2. Experimental Crystal data

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data reports ISSN 1600-5368 Crystal structure of bis{2,4-di-tert-butyl- 6-[(isopropylimino)methyl]phenolatoj 2 N,O}zinc dichloromethane monosolvate Yuan-Zeng Hao Guangzhou Super-Dragon Engineering

1 data reports ISSN Crystal structure of bis{2,4-di-tert-butyl- 6-[(isopropylimino)methyl]phenolatoj 2 N,O}zinc dichloromethane monosolvate Yuan-Zeng Hao Guangzhou Super-Dragon Engineering Plastics Co. Ltd, People s Republic of China, and Guangzhou Engineering, Technology Research Center, Guangzhou , People s Republic of China. *Correspondence hyz@gzselon.com Received 17 July 2014; accepted 15 October 2014 Edited by M. Weil, Vienna University of Technology, Austria In the title compound, [Zn(C 18 H 28 NO) 2 ]CH 2 Cl 2, the Zn II atom is N,O-chelated by two crystallographically independent salicylaldehyde imine ligands, leading to a distorted tetrahedral coordination sphere. The dihedral angle between the planes of the two metallacycles is (6). Intramolecular non-classical C HO hydrogen-bonding interactions are observed. In the crystal, the complex molecules stack into columns along the a axis. Dichloromethane solvent molecules are situated in the voids of this arrangement. Keywords: crystal structure; Schiff base; zinc; tetrahedral coordination. 2. Experimental 2.1. Crystal data [Zn(C 18 H 28 NO) 2 ]CH 2 Cl 2 M r = Monoclinic, P2 1 =n a = (17) Å b = (18) Å c = (2) Å = (2) 2.2. Data collection Bruker APEXII area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2007) T min = 0.725, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections V = (8) Å 3 Z =4 Mo K radiation = 0.82 mm 1 T = 173 K mm measured reflections 8281 independent reflections 6513 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.52 e Å 3 min = 0.37 e Å 3 CCDC reference: Table 1 Hydrogen-bond geometry (Å, ). 1. Related literature For backgroud to poly(lactide) (PLA) and its copolymers, see: Wheaton & Hayes (2011); Chen et al. (2006). For the use of bulky ligands coordinating to the active metal site to avoid undesirable transesterification during synthesis of lactides by ring-opening polymerization (ROP), see: Wu et al. (2006). For a highly active zinc catalyst for the controlled polymerization of lactides, see: Williams et al. (2003); Chamberlain et al. (2001). For the preparation of zinc salicylaldehydeimine complexes, see: Chisholm et al. (2001). D HA D H HA DA D HA C4 H4AO (3) 123 C5 H5CO (3) 123 C23 H23CO (3) 122 C24 H24AO (3) 124 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publcif (Westrip, 2010). Acknowledgements This project was supported by the National Torch Program projects of China (grant No GH031761). Supporting information for this paper is available from the IUCr electronic archives (Reference: WM5038). m390 Yuan-Zeng Hao doi: /s

2 data reports References Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Chamberlain, B. M., Cheng, M., Moore, D. R., Ovitt, T. M., Lobkovsky, E. B. & Coates, G. W. (2001). J. Am. Chem. Soc. 123, Chen, H.-Y., Tang, H.-Y. & Lin, C.-C. (2006). Macromolecules, 39, Chisholm, M. H., Gallucci, J. C., Zhen, H. & Huffman, J. C. (2001). Inorg. Chem. 40, Sheldrick, G. M. (2008). Acta Cryst. A64, Westrip, S. P. (2010). J. Appl. Cryst. 43, Wheaton, C. A. & Hayes, P. G. (2011). Comments Inorg. Chem. 32, Williams, C. K., Breyfogle, L. E., Choi, S. K., Nam, W., Young, V. J. Jr, Hillmyer, M. A. & Tolman, W. B. (2003). J. Am. Chem. Soc. 125, Wu, J.-C., Yu, T.-L., Chen, C.-T. & Lin, C.-C. (2006). Coord. Chem. Rev. 250, Yuan-Zeng Hao [Zn(C 18 H 28 NO) 2 ]CH 2 Cl 2 m391

3 supporting information [doi: /s ] Crystal structure of bis{2,4-di-tert-butyl-6-[(isopropylimino)methyl]phenolatoκ 2 N,O}zinc dichloromethane monosolvate Yuan-Zeng Hao S1. Experimental Synthesis of the ligand: Diisopropylamine (2.02 g, 20 mmol) was added dropwise to a solution of the 2,6-di-tert-butylsalicylaldehyde (4.68 g, 20 mmol) in dry ethanol (60 ml) at room temperature over a period of 5 min. The mixture was stirred at 353 K for four hours. Then the solvent was removed by rotary evaporation, and the residue was recrystallizated from methanol. The ligand was isolated as a yellow solid in 20% yield. Synthesis of the complex: In a Schlenk flask, ZnEt 2 (1.22 g, 10 mmol) was added to the solution of the salicylaldehydeimine ligand (10 mmol in tetrahydrofuran) at room temperature. The reaction mixture was stirred in the absence of light for 3 hours at room temperature and was then filtered in the dark and the volume of the solution reduced to 5.0 ml. Pentane was added to afford the product as a light-green solid in ca. 50% yield. Single-crystals suitable for X-ray diffraction were grown by slow evaporation of a solution of the title compound in dichlormethane at room temperature. S2. Refinement Reflection (011) was affected by the beamstop and was omitted from the refinement. H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with a C H distances of 0.95 (aromatic) and 0.99 Å (methylene) and with U iso (H) = 1.2U eq (C), and 0.98 Å for CH 3 [U iso (H)= 1.5U eq (C)]. Figure 1 The molecular structure of the title complex with atom labelling and displacement ellipsoids drawn at the 30% probability level. sup-1

4 Figure 2 View of the crystal structure of title compound; H atoms are omitted for clarity. Bis{2,4-di-tert-butyl-6-[(isopropylimino)methyl]phenolato-κ 2 N,O}zinc dichloromethane monosolvate Crystal data [Zn(C 18 H 28 NO) 2 ] CH 2 Cl 2 M r = Monoclinic, P2 1 /n Hall symbol: -P 2yn a = (17) Å b = (18) Å c = (2) Å β = (2) V = (8) Å 3 Z = 4 F(000) = 1496 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 5049 reflections θ = µ = 0.82 mm 1 T = 173 K Block, light-green mm sup-2

5 Data collection Bruker APEXII area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2007) T min = 0.725, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 413 parameters 0 restraints Primary atom site location: structure-invariant direct methods measured reflections 8281 independent reflections 6513 reflections with I > 2σ(I) R int = θ max = 27.1, θ min = 1.8 h = 17 8 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 ) + (0.0501P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.52 e Å 3 Δρ min = 0.37 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 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 Zn (16) (14) (11) (7) O (10) (9) (7) (3) N (12) (11) (8) (3) N (12) (10) (8) (3) O (10) (10) (7) (3) C (14) (13) (9) (4) C (14) (12) (10) (4) C (15) (13) (9) (4) C (15) (13) (10) (4) H * C (14) (13) (9) (4) C (15) (13) (10) (4) H * C (14) (13) (9) (4) H * C (15) (13) (10) (4) sup-3

6 C (15) (13) (11) (4) H * C (19) (15) (12) (5) H18A * H18B * H18C * C (16) (15) (11) (5) H24A * H24B * H24C * C (14) (13) (10) (4) H * C (16) (14) (10) (4) H * C (18) (14) (11) (5) H23A * H23B * H23C * C (15) (13) (11) (4) Cl (5) (5) (4) (17) Cl (7) (6) (4) (3) C (18) (14) (14) (5) H6A * H6B * H6C * C (14) (12) (9) (4) C (15) (13) (10) (4) H * C (18) (16) (11) (5) H22A * H22B * H22C * C (15) (13) (10) (4) H * C (15) (13) (10) (4) C (15) (14) (11) (4) C (15) (13) (10) (4) C (18) (15) (11) (5) H4A * H4B * H4C * C (3) (19) (13) (8) H35A * H35B * H35C * C (17) (16) (12) (5) H17A * H17B * sup-4

7 H17C * C (18) (14) (12) (5) H5A * H5B * H5C * C (17) (19) (12) (6) H30A * H30B * H30C * C (15) (14) (11) (4) C (14) (13) (9) (4) C (19) (18) (13) (6) H37A * H37B * C (17) (15) (12) (5) H29A * H29B * H29C * C (19) (15) (13) (5) H28A * H28B * H28C * C (2) (2) (13) (9) H36A * H36B * H36C * C (3) (2) (18) (11) H10A * H10B * H10C * C (2) (19) (2) (11) H12A * H12B * H12C * C (2) (3) (19) (12) H11A * H11B * H11C * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Zn (12) (12) (12) (9) (9) (8) O (7) (7) (7) (5) (6) (6) N (8) (8) (7) (7) (6) (6) N (8) (8) (8) (6) (7) (6) O (7) (8) (7) (6) (5) (6) C (9) (9) (8) (7) (7) (7) sup-5

8 C (9) (9) (9) (7) (7) (7) C (10) (9) (9) (8) (8) (7) C (10) (9) (9) (8) (8) (8) C (9) (9) (9) (7) (7) (7) C (10) (9) (9) (8) (8) (7) C (10) (9) (9) (7) (8) (7) C (10) (10) (9) (8) (8) (8) C (10) (9) (11) (8) (9) (8) C (13) (11) (12) (10) (10) (9) C (11) (11) (10) (9) (9) (9) C (9) (9) (9) (8) (8) (7) C (11) (11) (9) (9) (8) (8) C (12) (11) (11) (9) (9) (9) C (11) (9) (10) (8) (9) (8) Cl (4) (4) (4) (3) (3) (3) Cl (6) (5) (5) (4) (5) (4) C (13) (11) (15) (9) (12) (10) C (9) (9) (8) (7) (7) (7) C (9) (10) (9) (8) (8) (8) C (12) (13) (10) (10) (9) (9) C (10) (9) (9) (8) (8) (8) C (10) (10) (9) (8) (8) (7) C (10) (10) (11) (8) (9) (8) C (10) (10) (9) (8) (8) (8) C (13) (11) (11) (10) (10) (9) C (2) (16) (12) (15) (13) (11) C (12) (12) (13) (10) (10) (10) C (13) (11) (13) (9) (11) (9) C (12) (17) (12) (11) (10) (12) C (10) (11) (10) (8) (8) (8) C (9) (9) (9) (7) (7) (7) C (13) (15) (12) (11) (10) (11) C (12) (11) (12) (9) (10) (9) C (13) (12) (13) (10) (11) (10) C (2) (19) (13) (16) (13) (13) C (2) (2) (2) (18) (2) (17) C (19) (15) (3) (14) (2) (18) C (14) (3) (2) (17) (14) (2) Geometric parameters (Å, º) Zn1 O (13) C20 C (3) Zn1 O (13) C31 C (3) Zn1 N (15) C31 C (3) Zn1 N (16) C31 H O1 C (2) C22 H22A N2 C (2) C22 H22B N2 C (2) C22 H22C sup-6

9 N1 C (2) C25 C (3) N1 C (2) C25 H O2 C (2) C8 C (3) C1 C (3) C9 C (4) C1 C (3) C9 C (3) C19 C (3) C9 C (3) C19 C (3) C26 C (3) C2 C (3) C4 H4A C2 C (3) C4 H4B C7 C (3) C4 H4C C7 H C35 H35A C14 C (3) C35 H35B C14 C (3) C35 H35C C13 C (3) C17 H17A C13 H C17 H17B C15 H C17 H17C C21 C (3) C5 H5A C21 C (3) C5 H5B C21 C (3) C5 H5C C21 C (3) C30 C (3) C16 C (3) C30 H30A C16 C (3) C30 H30B C16 H C30 H30C C18 H18A C27 C (3) C18 H18B C27 C (3) C18 H18C C37 H37A C24 H24A C37 H37B C24 H24B C29 H29A C24 H24C C29 H29B C33 C (3) C29 H29C C33 H C28 H28A C34 C (3) C28 H28B C34 C (3) C28 H28C C34 H C36 H36A C23 H23A C36 H36B C23 H23B C36 H36C C23 H23C C10 H10A C3 C (3) C10 H10B C3 C (3) C10 H10C C3 C (3) C12 H12A Cl1 C (3) C12 H12B Cl2 C (3) C12 H12C C6 H6A C11 H11A C6 H6B C11 H11B C6 H6C C11 H11C O1 Zn1 O (6) H22B C22 H22C O1 Zn1 N (6) C20 C25 C (17) sup-7

10 O2 Zn1 N (6) C20 C25 H O1 Zn1 N (6) C26 C25 H O2 Zn1 N (6) C13 C8 C (17) N1 Zn1 N (6) C13 C8 C (17) C1 O1 Zn (12) C7 C8 C (17) C33 N2 C (16) C11 C9 C (3) C33 N2 Zn (13) C11 C9 C (3) C34 N2 Zn (12) C12 C9 C (2) C15 N1 C (16) C11 C9 C (18) C15 N1 Zn (13) C12 C9 C (17) C16 N1 Zn (12) C10 C9 C (19) C19 O2 Zn (12) C31 C26 C (17) O1 C1 C (17) C31 C26 C (18) O1 C1 C (17) C25 C26 C (17) C14 C1 C (16) C3 C4 H4A O2 C19 C (17) C3 C4 H4B O2 C19 C (17) H4A C4 H4B C32 C19 C (16) C3 C4 H4C C7 C2 C (17) H4A C4 H4C C7 C2 C (17) H4B C4 H4C C1 C2 C (16) C34 C35 H35A C2 C7 C (18) C34 C35 H35B C2 C7 H H35A C35 H35B C8 C7 H C34 C35 H35C C13 C14 C (17) H35A C35 H35C C13 C14 C (16) H35B C35 H35C C1 C14 C (16) C16 C17 H17A C8 C13 C (17) C16 C17 H17B C8 C13 H H17A C17 H17B C14 C13 H C16 C17 H17C N1 C15 C (17) H17A C17 H17C N1 C15 H H17B C17 H17C C14 C15 H C3 C5 H5A C22 C21 C (17) C3 C5 H5B C22 C21 C (17) H5A C5 H5B C20 C21 C (16) C3 C5 H5C C22 C21 C (17) H5A C5 H5C C20 C21 C (16) H5B C5 H5C C24 C21 C (18) C27 C30 H30A N1 C16 C (17) C27 C30 H30B N1 C16 C (16) H30A C30 H30B C17 C16 C (18) C27 C30 H30C N1 C16 H H30A C30 H30C C17 C16 H H30B C30 H30C C18 C16 H C30 C27 C (19) C16 C18 H18A C30 C27 C (17) C16 C18 H18B C28 C27 C (17) H18A C18 H18B C30 C27 C (18) sup-8

11 C16 C18 H18C C28 C27 C (17) H18A C18 H18C C26 C27 C (17) H18B C18 H18C C19 C32 C (16) C21 C24 H24A C19 C32 C (17) C21 C24 H24B C31 C32 C (17) H24A C24 H24B Cl2 C37 Cl (14) C21 C24 H24C Cl2 C37 H37A H24A C24 H24C Cl1 C37 H37A H24B C24 H24C Cl2 C37 H37B N2 C33 C (18) Cl1 C37 H37B N2 C33 H H37A C37 H37B C32 C33 H C27 C29 H29A N2 C34 C (17) C27 C29 H29B N2 C34 C (18) H29A C29 H29B C36 C34 C (2) C27 C29 H29C N2 C34 H H29A C29 H29C C36 C34 H H29B C29 H29C C35 C34 H C27 C28 H28A C21 C23 H23A C27 C28 H28B C21 C23 H23B H28A C28 H28B H23A C23 H23B C27 C28 H28C C21 C23 H23C H28A C28 H28C H23A C23 H23C H28B C28 H28C H23B C23 H23C C34 C36 H36A C5 C3 C (17) C34 C36 H36B C5 C3 C (17) H36A C36 H36B C6 C3 C (18) C34 C36 H36C C5 C3 C (17) H36A C36 H36C C6 C3 C (16) H36B C36 H36C C4 C3 C (16) C9 C10 H10A C3 C6 H6A C9 C10 H10B C3 C6 H6B H10A C10 H10B H6A C6 H6B C9 C10 H10C C3 C6 H6C H10A C10 H10C H6A C6 H6C H10B C10 H10C H6B C6 H6C C9 C12 H12A C25 C20 C (17) C9 C12 H12B C25 C20 C (16) H12A C12 H12B C19 C20 C (16) C9 C12 H12C C26 C31 C (18) H12A C12 H12C C26 C31 H H12B C12 H12C C32 C31 H C9 C11 H11A C21 C22 H22A C9 C11 H11B C21 C22 H22B H11A C11 H11B H22A C22 H22B C9 C11 H11C C21 C22 H22C H11A C11 H11C H22A C22 H22C H11B C11 H11C sup-9

12 O2 Zn1 O1 C (15) Zn1 N2 C34 C (2) N1 Zn1 O1 C (16) C7 C2 C3 C (2) N2 Zn1 O1 C (14) C1 C2 C3 C (2) O1 Zn1 N2 C (14) C7 C2 C3 C6 2.1 (3) O2 Zn1 N2 C (15) C1 C2 C3 C (18) N1 Zn1 N2 C (14) C7 C2 C3 C (2) O1 Zn1 N2 C (16) C1 C2 C3 C (2) O2 Zn1 N2 C (15) O2 C19 C20 C (17) N1 Zn1 N2 C (16) C32 C19 C20 C (3) O1 Zn1 N1 C (15) O2 C19 C20 C (3) O2 Zn1 N1 C (14) C32 C19 C20 C (16) N2 Zn1 N1 C (14) C22 C21 C20 C (3) O1 Zn1 N1 C (14) C24 C21 C20 C (2) O2 Zn1 N1 C (16) C23 C21 C20 C (2) N2 Zn1 N1 C (16) C22 C21 C20 C (17) O1 Zn1 O2 C (15) C24 C21 C20 C (2) N1 Zn1 O2 C (15) C23 C21 C20 C (2) N2 Zn1 O2 C (16) C19 C20 C25 C (3) Zn1 O1 C1 C (3) C21 C20 C25 C (18) Zn1 O1 C1 C (12) C14 C13 C8 C7 0.2 (3) Zn1 O2 C19 C (3) C14 C13 C8 C (18) Zn1 O2 C19 C (12) C2 C7 C8 C (3) O1 C1 C2 C (17) C2 C7 C8 C (18) C14 C1 C2 C7 1.5 (3) C13 C8 C9 C (3) O1 C1 C2 C3 1.8 (3) C7 C8 C9 C (3) C14 C1 C2 C (16) C13 C8 C9 C (3) C1 C2 C7 C8 0.2 (3) C7 C8 C9 C (2) C3 C2 C7 C (18) C13 C8 C9 C (3) O1 C1 C14 C (17) C7 C8 C9 C (3) C2 C1 C14 C (3) C32 C31 C26 C (3) O1 C1 C14 C (3) C32 C31 C26 C (18) C2 C1 C14 C (17) C20 C25 C26 C (3) C1 C14 C13 C8 1.9 (3) C20 C25 C26 C (18) C15 C14 C13 C (17) C31 C26 C27 C (3) C16 N1 C15 C (18) C25 C26 C27 C (19) Zn1 N1 C15 C (3) C31 C26 C27 C (2) C13 C14 C15 N (19) C25 C26 C27 C (2) C1 C14 C15 N1 2.9 (3) C31 C26 C27 C (2) C15 N1 C16 C (19) C25 C26 C27 C (2) Zn1 N1 C16 C (2) O2 C19 C32 C (17) C15 N1 C16 C (2) C20 C19 C32 C (3) Zn1 N1 C16 C (2) O2 C19 C32 C (3) C34 N2 C33 C (19) C20 C19 C32 C (17) Zn1 N2 C33 C (3) C26 C31 C32 C (3) C33 N2 C34 C (2) C26 C31 C32 C (18) Zn1 N2 C34 C (2) N2 C33 C32 C (3) C33 N2 C34 C (2) N2 C33 C32 C (19) sup-10

13 Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C4 H4A O (3) 123 C5 H5C O (3) 123 C23 H23C O (3) 122 C24 H24A O (3) 124 sup-11

Experimental. Crystal data. C 22 H 28 N 2 O 3 CH 4 O M r = Monoclinic, C2=c a = (4) Å b = (2) Å c = (5) Å = 96.

Experimental. Crystal data. C 22 H 28 N 2 O 3 CH 4 O M r = Monoclinic, C2=c a = (4) Å b = (2) Å c = (5) Å = 96. organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 N 0 -(3,5-Di-tert-butyl-4-hydroxybenzylidene)-2-hydroxybenzohydrazide methanol solvate Wagee A. Yehye, Azhar Ariffin*