#------------------------------------------------------------------------------ #$Date: 2012-11-14 14:21:35 +0200 (Wed, 14 Nov 2012) $ #$Revision: 68667 $ #$URL: file:///home/coder/svn-repositories/cod/cif/4/11/52/4115224.cif $ #------------------------------------------------------------------------------ # # This file is available in the Crystallography Open Database (COD), # http://www.crystallography.net/ # # All data on this site have been placed in the public domain by the # contributors. # data_4115224 loop_ _publ_author_name 'Douglass F. Taber' 'Timothy D. Neubert' 'Arnold L. Rheingold' _publ_section_title ; Synthesis of (-)-Morphine ; _journal_name_full 'Journal of the American Chemical Society' _journal_page_first 12416 _journal_page_last 12417 _journal_volume 124 _journal_year 2002 _chemical_formula_sum 'C19 H23 Br N O4' _chemical_formula_weight 409.29 _chemical_name_systematic ; ? ; _space_group_IT_number 5 _symmetry_cell_setting monoclinic _symmetry_space_group_name_Hall 'C 2y' _symmetry_space_group_name_H-M 'C 1 2 1' _atom_sites_solution_hydrogens geom _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _audit_creation_method SHELXL-97 _cell_angle_alpha 90.00 _cell_angle_beta 98.800(5) _cell_angle_gamma 90.00 _cell_formula_units_Z 4 _cell_length_a 14.771(3) _cell_length_b 5.0353(8) _cell_length_c 26.110(4) _cell_measurement_temperature 100 _cell_volume 1919.1(6) _computing_cell_refinement 'Bruker SMART' _computing_data_collection 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _diffrn_ambient_temperature 100 _diffrn_measured_fraction_theta_full 0.938 _diffrn_measured_fraction_theta_max 0.938 _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_radiation_monochromator graphite _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_reflns_av_R_equivalents 0.0464 _diffrn_reflns_av_sigmaI/netI 0.0805 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_l_max 34 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_number 6005 _diffrn_reflns_theta_full 28.30 _diffrn_reflns_theta_max 28.30 _diffrn_reflns_theta_min 2.99 _exptl_absorpt_coefficient_mu 2.164 _exptl_absorpt_correction_type none _exptl_crystal_density_diffrn 1.417 _exptl_crystal_density_meas 0 _exptl_crystal_F_000 844 _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.1 _refine_diff_density_max 1.592 _refine_diff_density_min -0.393 _refine_diff_density_rms 0.098 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.021(16) _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 0.949 _refine_ls_hydrogen_treatment mixed _refine_ls_matrix_type full _refine_ls_number_parameters 226 _refine_ls_number_reflns 3910 _refine_ls_number_restraints 1 _refine_ls_restrained_S_all 0.949 _refine_ls_R_factor_all 0.0716 _refine_ls_R_factor_gt 0.0553 _refine_ls_shift/su_max 0.007 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0785P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.1298 _refine_ls_wR_factor_ref 0.1357 _reflns_number_gt 3029 _reflns_number_total 3910 _reflns_threshold_expression >2sigma(I) _[local]_cod_data_source_file ja027882h-2_s1.cif _[local]_cod_data_source_block tab16a _cod_depositor_comments ; The following automatic conversions were performed: '_cell_measurement_temperature' value '100(0.1)' was changed to '100.00(10)' - precision was estimated. '_diffrn_ambient_temperature' value '100(0.1)' was changed to '100.00(10)' - precision was estimated. Automatic conversion script Id: cif_fix_values 1715 2011-07-08 13:25:40Z adriana ; _cod_original_cell_volume 1919.0(5) _cod_database_code 4115224 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' 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 Br1 Br 0.85044(3) 0.97472(12) 0.708295(19) 0.04174(18) Uani 1 1 d . N1 N 0.8823(3) 1.0509(7) 0.47939(17) 0.0252(10) Uani 1 1 d . H1A H 0.8821 1.2126 0.4666 0.030 Uiso 1 1 calc R O1 O 0.8813(2) 0.9348(8) 0.39765(13) 0.0272(8) Uani 1 1 d . O2 O 0.8965(2) 0.6125(7) 0.45892(14) 0.0305(8) Uani 1 1 d . O3 O 0.7385(5) 0.7117(16) 0.0562(3) 0.096(2) Uani 1 1 d . O4 O 0.7371(19) 0.387(5) 0.1147(11) 0.153(13) Uiso 0.40(2) 1 d P O4A O 0.7813(9) 0.337(2) 0.0880(5) 0.078(5) Uiso 0.60(2) 1 d P C1 C 0.8591(3) 0.9987(14) 0.63607(18) 0.0298(11) Uani 1 1 d . C2 C 0.9100(3) 1.2017(10) 0.6189(2) 0.0282(11) Uani 1 1 d . H2A H 0.9388 1.3309 0.6425 0.034 Uiso 1 1 calc R C3 C 0.9184(3) 1.2134(10) 0.5675(2) 0.0289(11) Uani 1 1 d . H3A H 0.9531 1.3522 0.5554 0.035 Uiso 1 1 calc R C4 C 0.8769(3) 1.0259(9) 0.53300(19) 0.0230(11) Uani 1 1 d . C5 C 0.8256(3) 0.8220(10) 0.5512(2) 0.0290(11) Uani 1 1 d . H5A H 0.7963 0.6925 0.5279 0.035 Uiso 1 1 calc R C6 C 0.8176(3) 0.8103(11) 0.6032(2) 0.0306(12) Uani 1 1 d . H6A H 0.7834 0.6718 0.6159 0.037 Uiso 1 1 calc R C7 C 0.8877(3) 0.8469(10) 0.4465(2) 0.0257(11) Uani 1 1 d . C8 C 0.8992(3) 0.7440(10) 0.3594(2) 0.0290(11) Uani 1 1 d . H8A H 0.8601 0.5851 0.3608 0.035 Uiso 1 1 calc R H8B H 0.9641 0.6878 0.3661 0.035 Uiso 1 1 calc R C9 C 0.8783(4) 0.8734(11) 0.3076(2) 0.0337(12) Uani 1 1 d . H9A H 0.9175 1.0324 0.3070 0.040 Uiso 1 1 calc R H9B H 0.8136 0.9328 0.3019 0.040 Uiso 1 1 calc R C10 C 0.8942(4) 0.6845(11) 0.2633(2) 0.0375(13) Uani 1 1 d . H10A H 0.9591 0.6272 0.2693 0.045 Uiso 1 1 calc R H10B H 0.8560 0.5242 0.2650 0.045 Uiso 1 1 calc R C11 C 0.8731(4) 0.8002(13) 0.2095(2) 0.0405(14) Uani 1 1 d . H11A H 0.9089 0.9685 0.2089 0.049 Uiso 1 1 calc R C12 C 0.7722(4) 0.8678(17) 0.1945(3) 0.062(2) Uani 1 1 d . H12A H 0.7539 0.9942 0.2196 0.094 Uiso 1 1 calc R H12B H 0.7355 0.7056 0.1945 0.094 Uiso 1 1 calc R H12C H 0.7621 0.9473 0.1599 0.094 Uiso 1 1 calc R C13 C 0.9051(4) 0.6069(15) 0.1697(2) 0.0481(15) Uani 1 1 d . H13A H 0.8751 0.4311 0.1731 0.058 Uiso 1 1 calc R C14 C 1.0123(5) 0.5621(18) 0.1774(3) 0.072(3) Uani 1 1 d . C15 C 1.0378(14) 0.586(7) 0.1254(8) 0.084(7) Uiso 0.55(5) 1 d P C15A C 1.0228(10) 0.448(4) 0.1228(5) 0.038(6) Uiso 0.45(5) 1 d P C16 C 0.9686(15) 0.684(8) 0.0866(7) 0.068(8) Uiso 0.50(7) 1 d P C16A C 0.9545(14) 0.570(7) 0.0844(7) 0.061(8) Uiso 0.50(7) 1 d P C17 C 0.8786(5) 0.7037(18) 0.1129(3) 0.0613(19) Uani 1 1 d . C18 C 0.7941(8) 0.5667(18) 0.0859(3) 0.074(3) Uani 1 1 d . C19 C 0.6571(6) 0.593(3) 0.0279(4) 0.104(4) Uani 1 1 d . H19A H 0.6232 0.7267 0.0053 0.156 Uiso 1 1 calc R H19B H 0.6184 0.5257 0.0523 0.156 Uiso 1 1 calc R H19C H 0.6744 0.4461 0.0068 0.156 Uiso 1 1 calc R 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 Br1 0.0345(2) 0.0474(3) 0.0448(3) 0.0050(4) 0.01107(19) -0.0002(4) N1 0.0229(19) 0.006(2) 0.047(3) 0.0029(15) 0.0068(18) 0.0006(14) O1 0.0257(14) 0.015(2) 0.0410(18) -0.0012(15) 0.0049(12) 0.0032(14) O2 0.0293(18) 0.0133(17) 0.050(2) 0.0003(16) 0.0091(16) 0.0006(14) O3 0.088(4) 0.106(6) 0.089(4) 0.015(4) 0.000(4) -0.009(4) C1 0.0217(18) 0.028(3) 0.040(2) -0.003(3) 0.0073(17) 0.005(3) C2 0.021(2) 0.021(3) 0.041(3) -0.003(2) 0.000(2) -0.002(2) C3 0.017(2) 0.019(3) 0.050(3) 0.000(2) 0.002(2) -0.0026(19) C4 0.0137(17) 0.009(3) 0.046(3) 0.0039(19) 0.0038(17) 0.0050(17) C5 0.021(2) 0.017(3) 0.049(3) -0.001(2) 0.006(2) -0.0012(19) C6 0.020(2) 0.026(3) 0.047(3) 0.001(2) 0.008(2) -0.002(2) C7 0.015(2) 0.014(2) 0.049(3) 0.000(2) 0.007(2) 0.0027(18) C8 0.025(2) 0.016(2) 0.046(3) -0.004(2) 0.008(2) 0.002(2) C9 0.028(2) 0.025(3) 0.048(3) -0.004(2) 0.005(2) 0.003(2) C10 0.033(3) 0.029(3) 0.051(3) -0.004(3) 0.009(2) 0.001(2) C11 0.036(3) 0.037(4) 0.049(4) 0.000(3) 0.008(3) 0.002(2) C12 0.048(4) 0.085(6) 0.054(4) 0.010(4) 0.007(3) 0.022(4) C13 0.046(3) 0.053(4) 0.046(4) 0.002(3) 0.008(3) 0.008(3) C14 0.051(4) 0.101(8) 0.066(4) -0.018(4) 0.015(3) 0.024(4) C17 0.057(4) 0.079(6) 0.047(4) -0.006(4) 0.009(3) 0.008(4) C18 0.110(7) 0.045(5) 0.053(5) 0.000(3) -0.028(4) 0.002(4) C19 0.062(5) 0.138(11) 0.104(7) -0.013(7) -0.009(5) -0.017(6) 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 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle C7 N1 C4 125.3(4) C7 O1 C8 116.5(4) C18 O3 C19 119.1(9) O4A O4 C18 50.8(14) O4 O4A C18 85.1(19) C6 C1 C2 121.7(4) C6 C1 Br1 119.1(4) C2 C1 Br1 119.1(4) C3 C2 C1 119.0(5) C2 C3 C4 120.9(5) C3 C4 C5 119.2(5) C3 C4 N1 119.8(4) C5 C4 N1 120.9(4) C6 C5 C4 119.7(5) C1 C6 C5 119.5(5) O2 C7 O1 124.0(5) O2 C7 N1 125.4(5) O1 C7 N1 110.6(4) O1 C8 C9 107.6(4) C8 C9 C10 112.1(5) C11 C10 C9 115.2(5) C10 C11 C12 112.4(5) C10 C11 C13 109.9(5) C12 C11 C13 110.9(5) C11 C13 C17 112.6(6) C11 C13 C14 114.0(5) C17 C13 C14 105.5(5) C15 C14 C15A 27.6(11) C15 C14 C13 105.3(9) C15A C14 C13 100.0(7) C15A C15 C16 95(3) C15A C15 C14 84(3) C16 C15 C14 115.5(16) C15A C15 C16A 71(3) C16 C15 C16A 23.8(10) C14 C15 C16A 110.8(16) C15 C15A C16A 80(3) C15 C15A C14 69(2) C16A C15A C14 108.7(14) C15 C15A C16 59(3) C16A C15A C16 21.4(9) C14 C15A C16 98.7(14) C16A C16 C15 87(4) C16A C16 C17 79(3) C15 C16 C17 105.9(15) C16A C16 C15A 60(3) C15 C16 C15A 26.2(13) C17 C16 C15A 99.4(16) C16 C16A C15A 98(3) C16 C16A C15 70(3) C15A C16A C15 28.6(11) C16 C16A C17 79(3) C15A C16A C17 108.8(12) C15 C16A C17 101.8(16) C18 C17 C13 112.0(7) C18 C17 C16A 100.4(13) C13 C17 C16A 102.8(8) C18 C17 C16 117.2(14) C13 C17 C16 106.7(8) C16A C17 C16 22.1(8) O4A C18 O3 120.1(12) O4A C18 C17 123.8(12) O3 C18 C17 115.8(8) O4A C18 O4 44.1(12) O3 C18 O4 106.8(13) C17 C18 O4 121.7(11) loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance Br1 C1 1.913(5) N1 C7 1.349(6) N1 C4 1.420(7) O1 C7 1.339(6) O1 C8 1.439(6) O2 C7 1.225(6) O3 C18 1.270(11) O3 C19 1.441(11) O4 O4A 1.06(3) O4 C18 1.51(3) O4A C18 1.175(12) C1 C6 1.361(8) C1 C2 1.383(8) C2 C3 1.368(7) C3 C4 1.382(7) C4 C5 1.402(6) C5 C6 1.382(7) C8 C9 1.490(8) C9 C10 1.543(7) C10 C11 1.509(8) C11 C12 1.520(8) C11 C13 1.549(9) C13 C17 1.553(9) C13 C14 1.580(9) C14 C15 1.47(2) C14 C15A 1.566(16) C15 C15A 0.73(3) C15 C16 1.41(3) C15 C16A 1.50(3) C15A C16A 1.45(2) C15A C16 1.65(3) C16 C16A 0.61(2) C16 C17 1.59(2) C16A C17 1.587(19) C17 C18 1.504(12)