# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Crousse Benoit' _publ_contact_author_email BENOIT.CROUSSE@U-PSUD.FR _publ_section_title ; Trifluoromethyl Nitrones: From Fluoral to Optically Active Hydroxylamines ; loop_ _publ_author_name B.Crousse 'Daniele Bonne-Delpon' 'Nathan Hinks' 'Milcent Thierry' # Attachment 'X-ray_of_2d.cif' data_2d _database_code_depnum_ccdc_archive 'CCDC 722468' #TrackingRef 'X-ray_of_2d.cif' _audit_creation_date 08-05-27 _audit_creation_method CRYSTALS_ver_12.85 _chemical_name_systematic ? _chemical_melting_point ? _publ_section_exptl_refinement # Some potentially useful phrases are donated by Bill Clegg: ; In the absence of significant anomalous scattering, Friedel pairs were merged. The absolute configuration was arbitrarily assigned. The relatively large ratio of minimum to maximum corrections applied in the multiscan process (1:nnn) reflect changes in the illuminated volume of the crystal. Changes in illuminated volume were kept to a minimum, and were taken into account (G\"orbitz, 1999) by the multi-scan inter-frame scaling (DENZO/SCALEPACK, Otwinowski & Minor, 1997). G\"orbitz, C. H. (1999). Acta Cryst. B55, 1090-1098. The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularise their geometry (C---H in the range 0.93--0.98, N---H in the range 0.86--0.89 N---H to 0.86 O---H = 0.82 \%A) and U~iso~(H) (in the range 1.2-1.5 times U~eq~ of the parent atom), after which the positions were refined with riding constraints. ; _publ_section_exptl_prep # Brief details or a reference. Include solvent if known ; ? ; # Hand-made tables can be put in the cif. The number of columns # is set in the loop header. # The contants of each column can either be a piece of text # without any spaces (eg a number) or other text enclosed in " " # Remove the leading # in the following example #geom_extra_table_head_A #; #Table 2. #Molecular parameters deviating most from MOGUL averages #; # #loop_ #_geom_extra_tableA_col_1 #_geom_extra_tableA_col_2 #_geom_extra_tableA_col_3 #_geom_extra_tableA_col_4 # #Parameter "Observed Value" "MOGUL Value" "MOGUL e.s.d" #N5-C6-C4 129 124 "7 (\%)" #C3-O10-C2 105 109 "2 (\%)" #C6-O7 1.25 1.22 ".02 (\%A)" # # End of 'script/refcif-b.dat' #end of refcif _cell_length_a 8.9962(12) _cell_length_b 5.0086(7) _cell_length_c 14.4090(14) _cell_angle_alpha 90 _cell_angle_beta 107.466(8) _cell_angle_gamma 90 _cell_volume 619.31(14) _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 1 21 1 ' _symmetry_space_group_name_Hall 'P 2yb' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,y+1/2,-z loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' F 0.0171 0.0103 3.5392 10.2825 2.6412 4.2944 1.5170 0.2615 1.0243 26.1476 0.2776 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 2 # Given Formula = C11 H12 F3 N1 O2 # Dc = 1.33 Fooo = 256.00 Mu = 1.20 M = 247.22 # Found Formula = C11 H12 F3 N1 O2 # Dc = 1.33 FOOO = 256.00 Mu = 1.20 M = 247.22 _chemical_formula_sum 'C11 H12 F3 N1 O2' _chemical_formula_moiety 'C11 H12 F3 N1 O2' _chemical_compound_source ? _chemical_formula_weight 247.22 _cell_measurement_reflns_used 46 _cell_measurement_theta_min 3 _cell_measurement_theta_max 21 _cell_measurement_temperature 200 _exptl_crystal_description stick _exptl_crystal_colour colourless _exptl_crystal_size_min 0.04 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_max 0.20 _exptl_crystal_density_diffrn 1.326 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 256 _exptl_absorpt_coefficient_mu 0.120 # Sheldrick geometric approximatio 0.99 1.00 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS (Siemens, 1996)' _exptl_absorpt_correction_T_min 0.99 _exptl_absorpt_correction_T_max 1.00 # For a Kappa CCD, set Tmin to 1.0 and # Tmax to the ratio of max:min frame scales in scale_all.log _diffrn_measurement_device 'Nonius KappaCCD' _diffrn_measurement_device_type Area _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method '\f & \w scans' # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'COLLECT (Nonius, 1997-2001).' _computing_cell_refinement 'Dirax/lsq (Duisenberg & Schreurs, 1989-2000)' _computing_data_reduction 'EvalCCD (Duisenberg & Schreurs 1990-2000)' _computing_structure_solution 'SHELXS 86 (Sheldrick, 1986)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time . _diffrn_standards_interval_count . _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 200 _diffrn_reflns_number 6590 _reflns_number_total 1982 _diffrn_reflns_av_R_equivalents 0.042 # Number of reflections with Friedels Law is 1982 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 1806 _diffrn_reflns_theta_min 3.153 _diffrn_reflns_theta_max 30.000 _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 26.100 _diffrn_measured_fraction_theta_full 0.994 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 18 _reflns_limit_h_min -12 _reflns_limit_h_max 12 _reflns_limit_k_min 0 _reflns_limit_k_max 7 _reflns_limit_l_min 0 _reflns_limit_l_max 20 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.48 _refine_diff_density_max 0.40 # The current dictionary definitions do not cover the # situation where the reflections used for refinement were # selected by a user-defined sigma threshold # The values actually used during refinement _oxford_reflns_threshold_expression_ref I>-10.0\s(I) _refine_ls_number_reflns 1980 _refine_ls_number_restraints 1 _refine_ls_number_parameters 156 _oxford_refine_ls_R_factor_ref 0.0928 _refine_ls_wR_factor_ref 0.1644 _refine_ls_goodness_of_fit_ref 1.0226 _refine_ls_shift/su_max 0.006893 # The values computed from all data _oxford_reflns_number_all 1980 _refine_ls_R_factor_all 0.0928 _refine_ls_wR_factor_all 0.1644 # The values computed with a 2 sigma cutoff - a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 1241 _refine_ls_R_factor_gt 0.0526 _refine_ls_wR_factor_gt 0.1377 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration unk _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_hydrogen_treatment refu # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method= Modified Sheldrick w=1/[\s^2^(F^2^) + ( 0.10P)^2^ + 0.00P] ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 ; # Insert your own references if required - in alphabetical order _publ_section_references ; Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Nonius (1997-2001). COLLECT. Nonius BV, Delft, The Netherlands. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, edited by C. W. Carter Jr & R. M. Sweet, pp. 307--326. New York: Academic Press. Siemens Industrial Automation, Inc (1996). SADABS: Area-Detector Absorption Correction;: Madison, WI. Sheldrick, G.M. (1986). SHELXS86. Program for the solution of crystal structures. Univ. of G\"ottingen, Federal Republic of Germany. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical Crystallography Laboratory, Oxford, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _oxford_atom_site_special_shape _atom_site_attached_hydrogens C1 C 0.8912(3) 0.9519(6) 0.73218(19) 0.0362 1.0000 Uani . . . . . . . C2 C 0.8005(3) 0.8410(9) 0.7973(2) 0.0544 1.0000 Uani . . . . . . . C3 C 0.8209(5) 0.8035(17) 0.9642(3) 0.1094 1.0000 Uani . . . . . . . C4 C 0.8206(3) 0.9014(6) 0.62332(19) 0.0356 1.0000 Uani . . . . . . . C5 C 0.7118(4) 0.7011(8) 0.5857(3) 0.0600 1.0000 Uani . . . . . . . C6 C 0.6507(4) 0.6648(9) 0.4853(3) 0.0715 1.0000 Uani . . . . . . . C7 C 0.6997(5) 0.8280(10) 0.4214(2) 0.0670 1.0000 Uani . . . . . . . C8 C 0.8084(4) 1.0224(9) 0.4582(2) 0.0655 1.0000 Uani . . . . . . . C9 C 0.8685(4) 1.0606(8) 0.5584(2) 0.0509 1.0000 Uani . . . . . . . C10 C 1.1731(3) 0.9876(6) 0.79846(19) 0.0362 1.0000 Uani . . . . . . . C11 C 1.3368(3) 0.8786(7) 0.8347(2) 0.0464 1.0000 Uani . . . . . . . O1 O 1.0608(2) 0.5777(5) 0.75965(17) 0.0520 1.0000 Uani . . . . . . . O2 O 0.8782(3) 0.9288(8) 0.89323(16) 0.0786 1.0000 Uani . . . . . . . N1 N 1.0537(3) 0.8311(5) 0.76574(15) 0.0345 1.0000 Uani . . . . . . . F1 F 1.3593(2) 0.7144(6) 0.91046(17) 0.0873 1.0000 Uani . . . . . . . F2 F 1.4370(2) 1.0825(6) 0.86191(19) 0.0858 1.0000 Uani . . . . . . . F3 F 1.3796(2) 0.7460(6) 0.76653(16) 0.0780 1.0000 Uani . . . . . . . H11 H 0.9010 1.1394 0.7421 0.090(4) 1.0000 Uiso . . . . . . . H21 H 0.7991 0.6515 0.7948 0.090(4) 1.0000 Uiso . . . . . . . H22 H 0.6967 0.9066 0.7771 0.090(4) 1.0000 Uiso . . . . . . . H31 H 0.8763 0.8685 1.0270 0.090(4) 1.0000 Uiso . . . . . . . H32 H 0.8348 0.6158 0.9621 0.090(4) 1.0000 Uiso . . . . . . . H33 H 0.7131 0.8424 0.9509 0.090(4) 1.0000 Uiso . . . . . . . H51 H 0.6789 0.5879 0.6288 0.090(4) 1.0000 Uiso . . . . . . . H61 H 0.5757 0.5287 0.4603 0.090(4) 1.0000 Uiso . . . . . . . H71 H 0.6579 0.8043 0.3531 0.090(4) 1.0000 Uiso . . . . . . . H81 H 0.8431 1.1321 0.4151 0.090(4) 1.0000 Uiso . . . . . . . H91 H 0.9433 1.1973 0.5828 0.090(4) 1.0000 Uiso . . . . . . . H101 H 1.1570 1.1748 0.7997 0.090(4) 1.0000 Uiso . . . . . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.0299(12) 0.0384(15) 0.0412(14) -0.0020(13) 0.0120(10) 0.0047(12) C2 0.0412(15) 0.079(2) 0.0470(16) -0.0020(19) 0.0193(12) 0.0019(18) C3 0.069(2) 0.211(8) 0.056(2) 0.034(4) 0.0291(19) 0.039(4) C4 0.0288(12) 0.0350(14) 0.0422(14) -0.0022(11) 0.0091(10) 0.0042(11) C5 0.0604(18) 0.053(2) 0.062(2) -0.0027(19) 0.0112(15) -0.016(2) C6 0.070(2) 0.060(2) 0.070(2) -0.018(2) -0.0023(19) -0.006(2) C7 0.072(2) 0.076(3) 0.0456(18) -0.013(2) 0.0056(16) 0.025(2) C8 0.070(2) 0.082(3) 0.0481(19) 0.009(2) 0.0236(17) 0.011(2) C9 0.0486(16) 0.0577(19) 0.0467(16) 0.0070(17) 0.0146(13) -0.0045(17) C10 0.0333(12) 0.0338(14) 0.0399(14) -0.0012(11) 0.0087(10) 0.0038(11) C11 0.0353(14) 0.0514(19) 0.0485(17) -0.0020(15) 0.0061(11) 0.0021(14) O1 0.0495(12) 0.0261(10) 0.0740(15) 0.0037(10) 0.0088(10) 0.0042(10) O2 0.0605(14) 0.137(3) 0.0425(13) 0.0015(16) 0.0214(11) 0.0020(17) N1 0.0348(11) 0.0306(12) 0.0376(12) 0.0010(11) 0.0099(9) 0.0056(10) F1 0.0619(12) 0.112(2) 0.0780(14) 0.0429(15) 0.0057(10) 0.0261(15) F2 0.0405(10) 0.0753(15) 0.122(2) -0.0169(16) -0.0060(11) -0.0037(12) F3 0.0419(9) 0.105(2) 0.0844(14) -0.0262(15) 0.0147(9) 0.0193(12) _refine_ls_extinction_coef 40 _refine_ls_extinction_method 'Larson (1970), Equation 22' loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag C1 . C2 . 1.522(4) yes C1 . C4 . 1.526(4) yes C1 . N1 . 1.520(3) yes C1 . H11 . 0.950 no C2 . O2 . 1.419(4) yes C2 . H21 . 0.950 no C2 . H22 . 0.950 no C3 . O2 . 1.422(6) yes C3 . H31 . 0.950 no C3 . H32 . 0.950 no C3 . H33 . 0.951 no C4 . C5 . 1.392(4) yes C4 . C9 . 1.392(4) yes C5 . C6 . 1.397(5) yes C5 . H51 . 0.950 no C6 . C7 . 1.398(6) yes C6 . H61 . 0.950 no C7 . C8 . 1.369(6) yes C7 . H71 . 0.950 no C8 . C9 . 1.395(5) yes C8 . H81 . 0.949 no C9 . H91 . 0.950 no C10 . C11 . 1.510(4) yes C10 . N1 . 1.298(3) yes C10 . H101 . 0.950 no C11 . F1 . 1.333(4) yes C11 . F2 . 1.340(4) yes C11 . F3 . 1.334(4) yes O1 . N1 . 1.275(3) yes loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag C2 . C1 . C4 . 116.0(2) yes C2 . C1 . N1 . 107.5(2) yes C4 . C1 . N1 . 109.0(2) yes C2 . C1 . H11 . 108.1 no C4 . C1 . H11 . 108.0 no N1 . C1 . H11 . 108.0 no C1 . C2 . O2 . 106.8(3) yes C1 . C2 . H21 . 110.2 no O2 . C2 . H21 . 110.1 no C1 . C2 . H22 . 110.2 no O2 . C2 . H22 . 110.1 no H21 . C2 . H22 . 109.5 no O2 . C3 . H31 . 109.5 no O2 . C3 . H32 . 109.5 no H31 . C3 . H32 . 109.5 no O2 . C3 . H33 . 109.5 no H31 . C3 . H33 . 109.4 no H32 . C3 . H33 . 109.4 no C1 . C4 . C5 . 123.1(3) yes C1 . C4 . C9 . 118.6(3) yes C5 . C4 . C9 . 118.3(3) yes C4 . C5 . C6 . 120.6(3) yes C4 . C5 . H51 . 119.7 no C6 . C5 . H51 . 119.7 no C5 . C6 . C7 . 120.2(4) yes C5 . C6 . H61 . 120.0 no C7 . C6 . H61 . 119.9 no C6 . C7 . C8 . 119.4(3) yes C6 . C7 . H71 . 120.3 no C8 . C7 . H71 . 120.3 no C7 . C8 . C9 . 120.5(3) yes C7 . C8 . H81 . 119.7 no C9 . C8 . H81 . 119.8 no C8 . C9 . C4 . 121.0(3) yes C8 . C9 . H91 . 119.5 no C4 . C9 . H91 . 119.5 no C11 . C10 . N1 . 121.5(3) yes C11 . C10 . H101 . 119.3 no N1 . C10 . H101 . 119.3 no C10 . C11 . F1 . 113.5(3) yes C10 . C11 . F2 . 109.0(3) yes F1 . C11 . F2 . 107.9(2) yes C10 . C11 . F3 . 113.1(2) yes F1 . C11 . F3 . 106.8(3) yes F2 . C11 . F3 . 106.1(3) yes C3 . O2 . C2 . 112.6(4) yes C1 . N1 . C10 . 119.1(2) yes C1 . N1 . O1 . 115.9(2) yes C10 . N1 . O1 . 124.9(3) yes