addenda and errata 5,17-Di-tert-butyl-25,27-dihydroxycalix[4]arene. Erratum

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1 addenda and errata Acta Crystallographica Section E Structure Reports Online ISSN ,17-Di-tert-butyl-25,27-dihydroxycalix[4]arene. Erratum Jeffrey C. Bryan,* Richard A. Sachleben and Agathe Urvoas Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN , USA In the paper by Bryan, Sachleben & Urvoas [Acta Cryst. E57, o781±o782], the chemical name in the title is incorrect. The correct title is 5,17-di-tert-butyl-25,27-dimethoxycalix[4]arene. Online 27 October 2001 Correspondence bryanjc@ornl.gov # 2001 International Union of Crystallography Printed in Great Britain ± all rights reserved e10 Jeffrey C. Bryan et al. C 38 H 44 O 2 DOI: /S Acta Cryst. (2001). E57, e10

2 organic papers Acta Crystallographica Section E Structure Reports Online ISSN ,17-Di-tert-butyl-25,27-dihydroxycalix[4]arene Jeffrey C. Bryan,* Richard A. Sachleben and Agathe Urvoas Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN , USA Half of the title compound, C 38 H 44 O 2, makes up the asymmetric unit; the whole molecule possesses inversion symmetry. The calix[4]arene conformation is similar to the unsubstituted calix[4]arene. Only one intermolecular interaction is noted. Received 28 June 2001 Accepted 18 July 2001 Online 27 July 2001 Correspondence bryanjc@ornl.gov Key indicators Single-crystal X-ray study T = 100 K Mean (C±C) = AÊ R factor = wr factor = Data-to-parameter ratio = 14.2 For details of how these key indicators were automatically derived from the article, see Comment The title compound was prepared as part of our investigations into the synthesis of new calix[4]arene-based crown ether extractants (Sachleben et al., 1999). Only half of the molecule makes up the asymmetric unit; the other half is generated by the crystallographic inversion centre [symmetry code:1 x; 1 y; 1 z, denoted (i) throughout this paper]. The conformation of a calix[4]arene is generally de ned in terms of the relative orientation of the arene rings with respect to the best plane de ned by the four calix methylene-c atoms (C17, C18, C17 i, and C18 i ). This methylene carbon plane is referred to as the reference plane (Perrin & Oehler, 1991). The planes of the two methoxy-substituted arene rings (A1 and A1 i ) are nearly perpendicular to the reference plane [84.5 (1) ], while the unsubstituted arene rings (A2 and A2 i ) appear to be roughly parallel to it [173.9 (1) ]. This calix con guration closely resembles that of the unsubstituted parent molecule, calix[4]arene (McMurry & Phelan, 1991) and that of tetra-tert-butyl-calix[4]arene (Grynszpan et al., 1991). Strangely, the more closely related tetra-tert-butyl-diethoxycalix[4]arene adopts a 1,3-alternate calix conformation (Ting et al., 1995). # 2001 International Union of Crystallography Printed in Great Britain ± all rights reserved Examination of the extended structure reveals only one intermolecular interaction worthy of mention, an edge±face arene interaction between A2 and A1. The H16A1 centroid distance is 2.64 A Ê and the C16ÐH16A1 centroid angle is 160. Acta Cryst. (2001). E57, o781±o782 DOI: /S X Jeffrey C. Bryan et al. C 38 H 44 O 2 o781

3 organic papers Re nement Re nement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = re ections 185 parameters H atoms treated by a mixture of independent and constrained re nement w = 1/[ 2 (F o 2 ) + (0.0547P) P] where P =(F o 2 +2F c 2 )/3 (/) max = max = 0.21 e A Ê 3 min = 0.22 e A Ê 3 Table 1 Selected geometric parameters (A Ê, ). OÐC (18) OÐC (2) C1ÐOÐC (14) OÐC1ÐC (15) OÐC1ÐC (15) Figure 1 The molecular structure of the title compound showing 50% displacement ellipsoids. Symmetry code: (i) 1 x; 1 y; 1 z. Experimental The title compound was prepared by alkylation of bis-9,12-tert-butyl- 25,27-dihydrocalix[4]arene using methyl iodide and potassium carbonate in re uxing acetonitrile. Crystals suitable for X-ray diffraction grew from fractions obtained following chromatography (SiO 2 ether/hexanes eluent). Crystal data C 38 H 44 O 2 M r = Monoclinic, P2 1 =n a = (8) A Ê b = (13) A Ê c = (9) A Ê = (8) V = (2) A Ê 3 Z =2 Data collection Nonius CAD-4 diffractometer! scans Absorption correction: none 3130 measured re ections 2618 independent re ections 2090 re ections with I > 2(I) R int = D x = Mg m 3 Mo K radiation Cell parameters from 25 re ections = 10.1±14.3 = 0.07 mm 1 T = 100 K Fragment, colourless mm max = 25.0 h =0! 10 k = 10! 21 l = 11! 11 3 standard re ections frequency: 120 min intensity decay: 5% A 1.1 mm collimator was used. All H atoms were placed in calculated positions, re ned using a riding model, and given an isotropic displacement parameter equal to 1.2 (CH, CH 2 ) or 1.5 (CH 3 ) times the equivalent isotropic displacement parameter of the atom to which they were attached. The CÐH distances used depended on the type of C atom: C methylene ÐH = 0.99, C methyl ÐH = 0.98, and C arene ÐH = 0.95 A Ê. Methyl-H atoms were allowed to rotate about the adjacent CÐC bond. Data collection: CAD-4-PC (Enraf±Nonius, 1993); cell re nement: CAD-4-PC; data reduction: XCAD-4 (Harms, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: PLATON (Spek, 2001). This research was sponsored by the Environmental Management Science Program of the Of ces of Science and Environmental Management, US Department of Energy, under contract number DE±AC05±00OR22725 with Oak Ridge National Laboratory, managed and operated by UT± Battelle, LLC. References Bruker (1997). SHELXTL. Version 5.10/IRIX. Bruker AXS, Madison, Wisconsin, USA. Enraf±Nonius (1993). CAD-4-PC. Version 1.2. Nonius, Delft, The Netherlands. Grynszpan, F., Goren, Z. & Biali, S. E. (1991). J. Org. Chem. 56, 532±536. Harms, K. (1995). XCAD-4. UniversitaÈt Marburg, Germany. McMurry, J. E. & Phelan, J. C. (1991). Tetrahedron Lett. 32, 5655±5658. Perrin, M. & Oehler, D. (1991). Calixarenes: A Versitile Class of Macrocyclic Compounds, edited by J. Vicens and V. BoÈhmer, pp. 65±85. Dordrecht: Kluwer. Sachleben, R. A., Urvoas, A., Bryan, J. C., Haverlock, T. J., Hay, B. P. & Moyer, B. A. (1999). J. Chem. Soc. Chem. Commun. pp. 1751±1752. Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473. Sheldrick, G. M. (1997). SHELXL97. University of GoÈttingen, Germany. Spek, A. L. (2001). PLATON. Utrecht University, The Netherlands. Ting, Y., Verboom, W. & Reinhoudt, D. (1995). Acta Cryst. C51, 1465±1467. o782 Jeffrey C. Bryan et al. C 38 H 44 O 2 Acta Cryst. (2001). E57, o781±o782

4 supporting information [doi: /s x] 5,17-Di-tert-butyl-25,27-dihydroxycalix[4]arene Jeffrey C. Bryan, Richard A. Sachleben and Agathe Urvoas S1. Comment The title compound was prepared as part of our investigations into the synthesis of new calix[4]arene-based crown ether extractants (Sachleben, et al., 1999). Only half of the molecule makes up the asymmetric unit, the other half is generated by the crystallographic inversion centre [symmetry code:1 - x, 1 - y, 1 - z, denoted (i) throughout this paper]. The conformation of a calix[4]arene is generally defined in terms of the relative orientation of the arene rings with respect to the best plane defined by the four calix methylene C atoms (C17, C18, C17 i, and C18 i ). This methylene carbon plane is referred to as the reference plane (Perrin & Oehler, 1991). The planes of the two methoxy-substituted arene rings (A1 and A1 i ) are nearly perpendicular to the reference plane [84.5 (1) ], while the unsubstituted arene rings (A2 and A2 i ) appear to be roughly parallel to it [173.9 (1) ]. This calix configuration closely resembles that of the unsubstituted parent molecule, calix[4]arene (McMurry & Phelan, 1991) and that of tetra-tert-butyl-calix[4]arene (Grynszpan et al., 1991). Strangely, the more closely related tetra-tert-butyl-diethoxy-calix[4]arene adopts a 1,3-alternate calix conformation (Ting et al., 1995). Examination of the extended structure reveals only one intermolecular interaction worthy of mention, an edge-face arene interaction between A2 and A1. The H16 A1 centroid distance is 2.64 Å and the C16 H16 A1 centroid angle is 160. S2. Experimental The title compound was prepared by alkylation of bis-9,12-tert-butyl-25,27-dihydrocalix[4]arene using methyl iodide and potassium carbonate in refluxing acetonitrile. Crystals suitable for X-ray diffraction grew from fractions obtained following chromatography (SiO 2 ether/hexanes eluent). S3. Refinement A 1.1 mm collimator was used. All H atoms were placed in calculated positions, refined using a riding model, and given an isotropic displacement parameter equal to 1.2 (CH, CH 2 ) or 1.5 (CH 3 ) times the equivalent isotropic displacement parameter of the atom to which they were attached. The C H distances used depended on the type of C atom: C methylene H = 0.99, C methyl H = 0.98, and C arene H = 0.95 Å. Methyl-H atoms were allowed to rotate about the adjacent C C bond. sup-1

5 Figure 1 The molecular structure of the title compound showing 50% displacement ellipsoids. Symmetry code: (i) 1 - x, 1 - y, 1 - z. (I) Crystal data C 38 H 44 O 2 M r = Monoclinic, P2 1 /n Hall symbol: -P 2yn a = (8) Å b = (13) Å c = (9) Å β = (8) V = (2) Å 3 Z = 2 Data collection Nonius CAD-4 diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans 3130 measured reflections F(000) = 576 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 25 reflections θ = µ = 0.07 mm 1 T = 100 K Fragment, colourless mm 2618 independent reflections 2090 reflections with I > 2σ(I) R int = θ max = 25.0, θ min = 2.2 h = 0 10 k = sup-2

6 l = standard reflections every 120 min intensity decay: 5% Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 185 parameters 0 restraints 0 constraints 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/[σ 2 (F o2 ) + (0.0547P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.21 e Å 3 Δρ min = 0.22 e Å 3 Special details Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq O (12) (6) (11) (3) C (17) (8) (15) (4) C (18) (7) (15) (4) C (17) (7) (15) (4) C (17) (7) (15) (4) C (17) (8) (15) (4) C (17) (7) (15) (4) C (18) (8) (15) (4) C (2) (9) (17) (5) C (2) (9) (18) (5) C (19) (9) (17) (5) C (17) (8) (14) (4) C (17) (8) (14) (4) C (17) (8) (14) (4) C (17) (8) (15) (4) C (18) (8) (15) (5) C (18) (8) (15) (4) C (18) (8) (15) (4) C (17) (8) (16) (4) C (2) (9) (18) (5) H * H * H8A * H8B * H8C * H9A * sup-3

7 H9B * H9C * H10A * H10B * H10C * H * H * H * H * H17A * H17B * H18A * H18B * H19A * H19B * H19C * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 O (6) (6) (6) (4) (4) (4) C (7) (7) (7) (6) (6) (6) C (7) (7) (7) (6) (6) (6) C (7) (7) (7) (6) (6) (6) C (8) (7) (7) (6) (6) (5) C (8) (7) (7) (6) (6) (5) C (7) (7) (7) (6) (6) (6) C (8) (8) (7) (6) (6) (6) C (9) (9) (8) (7) (7) (7) C (10) (9) (9) (7) (8) (7) C (8) (9) (8) (7) (7) (7) C (8) (8) (7) (6) (6) (6) C (7) (8) (7) (6) (6) (6) C (7) (8) (7) (6) (6) (6) C (7) (8) (7) (6) (6) (6) C (8) (8) (8) (6) (6) (6) C (8) (7) (7) (6) (6) (6) C (8) (7) (7) (6) (6) (6) C (7) (8) (7) (6) (6) (6) C (10) (9) (9) (8) (8) (7) Geometric parameters (Å, º) O C (18) C3 H O C (2) C5 H C1 C (2) C8 H8A 0.98 C1 C (2) C8 H8B 0.98 C2 C (2) C8 H8C 0.98 sup-4

8 C2 C (2) C9 H9A 0.98 C3 C (2) C9 H9B 0.98 C4 C (2) C9 H9C 0.98 C4 C (2) C10 H10A 0.98 C5 C (2) C10 H10B 0.98 C6 C18 i (2) C10 H10C 0.98 C7 C (2) C12 H C7 C (2) C14 H C7 C (2) C15 H C11 C (2) C16 H C11 C (2) C17 H17A 0.99 C11 C (2) C17 H17B 0.99 C12 C (2) C18 H18A 0.99 C13 C (2) C18 H18B 0.99 C13 C (2) C19 H19A 0.98 C14 C (2) C19 H19B 0.98 C15 C (2) C19 H19C 0.98 C1 O C (14) H8A C8 H8B 109 O C1 C (15) H8A C8 H8C 109 O C1 C (15) H8B C8 H8C 109 C2 C1 C (16) C7 C9 H9A 109 C1 C2 C (15) C7 C9 H9B 109 C1 C2 C (16) C7 C9 H9C 109 C3 C2 C (16) H9A C9 H9B 109 C2 C3 C (16) H9A C9 H9C 109 C3 C4 C (16) H9B C9 H9C 109 C3 C4 C (15) C7 C10 H10A 109 C5 C4 C (15) C7 C10 H10B 109 C4 C5 C (15) C7 C10 H10C 109 C1 C6 C (16) H10A C10 H10B 109 C1 C6 C18 i (15) H10A C10 H10C 109 C5 C6 C18 i (15) H10B C10 H10C 109 C4 C7 C (15) C11 C12 H C4 C7 C (14) C13 C12 H C4 C7 C (14) C13 C14 H C8 C7 C (15) C15 C14 H C8 C7 C (15) C14 C15 H C9 C7 C (16) C16 C15 H C12 C11 C (16) C11 C16 H C12 C11 C (15) C15 C16 H C16 C11 C (15) C2 C17 H17A 109 C11 C12 C (16) C2 C17 H17B 109 C12 C13 C (15) C11 C17 H17A 109 C12 C13 C (15) C11 C17 H17B 109 C14 C13 C (15) H17A C17 H17B 108 C13 C14 C (16) C13 C18 H18A 109 C14 C15 C (16) C13 C18 H18B 109 sup-5

9 C11 C16 C (16) H18A C18 H18B 108 C2 C17 C (15) C6 i C18 H18A 109 C6 i C18 C (15) C6 i C18 H18B 109 C2 C3 H3 119 O C19 H19A 109 C4 C3 H3 119 O C19 H19B 109 C4 C5 H5 119 O C19 H19C 109 C6 C5 H5 119 H19A C19 H19B 109 C7 C8 H8A 109 H19A C19 H19C 109 C7 C8 H8B 109 H19B C19 H19C 109 C7 C8 H8C 109 C19 O C1 C (18) C5 C4 C7 C (15) C19 O C1 C (18) C3 C4 C7 C (2) C1 O C19 H19B C5 C4 C7 C (19) C1 O C19 H19C C5 C4 C7 C (19) C1 O C19 H19A C4 C5 C6 C1 0.8 (2) O C1 C2 C (15) C4 C5 C6 C18 i (15) O C1 C2 C (2) C1 C6 C18 i C13 i (17) O C1 C6 C18 i 8.3 (2) C5 C6 C18 i C13 i (19) C2 C1 C6 C5 2.2 (2) C12 C11 C16 C (2) C2 C1 C6 C18 i (15) C17 C11 C16 C (16) O C1 C6 C (15) C16 C11 C17 C (16) C6 C1 C2 C3 1.4 (2) C17 C11 C12 C (16) C6 C1 C2 C (15) C12 C11 C17 C (2) C1 C2 C3 C4 0.9 (2) C16 C11 C12 C (2) C3 C2 C17 C (19) C11 C12 C13 C (2) C1 C2 C17 C (17) C11 C12 C13 C (16) C17 C2 C3 C (15) C12 C13 C18 C6 i 27.0 (2) C2 C3 C4 C5 2.3 (2) C12 C13 C14 C (2) C2 C3 C4 C (15) C18 C13 C14 C (16) C3 C4 C5 C6 1.5 (2) C14 C13 C18 C6 i (16) C7 C4 C5 C (15) C13 C14 C15 C (2) C3 C4 C7 C (17) C14 C15 C16 C (2) C3 C4 C7 C (17) Symmetry code: (i) x+1, y+1, z+1. Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C17 H17A O (19) 109 C18 H18A O i (19) 107 Symmetry code: (i) x+1, y+1, z+1. sup-6