# Supplementary Material (ESI) for Perkin Transactions # This journal is © The Royal Society of Chemistry 1999 # CCDC Number: 188/191 data_3e _publ_contact_author_name ' Takumi Oshima ' _publ_contact_author_address ; Department of Applied Chemistry Graduate School of Engineering Osaka University 1-16 Machikaneyama, Toyonaka Osaka 560-0043, Japan ; _publ_contact_author_phone ' +81-6-6850-5771 ' _publ_contact_author_fax ' +81-6-6850-5785 ' _publ_contact_author_email ' oshima@ch.wani.osaka-u.ac.jp ' _publ_requested_journal ' J. Chem. Soc., Perkin Trans. 2 ' _publ_section_title ; Kinetic Study of Thermolysis of Diarylhomonaphthoquinones. Endo/exo substituent and Solvent Effects ; _computing_data_collection 'MSC/AFC Diffractometer Control' _computing_cell_refinement 'MSC/AFC Diffractometer Control' _computing_data_reduction 'teXsan' _computing_structure_solution SHELXS86 _computing_structure_refinement 'teXsan' _computing_publication_material 'teXsan' _computing_molecular_graphics 'ORTEPII' _chemical_compound_source ? _chemical_name_common '2-bromo-3-diphenylmethylene-2,3-dihydro-1,4-naphthoquinone ' _chemical_formula_weight 403.27 _chemical_formula_analytical ? _chemical_formula_sum 'C23 H15 Br O2 ' _chemical_formula_moiety 'C23 H15 Br O2 ' _chemical_formula_structural ? _chemical_melting_point ' 170-171 ' _cell_length_a 18.062(4) _cell_length_b 19.795(9) _cell_length_c 9.931(2) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 3550(1) _cell_formula_units_Z 8 _cell_measurement_temperature 296.2 _cell_measurement_reflns_used 12 _cell_measurement_theta_min 22.5 _cell_measurement_theta_max 25.0 _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P b c a ' _symmetry_Int_Tables_number 61 _symmetry_space_group_name_Hall ? loop_ _symmetry_equiv_pos_as_xyz x,y,z 1/2+x,1/2-y,-z -x,1/2+y,1/2-z 1/2-x,-y,1/2+z -x,-y,-z 1/2-x,1/2+y,z x,1/2-y,1/2+z 1/2+x,y,1/2-z _exptl_crystal_description 'prismatic' _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.20 _exptl_crystal_density_diffrn 1.508 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1632 _exptl_absorpt_coefficient_mu 2.33 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_process_details '(North, Phillips & Mathews, 1968)' _exptl_absorpt_correction_T_min 0.574 _exptl_absorpt_correction_T_max 0.631 _diffrn_ambient_temperature 296.2 _diffrn_radiation_wavelength 0.7107 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'Rigaku rotating anode' _diffrn_radiation_monochromator graphite _diffrn_radiation_detector 'scintillation counter' _diffrn_measurement_device_type 'Rigaku AFC5R' _diffrn_measurement_method \w-2\q _diffrn_standards_number 3 _diffrn_standards_interval_count 100 _diffrn_standards_decay_% 1.35 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l 3 -2 -1 0 -4 -1 2 -5 0 _diffrn_reflns_number 5705 _reflns_number_total 5133 _reflns_number_gt 1712 _reflns_threshold_expression I>2\s(I) _diffrn_reflns_av_R_equivalents 0.00 _diffrn_reflns_av_sigmaI/netI 0.20 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.00 _diffrn_reflns_theta_max 30.0 _diffrn_reflns_reduction_process 'Lp corrections applied' loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.003 0.002 ;International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.1) ; 'H' 'H' 0.000 0.000 ;International Tables for Crystallography (1992, Vol. C, Table 6.1.1.2) ; 'O' 'O' 0.011 0.006 ;International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.1) ; 'Br' 'Br' -0.290 2.459 ;International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.1) ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[\s^2^(Fo^2^) + 0.0011(Fo^2^)^2^]' _refine_ls_hydrogen_treatment noref _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details ? _refine_ls_abs_structure_Flack ? _refine_ls_number_reflns 5133 _refine_ls_number_parameters 235 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_R_factor_all 0.260 _refine_ls_R_factor_gt 0.063 _refine_ls_wR_factor_all ? _refine_ls_wR_factor_ref 0.170 _refine_ls_wR_factor_gt 0.110 _refine_ls_goodness_of_fit_all ? _refine_ls_goodness_of_fit_ref 0.936 _refine_ls_shift/su_max 0.007 _refine_ls_shift/su_mean 0.002 _refine_diff_density_min -1.25 _refine_diff_density_max 1.67 _atoms_sites_solution_primary ' direct methods ' _atoms_sites_solution_secondary ' difference Fourier maps ' _publ_section_exptl_refinement ; The structure was refined on F^2^ anisotropically for non-hydrogen atoms. All hydrogen atoms were fixed at geometrically calculated positions. Some unreasonable peaks of magnitudes in excess of 1 e \%A^-3^ were observed having distances 0.92 and 0.99 \%A from Br1, 0.68 \%A from C1, and 1.64 \%A from C21. ; 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 Br1 Br 0.10876(3) 0.35956(3) 0.78546(7) 0.0506(2) Uani O1 O 0.0877(2) 0.5036(2) 0.6061(4) 0.051(1) Uani O2 O -0.0313(2) 0.2611(2) 0.5301(4) 0.050(1) Uani C1 C -0.1017(3) 0.3584(3) 0.7121(5) 0.031(1) Uani C2 C -0.0334(3) 0.3625(3) 0.6586(5) 0.030(1) Uani C3 C 0.0257(3) 0.4098(3) 0.7009(6) 0.037(2) Uani C4 C 0.0626(3) 0.4475(3) 0.5865(6) 0.035(2) Uani C5 C 0.0645(3) 0.4160(3) 0.4523(6) 0.033(2) Uani C6 C 0.1012(3) 0.4468(3) 0.3480(7) 0.042(2) Uani C7 C 0.1020(3) 0.4174(4) 0.2235(7) 0.054(2) Uani C8 C 0.0679(3) 0.3561(3) 0.2013(6) 0.050(2) Uani C9 C 0.0322(3) 0.3237(3) 0.3052(6) 0.041(2) Uani C10 C 0.0299(3) 0.3537(3) 0.4316(5) 0.032(2) Uani C11 C -0.0136(3) 0.3198(3) 0.5385(6) 0.036(2) Uani C12 C -0.1249(3) 0.3933(3) 0.8392(6) 0.036(2) Uani C13 C -0.0805(3) 0.3955(3) 0.9517(6) 0.043(2) Uani C14 C -0.1037(4) 0.4276(3) 1.0683(6) 0.056(2) Uani C15 C -0.1725(4) 0.4575(4) 1.0729(7) 0.064(2) Uani C16 C -0.2183(3) 0.4545(3) 0.9625(8) 0.056(2) Uani C17 C -0.1951(3) 0.4223(3) 0.8469(6) 0.044(2) Uani C18 C -0.1616(3) 0.3222(3) 0.6401(6) 0.039(2) Uani C19 C -0.1899(4) 0.2622(4) 0.6865(7) 0.064(2) Uani C20 C -0.2479(5) 0.2316(4) 0.6157(9) 0.085(3) Uani C21 C -0.2773(4) 0.2618(6) 0.5060(9) 0.085(3) Uani C22 C -0.2508(5) 0.3212(5) 0.4613(8) 0.077(3) Uani C23 C -0.1928(3) 0.3518(4) 0.5283(7) 0.055(2) Uani H1 H 0.0061 0.4413 0.7637 0.0439 Uiso H2 H 0.1261 0.4885 0.3623 0.0504 Uiso H3 H 0.1264 0.4395 0.1511 0.0645 Uiso H4 H 0.0690 0.3362 0.1143 0.0603 Uiso H5 H 0.0093 0.2811 0.2906 0.0492 Uiso H6 H -0.0331 0.3746 0.9494 0.0518 Uiso H7 H -0.0722 0.4290 1.1449 0.0676 Uiso H8 H -0.1883 0.4802 1.1522 0.0764 Uiso H9 H -0.2660 0.4747 0.9658 0.0677 Uiso H10 H -0.2274 0.4198 0.7716 0.0530 Uiso H11 H -0.1705 0.2418 0.7655 0.0769 Uiso H12 H -0.2668 0.1893 0.6451 0.1026 Uiso H13 H -0.3171 0.2408 0.4597 0.1021 Uiso H14 H -0.2718 0.3420 0.3841 0.0926 Uiso H15 H -0.1743 0.3939 0.4968 0.0658 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_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Br1 0.0374(3) 0.0606(4) 0.0539(4) 0.0013(4) -0.0081(3) 0.0106(4) O1 0.058(3) 0.039(3) 0.057(3) -0.015(2) 0.010(2) -0.003(2) O2 0.061(3) 0.033(3) 0.057(3) -0.006(2) 0.015(2) -0.006(2) C1 0.031(3) 0.028(3) 0.034(3) 0.002(3) 0.001(3) 0.001(3) C2 0.028(3) 0.032(3) 0.030(3) 0.003(3) -0.002(2) 0.003(3) C3 0.029(3) 0.040(3) 0.041(4) 0.006(3) 0.002(3) 0.000(3) C4 0.027(3) 0.033(3) 0.045(4) -0.002(3) 0.000(3) 0.005(3) C5 0.031(3) 0.029(3) 0.039(4) 0.005(3) -0.002(3) 0.008(3) C6 0.034(3) 0.050(4) 0.042(3) -0.005(3) 0.000(3) 0.006(3) C7 0.049(4) 0.071(4) 0.041(4) 0.000(4) 0.007(4) 0.012(4) C8 0.051(4) 0.066(4) 0.034(4) 0.009(4) -0.003(3) -0.006(4) C9 0.051(4) 0.043(4) 0.030(4) 0.000(3) 0.003(3) -0.004(3) C10 0.029(3) 0.036(3) 0.033(3) 0.011(3) 0.001(2) 0.006(3) C11 0.037(3) 0.035(3) 0.035(3) 0.002(3) 0.003(3) 0.001(3) C12 0.035(4) 0.028(3) 0.044(4) -0.006(3) 0.001(3) 0.008(3) C13 0.049(4) 0.046(4) 0.035(4) 0.011(3) -0.003(3) 0.000(3) C14 0.064(5) 0.064(5) 0.041(4) 0.000(4) 0.004(4) -0.009(4) C15 0.064(5) 0.066(5) 0.061(5) 0.000(4) 0.014(4) -0.022(4) C16 0.032(3) 0.058(5) 0.079(5) 0.003(3) 0.014(4) -0.013(4) C17 0.040(3) 0.048(4) 0.045(4) 0.000(3) 0.005(3) 0.005(3) C18 0.031(3) 0.046(4) 0.041(4) -0.005(3) 0.007(3) -0.012(3) C19 0.063(4) 0.079(5) 0.050(5) -0.035(4) 0.002(4) -0.004(4) C20 0.078(6) 0.094(7) 0.084(6) -0.045(5) 0.032(5) -0.021(6) C21 0.055(5) 0.124(9) 0.076(7) -0.016(6) 0.011(5) -0.049(6) C22 0.059(5) 0.107(7) 0.066(5) 0.016(5) -0.017(5) -0.029(5) C23 0.050(4) 0.066(5) 0.049(4) 0.005(4) -0.011(3) -0.016(4) loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 BR1 C3 1.986(5) 1_555 1_555 O1 C4 1.216(6) 1_555 1_555 O2 C11 1.209(6) 1_555 1_555 C1 C2 1.346(7) 1_555 1_555 C1 C12 1.498(8) 1_555 1_555 C1 C18 1.482(7) 1_555 1_555 C2 C3 1.482(7) 1_555 1_555 C2 C11 1.505(7) 1_555 1_555 C3 C4 1.514(7) 1_555 1_555 C4 C5 1.472(8) 1_555 1_555 C5 C6 1.373(7) 1_555 1_555 C5 C10 1.397(7) 1_555 1_555 C6 C7 1.367(8) 1_555 1_555 C7 C8 1.379(9) 1_555 1_555 C8 C9 1.375(8) 1_555 1_555 C9 C10 1.389(7) 1_555 1_555 C10 C11 1.481(7) 1_555 1_555 C12 C13 1.376(8) 1_555 1_555 C12 C17 1.393(7) 1_555 1_555 C13 C14 1.386(8) 1_555 1_555 C14 C15 1.378(9) 1_555 1_555 C15 C16 1.375(9) 1_555 1_555 C16 C17 1.378(8) 1_555 1_555 C18 C19 1.372(9) 1_555 1_555 C18 C23 1.377(8) 1_555 1_555 C19 C20 1.398(10) 1_555 1_555 C20 C21 1.351(12) 1_555 1_555 C21 C22 1.344(12) 1_555 1_555 C22 C23 1.380(9) 1_555 1_555 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_2 _geom_angle_site_symmetry_3 C2 C1 C12 124.1(5) 1_555 1_555 1_555 C2 C1 C18 120.5(5) 1_555 1_555 1_555 C12 C1 C18 115.2(4) 1_555 1_555 1_555 C1 C2 C3 125.9(5) 1_555 1_555 1_555 C1 C2 C11 119.9(5) 1_555 1_555 1_555 C3 C2 C11 114.1(4) 1_555 1_555 1_555 BR1 C3 C2 110.3(4) 1_555 1_555 1_555 BR1 C3 C4 103.4(3) 1_555 1_555 1_555 C2 C3 C4 114.6(5) 1_555 1_555 1_555 O1 C4 C3 119.6(5) 1_555 1_555 1_555 O1 C4 C5 121.6(5) 1_555 1_555 1_555 C3 C4 C5 118.7(5) 1_555 1_555 1_555 C4 C5 C6 120.4(5) 1_555 1_555 1_555 C4 C5 C10 119.8(5) 1_555 1_555 1_555 C6 C5 C10 119.8(5) 1_555 1_555 1_555 C5 C6 C7 119.9(6) 1_555 1_555 1_555 C6 C7 C8 121.0(6) 1_555 1_555 1_555 C7 C8 C9 120.0(6) 1_555 1_555 1_555 C8 C9 C10 119.5(5) 1_555 1_555 1_555 C5 C10 C9 119.8(5) 1_555 1_555 1_555 C5 C10 C11 122.1(5) 1_555 1_555 1_555 C9 C10 C11 118.0(5) 1_555 1_555 1_555 O2 C11 C2 122.1(5) 1_555 1_555 1_555 O2 C11 C10 121.8(5) 1_555 1_555 1_555 C2 C11 C10 116.2(5) 1_555 1_555 1_555 C1 C12 C13 122.4(5) 1_555 1_555 1_555 C1 C12 C17 119.4(5) 1_555 1_555 1_555 C13 C12 C17 118.2(6) 1_555 1_555 1_555 C12 C13 C14 121.1(6) 1_555 1_555 1_555 C13 C14 C15 119.8(6) 1_555 1_555 1_555 C14 C15 C16 119.8(6) 1_555 1_555 1_555 C15 C16 C17 120.1(6) 1_555 1_555 1_555 C12 C17 C16 120.9(6) 1_555 1_555 1_555 C1 C18 C19 121.9(6) 1_555 1_555 1_555 C1 C18 C23 118.8(6) 1_555 1_555 1_555 C19 C18 C23 119.1(6) 1_555 1_555 1_555 C18 C19 C20 119.0(7) 1_555 1_555 1_555 C19 C20 C21 120.5(8) 1_555 1_555 1_555 C20 C21 C22 120.8(8) 1_555 1_555 1_555 C21 C22 C23 119.7(8) 1_555 1_555 1_555 C18 C23 C22 120.8(7) 1_555 1_555 1_555