# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _publ_section_title ; Reactions of iridium hydride pincer complexes with dioxygen: New dioxygen complexes and reversible O2 binding ; loop_ _publ_author_name _publ_author_address 'D. Bridget Williams' ; Department of Chemistry Univ. of Washington Seattle, WA 98195 USA ; 'Werner Kaminsky' ; Department of Chemistry Univ. of Washington Seattle, WA 98195 USA ; 'Karen Goldberg' ; Department of Chemistry Univ. of Washington Seattle, WA 98195 USA ; 'James Mayer' ; Department of Chemistry Univ. of Washington Seattle, WA 98195 USA ; _publ_contact_author_address ; Department of Chemistry, BOX 351700 University of Washington Seattle, WA 98195 USA ; _publ_contact_author_email MAYER@CHEM.WASHINGTON.EDU _publ_contact_author_name 'Werner Kaminsky' # Attachment '_PCP_Ir_O2_2_shelxl.cif' data_shelxl _database_code_depnum_ccdc_archive 'CCDC 678650' _publ_section_abstract ; Abstract here ; _publ_section_comment ; Details and comments here ; _publ_section_exptl_prep ; details of preparation here ; _publ_section_exptl_refinement ; All H atoms were initially located in a difference Fourier map and were refined with a riding model. H atoms were placed in geometrically idealised positions and constrained to ride on their parent atoms with C---H distances in the range 0.95-1.00 \%A. U~iso~ values were fixed such that they were 1.2U~eq~ of their parent atom U~eq~ for CH's and 1.5U~eq~ of their parent atom U~eq~ in case of methyl groups. ; # start Validation Reply Form _vrf_PLAT112_shelxl ; RESPONSE: See below ; _vrf_PLAT113_shelxl ; RESPONSE: This structure is strongly disordered. Solving the structure in symmetry P1 confirmed the disorder. No larger unit cell was found. Chisquare statistics of aggreement shows Centrosymmetric: 0.618, Noncentrosymmetric 0.1946 Hypercentric 1.1078 favoring non-centrosymmetry. The ADDSYM test is not taking into account disordered atoms which are most carbons. The absence of a center of symmetry is most clearly seen in C5 that tilts out of the plane of the phenyl group. Subsequently the whole molecule is distorted. Thus, there is only I-4 symmetry in this structure. The Flack-enantiopole parameter 0.36(4) indicates some twinning involving rotation by 90 degrees around the c-axis. ; _vrf_PLAT432_shelxl ; . RESPONSE: Because of the disorder, abnormal inter-atomic distances appear between disordered mojeties. ; # end Validation Reply Form _publ_section_references ; Altomare, A.; Cascarano, G.; Giacovazzo, C.; Burla, M.C.; Polidori, G.; Camalli, M. (1994) J. Appl. Cryst. 27, 435-442. Beurskens, P.T., Admiraal, G., Beurskens, G., Bosman, W. P., Garcia-Granada, S., Gould, R. O., Smits, J. M. M. & Smykalla, C. (1996) The DIRDIF96 Program System. Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands. MacKay, S.; Gilmore, C.J.; Edwards, C.; Tremayne, M.; Stewart, N.; Shankland, K. (1998) "maXus: a computer program for the solution and refinement of crystal structures from diffraction data" University of Glasgow, Scotland, UK, Nonius BV, Delft, The Netherlands and MacScience Co. Ltd., Yokohama, Japan. Otwinowski, Z.; Minor, W. (1996) Methods in Enzymology, 276, 307-326. Sheldrick, G. M. (1997) SHELXL97 University of G\"ottingen, Germany. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; 'DBWIV181' ; _chemical_name_common DBWIV181 _chemical_melting_point ? _chemical_formula_moiety ' C8 H7 Ir O4 P2, C8 H18, C4 H6, C2 H4, C2, H2, H2, H2, H2' _chemical_formula_sum 'C24 H43 Ir O4 P2' _chemical_formula_weight 649.72 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' Ir Ir -1.4442 7.9887 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M 'I -4' _symmetry_space_group_name_Hall 'I -4' _symmetry_Int_Tables_number 82 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' 'y+1/2, -x+1/2, -z+1/2' '-y+1/2, x+1/2, -z+1/2' _cell_length_a 11.8620(4) _cell_length_b 11.8620(4) _cell_length_c 9.3140(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1310.55(8) _cell_formula_units_Z 2 _cell_measurement_temperature 130(2) _cell_measurement_reflns_used 853 _exptl_crystal_description prism _exptl_crystal_colour orange _exptl_crystal_size_max 0.48 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.17 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.646 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 652 _exptl_absorpt_coefficient_mu 5.243 _exptl_absorpt_correction_type 'multi-scan ' _exptl_absorpt_correction_T_min 0.1875 _exptl_absorpt_correction_T_max 0.4694 _exptl_absorpt_process_details HKL2000 _exptl_special_details ; Data was collected with \w and \f scans in 2^o^ increments with 20 second exposures per degree. Crystal-to-detector distance was 30 mm. 16059 full and partial reflection were integrated. ; _diffrn_ambient_temperature 130(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 'Nonius KappaCCD' _diffrn_measurement_method '\f and \w scans' _diffrn_reflns_number 1337 _diffrn_reflns_av_R_equivalents 0.0368 _diffrn_reflns_av_sigmaI/netI 0.0288 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.78 _diffrn_reflns_theta_max 28.26 _reflns_number_total 1337 _reflns_number_gt 1337 _reflns_threshold_expression >2sigma(I) _computing_data_collection KappaCCD _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution SIR97 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'maXus, Zortep' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0823P)^2^+5.9986P] 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 SHELXL _refine_ls_extinction_coef 0.0115(17) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.36(04) _refine_ls_number_reflns 1337 _refine_ls_number_parameters 120 _refine_ls_number_restraints 50 _refine_ls_R_factor_all 0.0390 _refine_ls_R_factor_gt 0.0390 _refine_ls_wR_factor_ref 0.0981 _refine_ls_wR_factor_gt 0.0981 _refine_ls_goodness_of_fit_ref 1.049 _refine_ls_restrained_S_all 1.049 _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 0.0000 0.5000 0.2500 0.0193(3) Uani 1 4 d S . . P1 P 0.1410(6) 0.3586(6) 0.2843(7) 0.0288(15) Uani 0.50 1 d PD . . O1 O 0.1178(17) 0.6204(17) 0.257(7) 0.037(5) Uani 0.50 1 d PU . . O2 O 0.0911(14) 0.5926(13) 0.3980(18) 0.038(3) Uani 0.50 1 d P . . C1 C 0.0000 0.5000 0.0347(19) 0.022(3) Uani 0.50 2 d SPU . . C2 C 0.068(2) 0.429(2) -0.037(3) 0.050(6) Uani 0.50 1 d PU . . C3 C 0.063(3) 0.427(3) -0.182(4) 0.064(7) Uani 0.50 1 d PU . . H3 H 0.1055 0.3724 -0.2339 0.077 Uiso 0.50 1 calc PR . . C4 C 0.0000 0.5000 -0.2500 0.032(3) Uani 1 4 d S . . H4 H 0.0000 0.5000 -0.3520 0.039 Uiso 0.50 2 calc SPR . . C5 C 0.119(3) 0.313(3) 0.038(4) 0.069(8) Uani 0.50 1 d PU . . H5A H 0.1894 0.2893 -0.0010 0.083 Uiso 0.50 1 d PR . . H5B H 0.0632 0.2566 0.0321 0.083 Uiso 0.50 1 d PRD . . C6 C 0.0641(15) 0.197(2) 0.327(2) 0.046(6) Uani 0.50 1 d PD . . C7 C 0.149(3) 0.114(3) 0.389(4) 0.074(9) Uani 0.50 1 d PD . . H7A H 0.1298 0.0964 0.4863 0.111 Uiso 0.50 1 d PR . . H7B H 0.2215 0.1499 0.3861 0.111 Uiso 0.50 1 d PR . . H7C H 0.1510 0.0462 0.3330 0.111 Uiso 0.50 1 d PR . . C8 C -0.023(3) 0.226(2) 0.443(3) 0.059(7) Uani 0.50 1 d PDU . . H8A H -0.0953 0.1891 0.4218 0.088 Uiso 0.50 1 d PR . . H8B H -0.0255 0.3041 0.4080 0.088 Uiso 0.50 1 d PR . . H8C H -0.0102 0.2259 0.5467 0.088 Uiso 0.50 1 d PR . . C9 C 0.010(3) 0.164(2) 0.186(3) 0.045(6) Uiso 0.50 1 d PD . . H9A H 0.0682 0.1494 0.1142 0.068 Uiso 0.50 1 calc PR . . H9B H -0.0394 0.2250 0.1528 0.068 Uiso 0.50 1 calc PRD . . H9C H -0.0354 0.0953 0.2001 0.068 Uiso 0.50 1 calc PR . . C11 C 0.3769(17) 0.341(2) 0.378(3) 0.067(8) Uiso 0.50 1 d PD . . H11A H 0.3733 0.3396 0.4829 0.100 Uiso 0.50 1 calc PR . . H11B H 0.4552 0.3519 0.3472 0.100 Uiso 0.50 1 calc PR . . H11C H 0.3484 0.2698 0.3393 0.100 Uiso 0.50 1 calc PR . . C10 C 0.3056(16) 0.4373(16) 0.322(2) 0.058(7) Uani 0.50 1 d PD . . C12 C 0.274(2) 0.527(2) 0.436(3) 0.071(9) Uiso 0.50 1 d PD . . H12A H 0.2221 0.5826 0.3937 0.106 Uiso 0.50 1 calc PR . . H12B H 0.3420 0.5658 0.4694 0.106 Uiso 0.50 1 calc PR . . H12C H 0.2368 0.4906 0.5180 0.106 Uiso 0.50 1 calc PR . . C13 C 0.332(3) 0.484(3) 0.174(3) 0.080 Uiso 0.50 1 d PD . . H13A H 0.2702 0.5304 0.1443 0.120 Uiso 0.50 1 d PR . . H13B H 0.3451 0.4263 0.1036 0.120 Uiso 0.50 1 d PR . . H13C H 0.3988 0.5298 0.1828 0.120 Uiso 0.50 1 d PR . . 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 0.0204(5) 0.019 0.0188(3) 0.000 0.000 0.000 P1 0.036(3) 0.031(3) 0.020(3) 0.0024(18) 0.0017(19) 0.024(2) O1 0.046(9) 0.041(8) 0.025(10) 0.000(9) -0.001(9) -0.025(6) O2 0.044(8) 0.034(7) 0.035(8) -0.012(6) -0.007(6) 0.006(6) C1 0.022(8) 0.023(8) 0.021(6) 0.000 0.000 -0.004(10) C2 0.057(8) 0.054(8) 0.039(8) -0.011(6) 0.009(6) 0.024(6) C3 0.070(11) 0.066(10) 0.056(10) -0.002(8) 0.002(8) 0.022(9) C4 0.027(4) 0.027(4) 0.043(8) 0.000 0.000 0.000 C5 0.081(11) 0.060(10) 0.068(11) 0.012(9) -0.013(9) -0.006(9) C6 0.011(7) 0.068(15) 0.060(15) 0.020(12) -0.002(8) 0.000(9) C7 0.10(3) 0.061(18) 0.07(2) 0.010(15) 0.001(18) -0.015(17) C8 0.062(10) 0.052(9) 0.062(11) 0.011(8) 0.012(8) -0.016(8) C10 0.10(2) 0.032(12) 0.047(15) 0.000(10) -0.001(15) 0.013(13) _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 O1 1.999(18) 8 ? Ir1 O1 1.999(18) . ? Ir1 O1 1.999(18) 7_455 ? Ir1 O1 1.999(18) 2_565 ? Ir1 C1 2.005(18) . ? Ir1 C1 2.005(18) 7_455 ? Ir1 O2 2.068(15) 2_565 ? Ir1 O2 2.068(15) . ? Ir1 O2 2.068(15) 7_455 ? Ir1 O2 2.068(15) 8 ? Ir1 P1 2.391(6) 2_565 ? Ir1 P1 2.391(6) 8 ? P1 O1 0.53(5) 7_455 ? P1 O2 1.889(19) 7_455 ? P1 C6 2.16(3) . ? P1 C10 2.192(18) . ? O1 P1 0.53(5) 8 ? O1 O2 1.39(7) . ? O2 C5 1.32(4) 8 ? O2 C2 1.35(3) 8 ? O2 C1 1.663(19) 7_455 ? O2 P1 1.889(19) 8 ? C1 C2 1.35(2) 2_565 ? C1 C2 1.35(2) . ? C1 O2 1.663(19) 7_455 ? C1 O2 1.663(19) 8 ? C2 O2 1.35(3) 7_455 ? C2 C3 1.35(5) . ? C2 C5 1.66(4) . ? C3 C4 1.31(3) . ? C3 H3 0.9500 . ? C4 C3 1.31(3) 2_565 ? C4 H4 0.9500 . ? C5 H5A 0.9571 . ? C5 H5B 0.9393 . ? C6 C13 1.01(5) 7_455 ? C6 C9 1.513(18) . ? C6 C7 1.521(19) . ? C6 C8 1.537(19) . ? C7 H7A 0.9600 . ? C7 H7B 0.9600 . ? C7 H7C 0.9600 . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C11 C10 1.511(16) . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C10 C9 0.93(4) 8 ? C10 C13 1.522(17) . ? C10 C12 1.555(17) . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? 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 O1 Ir1 O1 90.06(13) 8 . ? O1 Ir1 O1 176(4) 8 7_455 ? O1 Ir1 O1 90.06(13) . 7_455 ? O1 Ir1 O1 90.06(14) 8 2_565 ? O1 Ir1 O1 176(4) . 2_565 ? O1 Ir1 O1 90.06(13) 7_455 2_565 ? O1 Ir1 C1 88.1(19) 8 . ? O1 Ir1 C1 91.9(19) . . ? O1 Ir1 C1 88.1(19) 7_455 . ? O1 Ir1 C1 91.9(19) 2_565 . ? O1 Ir1 C1 91.9(19) 8 7_455 ? O1 Ir1 C1 88.1(19) . 7_455 ? O1 Ir1 C1 91.9(19) 7_455 7_455 ? O1 Ir1 C1 88.1(19) 2_565 7_455 ? C1 Ir1 C1 180.0 . 7_455 ? O1 Ir1 O2 91.1(14) 8 2_565 ? O1 Ir1 O2 136.3(19) . 2_565 ? O1 Ir1 O2 91.4(14) 7_455 2_565 ? O1 Ir1 O2 40(2) 2_565 2_565 ? C1 Ir1 O2 131.8(5) . 2_565 ? C1 Ir1 O2 48.2(5) 7_455 2_565 ? O1 Ir1 O2 91.4(14) 8 . ? O1 Ir1 O2 40(2) . . ? O1 Ir1 O2 91.1(14) 7_455 . ? O1 Ir1 O2 136.3(19) 2_565 . ? C1 Ir1 O2 131.8(5) . . ? C1 Ir1 O2 48.2(5) 7_455 . ? O2 Ir1 O2 96.4(10) 2_565 . ? O1 Ir1 O2 136.3(19) 8 7_455 ? O1 Ir1 O2 91.4(14) . 7_455 ? O1 Ir1 O2 40(2) 7_455 7_455 ? O1 Ir1 O2 91.1(14) 2_565 7_455 ? C1 Ir1 O2 48.2(5) . 7_455 ? C1 Ir1 O2 131.8(5) 7_455 7_455 ? O2 Ir1 O2 116.4(6) 2_565 7_455 ? O2 Ir1 O2 116.4(6) . 7_455 ? O1 Ir1 O2 40(2) 8 8 ? O1 Ir1 O2 91.1(14) . 8 ? O1 Ir1 O2 136.3(19) 7_455 8 ? O1 Ir1 O2 91.4(14) 2_565 8 ? C1 Ir1 O2 48.2(5) . 8 ? C1 Ir1 O2 131.8(5) 7_455 8 ? O2 Ir1 O2 116.4(6) 2_565 8 ? O2 Ir1 O2 116.4(6) . 8 ? O2 Ir1 O2 96.4(10) 7_455 8 ? O1 Ir1 P1 9.6(18) 8 2_565 ? O1 Ir1 P1 89.0(8) . 2_565 ? O1 Ir1 P1 174.1(19) 7_455 2_565 ? O1 Ir1 P1 90.5(8) 2_565 2_565 ? C1 Ir1 P1 97.67(16) . 2_565 ? C1 Ir1 P1 82.33(16) 7_455 2_565 ? O2 Ir1 P1 85.3(5) 2_565 2_565 ? O2 Ir1 P1 84.5(5) . 2_565 ? O2 Ir1 P1 145.9(5) 7_455 2_565 ? O2 Ir1 P1 49.5(5) 8 2_565 ? O1 Ir1 P1 90.5(8) 8 8 ? O1 Ir1 P1 9.6(18) . 8 ? O1 Ir1 P1 89.0(8) 7_455 8 ? O1 Ir1 P1 174.1(19) 2_565 8 ? C1 Ir1 P1 82.33(17) . 8 ? C1 Ir1 P1 97.67(17) 7_455 8 ? O2 Ir1 P1 145.9(5) 2_565 8 ? O2 Ir1 P1 49.5(5) . 8 ? O2 Ir1 P1 84.5(5) 7_455 8 ? O2 Ir1 P1 85.3(5) 8 8 ? P1 Ir1 P1 91.02(4) 2_565 8 ? O1 P1 O2 18(5) 7_455 7_455 ? O1 P1 C6 114(3) 7_455 . ? O2 P1 C6 108.4(8) 7_455 . ? O1 P1 C10 107(3) 7_455 . ? O2 P1 C10 106.3(8) 7_455 . ? C6 P1 C10 136.5(8) . . ? O1 P1 Ir1 38(5) 7_455 . ? O2 P1 Ir1 56.3(5) 7_455 . ? C6 P1 Ir1 110.6(6) . . ? C10 P1 Ir1 110.2(6) . . ? P1 O1 O2 155(6) 8 . ? P1 O1 Ir1 132(6) 8 . ? O2 O1 Ir1 72.7(15) . . ? C5 O2 C2 77(2) 8 8 ? C5 O2 O1 100(2) 8 . ? C2 O2 O1 176.6(19) 8 . ? C5 O2 C1 123(2) 8 7_455 ? C2 O2 C1 51.9(12) 8 7_455 ? O1 O2 C1 131.3(16) . 7_455 ? C5 O2 P1 93.5(18) 8 8 ? C2 O2 P1 169.8(15) 8 8 ? O1 O2 P1 6.9(10) . 8 ? C1 O2 P1 138.1(11) 7_455 8 ? C5 O2 Ir1 151(2) 8 . ? C2 O2 Ir1 115.8(14) 8 . ? O1 O2 Ir1 67.4(12) . . ? C1 O2 Ir1 64.0(8) 7_455 . ? P1 O2 Ir1 74.2(6) 8 . ? C2 C1 C2 121(3) 2_565 . ? C2 C1 O2 172.3(19) 2_565 7_455 ? C2 C1 O2 51.9(13) . 7_455 ? C2 C1 O2 51.9(13) 2_565 8 ? C2 C1 O2 172.3(19) . 8 ? O2 C1 O2 135.7(16) 7_455 8 ? C2 C1 Ir1 119.7(14) 2_565 . ? C2 C1 Ir1 119.7(14) . . ? O2 C1 Ir1 67.9(8) 7_455 . ? O2 C1 Ir1 67.9(8) 8 . ? C1 C2 O2 76.3(16) . 7_455 ? C1 C2 C3 119(2) . . ? O2 C2 C3 165(2) 7_455 . ? C1 C2 C5 122(3) . . ? O2 C2 C5 51.0(18) 7_455 . ? C3 C2 C5 115(2) . . ? C4 C3 C2 120(2) . . ? C4 C3 H3 120.1 . . ? C2 C3 H3 120.1 . . ? C3 C4 C3 122(3) . 2_565 ? C3 C4 H4 119.0 . . ? C3 C4 H4 119.0 2_565 . ? C2 C5 H5A 113.5 . . ? C2 C5 H5B 108.2 . . ? H5A C5 H5B 112.5 . . ? C13 C6 C9 60(2) 7_455 . ? C13 C6 C7 114(3) 7_455 . ? C9 C6 C7 116(2) . . ? C13 C6 C8 57(2) 7_455 . ? C9 C6 C8 112(2) . . ? C7 C6 C8 109(2) . . ? C13 C6 P1 135(2) 7_455 . ? C9 C6 P1 104.7(15) . . ? C7 C6 P1 111.3(18) . . ? C8 C6 P1 102.4(17) . . ? C6 C7 H7A 110.3 . . ? C6 C7 H7B 107.4 . . ? H7A C7 H7B 109.5 . . ? C6 C7 H7C 110.8 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C6 C8 H8A 110.3 . . ? C6 C8 H8B 89.9 . . ? H8A C8 H8B 109.5 . . ? C6 C8 H8C 126.0 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C6 C9 H9A 109.5 . . ? C6 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C6 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C9 C10 C11 120(3) 8 . ? C9 C10 C13 61(2) 8 . ? C11 C10 C13 118.0(16) . . ? C9 C10 C12 61(2) 8 . ? C11 C10 C12 114.8(15) . . ? C13 C10 C12 114.9(15) . . ? C9 C10 P1 136(2) 8 . ? C11 C10 P1 103.4(12) . . ? C13 C10 P1 101.3(12) . . ? C12 C10 P1 100.7(12) . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C10 C13 H13A 108.0 . . ? C10 C13 H13B 113.0 . . ? H13A C13 H13B 109.5 . . ? C10 C13 H13C 107.4 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O1 Ir1 P1 O1 177(4) 8 . . 7_455 ? O1 Ir1 P1 O1 -88(5) . . . 7_455 ? O1 Ir1 P1 O1 96(5) 2_565 . . 7_455 ? C1 Ir1 P1 O1 4(5) . . . 7_455 ? C1 Ir1 P1 O1 -176(5) 7_455 . . 7_455 ? O2 Ir1 P1 O1 136(5) 2_565 . . 7_455 ? O2 Ir1 P1 O1 -127(5) . . . 7_455 ? O2 Ir1 P1 O1 4(5) 7_455 . . 7_455 ? O2 Ir1 P1 O1 5(5) 8 . . 7_455 ? P1 Ir1 P1 O1 -176(5) 2_565 . . 7_455 ? P1 Ir1 P1 O1 -78(5) 8 . . 7_455 ? O1 Ir1 P1 O2 173(8) 8 . . 7_455 ? O1 Ir1 P1 O2 -91.4(19) . . . 7_455 ? O1 Ir1 P1 O2 -4(5) 7_455 . . 7_455 ? O1 Ir1 P1 O2 92(2) 2_565 . . 7_455 ? C1 Ir1 P1 O2 0.5(6) . . . 7_455 ? C1 Ir1 P1 O2 -179.5(6) 7_455 . . 7_455 ? O2 Ir1 P1 O2 132.1(7) 2_565 . . 7_455 ? O2 Ir1 P1 O2 -131.1(7) . . . 7_455 ? O2 Ir1 P1 O2 1.3(14) 8 . . 7_455 ? P1 Ir1 P1 O2 -179.5(6) 2_565 . . 7_455 ? P1 Ir1 P1 O2 -81.9(6) 8 . . 7_455 ? O1 Ir1 P1 C6 75(8) 8 . . . ? O1 Ir1 P1 C6 170(2) . . . . ? O1 Ir1 P1 C6 -103(5) 7_455 . . . ? O1 Ir1 P1 C6 -6.7(19) 2_565 . . . ? C1 Ir1 P1 C6 -98.4(7) . . . . ? C1 Ir1 P1 C6 81.6(7) 7_455 . . . ? O2 Ir1 P1 C6 33.1(8) 2_565 . . . ? O2 Ir1 P1 C6 130.0(8) . . . . ? O2 Ir1 P1 C6 -99.0(9) 7_455 . . . ? O2 Ir1 P1 C6 -97.7(10) 8 . . . ? P1 Ir1 P1 C6 81.6(7) 2_565 . . . ? P1 Ir1 P1 C6 179.2(7) 8 . . . ? O1 Ir1 P1 C10 -90(8) 8 . . . ? O1 Ir1 P1 C10 5.1(19) . . . . ? O1 Ir1 P1 C10 93(5) 7_455 . . . ? O1 Ir1 P1 C10 -171(2) 2_565 . . . ? C1 Ir1 P1 C10 97.1(7) . . . . ? C1 Ir1 P1 C10 -82.9(7) 7_455 . . . ? O2 Ir1 P1 C10 -131.4(8) 2_565 . . . ? O2 Ir1 P1 C10 -34.5(8) . . . . ? O2 Ir1 P1 C10 96.5(9) 7_455 . . . ? O2 Ir1 P1 C10 97.8(10) 8 . . . ? P1 Ir1 P1 C10 -82.9(7) 2_565 . . . ? P1 Ir1 P1 C10 14.7(6) 8 . . . ? O1 Ir1 O1 P1 -92(5) 8 . . 8 ? O1 Ir1 O1 P1 84(5) 7_455 . . 8 ? O1 Ir1 O1 P1 176(5) 2_565 . . 8 ? C1 Ir1 O1 P1 -4(5) . . . 8 ? C1 Ir1 O1 P1 176(5) 7_455 . . 8 ? O2 Ir1 O1 P1 176(4) 2_565 . . 8 ? O2 Ir1 O1 P1 176(5) . . . 8 ? O2 Ir1 O1 P1 44(5) 7_455 . . 8 ? O2 Ir1 O1 P1 -52(5) 8 . . 8 ? P1 Ir1 O1 P1 -102(5) 2_565 . . 8 ? O1 Ir1 O1 O2 92(2) 8 . . . ? O1 Ir1 O1 O2 -92(2) 7_455 . . . ? O1 Ir1 O1 O2 0.2(10) 2_565 . . . ? C1 Ir1 O1 O2 -179.8(10) . . . . ? C1 Ir1 O1 O2 0.2(10) 7_455 . . . ? O2 Ir1 O1 O2 0.4(19) 2_565 . . . ? O2 Ir1 O1 O2 -131.6(11) 7_455 . . . ? O2 Ir1 O1 O2 132.0(11) 8 . . . ? P1 Ir1 O1 O2 82.6(10) 2_565 . . . ? P1 Ir1 O1 O2 -176(5) 8 . . . ? P1 O1 O2 C5 -19(10) 8 . . 8 ? Ir1 O1 O2 C5 153(2) . . . 8 ? P1 O1 O2 C2 -12(40) 8 . . 8 ? Ir1 O1 O2 C2 160(35) . . . 8 ? P1 O1 O2 C1 -172(8) 8 . . 7_455 ? Ir1 O1 O2 C1 -0.3(16) . . . 7_455 ? Ir1 O1 O2 P1 172(10) . . . 8 ? P1 O1 O2 Ir1 -172(10) 8 . . . ? O1 Ir1 O2 C5 -157(4) 8 . . 8 ? O1 Ir1 O2 C5 -69(4) . . . 8 ? O1 Ir1 O2 C5 20(4) 7_455 . . 8 ? O1 Ir1 O2 C5 111(4) 2_565 . . 8 ? C1 Ir1 O2 C5 -68(4) . . . 8 ? C1 Ir1 O2 C5 112(4) 7_455 . . 8 ? O2 Ir1 O2 C5 112(4) 2_565 . . 8 ? O2 Ir1 O2 C5 -12(4) 7_455 . . 8 ? O2 Ir1 O2 C5 -125(4) 8 . . 8 ? P1 Ir1 O2 C5 -164(4) 2_565 . . 8 ? P1 Ir1 O2 C5 -68(4) 8 . . 8 ? O1 Ir1 O2 C2 93(2) 8 . . 8 ? O1 Ir1 O2 C2 -179(2) . . . 8 ? O1 Ir1 O2 C2 -90(2) 7_455 . . 8 ? O1 Ir1 O2 C2 1(2) 2_565 . . 8 ? C1 Ir1 O2 C2 -178.5(15) . . . 8 ? C1 Ir1 O2 C2 1.5(15) 7_455 . . 8 ? O2 Ir1 O2 C2 1.5(15) 2_565 . . 8 ? O2 Ir1 O2 C2 -122.2(16) 7_455 . . 8 ? O2 Ir1 O2 C2 125.2(16) 8 . . 8 ? P1 Ir1 O2 C2 86.1(17) 2_565 . . 8 ? P1 Ir1 O2 C2 -177.8(19) 8 . . 8 ? O1 Ir1 O2 O1 -88.5(16) 8 . . . ? O1 Ir1 O2 O1 88.8(16) 7_455 . . . ? O1 Ir1 O2 O1 -179.98(10) 2_565 . . . ? C1 Ir1 O2 O1 0.3(13) . . . . ? C1 Ir1 O2 O1 -179.7(13) 7_455 . . . ? O2 Ir1 O2 O1 -179.7(13) 2_565 . . . ? O2 Ir1 O2 O1 56.6(14) 7_455 . . . ? O2 Ir1 O2 O1 -56.0(13) 8 . . . ? P1 Ir1 O2 O1 -95.1(12) 2_565 . . . ? P1 Ir1 O2 O1 1.0(12) 8 . . . ? O1 Ir1 O2 C1 91.3(15) 8 . . 7_455 ? O1 Ir1 O2 C1 179.7(13) . . . 7_455 ? O1 Ir1 O2 C1 -91.5(15) 7_455 . . 7_455 ? O1 Ir1 O2 C1 -0.2(12) 2_565 . . 7_455 ? C1 Ir1 O2 C1 179.999(1) . . . 7_455 ? O2 Ir1 O2 C1 0.000(1) 2_565 . . 7_455 ? O2 Ir1 O2 C1 -123.7(3) 7_455 . . 7_455 ? O2 Ir1 O2 C1 123.7(3) 8 . . 7_455 ? P1 Ir1 O2 C1 84.6(4) 2_565 . . 7_455 ? P1 Ir1 O2 C1 -179.3(8) 8 . . 7_455 ? O1 Ir1 O2 P1 -89.4(16) 8 . . 8 ? O1 Ir1 O2 P1 -1.0(12) . . . 8 ? O1 Ir1 O2 P1 87.8(16) 7_455 . . 8 ? O1 Ir1 O2 P1 179.0(11) 2_565 . . 8 ? C1 Ir1 O2 P1 -0.7(8) . . . 8 ? C1 Ir1 O2 P1 179.3(8) 7_455 . . 8 ? O2 Ir1 O2 P1 179.3(8) 2_565 . . 8 ? O2 Ir1 O2 P1 55.6(8) 7_455 . . 8 ? O2 Ir1 O2 P1 -57.0(8) 8 . . 8 ? P1 Ir1 O2 P1 -96.1(4) 2_565 . . 8 ? O1 Ir1 C1 C2 1.7(16) 8 . . 2_565 ? O1 Ir1 C1 C2 -88.3(16) . . . 2_565 ? O1 Ir1 C1 C2 -178.3(16) 7_455 . . 2_565 ? O1 Ir1 C1 C2 91.7(16) 2_565 . . 2_565 ? C1 Ir1 C1 C2 -17(59) 7_455 . . 2_565 ? O2 Ir1 C1 C2 91.6(16) 2_565 . . 2_565 ? O2 Ir1 C1 C2 -88.4(16) . . . 2_565 ? O2 Ir1 C1 C2 -178.4(16) 7_455 . . 2_565 ? O2 Ir1 C1 C2 1.6(16) 8 . . 2_565 ? P1 Ir1 C1 C2 1.0(15) 2_565 . . 2_565 ? P1 Ir1 C1 C2 -89.0(15) 8 . . 2_565 ? O1 Ir1 C1 C2 -178.3(16) 8 . . . ? O1 Ir1 C1 C2 91.7(16) . . . . ? O1 Ir1 C1 C2 1.7(16) 7_455 . . . ? O1 Ir1 C1 C2 -88.3(16) 2_565 . . . ? C1 Ir1 C1 C2 163(59) 7_455 . . . ? O2 Ir1 C1 C2 -88.4(16) 2_565 . . . ? O2 Ir1 C1 C2 91.6(16) . . . . ? O2 Ir1 C1 C2 1.6(16) 7_455 . . . ? O2 Ir1 C1 C2 -178.4(16) 8 . . . ? P1 Ir1 C1 C2 -179.0(15) 2_565 . . . ? P1 Ir1 C1 C2 91.0(15) 8 . . . ? O1 Ir1 C1 O2 -179.8(9) 8 . . 7_455 ? O1 Ir1 C1 O2 90.2(9) . . . 7_455 ? O1 Ir1 C1 O2 0.2(9) 7_455 . . 7_455 ? O1 Ir1 C1 O2 -89.8(9) 2_565 . . 7_455 ? C1 Ir1 C1 O2 161(59) 7_455 . . 7_455 ? O2 Ir1 C1 O2 -90.001(1) 2_565 . . 7_455 ? O2 Ir1 C1 O2 90.000(2) . . . 7_455 ? O2 Ir1 C1 O2 180.000(2) 8 . . 7_455 ? P1 Ir1 C1 O2 179.5(6) 2_565 . . 7_455 ? P1 Ir1 C1 O2 89.5(6) 8 . . 7_455 ? O1 Ir1 C1 O2 0.2(9) 8 . . 8 ? O1 Ir1 C1 O2 -89.8(9) . . . 8 ? O1 Ir1 C1 O2 -179.8(9) 7_455 . . 8 ? O1 Ir1 C1 O2 90.2(9) 2_565 . . 8 ? C1 Ir1 C1 O2 -19(59) 7_455 . . 8 ? O2 Ir1 C1 O2 89.999(2) 2_565 . . 8 ? O2 Ir1 C1 O2 -90.000(2) . . . 8 ? O2 Ir1 C1 O2 180.000(2) 7_455 . . 8 ? P1 Ir1 C1 O2 -0.5(6) 2_565 . . 8 ? P1 Ir1 C1 O2 -90.5(6) 8 . . 8 ? C2 C1 C2 O2 178.1(19) 2_565 . . 7_455 ? O2 C1 C2 O2 -171(9) 8 . . 7_455 ? Ir1 C1 C2 O2 -1.9(19) . . . 7_455 ? C2 C1 C2 C3 -3(2) 2_565 . . . ? O2 C1 C2 C3 179(4) 7_455 . . . ? O2 C1 C2 C3 8(13) 8 . . . ? Ir1 C1 C2 C3 177(2) . . . . ? C2 C1 C2 C5 -158(3) 2_565 . . . ? O2 C1 C2 C5 24(2) 7_455 . . . ? O2 C1 C2 C5 -147(9) 8 . . . ? Ir1 C1 C2 C5 22(3) . . . . ? C1 C2 C3 C4 6(5) . . . . ? O2 C2 C3 C4 -178(10) 7_455 . . . ? C5 C2 C3 C4 163(3) . . . . ? C2 C3 C4 C3 -3(2) . . . 2_565 ? O1 P1 C6 C13 -35(6) 7_455 . . 7_455 ? O2 P1 C6 C13 -53(4) 7_455 . . 7_455 ? C10 P1 C6 C13 165(3) . . . 7_455 ? Ir1 P1 C6 C13 7(4) . . . 7_455 ? O1 P1 C6 C9 28(5) 7_455 . . . ? O2 P1 C6 C9 9.2(16) 7_455 . . . ? C10 P1 C6 C9 -132.1(15) . . . . ? Ir1 P1 C6 C9 69.3(15) . . . . ? O1 P1 C6 C7 154(5) 7_455 . . . ? O2 P1 C6 C7 136(2) 7_455 . . . ? C10 P1 C6 C7 -6(3) . . . . ? Ir1 P1 C6 C7 -164.3(19) . . . . ? O1 P1 C6 C8 -90(5) 7_455 . . . ? O2 P1 C6 C8 -108.1(18) 7_455 . . . ? C10 P1 C6 C8 110.5(19) . . . . ? Ir1 P1 C6 C8 -48.1(19) . . . . ? O1 P1 C10 C9 28(6) 7_455 . . 8 ? O2 P1 C10 C9 47(3) 7_455 . . 8 ? C6 P1 C10 C9 -171(3) . . . 8 ? Ir1 P1 C10 C9 -12(3) . . . 8 ? O1 P1 C10 C11 -153(5) 7_455 . . . ? O2 P1 C10 C11 -134.3(14) 7_455 . . . ? C6 P1 C10 C11 8(2) . . . . ? Ir1 P1 C10 C11 166.3(13) . . . . ? O1 P1 C10 C13 -31(5) 7_455 . . . ? O2 P1 C10 C13 -11.6(17) 7_455 . . . ? C6 P1 C10 C13 130.2(18) . . . . ? Ir1 P1 C10 C13 -71.1(16) . . . . ? O1 P1 C10 C12 88(5) 7_455 . . . ? O2 P1 C10 C12 106.7(15) 7_455 . . . ? C6 P1 C10 C12 -111.4(18) . . . . ? Ir1 P1 C10 C12 47.3(15) . . . . ? _diffrn_measured_fraction_theta_max 0.939 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.979 _refine_diff_density_max 1.195 _refine_diff_density_min -0.993 _refine_diff_density_rms 0.194