electronic papers Acta Crystallographica Section C
Crystal Structure Communications ISSN 0108-2701
(5S*,6R*)-1,7-Dioxadispiro[4.0.4.4]tetradecane-2,8-dione Rafael Roggenbuck et al. Electronic paper This paper is published electronically. It meets the data-validation criteria for publication in Acta Crystallographica Section C. The submission has been checked by a Section C Co-editor though the text in the `Comments' section is the responsibility of the authors. # 2000 International Union of Crystallography
Acta Cryst. (2000). C56, e356
Printed in Great Britain ± all rights reserved
Rafael Roggenbuck et al.
C12H16O4
electronic papers Acta Crystallographica Section C
Crystal Structure Communications ISSN 0108-2701
(5S*,6R*)-1,7-Dioxadispiro[4.0.4.4]tetradecane-2,8-dione Rafael Roggenbuck, Markus Schu È rmann, Hans Preut* and Peter Eilbracht Fachbereich Chemie, UniversitaÈt Dortmund, Otto-Hahn-Strasse 6, 44221 Dortmund, Germany Correspondence e-mail:
[email protected]
Data validation number: IUC0000175
The title compound, C12H16O4, (I), was prepared by oxidation of (5S*,6R*)-1,7-dioxadispiro[4.0.4.4]tetradecane-2,8-diol using silver(I) carbonate and posesses a cis con®guration of the two ®ve-membered-ring lactones fused spiro to the sixmembered carbocycle, which has a chair conformation. It represents an exceptional structure for bis-tetrahydrofuran units, which are interesting building blocks in natural products. The synthesis, spectroscopic data and X-ray structural analysis are described. The crystal contains discrete molecules separated by normal van der Waals distances.
Experimental Following the procedure of Nozaki et al. (1997) (5S*,6R*)-1,7-dioxadispiro[4.0.4.4]tetradecane-2,8-diol (300 mg, 1.31 mmol) and silver(I) carbonate (1.65 g, 5.98 mmol) in dry benzene (15 ml) were heated under re¯ux for 30 h. After cooling to room temperature, 2.5 g of celite was added and the mixture was stirred for an additional 10 min. The solid was ®ltered off and washed with methyl tert-butyl ether. After evaporation of the solvent, the crude product (lightyellow crystals, 260 mg) was recrystallized from 20 ml diethyl ether to give 212 mg (0.95 mmol, 72%) (5S*,6R*)-1,7-dioxadispiro[4.0.4.4]tetradecane-2,8-dione as colourless crystals. Analysis calculated for C12H16O4 (224.25 g molÿ1): C 64.27, H 7.19%; found: C 64.2, H 7.2%; MS (EI, 70 eV): m/z (%) = 224 (M+, 16), 206 (15), 178 (12), 162 (5), 150 (4), 124 (100), 111 (71), 96 (27), 83 (19), 67 (13), 55 (45); IR
Rafael Roggenbuck et al.
Crystal data C12H16O4 Mr = 224.25 Monoclinic, P21 =c Ê a = 6.8821 (2) A Ê b = 13.4754 (4) A Ê c = 12.0807 (4) A = 100.3383 (19) Ê3 V = 1102.16 (6) A Z=4
Dx = 1.351 Mg mÿ3 Mo K radiation Cell parameters from 9511 re¯ections = 3.37±27.47 = 0.101 mmÿ1 T = 291 (1) K Block, colourless 0.40 0.39 0.26 mm
Data collection
Received 9 June 2000 Accepted 26 June 2000
e356
(KBr) e [cmÿ1] = 2954 (s), 2940 (s), 2881 (m), 2863 (s), 1770 (vs), 1448 (m), 1280 (s), 1251 (s), 1193 (s), 1128 (s), 1035 (s), 983 (s), 925 (s); 1H NMR (400 MHz, DMSO-d6): (p.p.m.) = 1.46±1.76 (m, 6H), 1.87±1.95 (m, 2H), 2.00±2.18 (m, 4H), 2.50±2.61 (m, 2H), 2.71±2.81 (m, 2H); 13C NMR (100 MHz, DMSO-d6): (p.p.m.) = 20.96 (CH2), 26.43 (CH2), 28.06 (CH2), 33.00 (CH2), 87.80 (Cq), 176.02 (Cq, C O); m.p.: 394 K.
C12H16O4
Nonius KappaCCD diffractometer Method: 281 frames via !-rotation (! = 1 ) and 2 20 s per frame with three sets at different angles 9511 measured re¯ections 2492 independent re¯ections
1552 re¯ections with I > 2(I) Rint = 0.031 max = 27.47 h = ÿ8 ! 8 k = ÿ17 ! 17 l = ÿ15 ! 15 Intensity decay: none
Re®nement Re®nement on F 2 R[F 2 > 2(F 2)] = 0.038 wR(F 2) = 0.101 S = 0.953 2492 re¯ections 210 parameters All H-atom parameters re®ned
w = 1/[ 2(Fo2) + (0.0627P)2] where P = (Fo2 + 2Fc2)/3 (/)max < 0.001 Ê ÿ3 max = 0.157 e A Ê ÿ3 min = ÿ0.148 e A Extinction correction: SHELXL97 Extinction coef®cient: 0.035 (6)
All H atoms were located in a map and re®ned isotropically Ê ]. [CÐH 0.917 (15)±1.023 (15) A Data collection: COLLECT Software (Nonius, 1998); cell re®nement: DENZO and SCALEPACK (Otwinowski & Minor, 1996); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995).
References Nardelli, M. (1995). J. Appl. Cryst. 28, 659. Nozaki, K., Li, W., Horiuchi, T. & Takaya, H. (1997). Tetrahedron Lett. 38, 4611±4614. Nonius (1998). COLLECT Software. Nonius BV, Delft, The Netherlands. Otwinowski, Z. & Minor, W. (1996). Methods Enzymol. 276, 307±326. Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473. Sheldrick, G. M. (1997). SHELXL97. University of GoÈttingen, Germany.
Acta Cryst. (2000). C56, e356
supporting information
supporting information Acta Cryst. (2000). C56, e356
[doi:10.1107/S0108270100009173]
(5S*,6R*)-1,7-Dioxadispiro[4.0.4.4]tetradecane-2,8-dione Rafael Roggenbuck, Markus Schürmann, Hans Preut and Peter Eilbracht Computing details Data collection: COLLECT Software (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995). (I) Crystal data C12H16O4 Mr = 224.25 Monoclinic, P21/c a = 6.8821 (2) Å b = 13.4754 (4) Å c = 12.0807 (4) Å β = 100.3383 (19)° V = 1102.16 (6) Å3 Z=4
F(000) = 480 Dx = 1.351 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 9511 reflections θ = 3.4–27.5° µ = 0.10 mm−1 T = 291 K Block, colourless 0.40 × 0.39 × 0.26 mm
Data collection Nonius KappaCCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator Detector resolution: 10 vertical, 18 horizontal pixels mm-1 281 frames via ω–rotation (Δω=1°) and two times 20 s per frame with three sets at different κ angles scans
9511 measured reflections 2492 independent reflections 1552 reflections with I > 2σ(I) Rint = 0.031 θmax = 27.5°, θmin = 3.4° h = −8→8 k = −17→17 l = −15→15
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.038 wR(F2) = 0.101 S = 0.95 2492 reflections 210 parameters 0 restraints Primary atom site location: structure-invariant direct methods
Acta Cryst. (2000). C56, e356
Secondary atom site location: difference Fourier map Hydrogen site location: difference Fourier map All H-atom parameters refined Calculated w = 1/[σ2(Fo2) + (0.0627P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.16 e Å−3 Δρmin = −0.15 e Å−3 Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 Extinction coefficient: 0.035 (6)
sup-1
supporting information Special details Experimental. The data collection covered almost the whole sphere of reciprocal space. The crystal-to-detector distance was 3.4 cm. Crystal decay was monitored by repeating the initial frames at the end of the data collection and analysing the duplicate reflections there was no indication for any decay. 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 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 R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
O1 O2 O3 O4 C1 C2 H2A H2B C3 H3A H3B C4 H4A H4B C5 H5A H5B C6 C7 C8 H8A H8B C9 H9A H9B C10 C11 H11A H11B C12 H12A H12B
x
y
z
Uiso*/Ueq
−0.10929 (13) −0.31510 (15) 0.19961 (12) 0.33557 (14) 0.00572 (16) −0.0937 (2) −0.224 (2) −0.1144 (19) 0.0278 (2) 0.031 (2) −0.039 (2) 0.2356 (3) 0.315 (2) 0.224 (2) 0.3339 (2) 0.3528 (19) 0.468 (2) 0.21556 (16) −0.20784 (19) −0.1633 (2) −0.284 (3) −0.132 (2) −0.0009 (2) −0.0224 (19) 0.121 (2) 0.32307 (17) 0.4316 (2) 0.437 (3) 0.564 (3) 0.3215 (2) 0.400 (2) 0.228 (3)
0.25692 (6) 0.20079 (7) 0.24056 (6) 0.09793 (6) 0.34628 (8) 0.39840 (11) 0.4212 (10) 0.3491 (11) 0.48509 (12) 0.5369 (12) 0.5153 (12) 0.45213 (12) 0.5066 (12) 0.4045 (10) 0.40130 (10) 0.4472 (9) 0.3776 (9) 0.31332 (8) 0.26578 (9) 0.36326 (12) 0.4032 (12) 0.3510 (13) 0.40806 (10) 0.4732 (11) 0.4062 (9) 0.16367 (9) 0.17563 (12) 0.1136 (14) 0.1968 (12) 0.25662 (11) 0.2985 (11) 0.2252 (11)
0.66256 (8) 0.51315 (9) 0.83872 (7) 0.90372 (9) 0.69944 (10) 0.78622 (13) 0.7474 (12) 0.8424 (12) 0.84106 (14) 0.7847 (14) 0.8983 (15) 0.89227 (13) 0.9262 (14) 0.9567 (13) 0.80545 (13) 0.7453 (12) 0.8385 (12) 0.74988 (10) 0.55622 (12) 0.50787 (14) 0.4994 (14) 0.4375 (16) 0.59203 (11) 0.6083 (12) 0.5663 (12) 0.83560 (11) 0.73980 (15) 0.7016 (16) 0.7728 (16) 0.66823 (13) 0.6353 (12) 0.6070 (15)
0.0509 (3) 0.0689 (3) 0.0446 (3) 0.0620 (3) 0.0384 (3) 0.0516 (4) 0.059 (4)* 0.060 (4)* 0.0617 (4) 0.070 (4)* 0.084 (5)* 0.0629 (4) 0.074 (5)* 0.062 (4)* 0.0511 (4) 0.052 (4)* 0.061 (4)* 0.0389 (3) 0.0480 (3) 0.0581 (4) 0.087 (5)* 0.082 (5)* 0.0420 (3) 0.057 (4)* 0.058 (4)* 0.0457 (3) 0.0608 (4) 0.091 (6)* 0.089 (6)* 0.0535 (4) 0.060 (4)* 0.074 (5)*
Acta Cryst. (2000). C56, e356
sup-2
supporting information Atomic displacement parameters (Å2)
O1 O2 O3 O4 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12
U11
U22
U33
U12
U13
U23
0.0522 (5) 0.0677 (7) 0.0476 (5) 0.0637 (6) 0.0389 (6) 0.0484 (8) 0.0805 (11) 0.0807 (11) 0.0463 (8) 0.0408 (7) 0.0443 (7) 0.0643 (10) 0.0449 (7) 0.0424 (7) 0.0604 (10) 0.0551 (8)
0.0446 (5) 0.0631 (6) 0.0467 (5) 0.0494 (6) 0.0360 (6) 0.0589 (9) 0.0570 (9) 0.0529 (9) 0.0513 (8) 0.0400 (6) 0.0509 (8) 0.0604 (9) 0.0408 (8) 0.0415 (7) 0.0585 (9) 0.0572 (8)
0.0527 (6) 0.0724 (7) 0.0408 (5) 0.0707 (7) 0.0405 (7) 0.0509 (9) 0.0484 (9) 0.0501 (10) 0.0526 (9) 0.0373 (7) 0.0482 (8) 0.0462 (9) 0.0399 (8) 0.0512 (8) 0.0673 (10) 0.0520 (9)
−0.0111 (4) −0.0175 (5) 0.0057 (4) 0.0016 (4) −0.0040 (5) 0.0108 (6) 0.0164 (8) −0.0041 (8) −0.0045 (6) 0.0017 (5) −0.0006 (6) −0.0094 (7) 0.0015 (6) −0.0005 (5) 0.0176 (7) 0.0133 (7)
0.0009 (4) 0.0026 (5) 0.0115 (4) 0.0065 (5) 0.0079 (5) 0.0183 (7) 0.0136 (8) −0.0015 (8) 0.0010 (7) 0.0111 (5) 0.0068 (6) 0.0008 (7) 0.0067 (6) 0.0025 (6) 0.0219 (8) 0.0202 (7)
0.0083 (4) −0.0156 (5) 0.0123 (4) 0.0220 (5) 0.0042 (5) 0.0106 (7) −0.0062 (8) −0.0057 (8) 0.0093 (7) 0.0086 (5) −0.0052 (7) 0.0070 (7) 0.0066 (6) 0.0066 (7) 0.0116 (8) 0.0086 (7)
Geometric parameters (Å, º) O1—C7 O1—C1 O2—C7 O3—C10 O3—C6 O4—C10 C1—C2 C1—C6 C1—C9 C2—C3 C2—H2A C2—H2B C3—C4 C3—H3A C3—H3B C4—C5 C4—H4A
1.3461 (17) 1.4657 (14) 1.2020 (15) 1.3447 (15) 1.4723 (13) 1.2016 (14) 1.5222 (18) 1.5291 (16) 1.5355 (17) 1.518 (2) 0.986 (14) 0.978 (15) 1.519 (2) 0.979 (17) 0.985 (19) 1.510 (2) 0.961 (16)
C4—H4B C5—C6 C5—H5A C5—H5B C6—C12 C7—C8 C8—C9 C8—H8A C8—H8B C9—H9A C9—H9B C10—C11 C11—C12 C11—H11A C11—H11B C12—H12A C12—H12B
1.023 (15) 1.5240 (17) 0.980 (14) 0.992 (15) 1.5319 (17) 1.492 (2) 1.496 (2) 0.982 (18) 0.929 (18) 0.917 (15) 0.943 (15) 1.4945 (19) 1.509 (2) 0.959 (19) 0.967 (19) 0.921 (15) 0.983 (18)
C7—O1—C1 C10—O3—C6 O1—C1—C2 O1—C1—C6 C2—C1—C6 O1—C1—C9 C2—C1—C9 C6—C1—C9
111.68 (9) 111.26 (9) 107.67 (9) 107.60 (9) 111.62 (10) 104.83 (9) 112.52 (10) 112.15 (9)
C5—C6—C1 O3—C6—C12 C5—C6—C12 C1—C6—C12 O2—C7—O1 O2—C7—C8 O1—C7—C8 C7—C8—C9
109.95 (9) 104.09 (9) 113.16 (11) 114.39 (11) 120.91 (12) 128.72 (14) 110.37 (11) 105.67 (12)
Acta Cryst. (2000). C56, e356
sup-3
supporting information C3—C2—C1 C3—C2—H2A C1—C2—H2A C3—C2—H2B C1—C2—H2B H2A—C2—H2B C2—C3—C4 C2—C3—H3A C4—C3—H3A C2—C3—H3B C4—C3—H3B H3A—C3—H3B C5—C4—C3 C5—C4—H4A C3—C4—H4A C5—C4—H4B C3—C4—H4B H4A—C4—H4B C4—C5—C6 C4—C5—H5A C6—C5—H5A C4—C5—H5B C6—C5—H5B H5A—C5—H5B O3—C6—C5 O3—C6—C1
112.05 (11) 110.6 (8) 107.5 (8) 110.9 (8) 107.7 (8) 107.9 (11) 110.93 (12) 109.0 (9) 110.8 (9) 109.6 (10) 111.0 (9) 105.4 (13) 110.85 (13) 110.5 (9) 111.8 (9) 110.4 (8) 107.4 (8) 105.6 (13) 112.85 (12) 111.3 (7) 107.2 (8) 111.6 (8) 108.2 (8) 105.3 (12) 107.50 (10) 107.18 (8)
C7—C8—H8A C9—C8—H8A C7—C8—H8B C9—C8—H8B H8A—C8—H8B C8—C9—C1 C8—C9—H9A C1—C9—H9A C8—C9—H9B C1—C9—H9B H9A—C9—H9B O4—C10—O3 O4—C10—C11 O3—C10—C11 C10—C11—C12 C10—C11—H11A C12—C11—H11A C10—C11—H11B C12—C11—H11B H11A—C11—H11B C11—C12—C6 C11—C12—H12A C6—C12—H12A C11—C12—H12B C6—C12—H12B H12A—C12—H12B
107.0 (10) 111.5 (10) 107.5 (11) 115.1 (10) 109.6 (15) 105.12 (10) 113.7 (9) 108.6 (9) 111.3 (9) 111.7 (8) 106.4 (11) 121.12 (12) 128.72 (12) 110.16 (11) 104.62 (11) 110.2 (11) 114.4 (11) 105.9 (11) 111.2 (10) 110.1 (14) 103.88 (11) 114.6 (9) 111.0 (9) 108.2 (9) 112.2 (10) 107.1 (13)
C7—O1—C1—C2 C7—O1—C1—C6 C7—O1—C1—C9 O1—C1—C2—C3 C6—C1—C2—C3 C9—C1—C2—C3 C1—C2—C3—C4 C2—C3—C4—C5 C3—C4—C5—C6 C10—O3—C6—C5 C10—O3—C6—C1 C10—O3—C6—C12 C4—C5—C6—O3 C4—C5—C6—C1 C4—C5—C6—C12 O1—C1—C6—O3 C2—C1—C6—O3 C9—C1—C6—O3 O1—C1—C6—C5 C2—C1—C6—C5
109.29 (11) −130.26 (10) −10.72 (12) 172.78 (11) 54.90 (14) −72.21 (15) −55.13 (17) 55.12 (18) −56.16 (17) −103.82 (11) 138.02 (10) 16.46 (13) −61.29 (14) 55.06 (14) −175.66 (12) −55.05 (11) 62.87 (12) −169.83 (9) −171.61 (9) −53.69 (13)
C9—C1—C6—C5 O1—C1—C6—C12 C2—C1—C6—C12 C9—C1—C6—C12 C1—O1—C7—O2 C1—O1—C7—C8 O2—C7—C8—C9 O1—C7—C8—C9 C7—C8—C9—C1 O1—C1—C9—C8 C2—C1—C9—C8 C6—C1—C9—C8 C6—O3—C10—O4 C6—O3—C10—C11 O4—C10—C11—C12 O3—C10—C11—C12 C10—C11—C12—C6 O3—C6—C12—C11 C5—C6—C12—C11 C1—C6—C12—C11
73.62 (12) 59.78 (12) 177.70 (10) −54.99 (13) −177.58 (11) 1.85 (15) −172.54 (13) 8.09 (17) −14.03 (16) 15.00 (13) −101.72 (13) 131.45 (12) 177.81 (11) −1.99 (14) 166.63 (14) −13.59 (18) 22.61 (18) −23.69 (15) 92.71 (15) −140.31 (13)
Acta Cryst. (2000). C56, e356
sup-4
