S. Henkel, Ν. Meunier and V. Jäger

Zeitschrift f ü r Kristallographie - N e w Crystal Structures 2 1 2 , 2 2 3 - 2 2 5

© by R. O l d e n b o u r g Verlag, M ü n c h e n 1997

223

Crystal structure of (45,5/?,l ^/ 5)-5-benzyloxy- ^J /V-(l ^, -phenylethyl)-4-(2 ^/ thienyl)-tetrahydro-l,3-oxazin-2-one, C23H23NO3S

S. Henkel, Ν. Meunier and V. Jäger

Universität Stuttgart, Institut für Organische Chemie, Pfaffenwaldring 55, D-70569 Stuttgart, Germany Received September 9, 1996. CSD-No. 402624

C23H23N03S, monoclinic, P\2\ 1 (No. 4), a =17312(4) Â, b = 6 . 7 6 0 ( 1 ) Â , c =17.903(3) A, ß = 1 0 4 3 8 ( 2 )0, V = 2 0 2 9 . 5 Â , Ζ = 4 , R(F) =0.083, RvJF2) =0.191

Source of material: The title compound (see réf. 1) was prepared by cyclization with triphosgene (see refs. 2,3) of the correspond- ing 3-amino-l,2-diol. The latter was obtained by addition of 2-thienyllithium to

1

1 '-phenylethyl) glycerinaldimine (see refs. 4,5).

In the crystal the tide compound is present as a 1:1 -mixture of two conformers A and B. In both, the tetrahydrooxazinone ring adopts a half-chair

H6 (systematic ring numbering). The major dif- ference is that the phenyl group (in the O-benzyl part) of A is oriented

(torsional angle C3A-019A-C20A-C21A -155.67 degrees), in Β a

arrangement (73.80 degrees) prevails. In the crystal the spatial arrangement shows alternating linear strings each composed of one type only.

Table 1. Parameters used for the X-ray data collection

Table 2. Final atomic coordinates and displacement parameters (in Â2)

Crystal: colorless block, size 0.2 χ 0.35 χ 0.7 mm Wavelength: Mo Ka radiation (0.71073 Â)

μ: 1.83 cm"1

Diffractometer: Nicolet P3

Scan mode: Wyckoff

Τmeasurement'· 293 Κ

26max: 54°

N(hkl)unique'. 4794

Criterion for I0: ¡o >2 σ(/ο)

N(param)refine<n 506

Programs: SHELXS-86, SHELXL-93

Atom Site X y ζ t/i«.

H(2A) 2a 0.0668(4) 0.368(1) 0.2674(4) 0.060 H(3A) 2a 0.0229(6) 0.112(1) 0.3477(6) 0.091 H(4A1) 2a 0.1420(5) 0.092(1) 0.4403(5) 0.089 H(4A2) 2a 0.1219(5) -0.116(1) 0.4016(5) 0.089 H(7A) 2a 0.1686(4) 0.619(1) 0.2935(4) 0.059 H(71A) 2a 0.2909(5) 0.600(2) 0.3866(5) 0.108 H(71B) 2a 0.2987(5) 0.720(2) 0.3139(5) 0.108 H(71C) 2a 0.3298(5) 0.502(2) 0.3254(5) 0.108 H(9A) 2a 0.1619(5) 0.220(2) 0.1860(5) 0.107 H(10A) 2a 0.1494(7) 0.207(4) 0.0520(7) 0.163 H(11A) 2a 0.1832(9) 0.490(5) -0.0080(6) 0.198 H(12A) 2a 0.2198(8) 0.766(3) 0.0579(8) 0.159 H(13A) 2a 0.2318(5) 0.781(2) 0.1903(6) 0.115 H(16A) 2a 0.0595(7) 0.697(2) 0.5372(6) 0.103 H(17A) 2a -0.0524(7) 0.739(2) 0.4302(8) 0.121 H(18A) 2a -0.0394(4) 0.565(1) 0.3153(5) 0.072 H(20A) 2a -0.0088(9) 0.136(2) 0.180(1) 0.222 H(20B) 2a -0.0539(9) 0.059(2) 0.241(1) 0.222 H(22A) 2a -0.1400(8) -0.225(3) 0.2048(6) 0.134 H(23A) 2a -0.1690(7) -0.526(2) 0.1342(7) 0.122 H(24A) 2a -0.0839(8) -0.613(2) 0.0643(8) 0.138 H(25A) 2a 0.021(1) -0.433(3) 0.0503(8) 0.161 H(26A) 2a 0.0487(7) -0.171(2) 0.1213(7) 0.115 H(2B) 2a 0.5754(4) 0.173(1) 0.2808(4) 0.053 H(3B) 2a 0.5339(6) -0.092(1) 0.3576(5) 0.079 H(4B1) 2a 0.6560(6) -0.104(1) 0.4505(5) 0.087

224

Table 2. (Continued)

Atom Site

Table 2. (Continued)

Atom Site H(4B2) 2a 0.6352(6) -0.313(1) 0.4124(5) 0.087

H(7B) la 0.6772(4) 0.423(1) 0.3099(4) 0.054 H(71D) la 0.8051(5) 0.400(1) 0.3897(5) 0.093 H(71E) la 0.8010(5) 0.536(1) 0.3178(5) 0.093 H(71F) la 0.8354(5) 0.321(1) 0.3197(5) 0.093 H(9B) la 0.6623(5) 0.609(2) 0.1977(5) 0.081 H(10B) la 0.6405(6) 0.625(2) 0.0657(5) 0.110 H(11B) la 0.6596(6) 0.353(2) -0.0034(5) 0.104 H(12B) la 0.7014(6) 0.063(2) 0.0596(5) 0.096 H(13B) la 0.7235(5) 0.042(2) 0.1921(5) 0.079

H(16B) la 0.6047(5) 0.500(1) 0.5578(4) 0.068 H(17B) la 0.4772(5) 0.518(1) 0.4782(5) 0.077 H(18B) la 0.4595(3) 0.3422(8) 0.3459(3) 0.030 H(20C) la 0.4642(7) -0.266(2) 0.2576(8) 0.135 H(20D) la 0.5000(7) -0.333(2) 0.1895(8) 0.135 H(22B) la 0.3838(6) 0.027(3) 0.2369(7) 0.127 H(23B) la 0.3410(8) 0.318(3) 0.1735(9) 0.144 H(24B) la 0.4005(9) 0.423(3) 0.0789(8) 0.155 H(25B) la 0.4981(7) 0.231(3) 0.0467(7) 0.143 H(26B) la 0.5408(6) -0.049(3) 0.1121(6) 0.115

Table 3. Final atomic coordinates and displacement parameters (in Â2)

Atom Site χ y ζ Un U22 t/33 U12 Un U73 N(1A) la 0.1818(3) 0.3362(9) 0.3218(3) 0.057(3) 0.042(3) 0.047(3) 0.008(3) 0.017(3) -0.001(3) C(2A) la 0.0960(4) 0.327(1) 0.3193(4) 0.052(4) 0.040(4) 0.054(4) 0.000(4) 0.004(3) 0.002(4) C(3A) la 0.0723(6) 0.111(1) 0.3302(6) 0.071(6) 0.045(5) 0.108(7) -0.006(4) 0.015(5) -0.008(5) C(4A) la 0.1366(5) 0.019(1) 0.3927(5) 0.080(6) 0.039(5) 0.105(7) -0.002(5) 0.028(5) 0.017(5) CK5A) la 0.2107(3) 0.0185(9) 0.3719(3) 0.077(4) 0.050(3) 0.077(4) 0.017(3) 0.026(3) 0.016(3) C(6A) la 0.2317(5) 0.178(1) 0.3371(4) 0.063(5) 0.049(5) 0.051(4) 0.011(4) 0.017(4) 0.001(4) 0(6A) la 0.2965(4) 0.175(1) 0.3224(4) 0.089(4) 0.068(4) 0.083(4) 0.031(4) 0.039(3) 0.016(3) C(7A) 2a 0.2067(4) 0.516(1) 0.2879(4) 0.059(4) 0.038(4) 0.054(4) 0.010(4) 0.021(3) 0.003(3) C(71A) 2a 0.2893(5) 0.592(2) 0.3327(5) 0.084(6) 0.065(6) 0.066(5) -0.019(5) 0.016(5) -0.011(5) C(8A) 2a 0.1993(4) 0.499(2) 0.2019(4) 0.045(4) 0.088(7) 0.053(4) 0.013(5) 0.018(3) 0.015(5) C(9A) la 0.1743(5) 0.331(2) 0.1606(5) 0.076(6) 0.13(1) 0.052(5) 0.016(7) 0.006(4) -0.027(7) C(10A) 2a 0.1666(7) 0.321(4) 0.0800(7) 0.093(8) 0.25(2) 0.061(7) 0.03(1) 0.010(6) -0.04(1) C(11A) 2a 0.1862(9) 0.492(5) 0.0446(6) 0.11(1) 0.35(3) 0.043(6) 0.05(2) 0.029(6) 0.04(1) C(12A) la 0.2085(8) 0.654(3) 0.0835(8) 0.10(1) 0.23(2) 0.078(9) 0.02(1) 0.032(8) 0.07(1) C(13A) 2a 0.2159(5) 0.664(2) 0.1635(6) 0.064(6) 0.14(1) 0.086(7) 0.010(7) 0.026(5) 0.050(8) C(14A) 2a 0.0720(4) 0.461(1) 0.3742(4) 0.056(4) 0.029(3) 0.054(4) -0.003(3) 0.018(3) -0.001(3) C(16A) 2a 0.0555(7) 0.640(2) 0.4890(6) 0.108(8) 0.082(7) 0.090(7) -0.041(7) 0.069(6) -0.041(6) S(15A) 2a 0.1267(1) 0.4971(4) 0.4676(1) 0.080(1) 0.071(2) 0.058(1) -0.015(1) 0.018(1) -0.005(1) C(17A) 2a -0.0081(7) 0.664(2) 0.4281(8) 0.079(7) 0.071(7) 0.18(1) -0.019(6) 0.075(8) -0.042(8) C(18A) 2a -0.0008(4) 0.564(1) 0.3619(5) 0.040(4) 0.057(5) 0.081(5) -0.007(4) 0.013(4) -0.004(4) 0(19A) la 0.0606(4) -0.007(1) 0.2677(4) 0.115(5) 0.054(4) 0.114(5) -0.001(4) -0.025(4) -0.026(4) C(20A) la -0.0135(9) 0.026(2) 0.214(1) 0.17(1) 0.081(9) 0.23(2) 0.05(1) -0.10(1) -0.06(1) C(21A) la -0.0369(5) -0.153(2) 0.1674(5) 0.066(5) 0.063(6) 0.071(5) 0.011(5) -0.013(4) -0.017(5) C(22A) la -0.1077(8) -0.269(3) 0.1738(6) 0.12(1) 0.15(1) 0.078(7) 0.02(1) 0.032(6) 0.010(8) C(23A) 2a -0.1253(7) -0.448(2) 0.1326(7) 0.072(7) 0.11(1) 0.110(9) -0.032(7) 0.002(6) 0.016(8) C(24A) la -0.0741(8) -0.494(2) 0.0911(8) 0.089(9) 0.10(1) 0.14(1) 0.010(9) -0.011(8) 0.024(9) C(25A) la -0.011(1) -0.393(3) 0.0827(8) 0.13(1) 0.14(1) 0.12(1) 0.04(1) 0.02(1) -0.03(1) C(26A) la 0.0021(7) -0.237(2) 0.1235(7) 0.080(7) 0.11(1) 0.096(8) 0.010(7) 0.024(6) -0.014(8) N(1B) la 0.6925(3) 0.1396(8) 0.3295(3) 0.053(3) 0.036(3) 0.048(3) 0.006(3) 0.022(3) 0.003(3) C(2B) 2a 0.6075(4) 0.128(1) 0.3309(4) 0.054(4) 0.039(4) 0.041(4) 0.000(3) 0.015(3) 0.000(3) C(3B) 2a 0.5844(6) -0.088(1) 0.3421(5) 0.087(6) 0.041(4) 0.081(6) -0.023(4) 0.040(5) -0.021(4) C(4B) la 0.6494(6) -0.178(1) 0.4029(5) 0.116(7) 0.035(4) 0.081(6) 0.000(5) 0.052(5) 0.005(5) C(5B) la 0.7224(4) -0.1772(8) 0.3798(3) 0.103(4) 0.034(3) 0.091(4) 0.008(3) 0.034(3) 0.006(3) C(6B) la 0.7431(5) -0.014(1) 0.3455(4) 0.071(5) 0.044(4) 0.061(4) 0.011(4) 0.021(4) -0.002(4) CK6B) la 0.8083(4) -0.016(1) 0.3311(4) 0.072(4) 0.060(4) 0.095(4) 0.020(3) 0.033(3) 0.001(4) C(7B) 2a 0.7136(4) 0.324(1) 0.2976(4) 0.052(4) 0.034(3) 0.055(4) 0.008(3) 0.024(3) 0.001(3) C(71B) 2a 0.7963(5) 0.402(1) 0.3346(5) 0.061(5) 0.057(5) 0.064(5) -0.008(4) 0.009(4) -0.001(4) C(8B) 2a 0.6965(4) 0.325(1) 0.2101(4) 0.044(4) 0.052(4) 0.048(4) -0.006(4) 0.016(3) 0.004(4) C(9B) la 0.6708(5) 0.497(2) 0.1705(5) 0.068(5) 0.073(6) 0.065(5) 0.009(5) 0.023(4) 0.007(5) C(10B) la 0.6574(6) 0.506(2) 0.0911(5) 0.087(7) 0.13(1) 0.060(5) 0.027(8) 0.021(5) 0.027(7) C(11B) 2a 0.6687(6) 0.346(2) 0.0500(5) 0.076(6) 0.14(1) 0.051(5) 0.022(7) 0.023(4) 0.007(7) C(12B) la 0.6935(6) 0.174(2) 0.0876(5) 0.081(6) 0.102(8) 0.067(6) 0.003(6) 0.035(5) -0.024(6) C(13B) la 0.7071(5) 0.161(2) 0.1673(5) 0.068(5) 0.073(6) 0.063(5) -0.001(5) 0.028(4) -0.008(5) C(14B) la 0.5883(4) 0.2582(9) 0.3926(4) 0.054(4) 0.029(3) 0.044(4) -0.004(3) 0.016(3) 0.002(3) S(15B) la 0.6558(1) 0.3101(3) 0.4752(1) 0.090(2) 0.058(1) 0.061(1) 0.006(1) 0.024(1) -0.001(1) C(16B) la 0.5910(5) 0.440(1) 0.5097(4) 0.087(6) 0.044(4) 0.046(4) -0.013(4) 0.029(4) -0.008(3) C(17B) 2a 0.5181(5) 0.451(1) 0.4637(5) 0.066(5) 0.048(5) 0.087(6) 0.010(4) 0.036(5) -0.004(4) C(18B) la 0.5051(3) 0.3486(8) 0.3863(3) 0.034(3) 0.020(3) 0.027(2) 0.002(2) 0.019(2) -0.004(2) 0(19B) la 0.5785(4) -0.2020(9) 0.2740(4) 0.088(4) 0.058(4) 0.103(5) -0.013(4) 0.029(4) -0.036(4) C(20B) la 0.4995(7) -0.227(2) 0.2258(8) 0.103(9) 0.10(1) 0.14(1) -0.036(8) 0.043(8) -0.069(9) C(21B) la 0.4672(5) -0.042(2) 0.1816(6) 0.056(5) 0.106(9) 0.093(7) -0.030(6) 0.021(5) -0.061(7)

C23H23NO3S 225

Table 3. (Continued)

Atom Site U h U22 t/33 f/|2 Í/13 Í/23

C(22B) la C(23B) la Q 2 4 B ) 2a C(25B) la C(26B) la

0.4074(6) 0.3814(8) 0.4163(9) 0.4755(7) 0.5001(6)

0.070(3) 0.244(3) 0.305(3) 0.191(3) 0.024(3)

0.1985(7) 0.1609(9) 0.1049(8) 0.0862(7) 0.1246(6)

0.056(6) 0.072(7) 0.11(1) 0.067(7) 0.062(6)

0.18(2) 0.15(2) 0.15(1) 0.21(2) 0.15(1)

0.092(8) 0 . 1 2 ( 1 ) 0.11(1) 0.075(7) 0.076(7)

-0.019(8) 0.019(9) 0.01(1) -0.03(1) -0.004(8)

0.026(5) 0.003(7) -0.023(8) 0.006(6) 0.023(5)

-0.064(9) -0.06(1) -0.03(1) -0.03(1) -0.031(8)

Acknowledgments. We are grateful to the Fonds der Chemischen Industrie and the European Community (HCM network "Stereoselective Organic Syn- thesis") for financial support and to Deutscher Akademischer Auslandsdienst (DAAD) for awarding a doctoral fellowship to N. Meunier.

References

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2. Sicker, D.: A facile synthesis of 6-methoxy-2-oxo-2,3-dihydrobenzox- azole. Synthesis (1989) 875-876.

3. Peters, K.; Veith, U.; Jäger, V.: (-)-(4Λ,5Λ, 1 'S)-5-benzyloxy^-methyl-3- (l-phenyl-ethyl)-tetrahydro-l,3-oxazin-2-one. Z. Kristallogr. 212 (1997) 175-176.

4. Franz, T.; Hein, M.; Veith, U.; Jäger, V.; Peters, E.-M.; Peters, K.; von Schnering, H. G. : Einfache und variable Synthese optisch aktiver 1,2-Ami- noalkohole durch Grignard-Addition an Λ/,Ο-Dibenzylglyceraldimin und -lactaldimin. Angew. Chem. 106 (1994) 1308-1311; Angew. Chem. Int.

Ed. Engl. 3 3 (1994) 1298-1301.

5. Veith, U.; Leurs, S.; Jäger, V.: Auxiliary-controlled diastereoselection by iV-(l-phenylethyl) in Grignard additions to 2-O-benzylglyceraldehyde imines. J. Chem. Soc. Chem. Commun. (19%) 329-330.

6. Sheldrick, G. M.: SHELXS-86. Program for the solution of crystal struc- tures. University of Göttingen, Germany 1986.

7. Sheldrick, G. M.: SHELXL-93, a program for refining crystal structures.

University of Göttingen, Germany 1993.