Experimental. Crystal data. C 60 H 88 O 4 4CHCl 3 2H 2 O M r = Orthorhombic, Pbcn a = (6) Å b = (6) Å c = 25.

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1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN ,26,27,28-Tetrabutoxy-5,11,17,23- tetra-tert-butylcalix[4]arene chloroform tetrasolvate dihydrate Zhengyi Li, a Dinghao Yuan, b Haitao Xi a and Xiaoqiang Sun a * a Key Laboratory of Fine Chemical Engineering, Jiangsu Polytechnic University, Changzhou , Jiangsu, People s Republic of China, and b Gaochun County Environmental Protection Bureau, No. 5, Xuhe North Road, Chunxi Town, Gaochun city , Jiangsu, People s Republic of China Correspondence xqsun@jpu.edu.cn Received 2 May 2009; accepted 10 June 2009 Experimental Crystal data C 60 H 88 O 4 4CHCl 3 2H 2 O M r = Orthorhombic, Pbcn a = (6) Å b = (6) Å c = (11) Å Data collection Bruker SMART APEX CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2000) T min = 0.894, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections V = 8236 (5) Å 3 Z =4 Mo K radiation = 0.44 mm 1 T = 291 K mm measured reflections 8098 independent reflections 5524 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.82 e Å 3 min = 0.73 e Å 3 Key indicators: single-crystal X-ray study; T = 291 K; mean (C C) = Å; disorder in solvent or counterion; R factor = 0.053; wr factor = 0.117; data-toparameter ratio = The title compound, C 60 H 88 O 4 4CHCl 3 2H 2 O, is the alkylated product of 5,11,17,23-tetra-tert-butylcalix[4]arene. It adopts a distorted cone conformation which leads to an open cavity. All the phenolic rings are tilted so that their tert-butyl groups are pitched away from the calix cavity. Two opposite aromatic rings are close to being perpendicular to one another [dihedral angle 85.0 (2) ], while the other pair of opposite rings is almost parallel [dihedral angle 8.1 (2) ], and adjacent phenolic rings are almost perpendicular [dihedral angles 82.4 (1) or 87.9 (1) ]. In the crystal, the water molecule and calixarene interact by way of O HO hydrogen bonds. Related literature For calix[4]arene derivatives as supramolecular building blocks, see: Böhmer (1995); Homden & Redshaw (2008). For related structures, see: Rathore et al. (2000) and Brusko et al. (2005). For details of the synthesis, see: Matthews et al. (1999). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA O3 H3CO (8) 127 O5 H5CO5 i (13) 121 Symmetry code: (i) x þ 1; y þ 2; z þ 2. Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL. We gratefully acknowledge financial support from the Natural Science Foundation of China (No ). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: EZ2170). References Böhmer, V. (1995). Angew. Chem. Int. Ed. Engl. 34, Bruker (2000). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Brusko, V., Böhmer, V. & Bolte, M. (2005). Acta Cryst. E61, o4272 o4273. Homden, D. M. & Redshaw, C. (2008). Chem. Rev. 108, Matthews, S. E., Saadioui, M., Böhmer, V., Barboso, S., Arnaud-Neu, F., Schwing-Weill, M.-J., Carrera, A. G. & Dozol, J.-F. (1999). J. Prakt. Chem. 341, Rathore, R., Lindeman, S. V., Rao, K. S. S. P., Sun, D. & Kochi, J. K. (2000). Angew. Chem. Int. Ed. 39, Sheldrick, G. M. (2008). Acta Cryst. A64, Acta Cryst. (2009). E65, o1697 doi: /s x Li et al. o1697

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3 Acta Cryst. (2009). E65, o1697 [ doi: /s x ] 25,26,27,28-Tetrabutoxy-5,11,17,23-tetra-tert-butylcalix[4]arene chloroform tetrasolvate dihydrate Z. Li, D. Yuan, H. Xi and X. Sun Comment Derivatives of calix[4]arene, as one of the most important supramolecular building blocks, are useful in ion and metal complexation because they form suitable scaffolds for the development of new bulky and structurally well defined ligands (Böhmer, 1995; Homden & Redshaw 2008). As an important approach to obtain functionalized calixarenes, alkylation of the phenolic hydroxyl groups on the lower rim of the calixarene has been widely explored. The crystal structures of propyl (Rathore et al., 2000) and pentyl (Brusko et al., 2005) alkylated calix[4]arene have been reported. We herein present the structure of the tetrabutyl substituted calix[4]arene (Fig. 1). The title compound adopts a distorted cone conformation with a small cavity. All phenolic rings are tilted so that their tert-butyl groups are pitched away from the calix cavity, as defined by the angles which the aromatic rings make with the plane of the four bridging CH 2 moieties (C29, C30, C29A and C30A) which link them, viz (3) (C1 C6 or C1A C6A) and (1) (C15 C20 or C15A C15A). Two opposite aromatic rings (C15 C20 and C15A C20A) are close to being perpendicular to one another (dihedral angle 85.0 (2) ) while the other pair of opposite phenolic rings (C1 C6 and C1A C6A) are almost parallel (dihedral angle 8.1 (2) ), and the adjacent phenolic rings are almost perpendicular (dihedral angles 97.6 (1) or 92.1 (1) ). Experimental NaH (0.96 g, 40 mmol) and DMF (20 ml) were added to a suspension of 5,11,17,23-tetra(tert-butyl)calix[4]arene (3.25 g, 5 mmol) in DMF (30 ml) under argon. The suspension was stirred for 1 h, and then 1-bromobutane (5.48 g, 40 mol) was added. Stirring was continued at room temperature for 2 d. Water (100 ml) was added and the precipitate formed collected by filtration. The solid was dissolved in chloroform and washed with 15% HCl and water. The organic layer was dried and the solvent evaporated. Precipitation from chloroform/methanol gave the title compound as a white solid with sufficient purity (68% yield). Single crystals suitable for X-ray diffraction were obtained by evaporation of an methanol-chloroform solution. Refinement All the H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C H distances of Å, and with U iso (H) = 1.2 or 1.5U eq (C). H atoms bonded to O atoms were refined independently with isotropic displacement parameters. Each water molecule is located over three sites with refined occupancies of 0.3, 0.3 and 0.4, respectively. sup-1

4 Figures Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 25% probability level. H atoms and solvent molecules have been omitted for clarity. [symmetry code: -x + 1, y, -z + 3/2]. 25,26,27,28-Tetrabutoxy-5,11,17,23-tetra-tert-butylcalix[4]arene chloroform tetrasolvate dihydrate Crystal data C 60 H 88 O 4 4CHCl 3 2H 2 O F 000 = 2928 M r = D x = Mg m 3 Orthorhombic, Pbcn Mo Kα radiation, λ = Å Hall symbol: -P 2n 2ab Cell parameters from 3284 reflections a = (6) Å θ = º b = (6) Å µ = 0.44 mm 1 c = (11) Å T = 291 K V = 8236 (5) Å 3 Block, colourless Z = mm Data collection Bruker SMART APEX CCD diffractometer Radiation source: sealed tube Monochromator: graphite R int = T = 291 K θ max = 26.0º φ and ω scans θ min = 1.6º Absorption correction: multi-scan (SADABS; Bruker, 2000) T min = 0.894, T max = independent reflections 5524 reflections with I > 2σ(I) h = k = measured reflections l = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o 2 ) + (0.05P) P] where P = (F o 2 + 2F c 2 )/3 S = 1.06 (Δ/σ) max < reflections Δρ max = 0.82 e Å 3 sup-2

5 396 parameters Δρ min = 0.73 e Å 3 Primary atom site location: structure-invariant direct methods Extinction correction: none 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) C (15) (2) (14) (8) C (13) (2) (12) (7) C (12) (2) (11) (6) H * C (13) (2) (11) (7) C (11) (2) (10) (6) H * C (12) (2) (12) (7) C (12) (2) (11) (6) C (12) (2) (11) (7) H8A * H8B * H8C * C (10) (2) (11) (6) H9A * H9B * H9C * C (11) (2) (12) (7) H10B * H10C * H10A * C (12) (2) (11) (6) H11A * H11B * C (12) (2) (12) (7) H12A * H12B * C (12) (2) (11) (6) H13A * H13B * sup-3

6 C (11) (2) (11) (6) H14B * H14C * H14A * C (13) (3) (12) (7) C (12) (2) (12) (7) C (12) (2) (10) (6) H * C (12) (2) (12) (7) C (12) (2) (12) (6) H * C (12) (2) (11) (6) C (11) (2) (10) (6) C (13) (2) (12) (7) H22A * H22B * H22C * C (11) (2) (11) (6) H23A * H23B * H23C * C (12) (2) (11) (6) H24A * H24B * H24C * C (12) (2) (11) (6) H25A * H25B * C (11) (2) (12) (6) H26A * H26B * C (11) (19) (11) (6) H27A * H27B * C (12) (2) (11) (6) H28B * H28C * H28A * C (10) (17) (14) (5) H29A * H29B * C (16) (19) (10) (6) H30A * H30B * C (17) (2) (11) (7) H * C (15) (3) (14) (9) H * Cl (3) (5) (3) (18) sup-4

7 Cl (3) (6) (3) (18) Cl (3) (5) (3) (16) Cl (3) (5) (3) (18) Cl (3) (5) (3) (18) Cl (3) (5) (3) (18) O (8) (14) (8) (5) O (8) (14) (8) (5) O (3) (5) (3) (17) 0.30 H3A * 0.30 H3C * 0.30 O (17) (3) (3) (9) 0.40 H4B * 0.40 H4C * 0.40 O (3) (5) (3) (17) 0.30 H5B * 0.30 H5C * 0.30 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 C (19) (16) (19) (14) (14) (14) C (17) (16) (16) (13) (13) (13) C (15) (15) (14) (12) (12) (12) C (18) (15) (14) (13) (13) (12) C (15) (14) (12) (11) (11) (11) C (16) (16) (15) (12) (12) (12) C (16) (15) (13) (12) (12) (12) C (14) (16) (16) (12) (12) (13) C (15) (14) (13) (10) (10) (11) C (14) (16) (16) (12) (12) (13) C (15) (14) (14) (12) (12) (11) C (14) (16) (16) (12) (12) (13) C (15) (14) (13) (12) (12) (11) C (14) (16) (14) (12) (12) (12) C (15) (19) (16) (14) (12) (14) C (14) (17) (17) (12) (12) (13) C (15) (14) (13) (12) (12) (11) C (16) (17) (15) (13) (13) (13) C (14) (14) (16) (11) (12) (13) C (15) (14) (14) (12) (12) (12) C (14) (15) (13) (11) (11) (11) C (17) (16) (16) (13) (14) (14) C (14) (16) (15) (12) (12) (13) C (15) (15) (15) (12) (12) (12) C (15) (14) (14) (11) (12) (12) C (14) (15) (15) (11) (12) (12) C (13) (13) (14) (11) (11) (11) C (16) (14) (14) (12) (12) (11) sup-5

8 C (13) (13) (12) (10) (17) (16) C (16) (13) (13) (16) (15) (10) C (17) (13) (15) (17) (18) (12) C (2) (19) (19) (15) (15) (15) Cl (4) (4) (4) (3) (3) (3) Cl (4) (4) (4) (3) (3) (3) Cl (4) (3) (3) (3) (3) (3) Cl (4) (4) (4) (3) (3) (3) Cl (4) (3) (4) (3) (3) (3) Cl (4) (4) (3) (3) (3) (3) O (11) (11) (12) (8) (9) (9) O (11) (11) (12) (9) (9) (9) O (4) (4) (4) (3) (3) (3) O (2) (2) (2) (17) (3) (3) O (4) (4) (4) (3) (3) (3) Geometric parameters (Å, ) C1 C (4) C19 H C1 C (5) C20 C (4) C1 O (3) C21 C (4) C2 C (4) C21 C (4) C2 C30 i (4) C21 C (4) C3 C (4) C22 H22A C3 H C22 H22B C4 C (4) C22 H22C C4 C (4) C23 H23A C5 C (4) C23 H23B C5 H C23 H23C C6 C (4) C24 H24A C7 C (4) C24 H24B C7 C (4) C24 H24C C7 C (4) C25 O (3) C8 H8A C25 C (4) C8 H8B C25 H25A C8 H8C C25 H25B C9 H9A C26 C (4) C9 H9B C26 H26A C9 H9C C26 H26B C10 H10B C27 C (4) C10 H10C C27 H27A C10 H10A C27 H27B C11 O (4) C28 H28B C11 C (4) C28 H28C C11 H11A C28 H28A C11 H11B C29 H29A C12 C (4) C29 H29B C12 H12A C30 C2 i (4) C12 H12B C30 H30A sup-6

9 C13 C (4) C30 H30B C13 H13A C31 Cl (3) C13 H13B C31 Cl (4) C14 H14B C31 Cl (3) C14 H14C C31 H C14 H14A C32 Cl (3) C15 C (4) C32 Cl (3) C15 O (4) C32 Cl (3) C15 C (4) C32 H C16 C (4) O3 H3A C16 C (4) O3 H3C C17 C (4) O4 H4B C17 H O4 H4C C18 C (4) O5 H5B C18 C (4) O5 H5C C19 C (4) C6 C1 C (3) C15 C20 C (3) C6 C1 O (3) C15 C20 C (3) C2 C1 O (3) C19 C20 C (2) C3 C2 C (3) C23 C21 C (2) C3 C2 C30 i (3) C23 C21 C (2) C1 C2 C30 i (3) C22 C21 C (2) C4 C3 C (3) C23 C21 C (2) C4 C3 H C22 C21 C (2) C2 C3 H C24 C21 C (2) C3 C4 C (3) C21 C22 H22A C3 C4 C (3) C21 C22 H22B C5 C4 C (3) H22A C22 H22B C6 C5 C (3) C21 C22 H22C C6 C5 H H22A C22 H22C C4 C5 H H22B C22 H22C C1 C6 C (3) C21 C23 H23A C1 C6 C (3) C21 C23 H23B C5 C6 C (3) H23A C23 H23B C10 C7 C (2) C21 C23 H23C C10 C7 C (2) H23A C23 H23C C8 C7 C (2) H23B C23 H23C C10 C7 C (2) C21 C24 H24A C8 C7 C (2) C21 C24 H24B C9 C7 C (2) H24A C24 H24B C7 C8 H8A C21 C24 H24C C7 C8 H8B H24A C24 H24C H8A C8 H8B H24B C24 H24C C7 C8 H8C O2 C25 C (2) H8A C8 H8C O2 C25 H25A H8B C8 H8C C26 C25 H25A C7 C9 H9A O2 C25 H25B C7 C9 H9B C26 C25 H25B sup-7

10 H9A C9 H9B H25A C25 H25B C7 C9 H9C C25 C26 C (2) H9A C9 H9C C25 C26 H26A H9B C9 H9C C27 C26 H26A C7 C10 H10B C25 C26 H26B C7 C10 H10C C27 C26 H26B H10B C10 H10C H26A C26 H26B C7 C10 H10A C26 C27 C (2) H10B C10 H10A C26 C27 H27A H10C C10 H10A C28 C27 H27A O1 C11 C (2) C26 C27 H27B O1 C11 H11A C28 C27 H27B C12 C11 H11A H27A C27 H27B O1 C11 H11B C27 C28 H28B C12 C11 H11B C27 C28 H28C H11A C11 H11B H28B C28 H28C C13 C12 C (2) C27 C28 H28A C13 C12 H12A H28B C28 H28A C11 C12 H12A H28C C28 H28A C13 C12 H12B C6 C29 C (2) C11 C12 H12B C6 C29 H29A H12A C12 H12B C16 C29 H29A C12 C13 C (2) C6 C29 H29B C12 C13 H13A C16 C29 H29B C14 C13 H13A H29A C29 H29B C12 C13 H13B C20 C30 C2 i (2) C14 C13 H13B C20 C30 H30A H13A C13 H13B C2 i C30 H30A C13 C14 H14B C20 C30 H30B C13 C14 H14C C2 i C30 H30B H14B C14 H14C H30A C30 H30B C13 C14 H14A Cl2 C31 Cl (17) H14B C14 H14A Cl2 C31 Cl (19) H14C C14 H14A Cl3 C31 Cl (18) C20 C15 O (3) Cl2 C31 H C20 C15 C (3) Cl3 C31 H O2 C15 C (3) Cl1 C31 H C17 C16 C (3) Cl4 C32 Cl (19) C17 C16 C (3) Cl4 C32 Cl (19) C15 C16 C (2) Cl5 C32 Cl (19) C16 C17 C (3) Cl4 C32 H C16 C17 H Cl5 C32 H C18 C17 H Cl6 C32 H C19 C18 C (3) C11 O1 C (2) C19 C18 C (3) C15 O2 C (2) C17 C18 C (3) H3A O3 H3C C18 C19 C (3) H4B O4 H4C C18 C19 H H5B O5 H5C sup-8

11 C20 C19 H C6 C1 C2 C3 0.8 (5) C16 C17 C18 C (4) O1 C1 C2 C (3) C16 C17 C18 C (3) C6 C1 C2 C30 i (3) C17 C18 C19 C (4) O1 C1 C2 C30 i 7.8 (4) C21 C18 C19 C (3) C1 C2 C3 C4 0.7 (4) O2 C15 C20 C (3) C30 i C2 C3 C (3) C16 C15 C20 C (5) C2 C3 C4 C5 0.1 (4) O2 C15 C20 C (5) C2 C3 C4 C (3) C16 C15 C20 C (3) C3 C4 C5 C6 0.4 (4) C18 C19 C20 C (4) C7 C4 C5 C (2) C18 C19 C20 C (3) C2 C1 C6 C5 0.3 (5) C19 C18 C21 C (3) O1 C1 C6 C (3) C17 C18 C21 C (3) C2 C1 C6 C (3) C19 C18 C21 C (3) O1 C1 C6 C (4) C17 C18 C21 C (3) C4 C5 C6 C1 0.3 (4) C19 C18 C21 C (4) C4 C5 C6 C (3) C17 C18 C21 C (2) C3 C4 C7 C (3) O2 C25 C26 C (2) C5 C4 C7 C (4) C25 C26 C27 C (2) C3 C4 C7 C (3) C1 C6 C29 C (3) C5 C4 C7 C (3) C5 C6 C29 C (4) C3 C4 C7 C (3) C17 C16 C29 C (4) C5 C4 C7 C (3) C15 C16 C29 C (3) O1 C11 C12 C (2) C15 C20 C30 C2 i 73.2 (4) C11 C12 C13 C (2) C19 C20 C30 C2 i 95.8 (3) C20 C15 C16 C (5) C12 C11 O1 C (2) O2 C15 C16 C (3) C6 C1 O1 C (4) C20 C15 C16 C (3) C2 C1 O1 C (3) O2 C15 C16 C (4) C20 C15 O2 C (4) C15 C16 C17 C (4) C16 C15 O2 C (3) C29 C16 C17 C (3) C26 C25 O2 C (4) Symmetry codes: (i) x+1, y, z+3/2. Hydrogen-bond geometry (Å, ) D H A D H H A D A D H A O3 H3C O (8) 127 O5 H5C O5 ii (13) 121 Symmetry codes: (ii) x+1, y+2, z+2. sup-9

12 Fig. 1 sup-10