# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Marco Bella' _publ_contact_author_email MARCO.BELLA@UNIROMA1.IT _publ_section_title ; Synergic Asymmetric Organocatalysis (SAOc) of Cinchona Alkaloids and Secondary Amines in the Synthesis of Bicyclo[2.2.2]octan-2-ones ; loop_ _publ_author_name 'Marco Bella' 'Pier Paolo Cusella' 'Tecla Gasperi' 'Daniele M Scarpino Schietroma' 'Valerio Visca' # Attachment '214932.cif' #\#CIF_1.1 # CIF produced by WinGX routine CIF_UPDATE # Created on 2008-09-02 at 09:30:47 # Using CIFtbx version 2.6.2 16 Jun 1998 # Dictionary name : cif_core.dic # Dictionary vers : 2.3 # Request file : c:\program files\wingx\files\archive.dat # CIF files read : 08jo0024_0m struct #------------------ SECTION 1. GLOBAL INFORMATION ---------------------------# data_08jo0024_0m _database_code_depnum_ccdc_archive 'CCDC 701756' _audit_creation_date 2008-09-02T09:30:47-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C14 H15 Cl1 O2' _chemical_formula_sum 'C14 H15 Cl1 O2' _chemical_formula_weight 250.71 _chemical_compound_source 'synthesis as described' _chemical_absolute_configuration ad #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21 1' _symmetry_space_group_name_Hall 'P 2yb' _symmetry_Int_Tables_number 4 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 6.5376(3) _cell_length_b 6.4529(3) _cell_length_c 14.5419(5) _cell_angle_alpha 90 _cell_angle_beta 97.292(2) _cell_angle_gamma 90 _cell_volume 608.51(4) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 5117 _cell_measurement_theta_min 3.14 _cell_measurement_theta_max 28.16 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.15 _exptl_crystal_density_diffrn 1.368 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 264 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.3 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_max 0.940 _exptl_absorpt_correction_T_min 0.852 _exptl_absorpt_process_details ; SADABS (Sheldrick, 2004) ; #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_source 'fine-focus sealed tube' _diffrn_source_type ? _diffrn_detector_type 'APEX2 charged-coupled device' _diffrn_measurement_device_type 'Bruker X8 APEX-II diffractometer' _diffrn_measurement_method ; Narrow slices collected using \f- and \w-scans ; _diffrn_detector_area_resol_mean 12.00 _diffrn_standards_number 0 _diffrn_reflns_av_R_equivalents 0.0278 _diffrn_reflns_av_unetI/netI 0.0273 _diffrn_reflns_number 8211 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.82 _diffrn_reflns_theta_max 28.26 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.965 _diffrn_measured_fraction_theta_max 0.815 _reflns_number_total 2223 _reflns_number_gt 2110 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Apex2 (Bruker-Nonius, 2007)' _computing_cell_refinement 'Saint+ v7.53A(Bruker-Nonius, 2007)' _computing_data_reduction 'Saint+ v7.53A(Bruker-Nonius, 2007)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0535P)^2^+0.1395P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 2223 _refine_ls_number_parameters 155 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0374 _refine_ls_R_factor_gt 0.0344 _refine_ls_wR_factor_ref 0.0866 _refine_ls_wR_factor_gt 0.0852 _refine_ls_goodness_of_fit_ref 1.061 _refine_ls_restrained_S_all 1.06 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.06(6) _refine_diff_density_max 0.481 _refine_diff_density_min -0.215 _refine_diff_density_rms 0.052 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.2789(3) 0.8642(4) -0.07072(14) 0.0224(5) Uani 1 1 d . . . C2 C 0.3703(3) 0.8703(3) -0.15211(14) 0.0213(5) Uani 1 1 d . . . H2 H 0.4994 0.9368 -0.1537 0.026 Uiso 1 1 calc R . . C3 C 0.2686(3) 0.7774(3) -0.23065(13) 0.0163(4) Uani 1 1 d . . . H3 H 0.3287 0.7821 -0.2867 0.02 Uiso 1 1 calc R . . C4 C 0.0809(3) 0.6775(3) -0.22963(13) 0.0154(4) Uani 1 1 d . . . C5 C -0.0084(3) 0.6812(3) -0.14736(13) 0.0186(5) Uani 1 1 d . . . H5 H -0.1391 0.618 -0.1458 0.022 Uiso 1 1 calc R . . C6 C 0.0897(3) 0.7752(4) -0.06780(14) 0.0216(5) Uani 1 1 d . . . H6 H 0.0267 0.7777 -0.0124 0.026 Uiso 1 1 calc R . . C7 C -0.0158(3) 0.5646(3) -0.31553(13) 0.0158(4) Uani 1 1 d . . . H7 H 0.0547 0.6163 -0.3682 0.019 Uiso 1 1 calc R . . C8 C 0.0209(3) 0.3265(3) -0.30996(13) 0.0171(4) Uani 1 1 d . . . H8 H 0.1679 0.2972 -0.2853 0.021 Uiso 1 1 calc R . . C9 C -0.0266(3) 0.2419(4) -0.40879(14) 0.0214(5) Uani 1 1 d . . . H9A H 0.0736 0.2978 -0.448 0.026 Uiso 1 1 calc R . . H9B H -0.0151 0.0889 -0.4082 0.026 Uiso 1 1 calc R . . C10 C -0.2416(3) 0.3051(3) -0.44751(13) 0.0168(4) Uani 1 1 d . . . C11 C -0.3588(3) 0.4030(3) -0.37600(13) 0.0184(5) Uani 1 1 d . . . H11 H -0.5048 0.4312 -0.4025 0.022 Uiso 1 1 calc R . . C12 C -0.3502(3) 0.2559(4) -0.29207(14) 0.0211(5) Uani 1 1 d . . . H12A H -0.4138 0.1214 -0.312 0.025 Uiso 1 1 calc R . . H12B H -0.4294 0.3164 -0.2449 0.025 Uiso 1 1 calc R . . C13 C -0.1224(3) 0.2214(3) -0.24914(14) 0.0210(5) Uani 1 1 d . . . H13A H -0.1001 0.2803 -0.1858 0.025 Uiso 1 1 calc R . . H13B H -0.0922 0.0711 -0.2449 0.025 Uiso 1 1 calc R . . C14 C -0.2486(3) 0.6049(3) -0.34225(13) 0.0164(4) Uani 1 1 d . . . H14 H -0.3079 0.6554 -0.2863 0.02 Uiso 1 1 calc R . . O2 O -0.2689(2) 0.7642(2) -0.41068(10) 0.0226(4) Uani 1 1 d . . . H2A H -0.3941 0.7806 -0.4307 0.034 Uiso 1 1 calc R . . O1 O -0.3124(2) 0.2791(3) -0.52813(9) 0.0266(4) Uani 1 1 d . . . Cl1 Cl 0.41436(9) 0.96580(10) 0.03024(4) 0.03688(19) Uani 1 1 d . . . 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 0.0219(12) 0.0258(12) 0.0186(9) -0.0065(9) -0.0010(8) -0.0017(10) C2 0.0167(11) 0.0218(12) 0.0253(10) -0.0013(9) 0.0024(8) -0.0038(9) C3 0.0153(10) 0.0187(11) 0.0150(9) 0.0014(8) 0.0027(7) 0.0015(9) C4 0.0145(10) 0.0159(11) 0.0151(9) 0.0025(7) -0.0008(7) 0.0028(8) C5 0.0153(11) 0.0214(12) 0.0195(10) -0.0009(8) 0.0032(8) -0.0033(9) C6 0.0196(11) 0.0293(13) 0.0165(9) -0.0033(8) 0.0049(8) 0.0011(10) C7 0.0111(10) 0.0196(12) 0.0168(10) -0.0001(8) 0.0020(7) -0.0001(8) C8 0.0128(10) 0.0191(11) 0.0183(10) -0.0019(8) -0.0030(7) 0.0030(8) C9 0.0148(11) 0.0257(12) 0.0236(10) -0.0063(9) 0.0022(8) 0.0009(9) C10 0.0149(10) 0.0153(11) 0.0202(10) -0.0035(8) 0.0021(7) -0.0042(9) C11 0.0133(11) 0.0227(12) 0.0191(9) 0.0005(8) 0.0015(7) -0.0011(8) C12 0.0207(11) 0.0228(12) 0.0201(10) 0.0022(9) 0.0039(8) -0.0033(10) C13 0.0257(12) 0.0161(11) 0.0200(10) 0.0018(8) -0.0015(8) 0.0028(9) C14 0.0147(10) 0.0170(11) 0.0166(9) 0.0004(8) -0.0011(7) 0.0003(9) O2 0.0163(8) 0.0261(9) 0.0238(7) 0.0059(6) -0.0041(6) 0.0015(7) O1 0.0189(8) 0.0450(10) 0.0151(7) -0.0069(6) -0.0011(5) -0.0040(7) Cl1 0.0296(3) 0.0550(4) 0.0258(3) -0.0202(3) 0.0025(2) -0.0105(3) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 C6 1.369(3) . ? C1 C2 1.392(3) . ? C1 Cl1 1.743(2) . ? C2 C3 1.383(3) . ? C2 H2 0.95 . ? C3 C4 1.388(3) . ? C3 H3 0.95 . ? C4 C5 1.396(3) . ? C4 C7 1.513(3) . ? C5 C6 1.389(3) . ? C5 H5 0.95 . ? C6 H6 0.95 . ? C7 C14 1.544(3) . ? C7 C8 1.555(3) . ? C7 H7 1 . ? C8 C13 1.527(3) . ? C8 C9 1.532(3) . ? C8 H8 1 . ? C9 C10 1.503(3) . ? C9 H9A 0.99 . ? C9 H9B 0.99 . ? C10 O1 1.216(2) . ? C10 C11 1.507(3) . ? C11 C14 1.539(3) . ? C11 C12 1.541(3) . ? C11 H11 1 . ? C12 C13 1.556(3) . ? C12 H12A 0.99 . ? C12 H12B 0.99 . ? C13 H13A 0.99 . ? C13 H13B 0.99 . ? C14 O2 1.425(2) . ? C14 H14 1 . ? O2 H2A 0.84 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 C1 C2 121.67(19) . . ? C6 C1 Cl1 119.72(16) . . ? C2 C1 Cl1 118.58(17) . . ? C3 C2 C1 118.5(2) . . ? C3 C2 H2 120.8 . . ? C1 C2 H2 120.8 . . ? C2 C3 C4 121.71(18) . . ? C2 C3 H3 119.1 . . ? C4 C3 H3 119.1 . . ? C3 C4 C5 117.86(18) . . ? C3 C4 C7 119.48(17) . . ? C5 C4 C7 122.64(18) . . ? C6 C5 C4 121.49(19) . . ? C6 C5 H5 119.3 . . ? C4 C5 H5 119.3 . . ? C1 C6 C5 118.73(18) . . ? C1 C6 H6 120.6 . . ? C5 C6 H6 120.6 . . ? C4 C7 C14 114.94(17) . . ? C4 C7 C8 112.76(17) . . ? C14 C7 C8 108.68(17) . . ? C4 C7 H7 106.6 . . ? C14 C7 H7 106.6 . . ? C8 C7 H7 106.6 . . ? C13 C8 C9 108.57(17) . . ? C13 C8 C7 111.52(18) . . ? C9 C8 C7 106.96(17) . . ? C13 C8 H8 109.9 . . ? C9 C8 H8 109.9 . . ? C7 C8 H8 109.9 . . ? C10 C9 C8 108.87(17) . . ? C10 C9 H9A 109.9 . . ? C8 C9 H9A 109.9 . . ? C10 C9 H9B 109.9 . . ? C8 C9 H9B 109.9 . . ? H9A C9 H9B 108.3 . . ? O1 C10 C9 123.20(19) . . ? O1 C10 C11 123.9(2) . . ? C9 C10 C11 112.88(17) . . ? C10 C11 C14 108.44(17) . . ? C10 C11 C12 108.54(18) . . ? C14 C11 C12 107.47(16) . . ? C10 C11 H11 110.8 . . ? C14 C11 H11 110.8 . . ? C12 C11 H11 110.8 . . ? C11 C12 C13 110.03(17) . . ? C11 C12 H12A 109.7 . . ? C13 C12 H12A 109.7 . . ? C11 C12 H12B 109.7 . . ? C13 C12 H12B 109.7 . . ? H12A C12 H12B 108.2 . . ? C8 C13 C12 109.31(15) . . ? C8 C13 H13A 109.8 . . ? C12 C13 H13A 109.8 . . ? C8 C13 H13B 109.8 . . ? C12 C13 H13B 109.8 . . ? H13A C13 H13B 108.3 . . ? O2 C14 C11 112.94(15) . . ? O2 C14 C7 107.39(16) . . ? C11 C14 C7 110.14(17) . . ? O2 C14 H14 108.8 . . ? C11 C14 H14 108.8 . . ? C7 C14 H14 108.8 . . ? C14 O2 H2A 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 C1 C2 C3 -2.2(3) . . . . ? Cl1 C1 C2 C3 175.79(17) . . . . ? C1 C2 C3 C4 -0.7(3) . . . . ? C2 C3 C4 C5 2.9(3) . . . . ? C2 C3 C4 C7 -175.41(19) . . . . ? C3 C4 C5 C6 -2.2(3) . . . . ? C7 C4 C5 C6 176.0(2) . . . . ? C2 C1 C6 C5 2.8(3) . . . . ? Cl1 C1 C6 C5 -175.15(18) . . . . ? C4 C5 C6 C1 -0.6(3) . . . . ? C3 C4 C7 C14 -134.78(19) . . . . ? C5 C4 C7 C14 47.1(3) . . . . ? C3 C4 C7 C8 99.9(2) . . . . ? C5 C4 C7 C8 -78.3(2) . . . . ? C4 C7 C8 C13 77.7(2) . . . . ? C14 C7 C8 C13 -51.0(2) . . . . ? C4 C7 C8 C9 -163.77(17) . . . . ? C14 C7 C8 C9 67.6(2) . . . . ? C13 C8 C9 C10 65.0(2) . . . . ? C7 C8 C9 C10 -55.5(2) . . . . ? C8 C9 C10 O1 171.6(2) . . . . ? C8 C9 C10 C11 -8.5(3) . . . . ? O1 C10 C11 C14 -116.7(2) . . . . ? C9 C10 C11 C14 63.5(2) . . . . ? O1 C10 C11 C12 126.9(2) . . . . ? C9 C10 C11 C12 -53.0(2) . . . . ? C10 C11 C12 C13 60.6(2) . . . . ? C14 C11 C12 C13 -56.5(2) . . . . ? C9 C8 C13 C12 -56.0(2) . . . . ? C7 C8 C13 C12 61.6(2) . . . . ? C11 C12 C13 C8 -5.8(2) . . . . ? C10 C11 C14 O2 70.5(2) . . . . ? C12 C11 C14 O2 -172.39(16) . . . . ? C10 C11 C14 C7 -49.6(2) . . . . ? C12 C11 C14 C7 67.6(2) . . . . ? C4 C7 C14 O2 96.31(19) . . . . ? C8 C7 C14 O2 -136.27(17) . . . . ? C4 C7 C14 C11 -140.34(17) . . . . ? C8 C7 C14 C11 -12.9(2) . . . . ? # The following lines are used to test the character set of files sent by # network email or other means. They are not part of the CIF data set # abcdefghijklmnopqrstuvwxyzABCDEFGHIJKLMNOPQRSTUVWXYZ0123456789 # !@#$%^&*()_+{}:"~<>?|\-=[];'`,./ # END of CIF