#------------------------------------------------------------------------------ #$Date: 2013-12-28 09:07:06 +0200 (Sat, 28 Dec 2013) $ #$Revision: 91932 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/50/32/1503246.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_1503246 loop_ _publ_author_name 'Tang, Xiang-Ying' 'Wei, Yin' 'Shi, Min' _publ_section_title ; Thermally induced electrocyclic reaction of methylenecyclopropane methylene diketone derivatives: a facile method for the synthesis of spiro[2.5]octa-3,5-dienes. ; _journal_issue 22 _journal_name_full 'Organic letters' _journal_page_first 5120 _journal_page_last 5123 _journal_volume 12 _journal_year 2010 _chemical_formula_sum 'C19 H19 Br O2' _chemical_formula_weight 359.25 _chemical_name_systematic ; ? ; _space_group_IT_number 60 _symmetry_cell_setting orthorhombic _symmetry_space_group_name_Hall '-P 2n 2ab' _symmetry_space_group_name_H-M 'P b c n' _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 90.00 _cell_angle_gamma 90.00 _cell_formula_units_Z 8 _cell_length_a 25.683(3) _cell_length_b 12.1372(13) _cell_length_c 11.0178(12) _cell_measurement_reflns_used 1681 _cell_measurement_temperature 293(2) _cell_measurement_theta_max 37.604 _cell_measurement_theta_min 5.239 _cell_volume 3434.5(7) _computing_cell_refinement 'Bruker SMART' _computing_data_collection 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _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 293(2) _diffrn_measured_fraction_theta_full 0.999 _diffrn_measured_fraction_theta_max 0.999 _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 0.0982 _diffrn_reflns_av_sigmaI/netI 0.0845 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_h_min -31 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_number 17036 _diffrn_reflns_theta_full 25.50 _diffrn_reflns_theta_max 25.50 _diffrn_reflns_theta_min 1.86 _exptl_absorpt_coefficient_mu 2.398 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_correction_T_min 0.4643 _exptl_absorpt_correction_type empirical _exptl_absorpt_process_details sadabs _exptl_crystal_colour yellow _exptl_crystal_density_diffrn 1.390 _exptl_crystal_density_method 'not measured' _exptl_crystal_description prismatic _exptl_crystal_F_000 1472 _exptl_crystal_size_max 0.396 _exptl_crystal_size_mid 0.267 _exptl_crystal_size_min 0.175 _refine_diff_density_max 0.564 _refine_diff_density_min -0.730 _refine_diff_density_rms 0.047 _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_extinction_method SHELXL _refine_ls_goodness_of_fit_ref 0.941 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 202 _refine_ls_number_reflns 3201 _refine_ls_number_restraints 0 _refine_ls_restrained_S_all 0.941 _refine_ls_R_factor_all 0.1220 _refine_ls_R_factor_gt 0.0488 _refine_ls_shift/su_max 0.004 _refine_ls_shift/su_mean 0.001 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details ; calc [0.00000+1.00000exp(2.00(sin\q/\l)^2^)]/ [\s^2^(Fo^2^)+0.0000+0.0000*P+(0.0711P)^2^+0.0000sin\q/\l] where P = 0.33333Fo^2^ + 0.66667Fc^2^ ; _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.1294 _refine_ls_wR_factor_ref 0.1556 _reflns_number_gt 1260 _reflns_number_total 3201 _reflns_threshold_expression >2sigma(I) _[local]_cod_data_source_file ol102002f_si_001.cif _[local]_cod_data_source_block cd29608 _[local]_cod_cif_authors_sg_H-M Pbcn _cod_depositor_comments ; The following automatic conversions were performed: '_symmetry_cell_setting' value 'Orthorhombic' changed to 'orthorhombic' according to /home/saulius/struct/CIF-dictionaries/cif_core.dic dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26. Automatic conversion script Id: cif_fix_values 1715 2011-07-08 13:25:40Z adriana ; _cod_original_cell_volume 3434.5(6) _cod_database_code 1503246 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z+1/2' '-x, y, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z-1/2' 'x, -y, z-1/2' '-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 0.52888(2) 0.25490(5) 0.99119(8) 0.1437(4) Uani 1 1 d . O1 O 0.16643(14) 0.2287(3) 0.8597(4) 0.1073(13) Uani 1 1 d . O2 O 0.24472(10) -0.06134(19) 1.0719(3) 0.0606(8) Uani 1 1 d . C1 C 0.17365(18) 0.1297(4) 0.8740(4) 0.0718(13) Uani 1 1 d . C2 C 0.14638(18) 0.0466(4) 0.7971(4) 0.0813(15) Uani 1 1 d . H2A H 0.1682 0.0298 0.7276 0.098 Uiso 1 1 calc R H2B H 0.1144 0.0789 0.7668 0.098 Uiso 1 1 calc R C3 C 0.13318(16) -0.0608(3) 0.8622(4) 0.0602(11) Uani 1 1 d . C4 C 0.18290(15) -0.1046(3) 0.9205(4) 0.0614(11) Uani 1 1 d . H4A H 0.1738 -0.1628 0.9771 0.074 Uiso 1 1 calc R H4B H 0.2047 -0.1366 0.8578 0.074 Uiso 1 1 calc R C5 C 0.21331(14) -0.0189(3) 0.9861(3) 0.0467(10) Uani 1 1 d . C6 C 0.20888(15) 0.0895(3) 0.9663(4) 0.0519(10) Uani 1 1 d . C7 C 0.23737(16) 0.1635(3) 1.0445(4) 0.0628(12) Uani 1 1 d . H7 H 0.2307 0.2387 1.0414 0.075 Uiso 1 1 calc R C8 C 0.27272(16) 0.1257(3) 1.1202(4) 0.0644(12) Uani 1 1 d . H8 H 0.2902 0.1738 1.1717 0.077 Uiso 1 1 calc R C9 C 0.28433(15) 0.0079(3) 1.1231(4) 0.0551(11) Uani 1 1 d . C10 C 0.31240(17) -0.0454(4) 1.2253(5) 0.0821(15) Uani 1 1 d . H10A H 0.3008 -0.1179 1.2506 0.098 Uiso 1 1 calc R H10B H 0.3247 0.0015 1.2906 0.098 Uiso 1 1 calc R C11 C 0.33922(15) -0.0359(3) 1.1039(4) 0.0609(12) Uani 1 1 d . H11 H 0.3403 -0.1054 1.0587 0.073 Uiso 1 1 calc R C12 C 0.38457(15) 0.0362(3) 1.0806(4) 0.0547(11) Uani 1 1 d . C13 C 0.40057(16) 0.1193(3) 1.1563(4) 0.0621(11) Uani 1 1 d . H13 H 0.3820 0.1324 1.2274 0.075 Uiso 1 1 calc R C14 C 0.44298(18) 0.1839(4) 1.1309(5) 0.0724(13) Uani 1 1 d . H14 H 0.4532 0.2385 1.1850 0.087 Uiso 1 1 calc R C15 C 0.47017(18) 0.1677(4) 1.0258(6) 0.0812(15) Uani 1 1 d . C16 C 0.4552(2) 0.0874(5) 0.9477(5) 0.0879(16) Uani 1 1 d . H16 H 0.4733 0.0764 0.8756 0.105 Uiso 1 1 calc R C17 C 0.41233(17) 0.0214(4) 0.9762(4) 0.0743(14) Uani 1 1 d . H17 H 0.4025 -0.0340 0.9226 0.089 Uiso 1 1 calc R C18 C 0.11185(19) -0.1466(4) 0.7728(4) 0.0984(17) Uani 1 1 d . H18A H 0.1377 -0.1623 0.7123 0.148 Uiso 1 1 calc R H18B H 0.0811 -0.1182 0.7343 0.148 Uiso 1 1 calc R H18C H 0.1034 -0.2130 0.8158 0.148 Uiso 1 1 calc R C19 C 0.09250(17) -0.0394(4) 0.9599(4) 0.0736(14) Uani 1 1 d . H19A H 0.0858 -0.1062 1.0037 0.110 Uiso 1 1 calc R H19B H 0.0609 -0.0142 0.9226 0.110 Uiso 1 1 calc R H19C H 0.1051 0.0159 1.0148 0.110 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 0.0732(4) 0.1177(6) 0.2403(11) 0.0541(5) 0.0370(5) -0.0142(4) O1 0.110(3) 0.074(2) 0.138(3) 0.052(2) -0.017(2) 0.004(2) O2 0.0536(17) 0.0373(14) 0.091(2) 0.0059(14) -0.0207(16) -0.0013(13) C1 0.072(3) 0.065(3) 0.078(4) 0.025(3) 0.008(3) 0.002(3) C2 0.080(4) 0.104(4) 0.060(3) 0.017(3) -0.009(3) -0.002(3) C3 0.058(3) 0.069(3) 0.054(3) -0.003(2) -0.009(2) -0.002(2) C4 0.055(3) 0.050(2) 0.079(3) -0.011(2) -0.004(2) -0.001(2) C5 0.042(2) 0.042(2) 0.057(3) -0.0016(19) -0.002(2) -0.0008(18) C6 0.045(2) 0.043(2) 0.067(3) 0.008(2) 0.004(2) -0.0004(19) C7 0.052(3) 0.034(2) 0.102(4) -0.004(2) 0.009(3) -0.004(2) C8 0.052(3) 0.052(3) 0.089(4) -0.019(2) 0.002(2) -0.010(2) C9 0.047(2) 0.048(2) 0.070(3) -0.003(2) -0.001(2) -0.009(2) C10 0.067(3) 0.092(3) 0.087(4) 0.027(3) -0.019(3) -0.023(3) C11 0.051(3) 0.054(3) 0.077(3) 0.001(2) -0.010(2) 0.002(2) C12 0.045(2) 0.057(3) 0.062(3) -0.001(2) -0.007(2) 0.008(2) C13 0.054(3) 0.064(3) 0.069(3) -0.003(2) -0.002(2) 0.001(2) C14 0.063(3) 0.061(3) 0.094(4) -0.007(3) -0.006(3) -0.003(2) C15 0.056(3) 0.072(3) 0.116(5) 0.015(3) 0.007(3) 0.003(3) C16 0.067(3) 0.121(5) 0.076(4) 0.009(4) 0.014(3) 0.016(3) C17 0.055(3) 0.095(4) 0.073(4) -0.015(3) -0.010(3) 0.011(3) C18 0.087(4) 0.123(4) 0.085(4) -0.034(3) -0.019(3) -0.007(3) C19 0.058(3) 0.082(3) 0.081(4) 0.006(3) -0.005(3) -0.001(2) 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' 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 C5 O2 C9 118.5(3) O1 C1 C6 121.0(5) O1 C1 C2 121.3(5) C6 C1 C2 117.7(4) C1 C2 C3 114.5(4) C1 C2 H2A 108.6 C3 C2 H2A 108.6 C1 C2 H2B 108.6 C3 C2 H2B 108.6 H2A C2 H2B 107.6 C19 C3 C4 109.7(3) C19 C3 C2 109.8(4) C4 C3 C2 108.1(4) C19 C3 C18 109.0(4) C4 C3 C18 109.4(4) C2 C3 C18 110.9(4) C5 C4 C3 113.6(3) C5 C4 H4A 108.9 C3 C4 H4A 108.9 C5 C4 H4B 108.9 C3 C4 H4B 108.9 H4A C4 H4B 107.7 C6 C5 O2 122.8(3) C6 C5 C4 124.3(4) O2 C5 C4 112.8(3) C5 C6 C7 118.1(4) C5 C6 C1 120.0(4) C7 C6 C1 121.8(4) C8 C7 C6 120.7(4) C8 C7 H7 119.6 C6 C7 H7 119.6 C7 C8 C9 119.8(4) C7 C8 H8 120.1 C9 C8 H8 120.1 O2 C9 C8 114.8(3) O2 C9 C10 112.8(3) C8 C9 C10 122.8(4) O2 C9 C11 113.4(3) C8 C9 C11 121.9(3) C10 C9 C11 60.2(3) C9 C10 C11 61.1(3) C9 C10 H10A 117.7 C11 C10 H10A 117.7 C9 C10 H10B 117.7 C11 C10 H10B 117.7 H10A C10 H10B 114.8 C12 C11 C10 123.9(4) C12 C11 C9 123.1(3) C10 C11 C9 58.7(3) C12 C11 H11 113.5 C10 C11 H11 113.5 C9 C11 H11 113.5 C17 C12 C13 116.9(4) C17 C12 C11 118.6(4) C13 C12 C11 124.4(4) C14 C13 C12 122.2(4) C14 C13 H13 118.9 C12 C13 H13 118.9 C15 C14 C13 119.9(5) C15 C14 H14 120.1 C13 C14 H14 120.1 C16 C15 C14 119.7(5) C16 C15 Br1 120.2(5) C14 C15 Br1 120.1(4) C15 C16 C17 119.5(5) C15 C16 H16 120.2 C17 C16 H16 120.2 C12 C17 C16 121.7(4) C12 C17 H17 119.2 C16 C17 H17 119.2 C3 C18 H18A 109.5 C3 C18 H18B 109.5 H18A C18 H18B 109.5 C3 C18 H18C 109.5 H18A C18 H18C 109.5 H18B C18 H18C 109.5 C3 C19 H19A 109.5 C3 C19 H19B 109.5 H19A C19 H19B 109.5 C3 C19 H19C 109.5 H19A C19 H19C 109.5 H19B C19 H19C 109.5 loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance Br1 C15 1.881(5) O1 C1 1.227(5) O2 C5 1.345(4) O2 C9 1.435(4) C1 C6 1.446(6) C1 C2 1.491(6) C2 C3 1.526(5) C2 H2A 0.9700 C2 H2B 0.9700 C3 C19 1.522(6) C3 C4 1.525(5) C3 C18 1.535(5) C4 C5 1.489(5) C4 H4A 0.9700 C4 H4B 0.9700 C5 C6 1.338(5) C6 C7 1.444(6) C7 C8 1.316(5) C7 H7 0.9300 C8 C9 1.461(5) C8 H8 0.9300 C9 C10 1.485(6) C9 C11 1.522(5) C10 C11 1.509(6) C10 H10A 0.9700 C10 H10B 0.9700 C11 C12 1.479(5) C11 H11 0.9800 C12 C17 1.365(6) C12 C13 1.373(5) C13 C14 1.371(5) C13 H13 0.9300 C14 C15 1.366(6) C14 H14 0.9300 C15 C16 1.356(7) C16 C17 1.397(6) C16 H16 0.9300 C17 H17 0.9300 C18 H18A 0.9600 C18 H18B 0.9600 C18 H18C 0.9600 C19 H19A 0.9600 C19 H19B 0.9600 C19 H19C 0.9600 loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A C17 H17 Br1 0.93 3.35 3.695(5) 104.8 5_657 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 O1 C1 C2 C3 -146.5(4) C6 C1 C2 C3 33.3(6) C1 C2 C3 C19 67.0(5) C1 C2 C3 C4 -52.6(5) C1 C2 C3 C18 -172.6(4) C19 C3 C4 C5 -74.0(5) C2 C3 C4 C5 45.6(5) C18 C3 C4 C5 166.5(4) C9 O2 C5 C6 -16.1(5) C9 O2 C5 C4 166.4(3) C3 C4 C5 C6 -20.8(6) C3 C4 C5 O2 156.8(3) O2 C5 C6 C7 -2.9(6) C4 C5 C6 C7 174.4(4) O2 C5 C6 C1 -178.9(4) C4 C5 C6 C1 -1.6(6) O1 C1 C6 C5 175.2(4) C2 C1 C6 C5 -4.7(6) O1 C1 C6 C7 -0.7(7) C2 C1 C6 C7 179.5(4) C5 C6 C7 C8 10.4(6) C1 C6 C7 C8 -173.7(4) C6 C7 C8 C9 1.6(6) C5 O2 C9 C8 26.7(5) C5 O2 C9 C10 174.0(4) C5 O2 C9 C11 -119.9(4) C7 C8 C9 O2 -19.6(6) C7 C8 C9 C10 -163.3(4) C7 C8 C9 C11 123.9(5) O2 C9 C10 C11 104.8(4) C8 C9 C10 C11 -110.8(4) C9 C10 C11 C12 111.2(4) O2 C9 C11 C12 143.7(4) C8 C9 C11 C12 -0.2(6) C10 C9 C11 C12 -112.5(5) O2 C9 C11 C10 -103.8(4) C8 C9 C11 C10 112.3(5) C10 C11 C12 C17 166.4(4) C9 C11 C12 C17 -121.6(5) C10 C11 C12 C13 -14.7(6) C9 C11 C12 C13 57.3(6) C17 C12 C13 C14 -1.3(6) C11 C12 C13 C14 179.8(4) C12 C13 C14 C15 1.4(7) C13 C14 C15 C16 -0.4(7) C13 C14 C15 Br1 -179.3(3) C14 C15 C16 C17 -0.6(7) Br1 C15 C16 C17 178.3(3) C13 C12 C17 C16 0.2(6) C11 C12 C17 C16 179.2(4) C15 C16 C17 C12 0.7(7) _journal_paper_doi 10.1021/ol102002f