# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Guo-Xin Jin' _publ_contact_author_email GXJIN@FUDAN.EDU.CN _publ_section_title ; Half-sandwich Iridium-Bsed Neutral Organometallic Macrocycles Containing Pyridine-4-Thiolato Ligands ; loop_ _publ_author_name 'Guo-Xin Jin' 'Ying-Feng Han' 'Wei-Guo Jia' 'Yue-Jian Lin' # Attachment 'Complex_1.cif' data_f80405a _database_code_depnum_ccdc_archive 'CCDC 698542' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C45 H57 Cl3 Ir3 N3 S3' _chemical_formula_weight 1419.07 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' S S 0.1246 0.1234 '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' Ir Ir -1.4442 7.9887 '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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.838(3) _cell_length_b 17.675(7) _cell_length_c 18.572(7) _cell_angle_alpha 68.877(5) _cell_angle_beta 85.029(6) _cell_angle_gamma 88.798(5) _cell_volume 2695.9(18) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 827 _cell_measurement_theta_min 2.506 _cell_measurement_theta_max 23.408 _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.748 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1356 _exptl_absorpt_coefficient_mu 7.682 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.3920 _exptl_absorpt_correction_T_max 0.5138 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CCD area detector' _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_% 11.00 _diffrn_reflns_number 11192 _diffrn_reflns_av_R_equivalents 0.0674 _diffrn_reflns_av_sigmaI/netI 0.1092 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.99 _diffrn_reflns_theta_max 25.01 _reflns_number_total 9285 _reflns_number_gt 5578 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker 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^)+(0.0609P)^2^+0.0000P] 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 9285 _refine_ls_number_parameters 529 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0872 _refine_ls_R_factor_gt 0.0531 _refine_ls_wR_factor_ref 0.1231 _refine_ls_wR_factor_gt 0.1160 _refine_ls_goodness_of_fit_ref 0.854 _refine_ls_restrained_S_all 0.854 _refine_ls_shift/su_max 0.005 _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 Ir1 Ir 0.24020(5) 1.11226(3) 0.26024(3) 0.04302(15) Uani 1 1 d . . . Ir2 Ir 0.33873(5) 0.74157(3) 0.09524(3) 0.04647(15) Uani 1 1 d . . . Ir3 Ir -0.24469(5) 0.69279(3) 0.47489(3) 0.04851(16) Uani 1 1 d . . . S1 S 0.4365(3) 1.0300(2) 0.2362(2) 0.0545(9) Uani 1 1 d . . . S2 S 0.0760(4) 0.7229(2) 0.1282(2) 0.0626(10) Uani 1 1 d . . . S3 S -0.2957(4) 0.8334(2) 0.4297(2) 0.0635(10) Uani 1 1 d . . . N1 N 0.3386(11) 0.8226(6) 0.1556(5) 0.045(3) Uani 1 1 d . . . N2 N -0.1226(10) 0.7154(6) 0.3648(5) 0.047(3) Uani 1 1 d . . . N3 N 0.0839(10) 1.0135(6) 0.2993(6) 0.045(2) Uani 1 1 d . . . Cl1 Cl 0.1420(4) 1.1472(2) 0.13526(19) 0.0633(9) Uani 1 1 d . . . Cl2 Cl 0.4169(4) 0.6339(2) 0.2106(2) 0.0663(9) Uani 1 1 d . . . Cl3 Cl -0.0089(4) 0.6963(2) 0.5326(2) 0.0666(10) Uani 1 1 d . . . C1 C 0.3903(13) 0.9506(8) 0.2080(7) 0.050(3) Uani 1 1 d . . . C2 C 0.2565(12) 0.9468(7) 0.1717(7) 0.044(3) Uani 1 1 d . . . H2 H 0.1819 0.9862 0.1638 0.053 Uiso 1 1 calc R . . C3 C 0.2441(12) 0.8807(8) 0.1488(6) 0.046(3) Uani 1 1 d . . . H3 H 0.1563 0.8781 0.1256 0.055 Uiso 1 1 calc R . . C4 C 0.4656(13) 0.8257(8) 0.1948(8) 0.054(3) Uani 1 1 d . . . H4 H 0.5345 0.7834 0.2043 0.065 Uiso 1 1 calc R . . C5 C 0.4926(12) 0.8860(8) 0.2191(7) 0.050(3) Uani 1 1 d . . . H5 H 0.5801 0.8854 0.2437 0.060 Uiso 1 1 calc R . . C6 C 0.0073(13) 0.7228(8) 0.2175(8) 0.060(4) Uani 1 1 d . . . C7 C -0.1391(13) 0.7451(10) 0.2320(8) 0.075(5) Uani 1 1 d . . . H7 H -0.1996 0.7649 0.1907 0.090 Uiso 1 1 calc R . . C8 C -0.1990(13) 0.7396(9) 0.3027(8) 0.063(4) Uani 1 1 d . . . H8 H -0.3002 0.7538 0.3081 0.075 Uiso 1 1 calc R . . C9 C 0.0206(14) 0.6940(8) 0.3559(8) 0.057(4) Uani 1 1 d . . . H9 H 0.0756 0.6748 0.3993 0.068 Uiso 1 1 calc R . . C10 C 0.0913(13) 0.6988(8) 0.2856(7) 0.057(4) Uani 1 1 d . . . H10 H 0.1938 0.6866 0.2817 0.069 Uiso 1 1 calc R . . C11 C -0.1435(14) 0.8976(8) 0.3769(8) 0.057(4) Uani 1 1 d . . . C12 C -0.1789(14) 0.9731(8) 0.3241(8) 0.062(4) Uani 1 1 d . . . H12 H -0.2791 0.9857 0.3133 0.074 Uiso 1 1 calc R . . C13 C -0.0658(14) 1.0286(8) 0.2882(8) 0.055(3) Uani 1 1 d . . . H13 H -0.0923 1.0794 0.2544 0.067 Uiso 1 1 calc R . . C14 C 0.1138(13) 0.9419(8) 0.3464(7) 0.051(3) Uani 1 1 d . . . H14 H 0.2153 0.9294 0.3542 0.062 Uiso 1 1 calc R . . C15 C 0.0069(12) 0.8827(8) 0.3860(7) 0.050(3) Uani 1 1 d . . . H15 H 0.0374 0.8324 0.4191 0.059 Uiso 1 1 calc R . . C16 C 0.3354(17) 1.1280(8) 0.3562(8) 0.061(4) Uani 1 1 d . . . C17 C 0.1788(14) 1.1487(9) 0.3573(8) 0.054(4) Uani 1 1 d . . . C18 C 0.1494(16) 1.2148(8) 0.2894(8) 0.061(4) Uani 1 1 d . . . C19 C 0.2912(18) 1.2358(8) 0.2437(8) 0.060(4) Uani 1 1 d . . . C20 C 0.4010(13) 1.1868(8) 0.2844(9) 0.053(4) Uani 1 1 d . . . C21 C 0.422(2) 1.0659(12) 0.4194(12) 0.133(8) Uani 1 1 d . . . H21A H 0.3514 1.0264 0.4548 0.199 Uiso 1 1 calc R . . H21B H 0.4725 1.0931 0.4469 0.199 Uiso 1 1 calc R . . H21C H 0.4954 1.0392 0.3959 0.199 Uiso 1 1 calc R . . C22 C 0.0670(19) 1.1062(11) 0.4254(9) 0.110(7) Uani 1 1 d . . . H22A H 0.0777 1.0485 0.4399 0.165 Uiso 1 1 calc R . . H22B H -0.0344 1.1212 0.4115 0.165 Uiso 1 1 calc R . . H22C H 0.0866 1.1217 0.4683 0.165 Uiso 1 1 calc R . . C23 C 0.0009(17) 1.2541(12) 0.2744(14) 0.134(9) Uani 1 1 d . . . H23A H -0.0765 1.2203 0.3103 0.200 Uiso 1 1 calc R . . H23B H -0.0209 1.2619 0.2224 0.200 Uiso 1 1 calc R . . H23C H 0.0034 1.3057 0.2805 0.200 Uiso 1 1 calc R . . C24 C 0.310(2) 1.3073(10) 0.1656(10) 0.116(7) Uani 1 1 d . . . H24A H 0.2488 1.3517 0.1686 0.175 Uiso 1 1 calc R . . H24B H 0.2782 1.2906 0.1254 0.175 Uiso 1 1 calc R . . H24C H 0.4147 1.3241 0.1541 0.175 Uiso 1 1 calc R . . C25 C 0.5741(16) 1.1930(12) 0.2556(13) 0.132(9) Uani 1 1 d . . . H25A H 0.6328 1.1674 0.2990 0.198 Uiso 1 1 calc R . . H25B H 0.6037 1.2491 0.2314 0.198 Uiso 1 1 calc R . . H25C H 0.5917 1.1664 0.2189 0.198 Uiso 1 1 calc R . . C26 C 0.3453(16) 0.8180(9) -0.0243(8) 0.064(4) Uani 1 1 d . . . C27 C 0.3062(14) 0.7379(9) -0.0169(7) 0.055(3) Uani 1 1 d . . . C28 C 0.4287(14) 0.6873(9) 0.0141(8) 0.061(4) Uani 1 1 d . . . C29 C 0.5498(13) 0.7366(9) 0.0259(8) 0.059(4) Uani 1 1 d . . . C30 C 0.4865(14) 0.8189(7) -0.0024(6) 0.045(3) Uani 1 1 d . . . C31 C 0.2513(18) 0.8924(10) -0.0613(10) 0.098(6) Uani 1 1 d . . . H31A H 0.2775 0.9345 -0.0431 0.148 Uiso 1 1 calc R . . H31B H 0.1454 0.8789 -0.0477 0.148 Uiso 1 1 calc R . . H31C H 0.2715 0.9110 -0.1166 0.148 Uiso 1 1 calc R . . C32 C 0.1673(15) 0.7125(11) -0.0442(9) 0.093(6) Uani 1 1 d . . . H32A H 0.1159 0.7598 -0.0754 0.140 Uiso 1 1 calc R . . H32B H 0.1004 0.6817 -0.0002 0.140 Uiso 1 1 calc R . . H32C H 0.1969 0.6797 -0.0744 0.140 Uiso 1 1 calc R . . C33 C 0.4426(18) 0.5962(9) 0.0315(10) 0.091(5) Uani 1 1 d . . . H33A H 0.5175 0.5870 -0.0050 0.137 Uiso 1 1 calc R . . H33B H 0.3464 0.5746 0.0273 0.137 Uiso 1 1 calc R . . H33C H 0.4727 0.5698 0.0830 0.137 Uiso 1 1 calc R . . C34 C 0.6975(14) 0.7069(10) 0.0510(8) 0.080(5) Uani 1 1 d . . . H34A H 0.6860 0.6690 0.1033 0.120 Uiso 1 1 calc R . . H34B H 0.7605 0.7516 0.0483 0.120 Uiso 1 1 calc R . . H34C H 0.7440 0.6804 0.0178 0.120 Uiso 1 1 calc R . . C35 C 0.5816(17) 0.8894(9) -0.0010(10) 0.094(6) Uani 1 1 d . . . H35A H 0.6331 0.9163 -0.0513 0.140 Uiso 1 1 calc R . . H35B H 0.6550 0.8691 0.0365 0.140 Uiso 1 1 calc R . . H35C H 0.5166 0.9271 0.0128 0.140 Uiso 1 1 calc R . . C36 C -0.4699(15) 0.6689(9) 0.5362(10) 0.074(5) Uani 1 1 d . . . C37 C -0.3580(13) 0.6158(8) 0.5855(7) 0.050(3) Uani 1 1 d . . . C38 C -0.2898(15) 0.5665(8) 0.5468(10) 0.066(4) Uani 1 1 d . . . C39 C -0.3586(16) 0.5856(9) 0.4742(9) 0.067(4) Uani 1 1 d . . . C40 C -0.4661(15) 0.6500(9) 0.4689(9) 0.068(4) Uani 1 1 d . . . C41 C -0.5679(16) 0.7290(12) 0.5551(11) 0.107(6) Uani 1 1 d . . . H41A H -0.6007 0.7682 0.5083 0.161 Uiso 1 1 calc R . . H41B H -0.5119 0.7560 0.5811 0.161 Uiso 1 1 calc R . . H41C H -0.6549 0.7019 0.5884 0.161 Uiso 1 1 calc R . . C42 C -0.3249(18) 0.6107(10) 0.6652(8) 0.089(5) Uani 1 1 d . . . H42A H -0.4177 0.6159 0.6938 0.134 Uiso 1 1 calc R . . H42B H -0.2559 0.6537 0.6609 0.134 Uiso 1 1 calc R . . H42C H -0.2798 0.5594 0.6916 0.134 Uiso 1 1 calc R . . C43 C -0.175(2) 0.5010(10) 0.5758(11) 0.118(7) Uani 1 1 d . . . H43A H -0.0800 0.5250 0.5783 0.177 Uiso 1 1 calc R . . H43B H -0.1611 0.4717 0.5412 0.177 Uiso 1 1 calc R . . H43C H -0.2104 0.4645 0.6266 0.177 Uiso 1 1 calc R . . C44 C -0.3248(18) 0.5465(10) 0.4164(10) 0.102(6) Uani 1 1 d . . . H44A H -0.2411 0.5742 0.3808 0.153 Uiso 1 1 calc R . . H44B H -0.4125 0.5490 0.3886 0.153 Uiso 1 1 calc R . . H44C H -0.2989 0.4908 0.4424 0.153 Uiso 1 1 calc R . . C45 C -0.5782(16) 0.6867(11) 0.4073(10) 0.115(7) Uani 1 1 d . . . H45A H -0.6801 0.6784 0.4315 0.172 Uiso 1 1 calc R . . H45B H -0.5669 0.6609 0.3697 0.172 Uiso 1 1 calc R . . H45C H -0.5580 0.7438 0.3822 0.172 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 Ir1 0.0425(3) 0.0420(3) 0.0434(3) -0.0139(2) -0.0035(2) -0.0020(2) Ir2 0.0440(3) 0.0516(3) 0.0462(3) -0.0208(3) -0.0025(2) 0.0034(2) Ir3 0.0400(3) 0.0535(3) 0.0486(3) -0.0152(3) 0.0035(2) -0.0129(2) S1 0.0425(17) 0.058(2) 0.070(2) -0.0289(19) -0.0117(16) 0.0032(15) S2 0.0452(18) 0.094(3) 0.057(2) -0.037(2) -0.0035(16) -0.0065(18) S3 0.0454(18) 0.057(2) 0.085(3) -0.025(2) 0.0102(18) -0.0100(16) N1 0.052(6) 0.049(7) 0.041(6) -0.029(5) 0.013(5) 0.003(5) N2 0.031(5) 0.068(7) 0.037(6) -0.013(5) -0.008(5) -0.002(5) N3 0.039(6) 0.040(7) 0.056(7) -0.019(6) 0.002(5) -0.009(5) Cl1 0.075(2) 0.067(2) 0.050(2) -0.0200(19) -0.0170(17) 0.0073(18) Cl2 0.067(2) 0.060(2) 0.063(2) -0.0126(19) -0.0011(17) 0.0123(17) Cl3 0.0548(19) 0.080(3) 0.055(2) -0.0103(19) -0.0114(16) -0.0147(18) C1 0.049(7) 0.052(8) 0.044(8) -0.012(7) 0.006(6) 0.001(6) C2 0.035(6) 0.051(8) 0.053(8) -0.028(7) -0.004(6) 0.008(5) C3 0.032(6) 0.059(9) 0.035(7) -0.002(6) -0.005(5) 0.000(6) C4 0.049(8) 0.044(8) 0.075(10) -0.030(8) -0.009(7) 0.010(6) C5 0.038(7) 0.057(9) 0.058(9) -0.021(7) -0.030(6) 0.012(6) C6 0.040(7) 0.061(9) 0.082(11) -0.032(8) 0.003(7) -0.009(6) C7 0.037(7) 0.125(14) 0.052(10) -0.015(9) -0.018(6) 0.029(8) C8 0.032(7) 0.092(11) 0.060(10) -0.023(9) -0.004(7) 0.006(7) C9 0.048(8) 0.068(10) 0.056(9) -0.025(8) -0.004(7) 0.000(7) C10 0.036(7) 0.089(11) 0.041(8) -0.017(8) -0.001(6) 0.014(7) C11 0.060(9) 0.037(8) 0.070(10) -0.021(7) 0.016(7) -0.009(7) C12 0.044(7) 0.058(10) 0.090(11) -0.035(9) -0.003(7) -0.008(7) C13 0.064(9) 0.045(8) 0.057(9) -0.018(7) -0.008(7) 0.004(7) C14 0.040(7) 0.051(9) 0.061(9) -0.019(7) 0.008(6) -0.001(6) C15 0.036(7) 0.056(9) 0.051(8) -0.011(7) -0.008(6) -0.003(6) C16 0.091(11) 0.057(9) 0.043(9) -0.023(8) -0.017(8) -0.002(8) C17 0.048(8) 0.078(10) 0.051(9) -0.043(8) 0.005(6) -0.006(7) C18 0.082(10) 0.052(9) 0.058(10) -0.029(8) -0.011(8) 0.021(8) C19 0.101(11) 0.029(8) 0.052(9) -0.015(7) -0.004(8) -0.013(8) C20 0.049(7) 0.045(8) 0.082(11) -0.043(8) 0.003(7) -0.011(6) C21 0.19(2) 0.104(16) 0.131(19) -0.059(14) -0.091(16) 0.051(15) C22 0.122(14) 0.124(16) 0.087(13) -0.050(12) 0.038(11) -0.051(12) C23 0.078(11) 0.154(19) 0.24(3) -0.15(2) -0.043(14) 0.048(12) C24 0.19(2) 0.068(12) 0.084(14) -0.023(11) 0.008(13) -0.025(13) C25 0.061(10) 0.159(19) 0.23(2) -0.144(19) 0.013(13) -0.043(11) C26 0.073(10) 0.059(10) 0.055(9) -0.016(8) 0.003(8) 0.006(8) C27 0.052(8) 0.068(10) 0.049(9) -0.026(8) -0.010(6) 0.012(7) C28 0.054(8) 0.084(11) 0.061(9) -0.050(9) 0.007(7) 0.012(8) C29 0.037(7) 0.090(11) 0.058(9) -0.040(9) 0.014(6) -0.005(7) C30 0.062(8) 0.039(8) 0.028(7) -0.005(6) -0.012(6) 0.021(6) C31 0.096(12) 0.093(14) 0.078(13) -0.002(10) 0.013(10) 0.007(10) C32 0.063(9) 0.150(17) 0.085(13) -0.061(12) -0.020(9) 0.006(10) C33 0.116(13) 0.066(12) 0.099(14) -0.041(10) 0.003(11) 0.007(10) C34 0.050(8) 0.116(14) 0.068(11) -0.026(10) -0.009(7) 0.007(8) C35 0.112(13) 0.054(10) 0.102(14) -0.022(10) 0.038(11) -0.009(9) C36 0.052(9) 0.070(11) 0.095(13) -0.032(10) 0.043(9) -0.028(8) C37 0.045(7) 0.043(8) 0.050(9) 0.000(7) -0.002(6) -0.007(6) C38 0.053(8) 0.026(7) 0.102(13) -0.006(8) 0.005(8) -0.008(6) C39 0.056(9) 0.071(11) 0.081(12) -0.042(10) 0.020(8) -0.040(8) C40 0.048(8) 0.066(11) 0.083(12) -0.020(9) 0.014(8) -0.043(8) C41 0.062(10) 0.157(18) 0.121(16) -0.076(15) 0.011(10) 0.012(11) C42 0.120(13) 0.094(13) 0.053(10) -0.023(9) -0.011(9) -0.033(10) C43 0.126(15) 0.062(12) 0.133(18) 0.007(11) -0.023(13) 0.001(11) C44 0.106(13) 0.082(13) 0.132(16) -0.059(13) 0.018(12) -0.049(10) C45 0.063(10) 0.133(17) 0.113(16) 0.007(13) -0.037(10) -0.040(10) _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 Ir1 N3 2.120(9) . ? Ir1 C20 2.138(11) . ? Ir1 C16 2.142(12) . ? Ir1 C19 2.145(12) . ? Ir1 C17 2.147(11) . ? Ir1 C18 2.189(12) . ? Ir1 S1 2.357(3) . ? Ir1 Cl1 2.411(3) . ? Ir2 N1 2.114(9) . ? Ir2 C26 2.140(14) . ? Ir2 C28 2.150(11) . ? Ir2 C27 2.150(12) . ? Ir2 C30 2.177(12) . ? Ir2 C29 2.192(11) . ? Ir2 S2 2.349(3) . ? Ir2 Cl2 2.440(4) . ? Ir3 N2 2.133(9) . ? Ir3 C40 2.138(12) . ? Ir3 C39 2.168(12) . ? Ir3 C38 2.173(13) . ? Ir3 C36 2.176(11) . ? Ir3 C37 2.182(12) . ? Ir3 S3 2.366(4) . ? Ir3 Cl3 2.437(3) . ? S1 C1 1.731(13) . ? S2 C6 1.716(14) . ? S3 C11 1.758(12) . ? N1 C3 1.286(14) . ? N1 C4 1.402(15) . ? N2 C8 1.318(15) . ? N2 C9 1.327(14) . ? N3 C14 1.291(15) . ? N3 C13 1.363(15) . ? C1 C5 1.409(16) . ? C1 C2 1.426(16) . ? C2 C3 1.388(16) . ? C4 C5 1.332(15) . ? C6 C7 1.377(16) . ? C6 C10 1.446(17) . ? C7 C8 1.344(17) . ? C9 C10 1.372(16) . ? C11 C15 1.363(16) . ? C11 C12 1.391(18) . ? C12 C13 1.364(16) . ? C14 C15 1.377(15) . ? C16 C17 1.424(18) . ? C16 C20 1.445(18) . ? C16 C21 1.54(2) . ? C17 C18 1.416(18) . ? C17 C22 1.507(17) . ? C18 C19 1.427(18) . ? C18 C23 1.473(19) . ? C19 C20 1.373(18) . ? C19 C24 1.54(2) . ? C20 C25 1.568(17) . ? C26 C30 1.349(17) . ? C26 C27 1.420(17) . ? C26 C31 1.51(2) . ? C27 C28 1.414(18) . ? C27 C32 1.504(17) . ? C28 C29 1.473(17) . ? C28 C33 1.529(18) . ? C29 C34 1.448(17) . ? C29 C30 1.474(17) . ? C30 C35 1.526(17) . ? C36 C40 1.402(19) . ? C36 C41 1.48(2) . ? C36 C37 1.48(2) . ? C37 C38 1.412(18) . ? C37 C42 1.503(18) . ? C38 C39 1.45(2) . ? C38 C43 1.50(2) . ? C39 C40 1.45(2) . ? C39 C44 1.480(19) . ? C40 C45 1.53(2) . ? 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 N3 Ir1 C20 150.1(5) . . ? N3 Ir1 C16 110.7(5) . . ? C20 Ir1 C16 39.5(5) . . ? N3 Ir1 C19 149.2(5) . . ? C20 Ir1 C19 37.4(5) . . ? C16 Ir1 C19 65.6(5) . . ? N3 Ir1 C17 93.5(4) . . ? C20 Ir1 C17 63.5(4) . . ? C16 Ir1 C17 38.8(5) . . ? C19 Ir1 C17 64.0(5) . . ? N3 Ir1 C18 111.0(5) . . ? C20 Ir1 C18 63.3(5) . . ? C16 Ir1 C18 65.4(5) . . ? C19 Ir1 C18 38.4(5) . . ? C17 Ir1 C18 38.1(5) . . ? N3 Ir1 S1 91.6(3) . . ? C20 Ir1 S1 90.9(3) . . ? C16 Ir1 S1 95.7(4) . . ? C19 Ir1 S1 118.9(4) . . ? C17 Ir1 S1 132.2(4) . . ? C18 Ir1 S1 154.1(4) . . ? N3 Ir1 Cl1 86.7(3) . . ? C20 Ir1 Cl1 122.7(4) . . ? C16 Ir1 Cl1 159.2(4) . . ? C19 Ir1 Cl1 93.6(4) . . ? C17 Ir1 Cl1 132.5(4) . . ? C18 Ir1 Cl1 98.3(4) . . ? S1 Ir1 Cl1 95.21(12) . . ? N1 Ir2 C26 104.7(5) . . ? N1 Ir2 C28 155.3(4) . . ? C26 Ir2 C28 64.4(6) . . ? N1 Ir2 C27 141.7(5) . . ? C26 Ir2 C27 38.7(5) . . ? C28 Ir2 C27 38.4(5) . . ? N1 Ir2 C30 93.6(4) . . ? C26 Ir2 C30 36.4(4) . . ? C28 Ir2 C30 64.1(5) . . ? C27 Ir2 C30 63.0(5) . . ? N1 Ir2 C29 116.1(4) . . ? C26 Ir2 C29 65.0(5) . . ? C28 Ir2 C29 39.6(4) . . ? C27 Ir2 C29 65.7(5) . . ? C30 Ir2 C29 39.4(5) . . ? N1 Ir2 S2 88.8(3) . . ? C26 Ir2 S2 101.4(4) . . ? C28 Ir2 S2 114.6(4) . . ? C27 Ir2 S2 89.4(3) . . ? C30 Ir2 S2 136.6(3) . . ? C29 Ir2 S2 153.5(3) . . ? N1 Ir2 Cl2 88.9(3) . . ? C26 Ir2 Cl2 157.7(4) . . ? C28 Ir2 Cl2 96.0(4) . . ? C27 Ir2 Cl2 129.4(4) . . ? C30 Ir2 Cl2 126.8(3) . . ? C29 Ir2 Cl2 93.2(4) . . ? S2 Ir2 Cl2 96.47(13) . . ? N2 Ir3 C40 107.1(5) . . ? N2 Ir3 C39 93.7(4) . . ? C40 Ir3 C39 39.3(5) . . ? N2 Ir3 C38 116.6(5) . . ? C40 Ir3 C38 65.6(6) . . ? C39 Ir3 C38 39.1(5) . . ? N2 Ir3 C36 143.6(5) . . ? C40 Ir3 C36 37.9(5) . . ? C39 Ir3 C36 64.9(5) . . ? C38 Ir3 C36 65.5(5) . . ? N2 Ir3 C37 154.4(5) . . ? C40 Ir3 C37 64.8(5) . . ? C39 Ir3 C37 64.3(5) . . ? C38 Ir3 C37 37.8(5) . . ? C36 Ir3 C37 39.8(5) . . ? N2 Ir3 S3 86.3(3) . . ? C40 Ir3 S3 98.2(5) . . ? C39 Ir3 S3 135.2(5) . . ? C38 Ir3 S3 154.5(4) . . ? C36 Ir3 S3 89.5(4) . . ? C37 Ir3 S3 118.3(4) . . ? N2 Ir3 Cl3 90.7(3) . . ? C40 Ir3 Cl3 156.4(4) . . ? C39 Ir3 Cl3 126.5(5) . . ? C38 Ir3 Cl3 92.9(4) . . ? C36 Ir3 Cl3 125.7(5) . . ? C37 Ir3 Cl3 92.5(3) . . ? S3 Ir3 Cl3 98.27(13) . . ? C1 S1 Ir1 118.8(4) . . ? C6 S2 Ir2 117.6(4) . . ? C11 S3 Ir3 115.9(5) . . ? C3 N1 C4 114.5(10) . . ? C3 N1 Ir2 125.4(9) . . ? C4 N1 Ir2 118.9(8) . . ? C8 N2 C9 117.0(10) . . ? C8 N2 Ir3 118.4(8) . . ? C9 N2 Ir3 123.7(9) . . ? C14 N3 C13 115.6(10) . . ? C14 N3 Ir1 124.1(8) . . ? C13 N3 Ir1 118.9(8) . . ? C5 C1 C2 116.7(11) . . ? C5 C1 S1 118.7(10) . . ? C2 C1 S1 124.5(10) . . ? C3 C2 C1 116.0(11) . . ? N1 C3 C2 128.4(11) . . ? C5 C4 N1 123.4(11) . . ? C4 C5 C1 120.8(11) . . ? C7 C6 C10 112.4(12) . . ? C7 C6 S2 122.2(11) . . ? C10 C6 S2 125.5(9) . . ? C8 C7 C6 123.3(13) . . ? N2 C8 C7 123.8(11) . . ? N2 C9 C10 123.0(12) . . ? C9 C10 C6 120.4(11) . . ? C15 C11 C12 116.2(11) . . ? C15 C11 S3 126.2(11) . . ? C12 C11 S3 117.4(10) . . ? C13 C12 C11 119.7(12) . . ? N3 C13 C12 123.4(13) . . ? N3 C14 C15 124.9(11) . . ? C11 C15 C14 120.1(12) . . ? C17 C16 C20 103.6(12) . . ? C17 C16 C21 129.5(15) . . ? C20 C16 C21 126.6(15) . . ? C17 C16 Ir1 70.8(7) . . ? C20 C16 Ir1 70.1(7) . . ? C21 C16 Ir1 128.1(10) . . ? C18 C17 C16 110.9(12) . . ? C18 C17 C22 127.0(14) . . ? C16 C17 C22 122.1(15) . . ? C18 C17 Ir1 72.5(7) . . ? C16 C17 Ir1 70.4(7) . . ? C22 C17 Ir1 126.4(9) . . ? C17 C18 C19 106.2(12) . . ? C17 C18 C23 124.6(15) . . ? C19 C18 C23 129.1(16) . . ? C17 C18 Ir1 69.4(7) . . ? C19 C18 Ir1 69.1(7) . . ? C23 C18 Ir1 128.6(10) . . ? C20 C19 C18 108.3(12) . . ? C20 C19 C24 128.6(15) . . ? C18 C19 C24 122.9(15) . . ? C20 C19 Ir1 71.0(7) . . ? C18 C19 Ir1 72.4(7) . . ? C24 C19 Ir1 126.3(10) . . ? C19 C20 C16 110.9(12) . . ? C19 C20 C25 124.3(15) . . ? C16 C20 C25 124.8(15) . . ? C19 C20 Ir1 71.6(7) . . ? C16 C20 Ir1 70.4(7) . . ? C25 C20 Ir1 124.2(8) . . ? C30 C26 C27 109.5(13) . . ? C30 C26 C31 125.2(14) . . ? C27 C26 C31 124.9(14) . . ? C30 C26 Ir2 73.3(9) . . ? C27 C26 Ir2 71.1(8) . . ? C31 C26 Ir2 128.2(10) . . ? C28 C27 C26 107.5(12) . . ? C28 C27 C32 125.9(13) . . ? C26 C27 C32 126.4(14) . . ? C28 C27 Ir2 70.8(7) . . ? C26 C27 Ir2 70.3(8) . . ? C32 C27 Ir2 128.8(9) . . ? C27 C28 C29 109.4(12) . . ? C27 C28 C33 127.5(13) . . ? C29 C28 C33 123.1(13) . . ? C27 C28 Ir2 70.8(7) . . ? C29 C28 Ir2 71.7(6) . . ? C33 C28 Ir2 125.3(10) . . ? C34 C29 C28 125.1(13) . . ? C34 C29 C30 132.1(13) . . ? C28 C29 C30 102.4(11) . . ? C34 C29 Ir2 129.5(10) . . ? C28 C29 Ir2 68.6(6) . . ? C30 C29 Ir2 69.8(6) . . ? C26 C30 C29 111.1(12) . . ? C26 C30 C35 130.2(12) . . ? C29 C30 C35 118.6(12) . . ? C26 C30 Ir2 70.3(8) . . ? C29 C30 Ir2 70.8(6) . . ? C35 C30 Ir2 124.5(8) . . ? C40 C36 C41 126.9(17) . . ? C40 C36 C37 106.7(13) . . ? C41 C36 C37 126.4(15) . . ? C40 C36 Ir3 69.6(7) . . ? C41 C36 Ir3 125.8(10) . . ? C37 C36 Ir3 70.3(7) . . ? C38 C37 C36 108.6(12) . . ? C38 C37 C42 124.4(14) . . ? C36 C37 C42 127.0(14) . . ? C38 C37 Ir3 70.7(7) . . ? C36 C37 Ir3 69.9(7) . . ? C42 C37 Ir3 127.4(8) . . ? C37 C38 C39 107.9(12) . . ? C37 C38 C43 127.6(16) . . ? C39 C38 C43 124.4(16) . . ? C37 C38 Ir3 71.4(7) . . ? C39 C38 Ir3 70.3(8) . . ? C43 C38 Ir3 127.1(10) . . ? C40 C39 C38 107.2(12) . . ? C40 C39 C44 126.5(17) . . ? C38 C39 C44 126.2(16) . . ? C40 C39 Ir3 69.2(7) . . ? C38 C39 Ir3 70.6(7) . . ? C44 C39 Ir3 125.4(9) . . ? C36 C40 C39 109.6(15) . . ? C36 C40 C45 121.9(16) . . ? C39 C40 C45 128.0(16) . . ? C36 C40 Ir3 72.5(7) . . ? C39 C40 Ir3 71.5(7) . . ? C45 C40 Ir3 128.8(10) . . ? _diffrn_measured_fraction_theta_max 0.977 _diffrn_reflns_theta_full 25.01 _diffrn_measured_fraction_theta_full 0.977 _refine_diff_density_max 1.948 _refine_diff_density_min -1.358 _refine_diff_density_rms 0.204 # Attachment 'Complex_2.cif' data_f70624c _database_code_depnum_ccdc_archive 'CCDC 698543' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C28 H36 Cl8 Ir N3 S3' _chemical_formula_weight 986.58 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' S S 0.1246 0.1234 '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' Ir Ir -1.4442 7.9887 '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 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 15.650(4) _cell_length_b 8.128(2) _cell_length_c 30.788(8) _cell_angle_alpha 90.00 _cell_angle_beta 92.797(5) _cell_angle_gamma 90.00 _cell_volume 3911.8(17) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 668 _cell_measurement_theta_min 2.824 _cell_measurement_theta_max 16.921 _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.675 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1944 _exptl_absorpt_coefficient_mu 4.144 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.5753 _exptl_absorpt_correction_T_max 0.6820 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CCD area detector' _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_% 10.00 _diffrn_reflns_number 13549 _diffrn_reflns_av_R_equivalents 0.0915 _diffrn_reflns_av_sigmaI/netI 0.1450 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -34 _diffrn_reflns_limit_l_max 36 _diffrn_reflns_theta_min 1.32 _diffrn_reflns_theta_max 25.01 _reflns_number_total 6845 _reflns_number_gt 3826 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker 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^)+(0.0526P)^2^+0.0000P] 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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6845 _refine_ls_number_parameters 382 _refine_ls_number_restraints 4 _refine_ls_R_factor_all 0.1426 _refine_ls_R_factor_gt 0.0744 _refine_ls_wR_factor_ref 0.1601 _refine_ls_wR_factor_gt 0.1348 _refine_ls_goodness_of_fit_ref 0.981 _refine_ls_restrained_S_all 0.981 _refine_ls_shift/su_max 0.002 _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 Ir1 Ir 0.63323(3) 0.79376(7) 0.867821(17) 0.04917(19) Uani 1 1 d . . . S1 S 0.7620(2) 0.6447(4) 0.86643(13) 0.0659(10) Uani 1 1 d . . . S2 S 0.6643(2) 0.9857(4) 0.81269(11) 0.0619(10) Uani 1 1 d . . . S3 S 0.6794(2) 1.0137(4) 0.91345(11) 0.0602(9) Uani 1 1 d . . . N1 N 1.0183(8) 0.884(2) 0.8658(4) 0.084(4) Uani 1 1 d D . . H1A H 1.070(4) 0.908(16) 0.876(4) 0.07(4) Uiso 1 1 d D . . N2 N 0.7898(11) 0.784(3) 0.6968(5) 0.125(7) Uani 1 1 d . . . N3 N 0.7977(10) 0.880(3) 1.0442(5) 0.100(5) Uani 1 1 d . . . Cl1 Cl 0.0974(2) 0.3021(5) 0.88386(12) 0.0752(10) Uani 1 1 d D . . H1B H 0.107(19) 0.462(5) 0.886(10) 0.38(17) Uiso 1 1 d D . . Cl2 Cl 0.7874(2) 0.3745(5) 0.64816(12) 0.0730(11) Uani 1 1 d D . . H2A H 0.783(12) 0.535(2) 0.645(6) 0.20(8) Uiso 1 1 d D . . C1 C 1.0097(10) 0.724(2) 0.8680(5) 0.083(5) Uani 1 1 d . . . H1 H 1.0584 0.6588 0.8688 0.099 Uiso 1 1 calc R . . C2 C 0.9325(8) 0.6524(18) 0.8691(5) 0.072(4) Uani 1 1 d . . . H2 H 0.9285 0.5388 0.8720 0.086 Uiso 1 1 calc R . . C3 C 0.8584(8) 0.7480(16) 0.8657(4) 0.058(4) Uani 1 1 d . . . C4 C 0.8693(8) 0.9147(19) 0.8639(4) 0.070(4) Uani 1 1 d . . . H4 H 0.8216 0.9830 0.8628 0.084 Uiso 1 1 calc R . . C5 C 0.9497(10) 0.983(2) 0.8637(5) 0.088(5) Uani 1 1 d . . . H5 H 0.9564 1.0966 0.8620 0.106 Uiso 1 1 calc R . . C6 C 0.7578(12) 0.676(2) 0.7243(6) 0.110(7) Uani 1 1 d . . . H6 H 0.7614 0.5635 0.7189 0.133 Uiso 1 1 calc R . . C7 C 0.7192(10) 0.733(2) 0.7611(5) 0.089(5) Uani 1 1 d . . . H7 H 0.6990 0.6587 0.7811 0.107 Uiso 1 1 calc R . . C8 C 0.7108(8) 0.900(2) 0.7680(4) 0.062(4) Uani 1 1 d . . . C9 C 0.7448(10) 1.006(2) 0.7373(5) 0.087(5) Uani 1 1 d . . . H9 H 0.7396 1.1193 0.7409 0.104 Uiso 1 1 calc R . . C10 C 0.7853(12) 0.947(4) 0.7023(7) 0.126(8) Uani 1 1 d . . . H10 H 0.8094 1.0183 0.6827 0.152 Uiso 1 1 calc R . . C11 C 0.7992(10) 0.770(2) 1.0126(6) 0.096(6) Uani 1 1 d . . . H11 H 0.8259 0.6692 1.0175 0.116 Uiso 1 1 calc R . . C12 C 0.7617(9) 0.804(2) 0.9726(4) 0.072(4) Uani 1 1 d . . . H12 H 0.7617 0.7237 0.9512 0.087 Uiso 1 1 calc R . . C13 C 0.7251(8) 0.949(2) 0.9630(4) 0.065(4) Uani 1 1 d . . . C14 C 0.7268(10) 1.062(2) 0.9970(6) 0.086(5) Uani 1 1 d . . . H14 H 0.7038 1.1661 0.9920 0.103 Uiso 1 1 calc R . . C15 C 0.7611(13) 1.025(3) 1.0372(6) 0.104(6) Uani 1 1 d . . . H15 H 0.7589 1.1013 1.0597 0.125 Uiso 1 1 calc R . . C16 C 0.5624(4) 0.5940(10) 0.9001(3) 0.070(4) Uani 1 1 d G . . C17 C 0.5239(4) 0.7476(10) 0.9090(3) 0.100(7) Uani 1 1 d G . . C18 C 0.4932(4) 0.8165(9) 0.8688(3) 0.101(6) Uani 1 1 d G . . C19 C 0.5129(4) 0.7054(10) 0.8352(3) 0.088(5) Uani 1 1 d G . . C20 C 0.5556(4) 0.5679(9) 0.8545(3) 0.072(4) Uani 1 1 d G . . C21 C 0.6034(7) 0.4787(15) 0.9334(4) 0.163(10) Uani 1 1 d G . . H21A H 0.5954 0.5206 0.9621 0.244 Uiso 1 1 calc R . . H21B H 0.6635 0.4701 0.9288 0.244 Uiso 1 1 calc R . . H21C H 0.5775 0.3720 0.9305 0.244 Uiso 1 1 calc R . . C22 C 0.5167(7) 0.8242(16) 0.9532(4) 0.209(15) Uani 1 1 d G . . H22A H 0.4712 0.7721 0.9679 0.314 Uiso 1 1 calc R . . H22B H 0.5046 0.9395 0.9500 0.314 Uiso 1 1 calc R . . H22C H 0.5696 0.8099 0.9699 0.314 Uiso 1 1 calc R . . C23 C 0.4478(6) 0.9791(13) 0.8629(5) 0.235(17) Uani 1 1 d G . . H23A H 0.4396 1.0274 0.8909 0.353 Uiso 1 1 calc R . . H23B H 0.3932 0.9619 0.8480 0.353 Uiso 1 1 calc R . . H23C H 0.4816 1.0516 0.8461 0.353 Uiso 1 1 calc R . . C24 C 0.4920(7) 0.7293(17) 0.7873(4) 0.219(16) Uani 1 1 d G . . H24A H 0.5045 0.6301 0.7719 0.328 Uiso 1 1 calc R . . H24B H 0.5258 0.8179 0.7766 0.328 Uiso 1 1 calc R . . H24C H 0.4324 0.7553 0.7827 0.328 Uiso 1 1 calc R . . C25 C 0.5882(7) 0.4200(13) 0.8308(4) 0.159(10) Uani 1 1 d G . . H25A H 0.5796 0.4364 0.8000 0.238 Uiso 1 1 calc R . . H25B H 0.5576 0.3238 0.8393 0.238 Uiso 1 1 calc R . . H25C H 0.6481 0.4058 0.8380 0.238 Uiso 1 1 calc R . . C26 C 0.3041(12) 0.512(2) 0.8991(6) 0.117(7) Uani 1 1 d . . . H26A H 0.3132 0.6110 0.8821 0.141 Uiso 1 1 calc R . . H26B H 0.2443 0.4815 0.8951 0.141 Uiso 1 1 calc R . . Cl3 Cl 0.3680(4) 0.3558(9) 0.8816(3) 0.208(4) Uani 1 1 d . . . Cl4 Cl 0.3288(5) 0.5505(10) 0.9530(2) 0.187(3) Uani 1 1 d . . . C27 C 0.0545(14) 0.780(4) 0.0312(7) 0.243(18) Uani 1 1 d . . . H27A H 0.0021 0.7610 0.0460 0.291 Uiso 1 1 calc R . . H27B H 0.0700 0.8954 0.0347 0.291 Uiso 1 1 calc R . . Cl5 Cl 0.1396(4) 0.6499(9) 0.0539(3) 0.180(3) Uani 1 1 d . . . Cl6 Cl 0.0410(6) 0.7345(16) -0.0204(3) 0.311(7) Uani 1 1 d . . . C28 C 0.8999(15) 0.320(8) 0.7389(14) 0.75(8) Uani 1 1 d D . . H28A H 0.8787 0.2223 0.7236 0.895 Uiso 1 1 calc R . . H28B H 0.8851 0.4164 0.7217 0.895 Uiso 1 1 calc R . . Cl7 Cl 0.8582(6) 0.3333(11) 0.7938(3) 0.230(4) Uani 1 1 d . . . Cl8 Cl 1.0080(10) 0.308(3) 0.7506(4) 0.434(10) Uani 1 1 d 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 Ir1 0.0479(3) 0.0436(3) 0.0557(3) -0.0027(3) -0.0001(2) 0.0019(3) S1 0.0527(19) 0.054(2) 0.091(3) 0.000(2) 0.0076(19) 0.0067(16) S2 0.076(2) 0.055(2) 0.055(2) -0.0006(18) 0.0079(18) 0.0061(18) S3 0.071(2) 0.052(2) 0.057(2) -0.0030(18) -0.0046(18) -0.0015(17) N1 0.048(8) 0.117(13) 0.086(10) 0.017(10) -0.004(7) -0.020(9) N2 0.118(13) 0.18(2) 0.074(11) 0.014(14) -0.012(9) 0.056(15) N3 0.098(11) 0.140(16) 0.059(10) 0.012(11) -0.017(8) -0.040(11) Cl1 0.075(2) 0.084(3) 0.067(2) 0.004(2) 0.0077(18) -0.002(2) Cl2 0.060(2) 0.079(3) 0.080(3) -0.014(2) 0.0036(19) 0.0016(19) C1 0.061(10) 0.093(13) 0.096(13) 0.014(12) 0.020(8) 0.004(10) C2 0.057(9) 0.072(11) 0.087(11) 0.018(8) 0.005(8) 0.012(7) C3 0.054(8) 0.055(11) 0.066(9) -0.007(7) 0.007(7) -0.003(6) C4 0.056(8) 0.076(12) 0.079(10) -0.002(9) 0.003(7) -0.007(8) C5 0.064(10) 0.096(14) 0.104(13) 0.004(10) 0.004(10) -0.025(10) C6 0.154(18) 0.101(18) 0.075(13) -0.007(12) -0.015(12) 0.062(14) C7 0.119(13) 0.092(14) 0.058(10) -0.027(10) 0.013(9) 0.022(11) C8 0.065(8) 0.080(12) 0.041(8) -0.002(8) -0.002(7) 0.020(8) C9 0.102(12) 0.103(15) 0.057(10) 0.023(10) 0.017(9) 0.000(10) C10 0.109(15) 0.19(3) 0.087(16) 0.037(17) 0.032(12) 0.027(17) C11 0.096(12) 0.100(16) 0.091(14) 0.031(12) -0.015(11) -0.023(10) C12 0.092(10) 0.076(11) 0.048(9) 0.012(9) -0.009(8) -0.010(10) C13 0.064(9) 0.077(12) 0.055(9) 0.009(9) 0.005(7) -0.028(8) C14 0.091(11) 0.096(14) 0.071(12) -0.020(11) 0.002(10) -0.016(10) C15 0.111(15) 0.13(2) 0.068(14) -0.002(13) 0.015(11) -0.023(14) C16 0.057(8) 0.078(12) 0.075(11) 0.012(9) 0.004(8) -0.023(8) C17 0.056(9) 0.088(16) 0.157(19) -0.066(13) 0.038(11) -0.026(8) C18 0.040(8) 0.069(13) 0.19(2) 0.001(13) 0.004(11) -0.013(8) C19 0.085(11) 0.085(13) 0.090(12) 0.012(11) -0.027(9) -0.032(10) C20 0.078(10) 0.056(11) 0.084(12) -0.028(9) 0.013(9) -0.029(8) C21 0.130(17) 0.16(2) 0.19(2) 0.124(19) -0.029(15) -0.039(15) C22 0.16(2) 0.30(3) 0.18(2) -0.15(2) 0.128(19) -0.13(2) C23 0.051(11) 0.077(15) 0.58(6) 0.04(2) -0.01(2) 0.016(10) C24 0.17(2) 0.35(4) 0.134(19) 0.12(2) -0.091(16) -0.16(2) C25 0.18(2) 0.081(16) 0.22(2) -0.081(16) 0.083(19) -0.042(14) C26 0.124(15) 0.112(17) 0.111(15) 0.013(12) -0.033(12) -0.017(12) Cl3 0.109(4) 0.161(7) 0.349(11) -0.097(7) -0.027(6) 0.035(4) Cl4 0.229(7) 0.198(8) 0.134(5) 0.001(5) 0.002(5) -0.089(6) C27 0.111(17) 0.51(6) 0.11(2) -0.07(3) 0.064(16) -0.05(3) Cl5 0.128(5) 0.191(8) 0.223(8) 0.064(6) 0.020(5) -0.002(4) Cl6 0.246(10) 0.57(2) 0.116(6) 0.043(9) -0.017(6) -0.180(11) C28 0.65(11) 0.65(12) 1.01(17) 0.26(11) 0.74(13) 0.25(10) Cl7 0.233(9) 0.226(10) 0.227(9) -0.064(7) -0.029(7) 0.030(7) Cl8 0.291(14) 0.81(3) 0.198(11) -0.046(14) -0.002(10) -0.019(18) _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 Ir1 C18 2.200(6) . ? Ir1 C17 2.211(6) . ? Ir1 C19 2.211(6) . ? Ir1 C16 2.227(7) . ? Ir1 C20 2.228(6) . ? Ir1 S1 2.353(3) . ? Ir1 S3 2.365(3) . ? Ir1 S2 2.373(4) . ? S1 C3 1.728(13) . ? S2 C8 1.732(13) . ? S3 C13 1.733(15) . ? N1 C1 1.303(19) . ? N1 C5 1.34(2) . ? N2 C10 1.33(3) . ? N2 C6 1.34(2) . ? N3 C11 1.32(2) . ? N3 C15 1.32(2) . ? C1 C2 1.345(19) . ? C2 C3 1.396(16) . ? C3 C4 1.368(18) . ? C4 C5 1.376(17) . ? C6 C7 1.39(2) . ? C7 C8 1.384(19) . ? C8 C9 1.401(18) . ? C9 C10 1.36(2) . ? C11 C12 1.36(2) . ? C12 C13 1.337(19) . ? C13 C14 1.389(19) . ? C14 C15 1.36(2) . ? C16 C20 1.419(4) . ? C16 C17 1.419(4) . ? C16 C21 1.508(4) . ? C17 C18 1.419(4) . ? C17 C22 1.508(4) . ? C18 C19 1.419(4) . ? C18 C23 1.508(4) . ? C19 C20 1.419(4) . ? C19 C24 1.508(4) . ? C20 C25 1.508(4) . ? C26 Cl4 1.714(17) . ? C26 Cl3 1.722(19) . ? C27 Cl6 1.64(2) . ? C27 Cl5 1.81(3) . ? C28 Cl8 1.72(2) . ? C28 Cl7 1.84(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 C18 Ir1 C17 37.53(12) . . ? C18 Ir1 C19 37.52(13) . . ? C17 Ir1 C19 62.56(19) . . ? C18 Ir1 C16 62.46(18) . . ? C17 Ir1 C16 37.29(12) . . ? C19 Ir1 C16 62.29(18) . . ? C18 Ir1 C20 62.45(18) . . ? C17 Ir1 C20 62.30(18) . . ? C19 Ir1 C20 37.28(12) . . ? C16 Ir1 C20 37.14(12) . . ? C18 Ir1 S1 153.8(2) . . ? C17 Ir1 S1 127.6(3) . . ? C19 Ir1 S1 122.4(3) . . ? C16 Ir1 S1 94.5(2) . . ? C20 Ir1 S1 91.8(2) . . ? C18 Ir1 S3 101.8(3) . . ? C17 Ir1 S3 90.6(2) . . ? C19 Ir1 S3 138.1(3) . . ? C16 Ir1 S3 115.5(2) . . ? C20 Ir1 S3 151.6(2) . . ? S1 Ir1 S3 99.37(13) . . ? C18 Ir1 S2 101.2(2) . . ? C17 Ir1 S2 135.5(3) . . ? C19 Ir1 S2 95.0(2) . . ? C16 Ir1 S2 157.3(2) . . ? C20 Ir1 S2 122.6(2) . . ? S1 Ir1 S2 96.89(13) . . ? S3 Ir1 S2 81.99(12) . . ? C3 S1 Ir1 120.0(5) . . ? C8 S2 Ir1 114.4(6) . . ? C13 S3 Ir1 113.3(6) . . ? C1 N1 C5 121.0(14) . . ? C10 N2 C6 123(2) . . ? C11 N3 C15 120.3(17) . . ? N1 C1 C2 121.9(16) . . ? C1 C2 C3 120.0(15) . . ? C4 C3 C2 116.7(13) . . ? C4 C3 S1 126.3(10) . . ? C2 C3 S1 116.9(11) . . ? C3 C4 C5 121.1(14) . . ? N1 C5 C4 119.1(16) . . ? N2 C6 C7 119.1(19) . . ? C8 C7 C6 120.3(17) . . ? C7 C8 C9 117.1(14) . . ? C7 C8 S2 124.3(12) . . ? C9 C8 S2 118.6(13) . . ? C10 C9 C8 121.5(18) . . ? N2 C10 C9 119(2) . . ? N3 C11 C12 120.2(19) . . ? C13 C12 C11 122.8(17) . . ? C12 C13 C14 114.9(15) . . ? C12 C13 S3 128.0(13) . . ? C14 C13 S3 117.2(14) . . ? C15 C14 C13 122.3(18) . . ? N3 C15 C14 119.5(19) . . ? C20 C16 C17 108.0 . . ? C20 C16 C21 126.0 . . ? C17 C16 C21 126.0 . . ? C20 C16 Ir1 71.4(2) . . ? C17 C16 Ir1 70.7(2) . . ? C21 C16 Ir1 123.5(2) . . ? C16 C17 C18 108.0 . . ? C16 C17 C22 126.0 . . ? C18 C17 C22 126.0 . . ? C16 C17 Ir1 72.0(2) . . ? C18 C17 Ir1 70.8(2) . . ? C22 C17 Ir1 122.8(2) . . ? C19 C18 C17 108.0 . . ? C19 C18 C23 126.0 . . ? C17 C18 C23 126.0 . . ? C19 C18 Ir1 71.6(2) . . ? C17 C18 Ir1 71.6(2) . . ? C23 C18 Ir1 122.4(2) . . ? C18 C19 C20 108.0 . . ? C18 C19 C24 126.0 . . ? C20 C19 C24 126.0 . . ? C18 C19 Ir1 70.8(2) . . ? C20 C19 Ir1 72.0(2) . . ? C24 C19 Ir1 122.8(2) . . ? C16 C20 C19 108.0 . . ? C16 C20 C25 126.0 . . ? C19 C20 C25 126.0 . . ? C16 C20 Ir1 71.4(2) . . ? C19 C20 Ir1 70.7(2) . . ? C25 C20 Ir1 123.5(2) . . ? Cl4 C26 Cl3 109.2(11) . . ? Cl6 C27 Cl5 107.3(15) . . ? Cl8 C28 Cl7 102(2) . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 25.01 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 1.560 _refine_diff_density_min -0.656 _refine_diff_density_rms 0.140 # Attachment 'Complex_3.cif' data_f80707c _database_code_depnum_ccdc_archive 'CCDC 698544' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C80 H92 Ir4 N8 S8' _chemical_formula_weight 2190.90 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ir Ir -1.4442 7.9887 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pccn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z' '-x, y+1/2, -z+1/2' 'x+1/2, -y, -z+1/2' '-x, -y, -z' 'x-1/2, y-1/2, -z' 'x, -y-1/2, z-1/2' '-x-1/2, y, z-1/2' _cell_length_a 22.221(7) _cell_length_b 29.634(9) _cell_length_c 14.913(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 9820(5) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1009 _cell_measurement_theta_min 2.256 _cell_measurement_theta_max 20.484 _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.482 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4256 _exptl_absorpt_coefficient_mu 5.613 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.4865 _exptl_absorpt_correction_T_max 0.7294 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CCD area detector' _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_% 7.55 _diffrn_reflns_number 39019 _diffrn_reflns_av_R_equivalents 0.1245 _diffrn_reflns_av_sigmaI/netI 0.1594 _diffrn_reflns_limit_h_min -26 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -35 _diffrn_reflns_limit_k_max 33 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.15 _diffrn_reflns_theta_max 25.01 _reflns_number_total 8652 _reflns_number_gt 3881 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker 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^)+(0.0425P)^2^+0.0000P] 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 8652 _refine_ls_number_parameters 460 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1131 _refine_ls_R_factor_gt 0.0483 _refine_ls_wR_factor_ref 0.1078 _refine_ls_wR_factor_gt 0.0985 _refine_ls_goodness_of_fit_ref 0.777 _refine_ls_restrained_S_all 0.777 _refine_ls_shift/su_max 0.001 _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 Ir1 Ir 0.65116(2) 0.075604(15) 0.12346(3) 0.04812(14) Uani 1 1 d . . . Ir2 Ir 0.98415(2) 0.175456(15) 0.08285(3) 0.05042(15) Uani 1 1 d . . . N1 N 0.7211(4) 0.1170(3) 0.0753(6) 0.053(3) Uani 1 1 d . . . N2 N 0.5710(4) 0.2714(3) 0.1311(7) 0.054(3) Uani 1 1 d . . . N3 N 0.3878(7) 0.1267(5) 0.0575(12) 0.106(5) Uani 1 1 d . . . N4 N 0.9128(5) -0.0185(4) 0.1488(10) 0.082(4) Uani 1 1 d . . . S1 S 0.90814(14) 0.15708(10) -0.0216(2) 0.0568(9) Uani 1 1 d . . . S2 S 0.62562(14) 0.13236(9) 0.22877(19) 0.0532(8) Uani 1 1 d . . . S3 S 0.59128(15) 0.09946(11) -0.0005(2) 0.0619(9) Uani 1 1 d . . . S4 S 0.95134(16) 0.13070(10) 0.2071(2) 0.0656(10) Uani 1 1 d . . . C1 C 0.7611(5) 0.1360(4) 0.1320(8) 0.053(3) Uani 1 1 d . . . H1 H 0.7492 0.1397 0.1913 0.064 Uiso 1 1 calc R . . C2 C 0.8165(6) 0.1499(4) 0.1103(8) 0.060(4) Uani 1 1 d . . . H2 H 0.8406 0.1627 0.1544 0.072 Uiso 1 1 calc R . . C3 C 0.8399(5) 0.1456(3) 0.0205(9) 0.050(3) Uani 1 1 d . . . C4 C 0.7951(5) 0.1295(4) -0.0397(8) 0.057(3) Uani 1 1 d . . . H4 H 0.8038 0.1281 -0.1006 0.068 Uiso 1 1 calc R . . C5 C 0.7392(6) 0.1161(4) -0.0104(8) 0.057(3) Uani 1 1 d . . . H5 H 0.7120 0.1056 -0.0531 0.069 Uiso 1 1 calc R . . C6 C 0.5687(5) 0.2574(4) 0.2182(8) 0.059(3) Uani 1 1 d . . . H6 H 0.5530 0.2774 0.2602 0.071 Uiso 1 1 calc R . . C7 C 0.5881(5) 0.2155(4) 0.2493(8) 0.051(3) Uani 1 1 d . . . H7 H 0.5859 0.2083 0.3099 0.061 Uiso 1 1 calc R . . C8 C 0.6105(5) 0.1850(4) 0.1885(8) 0.049(3) Uani 1 1 d . . . C9 C 0.6154(5) 0.1992(4) 0.0992(8) 0.054(3) Uani 1 1 d . . . H9 H 0.6316 0.1798 0.0565 0.064 Uiso 1 1 calc R . . C10 C 0.5963(5) 0.2419(4) 0.0739(8) 0.054(3) Uani 1 1 d . . . H10 H 0.6013 0.2505 0.0144 0.065 Uiso 1 1 calc R . . C11 C 0.4163(8) 0.1309(5) -0.0213(13) 0.090(5) Uani 1 1 d . . . H11 H 0.3929 0.1400 -0.0698 0.108 Uiso 1 1 calc R . . C12 C 0.4774(7) 0.1230(4) -0.0391(9) 0.073(4) Uani 1 1 d . . . H12 H 0.4915 0.1260 -0.0975 0.088 Uiso 1 1 calc R . . C13 C 0.5180(6) 0.1108(4) 0.0295(9) 0.062(4) Uani 1 1 d . . . C14 C 0.4924(6) 0.1069(4) 0.1122(9) 0.066(4) Uani 1 1 d . . . H14 H 0.5148 0.0989 0.1625 0.079 Uiso 1 1 calc R . . C15 C 0.4271(8) 0.1161(5) 0.1175(12) 0.093(5) Uani 1 1 d . . . H15 H 0.4114 0.1139 0.1751 0.111 Uiso 1 1 calc R . . C16 C 0.9081(6) -0.0007(5) 0.2290(11) 0.087(5) Uani 1 1 d . . . H16 H 0.8985 -0.0196 0.2767 0.105 Uiso 1 1 calc R . . C17 C 0.9170(6) 0.0460(5) 0.2469(8) 0.084(5) Uani 1 1 d . . . H17 H 0.9096 0.0571 0.3042 0.100 Uiso 1 1 calc R . . C18 C 0.9364(5) 0.0750(4) 0.1809(8) 0.060(3) Uani 1 1 d . . . C19 C 0.9408(6) 0.0567(4) 0.0955(9) 0.075(4) Uani 1 1 d . . . H19 H 0.9511 0.0749 0.0470 0.090 Uiso 1 1 calc R . . C20 C 0.9292(6) 0.0089(5) 0.0826(11) 0.081(4) Uani 1 1 d . . . H20 H 0.9334 -0.0031 0.0253 0.097 Uiso 1 1 calc R . . C21 C 0.6082(6) 0.0094(4) 0.1410(10) 0.066(4) Uani 1 1 d . . . C22 C 0.6561(7) 0.0047(4) 0.0784(9) 0.059(3) Uani 1 1 d . . . C23 C 0.7098(6) 0.0165(4) 0.1221(10) 0.059(3) Uani 1 1 d . . . C24 C 0.6962(6) 0.0277(4) 0.2114(10) 0.065(4) Uani 1 1 d . . . C25 C 0.6344(7) 0.0235(4) 0.2234(9) 0.064(4) Uani 1 1 d . . . C26 C 0.5446(6) -0.0033(4) 0.1247(10) 0.110(6) Uani 1 1 d . . . H26A H 0.5432 -0.0297 0.0876 0.165 Uiso 1 1 calc R . . H26B H 0.5243 0.0211 0.0950 0.165 Uiso 1 1 calc R . . H26C H 0.5252 -0.0094 0.1809 0.165 Uiso 1 1 calc R . . C27 C 0.6505(6) -0.0128(4) -0.0162(8) 0.084(4) Uani 1 1 d . . . H27A H 0.6774 0.0035 -0.0547 0.126 Uiso 1 1 calc R . . H27B H 0.6099 -0.0089 -0.0366 0.126 Uiso 1 1 calc R . . H27C H 0.6606 -0.0443 -0.0174 0.126 Uiso 1 1 calc R . . C28 C 0.7697(6) 0.0140(4) 0.0782(9) 0.098(5) Uani 1 1 d . . . H28A H 0.7964 -0.0039 0.1143 0.147 Uiso 1 1 calc R . . H28B H 0.7859 0.0439 0.0718 0.147 Uiso 1 1 calc R . . H28C H 0.7656 0.0004 0.0201 0.147 Uiso 1 1 calc R . . C29 C 0.7416(7) 0.0372(4) 0.2835(9) 0.112(6) Uani 1 1 d . . . H29A H 0.7240 0.0567 0.3278 0.168 Uiso 1 1 calc R . . H29B H 0.7762 0.0516 0.2577 0.168 Uiso 1 1 calc R . . H29C H 0.7536 0.0094 0.3112 0.168 Uiso 1 1 calc R . . C30 C 0.6013(8) 0.0288(4) 0.3099(9) 0.123(7) Uani 1 1 d . . . H30A H 0.5937 -0.0004 0.3354 0.184 Uiso 1 1 calc R . . H30B H 0.5638 0.0440 0.2991 0.184 Uiso 1 1 calc R . . H30C H 0.6252 0.0463 0.3507 0.184 Uiso 1 1 calc R . . C31 C 1.0493(5) 0.2091(4) -0.0070(9) 0.061(4) Uani 1 1 d . . . C32 C 1.0647(6) 0.2180(5) 0.0856(10) 0.070(4) Uani 1 1 d . . . C33 C 1.0785(6) 0.1769(5) 0.1285(8) 0.075(4) Uani 1 1 d . . . C34 C 1.0711(6) 0.1426(4) 0.0611(10) 0.077(4) Uani 1 1 d . . . C35 C 1.0534(6) 0.1624(5) -0.0205(10) 0.074(4) Uani 1 1 d . . . C36 C 1.0367(5) 0.2441(5) -0.0773(8) 0.090(5) Uani 1 1 d . . . H36A H 1.0143 0.2308 -0.1255 0.135 Uiso 1 1 calc R . . H36B H 1.0741 0.2557 -0.1001 0.135 Uiso 1 1 calc R . . H36C H 1.0139 0.2683 -0.0514 0.135 Uiso 1 1 calc R . . C37 C 1.0707(6) 0.2647(4) 0.1270(9) 0.090(5) Uani 1 1 d . . . H37A H 1.0606 0.2632 0.1895 0.135 Uiso 1 1 calc R . . H37B H 1.0439 0.2852 0.0971 0.135 Uiso 1 1 calc R . . H37C H 1.1114 0.2751 0.1204 0.135 Uiso 1 1 calc R . . C38 C 1.1061(6) 0.1746(5) 0.2228(9) 0.107(5) Uani 1 1 d . . . H38A H 1.1492 0.1760 0.2184 0.160 Uiso 1 1 calc R . . H38B H 1.0946 0.1467 0.2510 0.160 Uiso 1 1 calc R . . H38C H 1.0918 0.1995 0.2579 0.160 Uiso 1 1 calc R . . C39 C 1.0891(7) 0.0912(5) 0.0799(11) 0.123(6) Uani 1 1 d . . . H39A H 1.1303 0.0898 0.0994 0.184 Uiso 1 1 calc R . . H39B H 1.0845 0.0740 0.0259 0.184 Uiso 1 1 calc R . . H39C H 1.0635 0.0790 0.1257 0.184 Uiso 1 1 calc R . . C40 C 1.0422(7) 0.1380(6) -0.1087(9) 0.118(6) Uani 1 1 d . . . H40A H 1.0110 0.1532 -0.1414 0.176 Uiso 1 1 calc R . . H40B H 1.0302 0.1075 -0.0968 0.176 Uiso 1 1 calc R . . H40C H 1.0785 0.1380 -0.1437 0.176 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 Ir1 0.0594(3) 0.0472(3) 0.0378(3) -0.0008(2) -0.0007(3) -0.0044(3) Ir2 0.0614(3) 0.0471(3) 0.0428(3) -0.0031(2) -0.0017(3) -0.0003(3) N1 0.074(7) 0.078(7) 0.009(5) -0.015(5) 0.006(5) -0.016(6) N2 0.063(7) 0.066(7) 0.034(6) -0.004(6) 0.018(6) -0.009(5) N3 0.105(13) 0.107(11) 0.107(14) -0.014(10) -0.035(11) 0.009(9) N4 0.091(9) 0.050(8) 0.103(12) 0.021(8) -0.025(9) 0.017(6) S1 0.060(2) 0.064(2) 0.046(2) -0.0069(16) 0.0037(17) -0.0146(17) S2 0.076(2) 0.0461(19) 0.0373(19) 0.0003(15) 0.0019(17) 0.0036(16) S3 0.071(2) 0.076(2) 0.039(2) 0.0007(16) -0.0055(18) -0.0009(18) S4 0.098(3) 0.055(2) 0.044(2) 0.0002(16) -0.0007(19) -0.0062(19) C1 0.064(9) 0.066(8) 0.028(8) -0.005(6) 0.004(7) 0.004(7) C2 0.067(9) 0.058(8) 0.055(10) -0.013(6) 0.012(8) -0.028(7) C3 0.037(8) 0.045(7) 0.067(10) -0.009(6) -0.012(7) -0.006(6) C4 0.056(9) 0.081(9) 0.033(8) 0.006(6) 0.007(7) -0.019(7) C5 0.073(10) 0.061(8) 0.038(9) -0.015(6) -0.004(7) -0.005(7) C6 0.063(9) 0.066(9) 0.047(9) -0.021(7) 0.019(7) -0.003(7) C7 0.062(9) 0.050(8) 0.041(8) 0.008(6) 0.000(6) 0.021(6) C8 0.048(8) 0.057(8) 0.044(8) -0.006(7) -0.004(6) 0.002(6) C9 0.059(8) 0.051(8) 0.051(9) 0.007(6) 0.009(7) 0.013(6) C10 0.077(9) 0.059(8) 0.027(8) 0.000(6) -0.004(7) 0.000(7) C11 0.091(15) 0.070(11) 0.109(16) -0.012(10) -0.021(12) 0.009(10) C12 0.098(12) 0.078(10) 0.044(9) 0.005(7) -0.020(9) -0.015(9) C13 0.093(11) 0.049(8) 0.043(9) -0.001(6) -0.016(9) -0.009(7) C14 0.057(10) 0.084(10) 0.057(10) -0.012(7) 0.001(8) -0.010(7) C15 0.117(15) 0.064(10) 0.098(14) -0.033(10) 0.042(12) -0.026(10) C16 0.116(13) 0.073(12) 0.072(13) 0.010(9) -0.026(10) -0.001(9) C17 0.142(14) 0.078(11) 0.030(9) 0.017(8) 0.010(9) 0.004(9) C18 0.073(9) 0.063(9) 0.043(9) -0.004(7) -0.006(7) 0.010(7) C19 0.102(11) 0.062(9) 0.061(11) 0.017(7) 0.010(8) 0.004(8) C20 0.084(11) 0.076(11) 0.083(12) -0.032(10) -0.022(9) 0.004(9) C21 0.076(11) 0.060(9) 0.063(11) 0.002(7) 0.006(9) -0.005(8) C22 0.077(10) 0.047(7) 0.053(9) 0.011(6) 0.002(9) -0.001(7) C23 0.057(10) 0.055(8) 0.065(10) 0.003(7) 0.018(9) -0.001(7) C24 0.064(11) 0.046(8) 0.086(12) -0.002(7) -0.014(9) 0.015(7) C25 0.097(13) 0.037(7) 0.058(10) 0.018(7) 0.019(9) 0.022(7) C26 0.110(13) 0.076(10) 0.143(15) -0.016(10) 0.030(11) -0.066(9) C27 0.094(11) 0.101(11) 0.056(10) -0.019(8) -0.009(9) 0.012(9) C28 0.118(13) 0.069(10) 0.107(13) 0.002(9) 0.017(11) 0.029(9) C29 0.188(17) 0.069(10) 0.078(12) 0.008(8) -0.071(12) -0.009(10) C30 0.24(2) 0.066(10) 0.064(11) 0.023(8) 0.054(12) -0.007(11) C31 0.073(10) 0.053(9) 0.058(10) 0.011(7) -0.006(8) -0.005(7) C32 0.065(9) 0.073(10) 0.073(11) -0.003(9) 0.000(8) -0.017(7) C33 0.111(12) 0.078(10) 0.035(8) 0.014(8) -0.015(8) 0.013(9) C34 0.089(11) 0.063(10) 0.080(12) 0.002(9) -0.016(9) 0.013(8) C35 0.066(10) 0.087(12) 0.069(12) 0.007(9) -0.008(8) -0.002(8) C36 0.073(10) 0.129(13) 0.068(10) 0.046(9) -0.008(8) -0.030(9) C37 0.108(12) 0.060(10) 0.103(12) -0.007(9) 0.014(10) 0.002(8) C38 0.127(14) 0.137(13) 0.057(10) 0.003(10) -0.043(9) -0.002(11) C39 0.135(15) 0.082(12) 0.152(17) 0.006(11) -0.025(12) 0.020(10) C40 0.114(13) 0.192(18) 0.047(11) -0.044(11) -0.008(9) 0.012(12) _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 Ir1 N1 2.107(9) . ? Ir1 C24 2.178(12) . ? Ir1 C25 2.179(11) . ? Ir1 C23 2.183(12) . ? Ir1 C21 2.197(12) . ? Ir1 C22 2.209(12) . ? Ir1 S2 2.370(3) . ? Ir1 S3 2.385(3) . ? Ir2 N2 2.120(10) 2_655 ? Ir2 C34 2.187(13) . ? Ir2 C32 2.191(12) . ? Ir2 C33 2.205(14) . ? Ir2 C31 2.210(12) . ? Ir2 C35 2.212(14) . ? Ir2 S1 2.361(3) . ? Ir2 S4 2.392(3) . ? N1 C5 1.341(12) . ? N1 C1 1.349(13) . ? N2 C10 1.346(13) . ? N2 C6 1.366(13) . ? N2 Ir2 2.120(10) 2_655 ? N3 C15 1.289(18) . ? N3 C11 1.342(18) . ? N4 C16 1.311(15) . ? N4 C20 1.329(16) . ? S1 C3 1.676(11) . ? S2 C8 1.707(11) . ? S3 C13 1.722(14) . ? S4 C18 1.728(12) . ? C1 C2 1.337(14) . ? C2 C3 1.443(15) . ? C3 C4 1.423(14) . ? C4 C5 1.375(14) . ? C6 C7 1.392(14) . ? C7 C8 1.373(13) . ? C8 C9 1.400(14) . ? C9 C10 1.387(14) . ? C11 C12 1.402(17) . ? C12 C13 1.412(15) . ? C13 C14 1.363(15) . ? C14 C15 1.479(18) . ? C16 C17 1.424(16) . ? C17 C18 1.375(15) . ? C18 C19 1.387(15) . ? C19 C20 1.454(16) . ? C21 C22 1.422(16) . ? C21 C25 1.422(16) . ? C21 C26 1.483(16) . ? C22 C23 1.403(15) . ? C22 C27 1.508(15) . ? C23 C24 1.406(16) . ? C23 C28 1.486(15) . ? C24 C25 1.391(16) . ? C24 C29 1.500(16) . ? C25 C30 1.493(16) . ? C31 C35 1.401(15) . ? C31 C32 1.447(16) . ? C31 C36 1.501(15) . ? C32 C33 1.411(16) . ? C32 C37 1.520(15) . ? C33 C34 1.438(17) . ? C33 C38 1.536(16) . ? C34 C35 1.407(17) . ? C34 C39 1.601(16) . ? C35 C40 1.521(16) . ? 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 Ir1 C24 104.2(5) . . ? N1 Ir1 C25 140.6(5) . . ? C24 Ir1 C25 37.2(4) . . ? N1 Ir1 C23 91.4(4) . . ? C24 Ir1 C23 37.6(4) . . ? C25 Ir1 C23 62.6(5) . . ? N1 Ir1 C21 151.8(4) . . ? C24 Ir1 C21 63.0(5) . . ? C25 Ir1 C21 37.9(4) . . ? C23 Ir1 C21 62.9(5) . . ? N1 Ir1 C22 114.5(4) . . ? C24 Ir1 C22 62.6(5) . . ? C25 Ir1 C22 62.8(5) . . ? C23 Ir1 C22 37.3(4) . . ? C21 Ir1 C22 37.7(4) . . ? N1 Ir1 S2 89.3(3) . . ? C24 Ir1 S2 100.0(4) . . ? C25 Ir1 S2 90.5(3) . . ? C23 Ir1 S2 135.9(4) . . ? C21 Ir1 S2 116.8(4) . . ? C22 Ir1 S2 152.7(3) . . ? N1 Ir1 S3 88.5(3) . . ? C24 Ir1 S3 156.5(3) . . ? C25 Ir1 S3 130.2(4) . . ? C23 Ir1 S3 124.3(4) . . ? C21 Ir1 S3 96.6(4) . . ? C22 Ir1 S3 94.2(3) . . ? S2 Ir1 S3 99.78(11) . . ? N2 Ir2 C34 153.0(4) 2_655 . ? N2 Ir2 C32 92.2(4) 2_655 . ? C34 Ir2 C32 62.4(5) . . ? N2 Ir2 C33 115.5(5) 2_655 . ? C34 Ir2 C33 38.2(4) . . ? C32 Ir2 C33 37.4(4) . . ? N2 Ir2 C31 104.4(4) 2_655 . ? C34 Ir2 C31 62.1(5) . . ? C32 Ir2 C31 38.4(4) . . ? C33 Ir2 C31 63.6(5) . . ? N2 Ir2 C35 140.2(5) 2_655 . ? C34 Ir2 C35 37.3(4) . . ? C32 Ir2 C35 62.9(5) . . ? C33 Ir2 C35 63.7(5) . . ? C31 Ir2 C35 36.9(4) . . ? N2 Ir2 S1 88.9(3) 2_655 . ? C34 Ir2 S1 115.6(4) . . ? C32 Ir2 S1 136.9(4) . . ? C33 Ir2 S1 152.7(4) . . ? C31 Ir2 S1 99.9(4) . . ? C35 Ir2 S1 89.8(4) . . ? N2 Ir2 S4 88.4(3) 2_655 . ? C34 Ir2 S4 97.9(4) . . ? C32 Ir2 S4 123.6(4) . . ? C33 Ir2 S4 93.5(3) . . ? C31 Ir2 S4 156.8(3) . . ? C35 Ir2 S4 130.9(4) . . ? S1 Ir2 S4 99.49(11) . . ? C5 N1 C1 114.1(10) . . ? C5 N1 Ir1 122.3(8) . . ? C1 N1 Ir1 121.0(8) . . ? C10 N2 C6 114.8(11) . . ? C10 N2 Ir2 120.7(8) . 2_655 ? C6 N2 Ir2 121.9(8) . 2_655 ? C15 N3 C11 108.1(17) . . ? C16 N4 C20 117.1(13) . . ? C3 S1 Ir2 116.6(4) . . ? C8 S2 Ir1 117.6(4) . . ? C13 S3 Ir1 112.5(5) . . ? C18 S4 Ir2 114.4(5) . . ? C2 C1 N1 125.7(11) . . ? C1 C2 C3 122.0(11) . . ? C4 C3 C2 111.2(10) . . ? C4 C3 S1 117.7(10) . . ? C2 C3 S1 131.0(9) . . ? C5 C4 C3 121.9(11) . . ? N1 C5 C4 124.6(11) . . ? N2 C6 C7 125.2(11) . . ? C8 C7 C6 118.5(11) . . ? C7 C8 C9 117.4(11) . . ? C7 C8 S2 116.1(9) . . ? C9 C8 S2 126.4(9) . . ? C10 C9 C8 120.5(11) . . ? N2 C10 C9 123.3(11) . . ? N3 C11 C12 127.4(17) . . ? C11 C12 C13 121.6(14) . . ? C14 C13 C12 114.3(13) . . ? C14 C13 S3 127.8(11) . . ? C12 C13 S3 117.8(12) . . ? C13 C14 C15 116.2(13) . . ? N3 C15 C14 132.3(16) . . ? N4 C16 C17 123.4(14) . . ? C18 C17 C16 121.1(13) . . ? C17 C18 C19 115.8(12) . . ? C17 C18 S4 119.6(10) . . ? C19 C18 S4 124.5(10) . . ? C18 C19 C20 119.3(12) . . ? N4 C20 C19 123.0(13) . . ? C22 C21 C25 106.9(12) . . ? C22 C21 C26 125.5(14) . . ? C25 C21 C26 127.3(14) . . ? C22 C21 Ir1 71.6(7) . . ? C25 C21 Ir1 70.4(7) . . ? C26 C21 Ir1 128.3(9) . . ? C23 C22 C21 107.9(12) . . ? C23 C22 C27 126.2(13) . . ? C21 C22 C27 125.8(13) . . ? C23 C22 Ir1 70.4(7) . . ? C21 C22 Ir1 70.7(7) . . ? C27 C22 Ir1 127.5(8) . . ? C22 C23 C24 108.5(12) . . ? C22 C23 C28 123.0(14) . . ? C24 C23 C28 128.4(14) . . ? C22 C23 Ir1 72.4(7) . . ? C24 C23 Ir1 71.0(7) . . ? C28 C23 Ir1 125.4(8) . . ? C25 C24 C23 108.2(12) . . ? C25 C24 C29 126.0(15) . . ? C23 C24 C29 125.4(14) . . ? C25 C24 Ir1 71.4(7) . . ? C23 C24 Ir1 71.4(7) . . ? C29 C24 Ir1 128.2(8) . . ? C24 C25 C21 108.6(12) . . ? C24 C25 C30 126.0(15) . . ? C21 C25 C30 125.2(15) . . ? C24 C25 Ir1 71.3(7) . . ? C21 C25 Ir1 71.7(7) . . ? C30 C25 Ir1 126.8(8) . . ? C35 C31 C32 107.6(11) . . ? C35 C31 C36 126.5(13) . . ? C32 C31 C36 125.7(12) . . ? C35 C31 Ir2 71.6(8) . . ? C32 C31 Ir2 70.1(7) . . ? C36 C31 Ir2 127.9(9) . . ? C33 C32 C31 109.0(11) . . ? C33 C32 C37 125.6(14) . . ? C31 C32 C37 125.1(13) . . ? C33 C32 Ir2 71.8(8) . . ? C31 C32 Ir2 71.5(7) . . ? C37 C32 Ir2 127.1(9) . . ? C32 C33 C34 105.6(11) . . ? C32 C33 C38 122.7(13) . . ? C34 C33 C38 130.9(13) . . ? C32 C33 Ir2 70.7(7) . . ? C34 C33 Ir2 70.2(8) . . ? C38 C33 Ir2 131.4(10) . . ? C35 C34 C33 110.0(12) . . ? C35 C34 C39 128.2(14) . . ? C33 C34 C39 121.4(13) . . ? C35 C34 Ir2 72.3(8) . . ? C33 C34 Ir2 71.6(8) . . ? C39 C34 Ir2 128.2(10) . . ? C31 C35 C34 107.8(13) . . ? C31 C35 C40 125.7(14) . . ? C34 C35 C40 126.5(14) . . ? C31 C35 Ir2 71.5(8) . . ? C34 C35 Ir2 70.4(8) . . ? C40 C35 Ir2 124.9(9) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.01 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.315 _refine_diff_density_min -1.026 _refine_diff_density_rms 0.158