table 1) (Desiraju, 2004) and π π stacking interactions (Zang et al., 2010), with centroid centroid distances of (2) and (3) between the benzene rings and between the pyridine rings (Fig. 3). Experimental All starting materials used in the synthesis were of analytical grade and obtained from commercial sources without further purification. The title compound was synthesized hydrothermally in a Teflon-lined stainless steel container by heating a mixture of benzene-1,3,5-tricarboxylic acid (0.011 g, 0.05 mmol), 5,5'-dimethyl-2,2'-bipyridine (0.009 g, 0.05 mmol), Zn(NO3)2.6H2O (0.015 g, 0.05 mmol) and NaOH (0.004 g, 0.1 mmol) in 7 ml of distilled water at 120 C for 3 d, and then cooled to room temperature. Washed with deionized water and dried, colorless block crystals of the title compound were obtained in 72% yield based on zinc. sup-1

5 Refinement H atoms were positioned geometrically and refined using a riding model, with C H = 0.93 (aromatic) and 0.96 (methyl) Å and with Uiso(H) = 1.2(1.5 for methyl)ueq(c). The approximate positions of the water H atoms were obtained from a difference Fourier map, then restrained to ideal configuration and fixed in the final stages of the refinement. Figures Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) x - 1, y, z; () -x + 1, -y - 1, -z + 1.] Fig. 2. The one-dimensional ladder structure in the title compound. Fig. 3. A view of the three-dimensional supramolecular structure in the title compound. Dashed lines represent hydrogen bonds. Poly[[hexaaquabis(µ3-benzene-1,3,5-tricarboxylato- κ3o1:o3:o5)bis(5,5'-dimethyl-2,2'-bipyridineκ2n,n')trizinc] hexahydrate] Crystal data [Zn3(C9H3O6)2(C12H12N2)2(H2O)6] 6H2O Z=1 Mr = F(000) = 616 Triclinic, P1 Dx = Mg m 3 Hall symbol: -P 1 a = (10) Å b = (10) Å Mo Kα radiation, λ = Å Cell parameters from 3902 reflections θ = c = (1) Å µ = 1.54 mm 1 T = 296 K Block, colourless mm α = (8) β = (8) γ = (8) V = (19) Å3 sup-2

6 Data collection Bruker APEXII CCD diffractometer Radiation source: fine-focus sealed tube 4330 independent reflections graphite 3426 reflections with I > 2σ(I) Rint = φ and ω scans θmax = 25.0, θmin = 3.0 Absorption correction: multi-scan (SADABS; Bruker, 2001) Tmin = 0.739, Tmax = h = k = l = measured reflections Refinement R[F2 > 2σ(F2)] = Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites wr(f2) = H-atom parameters constrained Refinement on F2 Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0713P) P] S = 1.01 where P = (Fo2 + 2Fc2)/ reflections (Δ/σ)max < parameters Δρmax = 0.74 e Å 3 12 restraints Δρmin = 0.59 e Å 3 Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) Zn1 Zn2 O1 O2 O3 O4 O5 O6 O1W H1WA H1WB O2W H2WA H2WB O3W H3WB H3WC O4W x y z Uiso*/Ueq Occ. (<1) (4) (2) (3) (3) (2) (3) (3) (3) (3) (3) (14) (4) (3) (3) (2) (2) (2) (3) (3) (3) (3) (16) (4) (2) (3) (2) (2) (3) (3) (2) (3) (3) (12) (16) (2) (7) (7) (7) (6) (7) (7) (7) 0.050* 0.050* (8) 0.065* 0.065* (8) 0.061* 0.061* (3) (9) sup-3

7 H4WA H4WB O4W' H4WD H4WE O5W H5WA H5WC O6W H6WB H6WD N1 N2 C1 C2 C3 C4 C5 H5 C6 C7 H7 C8 C9 H9 C10 H10 C11 C12 H12A H12B H12C C13 H13 C14 H14 C15 C16 C17 H17 C18 H18 C19 C20 H20A H20B H20C C21 H21 sup (10) (5) (5) (3) (3) (4) (4) (4) (3) (3) (3) (3) (4) (4) (4) (4) (6) (5) (5) (4) (4) (4) (5) (4) (5) (4) (10) (6) (5) (3) (3) (4) (4) (4) (4) (4) (3) (3) (3) (4) (4) (5) (5) (5) (5) (4) (4) (4) (4) (4) (5) (4) (9) (6) (4) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (4) (4) (5) (4) (4) (3) (4) (4) (4) (4) (5) (4) * 0.175* (3) 0.175* 0.175* (2) 0.213* 0.213* (18) 0.157* 0.157* (8) (7) (8) (8) (8) (8) (8) 0.028* (8) (8) 0.024* (8) (8) 0.027* (10) 0.045* (11) (15) 0.093* 0.093* 0.093* (11) 0.054* (11) 0.050* (9) (9) (11) 0.046* (12) 0.053* (11) (13) 0.080* 0.080* 0.080* (10) 0.041* (9) (9) (9) (9) (9)

8 Atomic displacement parameters (Å2) Zn1 Zn2 O1 O2 O3 O4 O5 O6 O1W O2W O3W O4W O4W' O5W O6W N1 N2 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 U (3) (4) (14) (17) (15) (13) (16) (15) (15) (2) (16) (3) (3) (4) (4) (19) (17) (19) (2) (2) (19) (19) (18) (18) (2) (19) (3) (3) (4) (3) (3) (2) (2) (3) (3) (2) (3) (2) U (3) (3) (15) (16) (14) (14) (14) (14) (17) (16) (15) (3) (3) (4) (4) (18) (18) (2) (19) (19) (2) (18) (18) (17) (18) (19) (2) (3) (3) (3) (3) (2) (2) (2) (2) (2) (3) (2) U (3) (4) (18) (2) (18) (18) (19) (2) (16) (2) (2) (3) (3) (6) (3) (19) (2) (2) (19) (2) (2) (2) (2) (2) (2) (2) (3) (3) (4) (3) (3) (2) (3) (2) (3) (3) (4) (3) U (17) (3) (11) (12) (11) (11) (11) (11) (12) (14) (12) (14) (14) (3) (3) (14) (13) (16) (15) (17) (15) (15) (14) (14) (15) (15) (19) (2) (3) (2) (2) (17) (16) (2) (2) (18) (2) (18) U (18) (3) (12) (15) (13) (12) (14) (14) (12) (16) (14) (15) (15) (4) (3) (15) (14) (15) (15) (16) (15) (16) (15) (15) (15) (15) (2) (2) (3) (2) (2) (18) (18) (2) (2) (2) (3) (19) U (19) (3) (13) (14) (12) (13) (13) (14) (13) (14) (15) (15) (15) (4) (3) (15) (15) (17) (15) (16) (16) (16) (16) (15) (16) (16) (2) (2) (3) (2) (2) (19) (18) (19) (2) (2) (3) (19) Geometric parameters (Å, ) Zn1 O4i Zn1 O1 Zn1 O1W (2) N2 C (5) (3) (3) N2 C21 C1 C (5) (5) sup-5

9 Zn1 N2 Zn1 N (3) (3) C2 C6 C3 C (5) (5) Zn2 O6 Zn2 O (2) C4 C (5) (2) C4 C (5) Zn2 O3W Zn2 O3W Zn2 O2W (3) C5 C (5) (3) (3) C5 H5 C6 C (5) Zn2 O2W O1 C1 O2 C1 O3 C2 O4 C (3) C7 C (5) (4) (5) (4) (4) C7 H7 C8 C9 C9 H9 C10 C (5) (6) O4 Zn1i O5 C3 O6 C3 O1W H1WA O1W H1WB O2W H2WA O2W H2WB O3W H3WB O3W H3WC O4W H4WA O4W H4WB O4W H4WE (2) C10 H (4) (4) C11 C13 C11 C12 C12 H12A C12 H12B C12 H12C C13 C14 C13 H13 C14 C15 C14 H14 C15 C16 C16 C (6) (7) (7) (6) (6) (5) O4W' O4W'iv O4W' H4WB O4W' H4WD O4W' H4WE O5W H5WA O5W H5WC O6W H6WB O6W H6WD N1 C10 N1 C (2) C17 C (6) (5) (5) C17 H17 C18 C19 C18 H18 C19 C21 C19 C20 C20 H20A C20 H20B C20 H20C C21 H (6) (6) (6) O4i Zn1 O (10) O6 C3 C (3) (11) C9 C4 C (3) (11) C9 C4 C (3) O4 Zn1 N2 O1 Zn1 N2 O1W Zn1 N (11) C5 C4 C (3) (11) (12) C4 C5 C6 C4 C5 H (3) O4i Zn1 N1 O1 Zn1 N1 O1W Zn1 N1 N2 Zn1 N (12) C6 C5 H (12) (11) (13) C7 C6 C5 C7 C6 C2 C5 C6 C (3) (3) (3) (15) C6 C7 C (3) (11) C6 C7 H i O4 Zn1 O1W O1 Zn1 O1W i O6 Zn2 O6 O6 Zn2 O3W sup-6

10 O6 Zn2 O3W (11) C8 C7 H (11) C9 C8 C (3) (11) C9 C8 C (3) O3W Zn2 O3W C7 C8 C (3) O6 Zn2 O2W O6 Zn2 O2W (11) C4 C9 C (3) (11) C4 C9 H (12) C8 C9 H (12) N1 C10 C (4) (11) N1 C10 H (11) C11 C10 H O3W Zn2 O2W (12) C13 C11 C (4) O3W Zn2 O2W (12) C13 C11 C (4) O2W Zn2 O2W C1 O1 Zn C10 C11 C (4) (2) C11 C12 H12A C2 O4 Zn1 C3 O6 Zn2 Zn1 O1W H1WA Zn1 O1W H1WB H1WA O1W H1WB Zn2 O2W H2WA Zn2 O2W H2WB H2WA O2W H2WB Zn2 O3W H3WB Zn2 O3W H3WC H3WB O3W H3WC H4WA O4W H4WB H4WA O4W H4WE H4WB O4W H4WE (2) C11 C12 H12B (2) H12A C12 H12B C11 C12 H12C H12A C12 H12C H12B C12 H12C C14 C13 C11 C14 C13 H13 C11 C13 H13 C13 C14 C15 C13 C14 H14 C15 C14 H14 N1 C15 C14 N1 C15 C16 C14 C15 C (4) (4) (4) (4) (4) O4W'iv O4W' H4WB N2 C16 C (4) 78.5 N2 C16 C (3) 71.6 C17 C16 C (4) C18 C17 C (4) (4) (3) (3) (3) (3) (3) (3) (3) (3) (3) C18 C17 H17 C16 C17 H17 C17 C18 C19 C17 C18 H18 C19 C18 H18 C18 C19 C21 C18 C19 C20 C21 C19 C20 C19 C20 H20A C19 C20 H20B H20A C20 H20B C19 C20 H20C H20A C20 H20C H20B C20 H20C (4) (4) (4) (4) O6 Zn2 O3W O6 Zn2 O3W O3W Zn2 O2W O3W Zn2 O2W O6 Zn2 O2W O6 Zn2 O2W i iv O4W' O4W' H4WD H4WB O4W' H4WD iv O4W' O4W' H4WE H4WB O4W' H4WE H4WD O4W' H4WE H5WA O5W H5WC H6WB O6W H6WD C10 N1 C15 C10 N1 Zn1 C15 N1 Zn1 C16 N2 C21 C16 N2 Zn1 C21 N2 Zn1 O2 C1 O1 O2 C1 C4 O1 C1 C4 O3 C2 O4 sup-7

11 O3 C2 C6 O4 C2 C6 O5 C3 O6 O5 C3 C (3) (3) (3) (3) N2 C21 C19 N2 C21 H21 C19 C21 H (4) O4i Zn1 O1 C1 O1W Zn1 O1 C1 N2 Zn1 O1 C1 N1 Zn1 O1 C (2) C2 C6 C7 C (3) 81.3 (3) 22.0 (3) 90.9 (3) C6 C7 C8 C9 C6 C7 C8 C3 O5 C3 C8 C9 0.1 (6) (3) (4) O3W Zn2 O6 C3 O3W Zn2 O6 C3 O2W Zn2 O6 C (4) O6 C3 C8 C9 3.0 (5) 28.0 (4) (4) O5 C3 C8 C7 O6 C3 C8 C7 1.3 (6) (3) O2W Zn2 O6 C (4) C5 C4 C9 C8 0.1 (6) O4i Zn1 N1 C10 O1 Zn1 N1 C10 N2 Zn1 N1 C (3) C1 C4 C9 C (3) 38.1 (3) (3) C7 C8 C9 C4 C3 C8 C9 C4 0.2 (6) (3) O4i Zn1 N1 C15 O1 Zn1 N1 C15 N2 Zn1 N1 C (3) C15 N1 C10 C (6) (3) 2.4 (3) Zn1 N1 C10 C11 N1 C10 C11 C (3) 0.3 (7) O4i Zn1 N2 C16 O1 Zn1 N2 C16 O1W Zn1 N2 C16 N1 Zn1 N2 C (3) N1 C10 C11 C (4) 76.6 (3) (3) 2.9 (3) C10 C11 C13 C14 C12 C11 C13 C14 C11 C13 C14 C (7) (5) 0.1 (7) O4i Zn1 N2 C21 O1 Zn1 N2 C21 O1W Zn1 N2 C21 N1 Zn1 N2 C21 Zn1 O1 C1 O2 Zn1 O1 C1 C (3) C10 N1 C15 C (6) (3) 1.3 (3) (3) 6.0 (5) (3) Zn1 N1 C15 C14 C10 N1 C15 C16 Zn1 N1 C15 C16 C13 C14 C15 N1 C13 C14 C15 C (3) (3) 1.7 (4) 0.1 (6) (4) Zn1i O4 C2 O3 2.2 (5) C21 N2 C16 C (6) i (2) Zn1 N2 C16 C17 Zn1 O4 C2 C6 Zn2 O6 C3 O (6) C21 N2 C16 C15 Zn2 O6 C3 C (2) Zn1 N2 C16 C15 O2 C1 C4 C (4) N1 C15 C16 N2 O1 C1 C4 C9 0.1 (5) C14 C15 C16 N2 O2 C1 C4 C5 0.3 (6) N1 C15 C16 C17 O1 C1 C4 C (3) C14 C15 C16 C17 C9 C4 C5 C6 0.1 (6) N2 C16 C17 C18 C1 C4 C5 C (3) C15 C16 C17 C18 C4 C5 C6 C7 0.1 (6) C16 C17 C18 C19 C4 C5 C6 C (3) C17 C18 C19 C21 O3 C2 C6 C (3) C17 C18 C19 C20 O4 C2 C6 C (5) C16 N2 C21 C19 O3 C2 C6 C5 9.1 (5) Zn1 N2 C21 C19 O4 C2 C6 C (3) C18 C19 C21 N2 C5 C6 C7 C8 0.0 (6) C20 C19 C21 N2 Symmetry codes: (i) x 1, y, z; () x+1, y 1, z+1; (i) x+1, y, z; (iv) x+1, y+1, z. sup (3) (3) 3.0 (4) 0.8 (5) (4) (4) 2.0 (6) 1.3 (6) (4) 0.8 (7) 0.1 (6) (4) 0.0 (6) (3) 0.6 (6) (4)

12 Hydrogen-bond geometry (Å, ) D H A D H H A D A D H A (4) (5) (4) (6) 135 O3W H3WB O3v O3W H3WC O5 O4W H4WA O5W O4W' H4WD O2 O5W H5WA O6W (4) (4) (19) (11) (9) O5W H5WC O6vi (7) 164 vi (5) 154 ix (6) 154 O1W H1WA O5 v O1W H1WB O6W O2W H2WA O2 vi v O2W H2WB O5W O6W H6WB O1 v O6W H6WD O4 Symmetry codes: (v) x+1, y, z+1; (vi) x, y+1, z+1; (v) x, y 1, z; (vi) x, y+1, z; (ix) x 1, y+1, z. sup-9

13 Fig. 1 sup-10

14 Fig. 2 sup-11

15 Fig. 3 sup-12