The crystal structure of the title bicyclic oxazolidindione, C7H6Cl3NO3, confirmed the absolute stereochemistry as 2R,5S

David J. Watkin

Francesco Punzo

Mark G Moloney

Richard Pike

Terry Panchal

Undetermined

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organic paperso42 Francesco Punzo et al.  C7H6Cl3NO3 doi:10.1107/S1600536804031605 Acta Cryst. (2005). E61, o42±o44Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368(2R,5S)-2-Trichloromethyl-3-oxa-1-azabicyclo-[3.3.0]octane-4,8-dioneFrancesco Punzo,a*³ David J.Watkin,b Richard Pike,c MarkMoloneyc and Terry PanchaldaDipartimento di Scienze Chimiche, FacoltaÁ diFarmacia, UniversitaÁ di Catania, Viale A. Doria6, 95125, Catania, Italy, bDepartment ofChemical Crystallography, Chemical ResearchLaboratory, Mansfield Road, Oxford OX1 3TA,England, cDepartment of Organic Chemistry,Chemical Research Laboratory, Mansfield Road,Oxford OX1 3TA, England, and dMedicinalChemistry II, GlaxoSmithKline, New FrontiersScience Park, Harlow, Essex CM19 5AW,England³ Visiting scientist at the Department ofChemical Crystallography, Chemical ResearchLaboratory, Mansfield Road, Oxford OX1 3TA,England.Correspondence e-mail:francesco.punzo@chemistry.oxford.ac.ukKey indicatorsSingle-crystal X-ray studyT = 190 KMean (C±C) = 0.002 AÊR factor = 0.027wR factor = 0.064Data-to-parameter ratio = 21.0For details of how these key indicators wereautomatically derived from the article, seehttp://journals.iucr.org/e.# 2005 International Union of CrystallographyPrinted in Great Britain ± all rights reservedThe crystal structure of the title bicyclic oxazolidindione,C7H6Cl3NO3, con®rmed the absolute stereochemistry as2R,5S.CommentNatural -amino acids are at the core of many naturalproducts (Ikota, 1992). (S)-pyroglutamic acid, in particular,forms the core of many excitatory amino acids, such askaitocephalin (Watanabe et al., 2002) and kainic acid(Oppolzer & Thirring, 1982). Synthetic routes to these classesof compounds require stereochemical control at variouspositions around a pyrrolidine ring. Seebach's method of theso-called self-reproduction of chirality involves a dualprotection of the amine and carboxylic acid of (S)-proline withpivaldehyde to give a bicyclic system (Seebach et al., 1983).The analogous protection of (S)-pyroglutamic acid was foundto be unfavourable for pivaldehyde, the resulting productbeing particularly unstable (Dikshit et al., 1995). However,analogous protection of (S)-pyroglutamic acid with chloral(Amedjkouh & Ahlberg, 2002) provided the title compound,(3) (shown in Fig. 1 and Table 1), as an air-stable crystallinesolid.ExperimentalThe title compound was prepared by the method described byAmedjkouh & Ahlberg (2002). Slow recrystallization from ethylacetate gave colourless needle-like crystals. These tend to fracturewhen cut and therefore a large crystal was used. The multi-scantechnique was used to correct for changes in the illuminated volume.Crystal dataC7H6Cl3NO3Mr = 258.49Orthorhombic, P212121a = 6.0480 (1) AÊb = 10.1735 (3) AÊc = 15.5791 (4) AÊV = 958.57 (4) AÊ 3Z = 4Dx = 1.791 Mg mÿ3Mo K radiationCell parameters from 1485re¯ections = 5±30 = 0.93 mmÿ1T = 190 KNeedle, colourless0.80  0.20  0.20 mmReceived 25 November 2004Accepted 30 November 2004Online 11 December 2004Data collectionNonius KappaCCD diffractometer! scansAbsorption correction: none2708 measured re¯ections2692 independent re¯ections2545 re¯ections with I > 2(I)Rint = 0.028max = 30.0h = ÿ8! 8k = ÿ14! 14l = ÿ21! 21RefinementRe®nement on F 2R[F 2 > 2(F 2)] = 0.027wR(F 2) = 0.064S = 0.952692 re¯ections128 parametersH-atom parameters constrainedw = 1/[2(F 2) + 0.02 + 0.49p] wherep = [max(Fo2,0) + 2Fc2]/3(/)max = 0.001max = 0.27 e AÊÿ3min = ÿ0.26 e AÊ ÿ3Absolute structure: Flack (1983),1104 Friedel pairsFlack parameter = 0.01 (6)Table 1Selected geometric parameters (AÊ , ).C1ÐC2 1.544 (2)C1ÐCl12 1.7638 (16)C1ÐCl13 1.7617 (17)C1ÐCl14 1.7716 (16)C2ÐN3 1.4352 (19)C2ÐO6 1.4314 (19)N3ÐC4 1.457 (2)N3ÐC10 1.391 (2)C4ÐC5 1.516 (2)C4ÐC8 1.547 (2)C5ÐO6 1.366 (2)C5ÐO7 1.191 (2)C8ÐC9 1.531 (3)C9ÐC10 1.514 (3)C10ÐO11 1.207 (2)C2ÐC1ÐCl12 110.98 (10)C2ÐC1ÐCl13 108.10 (11)Cl12ÐC1ÐCl13 110.16 (9)C2ÐC1ÐCl14 108.76 (11)Cl12ÐC1ÐCl14 109.83 (9)Cl13ÐC1ÐCl14 108.97 (8)C1ÐC2ÐN3 113.21 (12)C1ÐC2ÐO6 108.34 (12)N3ÐC2ÐO6 105.82 (11)C2ÐN3ÐC4 110.58 (12)C2ÐN3ÐC10 121.30 (13)C4ÐN3ÐC10 112.34 (13)N3ÐC4ÐC5 102.17 (14)N3ÐC4ÐC8 105.25 (13)C5ÐC4ÐC8 117.03 (14)C4ÐC5ÐO6 109.41 (14)C4ÐC5ÐO7 129.11 (18)O6ÐC5ÐO7 121.44 (16)C2ÐO6ÐC5 110.71 (12)C4ÐC8ÐC9 102.61 (13)C8ÐC9ÐC10 104.36 (14)C9ÐC10ÐN3 106.57 (14)C9ÐC10ÐO11 129.32 (16)N3ÐC10ÐO11 124.11 (16)The H atoms were all seen in a difference map but those attachedto C atoms were repositioned geometrically. The H atoms wereinitially re®ned with soft restraints on the bonds to regularize theirgeometry [bond lengths to accepted values, angles either set bysymmetry or to accepted values, and Uiso(H) dependent on theadjacent bonded atom], after which they were re®ned with ridingconstraints only. CÐH = 0.93±0.98 AÊ and Uiso(H) = 1.2Ueq(C).Data collection: COLLECT (Nonius, 1997±2001); cell re®nement:DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduc-tion: DENZO/SCALEPACK; program(s) used to solve structure:SIR92 (Altomare et al., 1994); program(s) used to re®ne structure:CRYSTALS (Betteridge et al., 2003); molecular graphics:CAMERON (Watkin et al., 1996); software used to prepare materialfor publication: CRYSTALS.RP thanks the EPSRC for a grant and GlaxoSmithKline fora CASE award.ReferencesAltomare, A., Cascarano, G., Giacovazzo G., Guagliardi, A., Burla, M. C.,Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435±435.Amedjkouh, M. & Ahlberg, P. (2002). Tetrahedron Asymmetry, 13, 2229±2234.organic papersActa Cryst. (2005). E61, o42±o44 Francesco Punzo et al.  C7H6Cl3NO3 o43Figure 2Packing diagram of (3), viewed down the a axis.Figure 1The molecular structure of (3), with displacement ellipsoids drawn at the50% probability level. H-atom radii are arbitrary. Cl atoms are displayedin bright green.Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J.(2003). J. Appl. Cryst. 36, 1487.Dikshit, D. K., Maheshwari, A. & Panday, S. K. (1995). Tetrahedron Lett. 36,6131±6134.Flack, H. D. (1983). Acta Cryst. A39, 876±881.Ikota, N. (1992). Tetrahedron Lett. 33, 2553±2556.Nonius (1997±2001). COLLECT. Nonius BV, Delft, The Netherlands.Oppolzer, W. & Thirring, K. (1982). J. Am. Chem. Soc. 104, 4978±4979.Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M.Sweet, pp. 307±326. New York: Academic Press.Seebach, D., Boes, M., Naef, R. & Schweizer, W. B. (1983). J. Am. Chem. Soc.105, 5390±5398.Watanabe, H., Okue, M., Kobayashi, H. & Kitahara T. (2002). TetrahedronLett. 43, 857±860.Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. ChemicalCrystallography Laboratory, Oxford, England.organic paperso44 Francesco Punzo et al.  C7H6Cl3NO3 Acta Cryst. (2005). E61, o42±o44supporting informationsup-1Acta Cryst. (2005). E61, o42–o44    supporting informationActa Cryst. (2005). E61, o42–o44    [https://doi.org/10.1107/S1600536804031605](2R,5S)-2-Trichloromethyl-3-oxa-1-azabicyclo[3.3.0]octane-4,8-dioneFrancesco Punzo, David J. Watkin, Richard Pike, Mark Moloney and Terry Panchal(2R,5S)-2-Trichloromethyl-3-oxa-1-azabicyclo[3,3,0]octane-4,8-dione Crystal data C7H6Cl3NO3Mr = 258.49Orthorhombic, P212121a = 6.0480 (1) Åb = 10.1735 (3) Åc = 15.5791 (4) ÅV = 958.57 (4) Å3Z = 4F(000) = 520Dx = 1.791 Mg m−3Mo Kα radiation, λ = 0.71073 ÅCell parameters from 1485 reflectionsθ = 5–30°µ = 0.93 mm−1T = 190 KNeedle, colourless0.80 × 0.20 × 0.20 mmData collection Nonius KappaCCD diffractometerGraphite monochromatorω scansAbsorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)Tmin = 0.83, Tmax = 0.832708 measured reflections2692 independent reflections2545 reflections with I > 2σ(I)Rint = 0.028θmax = 30.0°, θmin = 5.2°h = −8→8k = −14→14l = −21→21Refinement Refinement on F2Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.027wR(F2) = 0.064S = 0.962692 reflections128 parameters0 restraintsPrimary atom site location: structure-invariant direct methodsHydrogen site location: inferred from neighbouring sitesH-atom parameters constrainedw = 1/[sigma2(F2) + 0.02 + 0.49p] where p = (max(Fo2,0) + 2Fc2)/3 Method = SHELXL 97 (Sheldrick, 1997)(Δ/σ)max = 0.001Δρmax = 0.27 e Å−3Δρmin = −0.26 e Å−3Absolute structure: Flack, (1983), 1104 Friedel-pairsAbsolute structure parameter: 0.01 (6)Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) x y z Uiso*/UeqC1 0.8490 (2) 0.15246 (16) 0.24808 (9) 0.0240C2 0.8540 (2) 0.14921 (15) 0.14903 (9) 0.0205N3 0.9665 (2) 0.03633 (13) 0.11515 (8) 0.0210supporting informationsup-2Acta Cryst. (2005). E61, o42–o44    C4 1.1804 (3) 0.07368 (16) 0.07969 (10) 0.0247C5 1.1657 (3) 0.22241 (17) 0.07900 (10) 0.0286O6 0.9761 (2) 0.26093 (11) 0.11948 (7) 0.0252O7 1.2939 (3) 0.30057 (14) 0.05136 (10) 0.0485C8 1.1938 (3) 0.00394 (17) −0.00842 (11) 0.0296C9 1.0262 (3) −0.10780 (18) 0.00128 (12) 0.0322C10 0.8571 (3) −0.05505 (15) 0.06413 (10) 0.0258O11 0.6642 (2) −0.08309 (13) 0.07187 (9) 0.0354Cl12 1.11902 (7) 0.15831 (5) 0.29063 (3) 0.0363Cl13 0.71158 (9) 0.01009 (4) 0.28416 (3) 0.0407Cl14 0.69808 (8) 0.29265 (4) 0.28155 (3) 0.0352H21 0.7008 0.1531 0.1278 0.0237*H41 1.3021 0.0455 0.1181 0.0286*H81 1.3388 −0.0319 −0.0172 0.0351*H82 1.1486 0.0656 −0.0533 0.0354*H91 1.1002 −0.1859 0.0264 0.0391*H92 0.9571 −0.1357 −0.0533 0.0390*Atomic displacement parameters (Å2) U11 U22 U33 U12 U13 U23C1 0.0243 (7) 0.0219 (7) 0.0259 (6) 0.0005 (7) 0.0032 (5) 0.0002 (6)C2 0.0194 (6) 0.0182 (6) 0.0240 (6) 0.0008 (6) −0.0022 (5) 0.0006 (6)N3 0.0192 (6) 0.0211 (6) 0.0227 (6) 0.0007 (5) −0.0001 (5) −0.0013 (5)C4 0.0212 (7) 0.0296 (8) 0.0233 (7) 0.0000 (6) 0.0009 (6) −0.0030 (6)C5 0.0334 (9) 0.0304 (8) 0.0219 (7) −0.0084 (7) 0.0034 (6) −0.0047 (6)O6 0.0324 (6) 0.0197 (5) 0.0235 (5) −0.0020 (5) 0.0008 (5) 0.0012 (4)O7 0.0617 (10) 0.0415 (7) 0.0423 (7) −0.0242 (7) 0.0251 (7) −0.0099 (6)C8 0.0294 (8) 0.0336 (8) 0.0257 (7) 0.0051 (7) 0.0026 (6) −0.0059 (6)C9 0.0408 (10) 0.0271 (8) 0.0286 (8) 0.0018 (7) −0.0021 (7) −0.0071 (6)C10 0.0301 (8) 0.0200 (7) 0.0272 (7) −0.0006 (6) −0.0058 (6) 0.0000 (6)O11 0.0297 (6) 0.0305 (6) 0.0458 (7) −0.0069 (5) −0.0053 (5) −0.0043 (5)Cl12 0.03185 (19) 0.0504 (2) 0.02677 (17) 0.0041 (2) −0.00816 (15) −0.0008 (2)Cl13 0.0530 (3) 0.02717 (19) 0.0420 (2) −0.00685 (19) 0.0198 (2) 0.00310 (18)Cl14 0.0385 (2) 0.02754 (19) 0.0396 (2) 0.00699 (17) 0.00566 (19) −0.00887 (17)Geometric parameters (Å, º) C1—C2 1.544 (2) C4—H41 0.991C1—Cl12 1.7638 (16) C5—O6 1.366 (2)C1—Cl13 1.7617 (17) C5—O7 1.191 (2)C1—Cl14 1.7716 (16) C8—C9 1.531 (3)C2—N3 1.4352 (19) C8—H81 0.960C2—O6 1.4314 (19) C8—H82 0.978C2—H21 0.985 C9—C10 1.514 (3)N3—C4 1.457 (2) C9—H91 0.993N3—C10 1.391 (2) C9—H92 0.989C4—C5 1.516 (2) C10—O11 1.207 (2)supporting informationsup-3Acta Cryst. (2005). E61, o42–o44    C4—C8 1.547 (2)C2—C1—Cl12 110.98 (10) C8—C4—H41 111.354C2—C1—Cl13 108.10 (11) C4—C5—O6 109.41 (14)Cl12—C1—Cl13 110.16 (9) C4—C5—O7 129.11 (18)C2—C1—Cl14 108.76 (11) O6—C5—O7 121.44 (16)Cl12—C1—Cl14 109.83 (9) C2—O6—C5 110.71 (12)Cl13—C1—Cl14 108.97 (8) C4—C8—C9 102.61 (13)C1—C2—N3 113.21 (12) C4—C8—H81 110.425C1—C2—O6 108.34 (12) C9—C8—H81 109.705N3—C2—O6 105.82 (11) C4—C8—H82 108.963C1—C2—H21 108.457 C9—C8—H82 111.198N3—C2—H21 110.761 H81—C8—H82 113.404O6—C2—H21 110.199 C8—C9—C10 104.36 (14)C2—N3—C4 110.58 (12) C8—C9—H91 109.562C2—N3—C10 121.30 (13) C10—C9—H91 109.503C4—N3—C10 112.34 (13) C8—C9—H92 114.037N3—C4—C5 102.17 (14) C10—C9—H92 111.890N3—C4—C8 105.25 (13) H91—C9—H92 107.434C5—C4—C8 117.03 (14) C9—C10—N3 106.57 (14)N3—C4—H41 110.794 C9—C10—O11 129.32 (16)C5—C4—H41 109.699 N3—C10—O11 124.11 (16)

(2R,5S)-2-Tri­chloro­methyl-3-oxa-1-aza­bi­cyclo­[3.3.0]­octane-4,8-dione

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(2R,5S)-2-Trichloromethyl-3-oxa-1-azabicyclo[3.3.0]octane-4,8-dione

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(2R,5S)-2-Tri­chloro­methyl-3-oxa-1-aza­bi­cyclo­[3.3.0]­octane-4,8-dione

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(2R,5S)-2-Trichloromethyl-3-oxa-1-azabicyclo[3.3.0]octane-4,8-dione