Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2004 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Professor Sunney I. Chan' _publ_contact_author_address ; Institute of Chemistry Academia Sinica 128 Academia Road Section 2 Nankang Taipei 115 TAIWAN ; _publ_contact_author_email chans@chem.sinica.edu.tw _publ_contact_author_phone 886-2-2789-8654 _publ_contact_author_fax 886-2-2789-8654 _publ_section_title ; Spectroscopic Characterization of the Oxo-Transfer Reaction from a Bis(m-oxo)dicopper(III) complex to Triphenylphosphine ; loop_ _publ_author_name 'Sunney I. Chan' 'Svetlana V. Pavlova' 'Kelvin H.-C. Chen' data_compound_1 _database_code_depnum_ccdc_archive 'CCDC 245728' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C20 H50 Cl2 Cu2 N4 O10' _chemical_formula_sum 'C20 H50 Cl2 Cu2 N4 O10' _chemical_formula_weight 704.62 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 '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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 7.6177(10) _cell_length_b 17.850(3) _cell_length_c 13.9471(17) _cell_angle_alpha 90 _cell_angle_beta 122.147(12) _cell_angle_gamma 90 _cell_volume 1605.7(4) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 7.472 _cell_measurement_theta_max 16.420 _exptl_crystal_description prism _exptl_crystal_colour 'dark red' _exptl_crystal_size_max 0.3025 _exptl_crystal_size_mid 0.1875 _exptl_crystal_size_min 0.036 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.453 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 740 _exptl_absorpt_coefficient_mu 1.542 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_correction_T_min 0.8568 _exptl_absorpt_correction_T_max 0.9448 _exptl_absorpt_process_details ; North A.C.T., Phillips D.C. & Mathews F.S. (1968) Acta. Cryst. A24, 351 Number of psi-scan sets used was 4 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Enraf Nonius TurboCAD4' _diffrn_measurement_method 'non-profiled omega/2theta scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 3 _diffrn_reflns_number 3036 _diffrn_reflns_av_R_equivalents 0.0220 _diffrn_reflns_av_sigmaI/netI 0.0413 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.07 _diffrn_reflns_theta_max 25.00 _reflns_number_total 2814 _reflns_number_gt 1880 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CAD4 Express (Enraf Nonius, 1994)' _computing_cell_refinement 'CAD4 Express (Enraf Nonius, 1994)' _computing_data_reduction 'XCAD4 (Harms & Wocadlo, 1995)' _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)' _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^ > 2sigma(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^)+(0.0523P)^2^+0.8147P] 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 noref _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0040(7) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2814 _refine_ls_number_parameters 201 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0740 _refine_ls_R_factor_gt 0.0355 _refine_ls_wR_factor_ref 0.1084 _refine_ls_wR_factor_gt 0.0935 _refine_ls_goodness_of_fit_ref 1.023 _refine_ls_restrained_S_all 1.023 _refine_ls_shift/su_max 0.140 _refine_ls_shift/su_mean 0.001 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 0.8842(8) 0.1496(2) 0.2341(3) 0.0654(13) Uani 1 1 d . . . H11A H 0.7736 0.1783 0.2314 0.067(15) Uiso 1 1 d R . . H11B H 0.8725 0.1551 0.1618 0.056(11) Uiso 1 1 d R . . C2 C 1.0871(8) 0.1796(3) 0.3254(3) 0.0720(15) Uani 1 1 d . . . H12A H 1.1969 0.1587 0.3181 0.11(2) Uiso 1 1 d R . . H12B H 1.0885 0.2336 0.3179 0.069(13) Uiso 1 1 d R . . C3 C 0.6402(6) 0.0465(2) 0.1867(3) 0.0579(11) Uani 1 1 d . . . H3A H 0.5773 0.0666 0.1107 0.074(14) Uiso 1 1 d R . . H3B H 0.6322 -0.0077 0.1807 0.041(10) Uiso 1 1 d R . . C4 C 0.5189(9) 0.0729(3) 0.2373(5) 0.0812(15) Uani 1 1 d . . . H4A H 0.3773 0.0572 0.1896 0.10(2) Uiso 1 1 d R . . H4B H 0.5767 0.0517 0.3114 0.10(2) Uiso 1 1 d R . . H4C H 0.5247 0.1266 0.2428 0.12(2) Uiso 1 1 d R . . C5 C 0.9864(8) 0.0170(3) 0.2240(4) 0.0689(13) Uani 1 1 d . . . H5A H 0.9923 -0.0325 0.2542 0.094(18) Uiso 1 1 d R . . H5B H 1.1294 0.0356 0.2640 0.11(2) Uiso 1 1 d R . . C6 C 0.9099(11) 0.0094(4) 0.1006(5) 0.103(2) Uani 1 1 d . . . H6A H 1.0022 -0.0233 0.0933 0.18(4) Uiso 1 1 d R . . H6B H 0.7726 -0.0112 0.0597 2.0(9) Uiso 1 1 d R . . H6C H 0.9091 0.0577 0.0704 0.21(4) Uiso 1 1 d R . . C7 C 1.0127(8) 0.2129(2) 0.4729(5) 0.0693(13) Uani 1 1 d . . . H7A H 0.8665 0.2119 0.4142 0.064(13) Uiso 1 1 d R . . H7B H 1.0264 0.1938 0.5417 0.073(15) Uiso 1 1 d R . . C8 C 1.0880(12) 0.2943(3) 0.4944(8) 0.112(2) Uani 1 1 d . . . H8A H 1.0078 0.3226 0.5163 0.20(4) Uiso 1 1 d R . . H8B H 1.2319 0.2965 0.5535 0.17(4) Uiso 1 1 d R . . H8C H 1.0698 0.3149 0.4261 0.21(5) Uiso 1 1 d R . . C9 C 1.3513(7) 0.1638(3) 0.5261(4) 0.0665(12) Uani 1 1 d . . . H9A H 1.4089 0.2096 0.5165 0.087(16) Uiso 1 1 d R . . H9B H 1.3698 0.1655 0.6005 0.11(2) Uiso 1 1 d R . . C10 C 1.4721(9) 0.0984(4) 0.5212(5) 0.0911(17) Uani 1 1 d . . . H10A H 1.6158 0.1036 0.5796 0.11(2) Uiso 1 1 d R . . H10B H 1.4188 0.0528 0.5326 0.10(2) Uiso 1 1 d R . . H10C H 1.4581 0.0970 0.4486 0.14(3) Uiso 1 1 d R . . Cl Cl 0.47656(18) 0.32798(6) 0.33994(9) 0.0631(3) Uani 1 1 d . . . Cu Cu 0.99651(8) 0.05867(2) 0.42211(4) 0.04512(18) Uani 1 1 d . . . N1 N 0.8616(5) 0.06938(17) 0.2530(2) 0.0469(8) Uani 1 1 d . . . N2 N 1.1248(5) 0.16092(17) 0.4389(3) 0.0504(8) Uani 1 1 d . . . O1 O 0.9118(6) -0.04162(16) 0.4237(3) 0.0679(10) Uani 1 1 d . . . O11 O 0.2644(5) 0.34876(19) 0.2680(3) 0.0857(11) Uani 1 1 d . . . O12 O 0.4952(7) 0.2544(2) 0.3119(4) 0.1289(18) Uani 1 1 d . . . O13 O 0.5978(6) 0.3771(2) 0.3209(4) 0.1129(14) Uani 1 1 d . . . O14 O 0.5335(8) 0.3312(3) 0.4514(3) 0.1359(19) Uani 1 1 d . . . H2 H 0.850(7) -0.066(2) 0.380(4) 0.057(15) Uiso 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 0.080(3) 0.057(3) 0.042(2) 0.0087(19) 0.021(2) -0.020(3) C2 0.095(4) 0.063(3) 0.049(2) 0.004(2) 0.032(2) -0.032(3) C3 0.061(3) 0.052(2) 0.047(2) -0.0012(19) 0.020(2) -0.013(2) C4 0.076(4) 0.072(4) 0.100(4) 0.001(3) 0.049(3) 0.003(3) C5 0.067(3) 0.092(4) 0.056(3) -0.010(3) 0.039(3) -0.014(3) C6 0.140(6) 0.115(5) 0.071(4) -0.011(4) 0.067(4) -0.008(5) C7 0.070(3) 0.047(3) 0.084(3) -0.008(2) 0.036(3) 0.000(2) C8 0.119(6) 0.048(3) 0.163(7) -0.017(4) 0.073(6) -0.001(3) C9 0.067(3) 0.060(3) 0.059(3) 0.000(2) 0.025(2) -0.012(2) C10 0.074(4) 0.095(5) 0.094(4) 0.004(3) 0.038(3) 0.015(3) Cl 0.0770(8) 0.0459(6) 0.0552(6) 0.0033(5) 0.0276(6) 0.0029(5) Cu 0.0644(3) 0.0334(2) 0.0353(3) -0.00118(19) 0.0250(2) -0.0084(2) N1 0.0553(19) 0.0455(18) 0.0365(15) 0.0002(14) 0.0221(15) -0.0077(15) N2 0.064(2) 0.0411(17) 0.0427(17) -0.0008(14) 0.0258(17) -0.0096(16) O1 0.116(3) 0.0392(16) 0.0361(15) -0.0059(13) 0.0319(18) -0.0277(17) O11 0.078(2) 0.073(2) 0.084(2) 0.0212(19) 0.028(2) 0.0132(19) O12 0.112(3) 0.067(3) 0.183(5) -0.021(3) 0.062(3) 0.018(2) O13 0.099(3) 0.107(3) 0.140(4) 0.022(3) 0.069(3) -0.015(3) O14 0.156(4) 0.166(5) 0.055(2) -0.007(3) 0.036(3) -0.033(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 N1 1.483(5) . ? C1 C2 1.484(6) . ? C1 H11A 0.9691 . ? C1 H11B 0.9700 . ? C2 N2 1.488(5) . ? C2 H12A 0.9695 . ? C2 H12B 0.9701 . ? C3 N1 1.486(5) . ? C3 C4 1.506(7) . ? C3 H3A 0.9700 . ? C3 H3B 0.9702 . ? C4 H4A 0.9602 . ? C4 H4B 0.9598 . ? C4 H4C 0.9600 . ? C5 C6 1.500(6) . ? C5 N1 1.533(6) . ? C5 H5A 0.9699 . ? C5 H5B 0.9808 . ? C6 H6A 0.9586 . ? C6 H6B 0.9597 . ? C6 H6C 0.9597 . ? C7 N2 1.497(5) . ? C7 C8 1.533(7) . ? C7 H7A 0.9700 . ? C7 H7B 0.9702 . ? C8 H8A 0.9589 . ? C8 H8B 0.9598 . ? C8 H8C 0.9600 . ? C9 N2 1.492(5) . ? C9 C10 1.510(7) . ? C9 H9A 0.9707 . ? C9 H9B 0.9698 . ? C10 H10A 0.9600 . ? C10 H10B 0.9606 . ? C10 H10C 0.9599 . ? Cl O14 1.375(4) . ? Cl O13 1.398(4) . ? Cl O12 1.399(4) . ? Cl O11 1.425(4) . ? Cu O1 1.899(3) 3_756 ? Cu O1 1.908(3) . ? Cu N1 2.018(3) . ? Cu N2 2.026(3) . ? Cu Cu 2.9992(9) 3_756 ? O1 Cu 1.899(3) 3_756 ? O1 H2 0.68(4) . ? 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 N1 C1 C2 111.3(4) . . ? N1 C1 H11A 109.6 . . ? C2 C1 H11A 109.3 . . ? N1 C1 H11B 109.2 . . ? C2 C1 H11B 109.4 . . ? H11A C1 H11B 107.9 . . ? C1 C2 N2 110.8(4) . . ? C1 C2 H12A 109.5 . . ? N2 C2 H12A 109.7 . . ? C1 C2 H12B 109.4 . . ? N2 C2 H12B 109.3 . . ? H12A C2 H12B 108.0 . . ? N1 C3 C4 113.5(4) . . ? N1 C3 H3A 108.4 . . ? C4 C3 H3A 109.1 . . ? N1 C3 H3B 109.1 . . ? C4 C3 H3B 108.9 . . ? H3A C3 H3B 107.7 . . ? C3 C4 H4A 109.1 . . ? C3 C4 H4B 109.8 . . ? H4A C4 H4B 109.4 . . ? C3 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? C6 C5 N1 116.2(5) . . ? C6 C5 H5A 108.5 . . ? N1 C5 H5A 109.3 . . ? C6 C5 H5B 108.7 . . ? N1 C5 H5B 107.4 . . ? H5A C5 H5B 106.4 . . ? C5 C6 H6A 108.5 . . ? C5 C6 H6B 110.6 . . ? H6A C6 H6B 109.4 . . ? C5 C6 H6C 109.3 . . ? H6A C6 H6C 109.4 . . ? H6B C6 H6C 109.5 . . ? N2 C7 C8 115.5(5) . . ? N2 C7 H7A 108.2 . . ? C8 C7 H7A 109.0 . . ? N2 C7 H7B 108.4 . . ? C8 C7 H7B 108.0 . . ? H7A C7 H7B 107.4 . . ? C7 C8 H8A 109.0 . . ? C7 C8 H8B 110.2 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.2 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.4 . . ? N2 C9 C10 113.8(4) . . ? N2 C9 H9A 109.2 . . ? C10 C9 H9A 108.2 . . ? N2 C9 H9B 108.7 . . ? C10 C9 H9B 109.1 . . ? H9A C9 H9B 107.7 . . ? C9 C10 H10A 109.5 . . ? C9 C10 H10B 109.0 . . ? H10A C10 H10B 109.5 . . ? C9 C10 H10C 109.9 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? O14 Cl O13 110.2(3) . . ? O14 Cl O12 109.7(3) . . ? O13 Cl O12 111.2(3) . . ? O14 Cl O11 110.0(3) . . ? O13 Cl O11 108.7(2) . . ? O12 Cl O11 107.0(3) . . ? O1 Cu O1 76.03(14) 3_756 . ? O1 Cu N1 171.86(14) 3_756 . ? O1 Cu N1 97.93(12) . . ? O1 Cu N2 98.61(13) 3_756 . ? O1 Cu N2 172.11(15) . . ? N1 Cu N2 87.93(12) . . ? O1 Cu Cu 38.12(9) 3_756 3_756 ? O1 Cu Cu 37.91(9) . 3_756 ? N1 Cu Cu 135.60(9) . 3_756 ? N2 Cu Cu 136.46(9) . 3_756 ? C1 N1 C3 110.9(3) . . ? C1 N1 C5 113.2(4) . . ? C3 N1 C5 109.0(3) . . ? C1 N1 Cu 105.3(2) . . ? C3 N1 Cu 113.9(2) . . ? C5 N1 Cu 104.4(2) . . ? C2 N2 C9 110.1(3) . . ? C2 N2 C7 112.2(4) . . ? C9 N2 C7 109.0(3) . . ? C2 N2 Cu 105.7(2) . . ? C9 N2 Cu 113.8(3) . . ? C7 N2 Cu 105.8(3) . . ? Cu O1 Cu 103.97(14) 3_756 . ? Cu O1 H2 125(4) 3_756 . ? Cu O1 H2 131(4) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 24.98 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.499 _refine_diff_density_min -0.349 _refine_diff_density_rms 0.062