# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name 'Li-Min Zheng' 'Yu Chen' 'Li-Rong Guo' 'Yizhi Li' 'Feng Zhu' _publ_contact_author_name 'Li-Min Zheng' _publ_contact_author_email LMZHENG@NETRA.NJU.EDU.CN _publ_section_title ; Magnetic and Electrochemical Properties of Layered Copper Compounds based on 4-(3-Bromothienyl)phosphonate (BTP): Weak Ferromagnetism Observed in [Cu2(4,4'-bpy)0.5(BTP)2]*H2O ; # Attachment '1#-Cu-Br-3TP.cif' data_1 _database_code_depnum_ccdc_archive 'CCDC 727738' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C4 H4 Br Cu O4 P S' _chemical_formula_sum 'C4 H4 Br Cu O4 P S' _chemical_formula_weight 322.55 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 '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' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/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 13.578(11) _cell_length_b 7.587(6) _cell_length_c 7.956(6) _cell_angle_alpha 90.00 _cell_angle_beta 99.822(12) _cell_angle_gamma 90.00 _cell_volume 807.5(11) _cell_formula_units_Z 4 _cell_measurement_temperature 291(2) _cell_measurement_reflns_used 979 _cell_measurement_theta_min 3.04 _cell_measurement_theta_max 24.32 _exptl_crystal_description plate _exptl_crystal_colour blue _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.653 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 620 _exptl_absorpt_coefficient_mu 8.074 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.16 _exptl_absorpt_correction_T_max 0.38 _exptl_absorpt_process_details 'SADABS: Bruker, 2000' _exptl_special_details ; ? ; _diffrn_ambient_temperature 291(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Smart Aepex CCD' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4183 _diffrn_reflns_av_R_equivalents 0.0444 _diffrn_reflns_av_sigmaI/netI 0.0487 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 3.05 _diffrn_reflns_theta_max 25.99 _reflns_number_total 1582 _reflns_number_gt 1302 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 2000)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker, 2000)' _computing_structure_solution 'SHELXTL (Bruker, 2000)' _computing_structure_refinement SHELXTL _computing_molecular_graphics SHELXTL _computing_publication_material SHELXTL _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^)+(0.08P)^2^+1.99P] 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_extinction_coef ? _refine_ls_number_reflns 1582 _refine_ls_number_parameters 109 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0738 _refine_ls_R_factor_gt 0.0556 _refine_ls_wR_factor_ref 0.1417 _refine_ls_wR_factor_gt 0.1348 _refine_ls_goodness_of_fit_ref 1.077 _refine_ls_restrained_S_all 1.077 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 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 Br1 Br 0.17442(6) 0.40162(11) 0.42235(11) 0.0402(3) Uani 1 1 d . . . C1 C 0.2586(7) 0.7542(11) 0.4365(10) 0.0372(19) Uani 1 1 d . . . C2 C 0.1718(6) 0.6521(11) 0.4192(12) 0.040(2) Uani 1 1 d . . . C3 C 0.0842(7) 0.7369(12) 0.4028(11) 0.0390(19) Uani 1 1 d . . . H3 H 0.0219 0.6835 0.3942 0.047 Uiso 1 1 calc R . . C4 C 0.2339(7) 0.9292(13) 0.4274(11) 0.045(2) Uani 1 1 d . . . H4 H 0.2798 1.0210 0.4348 0.054 Uiso 1 1 calc R . . Cu1 Cu 0.50025(7) 0.99680(11) 0.69128(11) 0.0258(3) Uani 1 1 d . . . O1 O 0.4035(4) 0.5811(8) 0.6289(7) 0.0373(13) Uani 1 1 d . . . O2 O 0.4498(5) 0.8583(8) 0.4836(7) 0.0402(14) Uani 1 1 d . . . O3 O 0.4003(4) 0.5813(8) 0.3088(8) 0.0398(14) Uani 1 1 d . . . O1W O 0.6278(4) 0.7500(8) 0.7788(7) 0.0399(14) Uani 1 1 d . . . H1A H 0.6428 0.8545 0.7540 0.048 Uiso 1 1 d R . . H1B H 0.6694 0.7138 0.8639 0.048 Uiso 1 1 d R . . P1 P 0.38630(18) 0.6866(3) 0.4664(3) 0.0398(6) Uani 1 1 d . . . S1 S 0.10510(17) 0.9563(3) 0.4002(3) 0.0392(5) 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 Br1 0.0422(5) 0.0382(5) 0.0421(5) -0.0044(4) 0.0127(4) -0.0098(4) C1 0.051(5) 0.030(4) 0.029(4) -0.008(3) 0.003(3) -0.001(4) C2 0.042(5) 0.027(4) 0.050(5) 0.013(4) 0.003(4) 0.004(4) C3 0.044(5) 0.038(5) 0.037(5) -0.001(4) 0.011(4) 0.004(4) C4 0.047(5) 0.048(5) 0.039(5) 0.005(4) 0.006(4) 0.004(4) Cu1 0.0314(5) 0.0237(5) 0.0230(5) 0.0024(3) 0.0070(4) -0.0024(4) O1 0.028(3) 0.046(3) 0.036(3) 0.001(3) 0.001(2) -0.004(2) O2 0.048(3) 0.035(3) 0.036(3) 0.006(2) 0.001(3) -0.008(3) O3 0.041(3) 0.035(3) 0.046(4) -0.007(3) 0.013(3) -0.001(3) O1W 0.037(3) 0.041(3) 0.045(3) 0.004(3) 0.016(3) 0.011(3) P1 0.0436(13) 0.0346(12) 0.0407(13) 0.0013(9) 0.0054(10) 0.0008(9) S1 0.0406(12) 0.0325(11) 0.0444(12) 0.0035(9) 0.0067(9) 0.0107(9) _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 Br1 C2 1.901(9) . ? C1 C4 1.368(12) . ? C1 C2 1.396(12) . ? C1 P1 1.785(9) . ? C2 C3 1.339(12) . ? C3 S1 1.690(9) . ? C3 H3 0.9300 . ? C4 S1 1.737(10) . ? C4 H4 0.9300 . ? Cu1 O3 1.871(6) 4_576 ? Cu1 O1 1.878(6) 2_656 ? Cu1 O2 1.979(6) . ? Cu1 O2 1.982(6) 3_676 ? Cu1 Cu1 3.043(3) 3_676 ? O1 P1 1.504(6) . ? O1 Cu1 1.878(6) 2_646 ? O2 P1 1.555(6) . ? O2 Cu1 1.982(6) 3_676 ? O3 P1 1.526(6) . ? O3 Cu1 1.871(6) 4_575 ? O1W H1A 0.8501 . ? O1W H1B 0.8499 . ? 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 C4 C1 C2 109.8(8) . . ? C4 C1 P1 120.6(7) . . ? C2 C1 P1 129.6(7) . . ? C3 C2 C1 117.6(9) . . ? C3 C2 Br1 119.7(7) . . ? C1 C2 Br1 122.6(7) . . ? C2 C3 S1 109.0(7) . . ? C2 C3 H3 125.5 . . ? S1 C3 H3 125.5 . . ? C1 C4 S1 110.7(8) . . ? C1 C4 H4 124.6 . . ? S1 C4 H4 124.6 . . ? O3 Cu1 O1 101.3(3) 4_576 2_656 ? O3 Cu1 O2 94.1(3) 4_576 . ? O1 Cu1 O2 156.1(3) 2_656 . ? O3 Cu1 O2 153.0(3) 4_576 3_676 ? O1 Cu1 O2 94.0(3) 2_656 3_676 ? O2 Cu1 O2 79.6(3) . 3_676 ? O3 Cu1 Cu1 128.8(2) 4_576 3_676 ? O1 Cu1 Cu1 129.75(19) 2_656 3_676 ? O2 Cu1 Cu1 39.84(17) . 3_676 ? O2 Cu1 Cu1 39.77(17) 3_676 3_676 ? P1 O1 Cu1 145.3(4) . 2_646 ? P1 O2 Cu1 128.8(4) . . ? P1 O2 Cu1 130.8(4) . 3_676 ? Cu1 O2 Cu1 100.4(3) . 3_676 ? P1 O3 Cu1 141.2(4) . 4_575 ? H1A O1W H1B 109.5 . . ? O1 P1 O3 113.9(4) . . ? O1 P1 O2 111.6(3) . . ? O3 P1 O2 111.5(4) . . ? O1 P1 C1 105.8(4) . . ? O3 P1 C1 107.1(3) . . ? O2 P1 C1 106.4(4) . . ? C3 S1 C4 92.8(5) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.99 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.561 _refine_diff_density_min -0.658 _refine_diff_density_rms 0.149 # Attachment '2#-Cu-44bpy-Br-3TP.cif' data_2 _database_code_depnum_ccdc_archive 'CCDC 727739' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C13 H8 Br2 Cu2 N O6 P2 S2, 0.5(H1.20 O0.60), 0.7(H2 O)' _chemical_formula_sum 'C13 H10 Br2 Cu2 N O7 P2 S2' _chemical_formula_weight 705.18 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 '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' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P-1 ' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 4.7153(9) _cell_length_b 14.432(3) _cell_length_c 17.623(3) _cell_angle_alpha 70.972(4) _cell_angle_beta 88.635(5) _cell_angle_gamma 85.609(4) _cell_volume 1130.5(4) _cell_formula_units_Z 2 _cell_measurement_temperature 291(2) _cell_measurement_reflns_used 1421 _cell_measurement_theta_min 2.59 _cell_measurement_theta_max 24.12 _exptl_crystal_description prism _exptl_crystal_colour blue _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.072 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 682 _exptl_absorpt_coefficient_mu 5.776 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.24 _exptl_absorpt_correction_T_max 0.32 _exptl_absorpt_process_details 'SADABS; Bruker, 2000' _exptl_special_details ; ? ; _diffrn_ambient_temperature 291(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Smart Apex CCD' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6161 _diffrn_reflns_av_R_equivalents 0.0229 _diffrn_reflns_av_sigmaI/netI 0.0527 _diffrn_reflns_limit_h_min -5 _diffrn_reflns_limit_h_max 5 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.22 _diffrn_reflns_theta_max 26.00 _reflns_number_total 4348 _reflns_number_gt 3401 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 2000)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker, 2000)' _computing_structure_solution 'SHELXTL (Bruker, 2000)' _computing_structure_refinement SHELXTL _computing_molecular_graphics SHELXTL _computing_publication_material SHELXTL _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^)+(0.07P)^2^+1.99P] 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_extinction_coef ? _refine_ls_number_reflns 4348 _refine_ls_number_parameters 277 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0755 _refine_ls_R_factor_gt 0.0514 _refine_ls_wR_factor_ref 0.1255 _refine_ls_wR_factor_gt 0.1176 _refine_ls_goodness_of_fit_ref 1.012 _refine_ls_restrained_S_all 1.012 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 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 Br1 Br 0.96537(15) 0.72626(5) 0.21943(4) 0.03993(19) Uani 1 1 d . . . Br2 Br 0.56569(16) 0.14418(5) 0.32323(4) 0.0462(2) Uani 1 1 d . . . C1 C 0.6384(15) 0.7049(5) 0.0897(4) 0.0379(15) Uani 1 1 d . . . C2 C 0.4475(15) 0.7569(5) 0.0294(4) 0.0396(16) Uani 1 1 d . . . H2 H 0.3638 0.7290 -0.0045 0.047 Uiso 1 1 calc R . . C3 C 0.6058(15) 0.8643(5) 0.1007(4) 0.0378(15) Uani 1 1 d . . . H3 H 0.6463 0.9145 0.1202 0.045 Uiso 1 1 calc R . . C4 C 0.7156(14) 0.7703(5) 0.1292(4) 0.0348(14) Uani 1 1 d . . . C5 C 0.9092(13) 0.1975(4) 0.1776(4) 0.0307(13) Uani 1 1 d . . . C6 C 0.8099(14) 0.1230(5) 0.2410(4) 0.0378(15) Uani 1 1 d . . . C7 C 0.8875(15) 0.0314(5) 0.2405(4) 0.0411(16) Uani 1 1 d . . . H7 H 0.8308 -0.0254 0.2788 0.049 Uiso 1 1 calc R . . C8 C 1.0692(14) 0.1554(5) 0.1305(4) 0.0366(15) Uani 1 1 d . . . H8 H 1.1568 0.1924 0.0837 0.044 Uiso 1 1 calc R . . C9 C 0.3197(14) 0.5200(5) 0.3423(4) 0.0344(14) Uani 1 1 d . . . H9 H 0.4535 0.5574 0.3088 0.041 Uiso 1 1 calc R . . C10 C 0.2352(14) 0.5432(5) 0.4113(4) 0.0361(15) Uani 1 1 d . . . H10 H 0.3074 0.5963 0.4212 0.043 Uiso 1 1 calc R . . C11 C 0.0480(15) 0.4882(5) 0.4636(4) 0.0359(14) Uani 1 1 d . . . C12 C -0.0566(15) 0.4127(5) 0.4428(4) 0.0386(15) Uani 1 1 d . . . H12 H -0.1882 0.3732 0.4755 0.046 Uiso 1 1 calc R . . C13 C 0.0376(16) 0.3967(5) 0.3726(4) 0.0421(16) Uani 1 1 d . . . H13 H -0.0344 0.3452 0.3600 0.050 Uiso 1 1 calc R . . Cu1 Cu 0.33625(16) 0.42073(6) 0.22284(5) 0.0322(2) Uani 1 1 d . . . Cu2 Cu 1.24906(16) 0.47526(5) 0.05274(4) 0.02860(19) Uani 1 1 d . . . N1 N 0.2216(11) 0.4492(4) 0.3226(3) 0.0321(11) Uani 1 1 d . . . O1 O 1.0381(10) 0.5517(3) 0.1105(2) 0.0365(10) Uani 1 1 d . . . O2 O 0.5757(9) 0.5550(3) 0.0407(2) 0.0339(10) Uani 1 1 d . . . O3 O 0.5864(10) 0.5278(3) 0.1921(3) 0.0391(11) Uani 1 1 d . . . O4 O 0.9918(10) 0.3726(4) 0.0786(3) 0.0389(11) Uani 1 1 d . . . O5 O 1.0121(10) 0.3442(3) 0.2287(3) 0.0402(11) Uani 1 1 d . . . O6 O 0.5428(10) 0.3530(3) 0.1597(3) 0.0356(10) Uani 1 1 d . . . O7 O 0.473(3) 0.7830(10) 0.4041(8) 0.050(3) Uani 0.40 1 d P . . H7A H 0.3900 0.8375 0.4189 0.061 Uiso 0.40 1 d PR . . H7C H 0.5771 0.8071 0.3550 0.061 Uiso 0.40 1 d PR . . O8 O 0.996(4) 0.8588(13) 0.4649(11) 0.051(4) Uani 0.30 1 d P . . H8D H 0.8423 0.8327 0.4629 0.061 Uiso 0.30 1 d PR . . H8B H 1.1194 0.8426 0.4346 0.061 Uiso 0.30 1 d PR . . O9 O 0.5000 1.0000 0.5000 0.048(3) Uani 0.60 2 d SP . . H9D H 0.6252 0.9614 0.4881 0.058 Uiso 0.30 1 d PR . . H9B H 0.3829 1.0236 0.4614 0.058 Uiso 0.30 1 d PR . . P1 P 0.7168(3) 0.57642(12) 0.11116(9) 0.0293(3) Uani 1 1 d . . . P2 P 0.8647(3) 0.32584(12) 0.16033(10) 0.0301(3) Uani 1 1 d . . . S1 S 0.3822(3) 0.87627(12) 0.02362(9) 0.0328(3) Uani 1 1 d . . . S2 S 1.0966(3) 0.03191(11) 0.16297(10) 0.0335(4) 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 Br1 0.0451(4) 0.0396(4) 0.0373(4) -0.0156(3) -0.0138(3) 0.0016(3) Br2 0.0481(4) 0.0435(4) 0.0331(4) 0.0074(3) 0.0033(3) -0.0088(3) C1 0.037(4) 0.035(3) 0.037(4) -0.008(3) 0.013(3) 0.000(3) C2 0.042(4) 0.038(4) 0.039(4) -0.015(3) 0.005(3) 0.007(3) C3 0.040(4) 0.040(4) 0.035(3) -0.014(3) 0.005(3) -0.001(3) C4 0.036(3) 0.034(3) 0.029(3) -0.004(3) 0.001(3) 0.001(3) C5 0.032(3) 0.027(3) 0.028(3) -0.002(2) -0.011(2) -0.002(2) C6 0.034(4) 0.034(3) 0.040(4) -0.004(3) 0.000(3) -0.003(3) C7 0.046(4) 0.033(4) 0.032(3) 0.007(3) -0.004(3) -0.008(3) C8 0.035(3) 0.029(3) 0.038(3) -0.001(3) 0.004(3) -0.001(3) C9 0.032(3) 0.037(3) 0.035(3) -0.014(3) 0.013(3) -0.003(3) C10 0.035(3) 0.034(3) 0.043(4) -0.014(3) 0.018(3) -0.020(3) C11 0.043(4) 0.037(4) 0.031(3) -0.017(3) 0.005(3) 0.000(3) C12 0.035(4) 0.053(4) 0.030(3) -0.015(3) 0.011(3) -0.014(3) C13 0.047(4) 0.046(4) 0.034(3) -0.011(3) 0.017(3) -0.019(3) Cu1 0.0330(4) 0.0308(4) 0.0347(4) -0.0128(3) 0.0071(3) -0.0070(3) Cu2 0.0330(4) 0.0297(4) 0.0282(4) -0.0155(3) 0.0083(3) -0.0084(3) N1 0.035(3) 0.030(3) 0.035(3) -0.015(2) 0.003(2) -0.003(2) O1 0.043(3) 0.043(3) 0.026(2) -0.015(2) 0.0096(19) -0.004(2) O2 0.030(2) 0.044(3) 0.026(2) -0.0103(19) 0.0007(17) -0.0012(19) O3 0.042(3) 0.041(3) 0.031(2) -0.007(2) -0.0011(19) -0.009(2) O4 0.042(3) 0.044(3) 0.029(2) -0.008(2) 0.0039(19) -0.014(2) O5 0.041(3) 0.042(3) 0.030(2) 0.001(2) 0.0034(19) -0.014(2) O6 0.041(3) 0.036(2) 0.031(2) -0.0101(19) 0.0033(19) -0.010(2) O7 0.048(8) 0.049(7) 0.058(8) -0.021(6) 0.024(6) -0.021(6) O8 0.056(11) 0.044(10) 0.050(10) -0.012(8) 0.008(8) -0.012(8) O9 0.050(7) 0.041(7) 0.043(7) 0.001(5) -0.005(5) -0.002(5) P1 0.0321(8) 0.0285(8) 0.0288(8) -0.0118(6) 0.0013(6) -0.0011(6) P2 0.0310(8) 0.0307(8) 0.0292(8) -0.0104(6) 0.0084(6) -0.0056(6) S1 0.0338(8) 0.0341(8) 0.0290(8) -0.0100(6) -0.0037(6) 0.0064(6) S2 0.0323(8) 0.0276(8) 0.0340(8) -0.0020(6) -0.0028(6) 0.0027(6) _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 Br1 C4 1.906(6) . ? Br2 C6 1.917(7) . ? C1 C2 1.387(10) . ? C1 C4 1.414(10) . ? C1 P1 1.779(7) . ? C2 S1 1.697(7) . ? C2 H2 0.9300 . ? C3 C4 1.350(10) . ? C3 S1 1.695(7) . ? C3 H3 0.9300 . ? C5 C8 1.362(9) . ? C5 C6 1.376(9) . ? C5 P2 1.774(6) . ? C6 C7 1.348(10) . ? C7 S2 1.664(8) . ? C7 H7 0.9300 . ? C8 S2 1.681(7) . ? C8 H8 0.9300 . ? C9 N1 1.300(8) . ? C9 C10 1.404(9) . ? C9 H9 0.9300 . ? C10 C11 1.361(9) . ? C10 H10 0.9300 . ? C11 C12 1.384(10) . ? C11 C11 1.482(12) 2_566 ? C12 C13 1.389(9) . ? C12 H12 0.9300 . ? C13 N1 1.317(8) . ? C13 H13 0.9300 . ? Cu1 O6 1.911(5) . ? Cu1 O5 1.935(5) 1_455 ? Cu1 O3 1.943(5) . ? Cu1 N1 1.985(5) . ? Cu1 Cu2 2.8716(12) 1_455 ? Cu2 O4 1.919(5) . ? Cu2 O1 1.939(4) . ? Cu2 O2 1.959(5) 1_655 ? Cu2 O2 1.984(4) 2_765 ? Cu2 Cu1 2.8716(12) 1_655 ? Cu2 Cu2 2.9271(16) 2_765 ? Cu2 Cu2 2.9580(15) 2_865 ? O1 P1 1.530(5) . ? O2 P1 1.549(5) . ? O2 Cu2 1.959(5) 1_455 ? O2 Cu2 1.984(4) 2_765 ? O3 P1 1.508(5) . ? O4 P2 1.509(5) . ? O5 P2 1.511(5) . ? O5 Cu1 1.935(5) 1_655 ? O6 P2 1.538(5) . ? O7 H7A 0.9600 . ? O7 H7C 0.9600 . ? O8 H8D 0.8501 . ? O8 H8B 0.8501 . ? O9 H9D 0.8500 . ? O9 H9B 0.8500 . ? 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 C2 C1 C4 107.4(6) . . ? C2 C1 P1 120.6(6) . . ? C4 C1 P1 131.7(5) . . ? C1 C2 S1 113.2(6) . . ? C1 C2 H2 123.4 . . ? S1 C2 H2 123.4 . . ? C4 C3 S1 109.1(6) . . ? C4 C3 H3 125.5 . . ? S1 C3 H3 125.5 . . ? C3 C4 C1 117.5(6) . . ? C3 C4 Br1 121.7(5) . . ? C1 C4 Br1 120.8(5) . . ? C8 C5 C6 107.7(6) . . ? C8 C5 P2 124.1(5) . . ? C6 C5 P2 128.0(6) . . ? C7 C6 C5 115.1(7) . . ? C7 C6 Br2 120.9(5) . . ? C5 C6 Br2 123.9(5) . . ? C6 C7 S2 112.0(5) . . ? C6 C7 H7 124.0 . . ? S2 C7 H7 124.0 . . ? C5 C8 S2 115.1(5) . . ? C5 C8 H8 122.4 . . ? S2 C8 H8 122.4 . . ? N1 C9 C10 123.7(6) . . ? N1 C9 H9 118.1 . . ? C10 C9 H9 118.1 . . ? C11 C10 C9 120.2(6) . . ? C11 C10 H10 119.9 . . ? C9 C10 H10 119.9 . . ? C10 C11 C12 116.1(6) . . ? C10 C11 C11 121.4(8) . 2_566 ? C12 C11 C11 122.4(8) . 2_566 ? C11 C12 C13 119.2(6) . . ? C11 C12 H12 120.4 . . ? C13 C12 H12 120.4 . . ? N1 C13 C12 124.6(7) . . ? N1 C13 H13 117.7 . . ? C12 C13 H13 117.7 . . ? O6 Cu1 O5 91.3(2) . 1_455 ? O6 Cu1 O3 92.5(2) . . ? O5 Cu1 O3 162.04(19) 1_455 . ? O6 Cu1 N1 156.0(2) . . ? O5 Cu1 N1 92.0(2) 1_455 . ? O3 Cu1 N1 91.7(2) . . ? O6 Cu1 Cu2 58.53(14) . 1_455 ? O5 Cu1 Cu2 83.75(13) 1_455 1_455 ? O3 Cu1 Cu2 83.29(13) . 1_455 ? N1 Cu1 Cu2 145.49(16) . 1_455 ? O4 Cu2 O1 95.0(2) . . ? O4 Cu2 O2 166.5(2) . 1_655 ? O1 Cu2 O2 91.32(19) . 1_655 ? O4 Cu2 O2 95.6(2) . 2_765 ? O1 Cu2 O2 157.61(19) . 2_765 ? O2 Cu2 O2 82.8(2) 1_655 2_765 ? O4 Cu2 Cu1 85.72(14) . 1_655 ? O1 Cu2 Cu1 61.86(14) . 1_655 ? O2 Cu2 Cu1 86.72(12) 1_655 1_655 ? O2 Cu2 Cu1 138.68(13) 2_765 1_655 ? O4 Cu2 Cu2 67.20(14) . 2_765 ? O1 Cu2 Cu2 84.60(14) . 2_765 ? O2 Cu2 Cu2 125.46(13) 1_655 2_765 ? O2 Cu2 Cu2 81.39(13) 2_765 2_765 ? Cu1 Cu2 Cu2 135.04(4) 1_655 2_765 ? O4 Cu2 Cu2 135.17(15) . 2_865 ? O1 Cu2 Cu2 129.45(15) . 2_865 ? O2 Cu2 Cu2 41.71(13) 1_655 2_865 ? O2 Cu2 Cu2 41.08(13) 2_765 2_865 ? Cu1 Cu2 Cu2 117.76(4) 1_655 2_865 ? Cu2 Cu2 Cu2 106.50(5) 2_765 2_865 ? C9 N1 C13 116.2(6) . . ? C9 N1 Cu1 122.8(5) . . ? C13 N1 Cu1 121.0(5) . . ? P1 O1 Cu2 128.4(3) . . ? P1 O2 Cu2 124.0(3) . 1_455 ? P1 O2 Cu2 130.0(3) . 2_765 ? Cu2 O2 Cu2 97.2(2) 1_455 2_765 ? P1 O3 Cu1 128.6(3) . . ? P2 O4 Cu2 125.2(3) . . ? P2 O5 Cu1 127.7(3) . 1_655 ? P2 O6 Cu1 127.9(3) . . ? H7A O7 H7C 109.5 . . ? H8D O8 H8B 109.5 . . ? H9D O9 H9B 109.5 . . ? O3 P1 O1 112.2(3) . . ? O3 P1 O2 114.2(3) . . ? O1 P1 O2 109.7(2) . . ? O3 P1 C1 106.0(3) . . ? O1 P1 C1 110.9(3) . . ? O2 P1 C1 103.4(3) . . ? O4 P2 O5 114.9(3) . . ? O4 P2 O6 110.8(3) . . ? O5 P2 O6 111.8(3) . . ? O4 P2 C5 105.2(3) . . ? O5 P2 C5 106.6(3) . . ? O6 P2 C5 106.9(3) . . ? C3 S1 C2 92.8(4) . . ? C7 S2 C8 90.0(3) . . ? _diffrn_measured_fraction_theta_max 0.979 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.979 _refine_diff_density_max 0.419 _refine_diff_density_min -0.738 _refine_diff_density_rms 0.115