#------------------------------------------------------------------------------ #$Date: 2020-05-02 00:48:18 +0300 (Sat, 02 May 2020) $ #$Revision: 251384 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/55/79/1557983.cif $ #------------------------------------------------------------------------------ # # This file is available in the Crystallography Open Database (COD), # http://www.crystallography.net/ # # All data on this site have been placed in the public domain by the # contributors. # data_1557983 loop_ _publ_author_name 'Gonz\'alez-Lainez, Miguel' 'Jim\'enez, M. Victoria' 'Passarelli, Vincenzo' 'P\'erez-Torrente, Jes\'us J.' _publ_section_title ; Effective N-methylation of nitroarenes with methanol catalyzed by a functionalized NHC-based iridium catalyst: a green approach to N-methyl amines ; _journal_name_full 'Catalysis Science & Technology' _journal_paper_doi 10.1039/D0CY00707B _journal_year 2020 _chemical_formula_moiety 'C23 H33 Br Ir N3 O' _chemical_formula_sum 'C23 H33 Br Ir N3 O' _chemical_formula_weight 639.63 _space_group_crystal_system monoclinic _space_group_IT_number 14 _space_group_name_Hall '-P 2ybc' _space_group_name_H-M_alt 'P 1 21/c 1' _atom_sites_solution_hydrogens mixed _atom_sites_solution_primary heavy _atom_sites_solution_secondary difmap _audit_creation_method SHELXL-2014/7 _audit_update_record ; 2020-04-06 deposited with the CCDC. 2020-05-01 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 98.5950(10) _cell_angle_gamma 90 _cell_formula_units_Z 4 _cell_length_a 8.5663(3) _cell_length_b 11.0966(4) _cell_length_c 24.1272(9) _cell_measurement_reflns_used 9956 _cell_measurement_temperature 100(2) _cell_measurement_theta_max 29.449 _cell_measurement_theta_min 2.404 _cell_volume 2267.70(14) _computing_cell_refinement 'SAINT+ v. 6.45 (Bruker AXS, 2003)' _computing_data_collection 'SMART v. 5.611 (Bruker AXS, 2000)' _computing_data_reduction 'SAINT+ v. 6.45 (Bruker AXS, 2003)' _computing_molecular_graphics 'XP program, SHELXTL v6.12, Bruker2000' _computing_publication_material 'XCIF program, SHELXTLv6.12, BrukerAXS' _computing_structure_refinement 'SHELXL-2014/7 (Sheldrick, 2014)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _diffrn_ambient_temperature 100(2) _diffrn_detector_area_resol_mean 8.26 _diffrn_measured_fraction_theta_full 1.000 _diffrn_measured_fraction_theta_max 0.950 _diffrn_measurement_device_type 'Bruker SMART APEX-DUO CCD system' _diffrn_measurement_method '\w rotations with narrow frames' _diffrn_radiation_monochromator graphite _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_reflns_av_R_equivalents 0.0451 _diffrn_reflns_av_unetI/netI 0.0342 _diffrn_reflns_Laue_measured_fraction_full 1.000 _diffrn_reflns_Laue_measured_fraction_max 0.950 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_l_max 33 _diffrn_reflns_limit_l_min -33 _diffrn_reflns_number 34038 _diffrn_reflns_point_group_measured_fraction_full 1.000 _diffrn_reflns_point_group_measured_fraction_max 0.950 _diffrn_reflns_theta_full 25.000 _diffrn_reflns_theta_max 29.650 _diffrn_reflns_theta_min 1.707 _exptl_absorpt_coefficient_mu 7.669 _exptl_absorpt_correction_T_max 0.3851 _exptl_absorpt_correction_T_min 0.2975 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; SADABS: Area-Detector Absorption Correction. (1996) Bruker-AXS within SAINT+ package, v. 6.45. ; _exptl_crystal_colour yellow _exptl_crystal_density_diffrn 1.874 _exptl_crystal_description prism _exptl_crystal_F_000 1248 _exptl_crystal_size_max 0.150 _exptl_crystal_size_mid 0.120 _exptl_crystal_size_min 0.100 _refine_diff_density_max 1.359 _refine_diff_density_min -0.609 _refine_diff_density_rms 0.131 _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.019 _refine_ls_hydrogen_treatment mixed _refine_ls_matrix_type full _refine_ls_number_parameters 282 _refine_ls_number_reflns 6081 _refine_ls_number_restraints 4 _refine_ls_restrained_S_all 1.019 _refine_ls_R_factor_all 0.0313 _refine_ls_R_factor_gt 0.0236 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(0.0245P)^2^+0.1667P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0490 _refine_ls_wR_factor_ref 0.0514 _reflns_Friedel_coverage 0.000 _reflns_number_gt 5219 _reflns_number_total 6081 _reflns_threshold_expression 'I > 2\s(I)' _cod_data_source_file d0cy00707b2.cif _cod_data_source_block cmpd_2_VPX73 _cod_original_sg_symbol_H-M 'P 21/c' _cod_database_code 1557983 _shelx_shelxl_version_number 2014/7 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _shelx_res_file ; shelx.res created by SHELXL-2014/7 TITL mo_VPX73D_0m in P2(1)/c CELL 0.71073 8.5663 11.0966 24.1272 90.000 98.595 90.000 ZERR 4.00 0.0003 0.0004 0.0009 0.000 0.001 0.000 LATT 1 SYMM - X, 1/2 + Y, 1/2 - Z SFAC C H N O BR IR UNIT 92 132 12 4 4 4 MERG 2 DFIX 1.00 0.02 C20 H20 C21 H21 C24 H24 C25 H26 FMAP 2 PLAN 10 ACTA 50.00 BOND $H L.S. 4 TEMP -173.00 WGHT 0.024500 0.166700 FVAR 0.26275 C1 1 0.012480 0.011177 0.114995 11.00000 0.01620 0.01297 = 0.01649 0.00272 0.00431 -0.00278 C3 1 -0.180555 -0.072406 0.053226 11.00000 0.01769 0.01920 = 0.02219 -0.00127 -0.00146 -0.00277 AFIX 43 H3 2 -0.282866 -0.090710 0.034034 11.00000 -1.20000 AFIX 0 C4 1 -0.044475 -0.121621 0.043321 11.00000 0.02193 0.01621 = 0.01842 -0.00347 0.00002 -0.00134 AFIX 43 H4 2 -0.031304 -0.179797 0.015505 11.00000 -1.20000 AFIX 0 C6 1 -0.274218 0.083273 0.117052 11.00000 0.01324 0.02079 = 0.02236 -0.00029 0.00461 0.00284 C7 1 -0.360361 0.001239 0.152891 11.00000 0.02054 0.02966 = 0.02765 0.00128 0.00977 0.00019 AFIX 137 H7A 2 -0.288594 -0.021904 0.186729 11.00000 -1.50000 H7B 2 -0.396491 -0.071186 0.131496 11.00000 -1.50000 H7C 2 -0.451521 0.043931 0.163550 11.00000 -1.50000 AFIX 0 C8 1 -0.387886 0.126256 0.066233 11.00000 0.02915 0.03855 = 0.02647 0.00394 0.00645 0.01668 AFIX 137 H8A 2 -0.436954 0.056413 0.045705 11.00000 -1.50000 H8B 2 -0.329871 0.173322 0.041626 11.00000 -1.50000 H8C 2 -0.469934 0.176676 0.078685 11.00000 -1.50000 AFIX 0 C9 1 -0.208422 0.193421 0.150048 11.00000 0.01740 0.02354 = 0.03815 -0.00716 0.00765 0.00268 AFIX 137 H9A 2 -0.295416 0.239844 0.161596 11.00000 -1.50000 H9B 2 -0.151114 0.243795 0.126475 11.00000 -1.50000 H9C 2 -0.136325 0.167626 0.183343 11.00000 -1.50000 AFIX 0 C10 1 0.241356 -0.090677 0.082264 11.00000 0.01221 0.01778 = 0.02630 -0.00400 0.00743 0.00005 AFIX 23 H10A 2 0.300433 -0.045722 0.114139 11.00000 -1.20000 H10B 2 0.271637 -0.057094 0.047373 11.00000 -1.20000 AFIX 0 C11 1 0.290881 -0.221821 0.087033 11.00000 0.01640 0.01601 = 0.01527 -0.00287 0.00208 0.00134 C13 1 0.479195 -0.359525 0.071182 11.00000 0.01527 0.01930 = 0.01261 -0.00183 0.00126 0.00172 C14 1 0.397729 -0.453468 0.092562 11.00000 0.01916 0.01507 = 0.01733 -0.00181 0.00054 0.00179 AFIX 43 H14 2 0.436811 -0.533656 0.093240 11.00000 -1.20000 AFIX 0 C15 1 0.259598 -0.427272 0.112620 11.00000 0.01613 0.01704 = 0.02414 0.00041 0.00144 -0.00399 AFIX 43 H15 2 0.202883 -0.488998 0.128266 11.00000 -1.20000 AFIX 0 C16 1 0.203545 -0.308814 0.109737 11.00000 0.01463 0.01733 = 0.01728 -0.00020 0.00475 0.00177 AFIX 43 H16 2 0.107942 -0.288550 0.123023 11.00000 -1.20000 AFIX 0 C17 1 0.633366 -0.379072 0.049293 11.00000 0.01602 0.01750 = 0.02048 -0.00106 0.00170 0.00313 AFIX 23 H17A 2 0.621624 -0.355009 0.009373 11.00000 -1.20000 H17B 2 0.716363 -0.328063 0.070559 11.00000 -1.20000 AFIX 0 C19 1 0.832762 -0.518240 0.040724 11.00000 0.01778 0.03157 = 0.03413 -0.00115 0.00588 0.00814 AFIX 137 H19A 2 0.837272 -0.485263 0.003316 11.00000 -1.50000 H19B 2 0.857139 -0.604545 0.040994 11.00000 -1.50000 H19C 2 0.910017 -0.476716 0.068265 11.00000 -1.50000 AFIX 0 C20 1 0.353829 0.184945 0.229940 11.00000 0.02335 0.02170 = 0.02002 -0.00252 0.00072 -0.00934 C21 1 0.217568 0.242314 0.240268 11.00000 0.02866 0.01504 = 0.01888 -0.00333 0.00211 -0.00480 C22 1 0.131378 0.216875 0.289677 11.00000 0.03963 0.02191 = 0.01988 -0.00431 0.00788 -0.00082 AFIX 23 H22A 2 0.028534 0.259255 0.283742 11.00000 -1.20000 H22B 2 0.194018 0.249846 0.324148 11.00000 -1.20000 AFIX 0 C23 1 0.102398 0.081588 0.298314 11.00000 0.02946 0.02558 = 0.02257 -0.00207 0.01086 0.00175 AFIX 23 H23B 2 0.191704 0.047847 0.324499 11.00000 -1.20000 H23A 2 0.005217 0.071430 0.315471 11.00000 -1.20000 AFIX 0 C24 1 0.085304 0.012254 0.243231 11.00000 0.01991 0.01716 = 0.02057 0.00059 0.00719 -0.00277 C25 1 0.216771 -0.043528 0.224124 11.00000 0.02058 0.01669 = 0.01999 0.00363 0.00478 -0.00044 C26 1 0.382575 -0.037700 0.255432 11.00000 0.02536 0.02627 = 0.02338 0.00965 0.00505 0.00643 AFIX 23 H26A 2 0.455272 -0.076228 0.232487 11.00000 -1.20000 H26B 2 0.387664 -0.084098 0.290704 11.00000 -1.20000 AFIX 0 C27 1 0.438802 0.092804 0.269511 11.00000 0.01986 0.03509 = 0.02464 0.00275 -0.00083 -0.00198 AFIX 23 H27B 2 0.421945 0.112145 0.308234 11.00000 -1.20000 H27A 2 0.553505 0.098061 0.268091 11.00000 -1.20000 AFIX 0 N2 3 -0.145201 0.010131 0.096567 11.00000 0.01172 0.01585 = 0.01932 -0.00013 0.00278 0.00025 N5 3 0.072784 -0.070630 0.081750 11.00000 0.01211 0.01341 = 0.01850 -0.00228 0.00422 -0.00014 N12 3 0.426900 -0.245413 0.068048 11.00000 0.01480 0.01641 = 0.01507 -0.00159 0.00092 0.00095 O18 4 0.678834 -0.501123 0.054640 11.00000 0.01699 0.01966 = 0.03977 -0.00011 0.01131 0.00600 BR 5 0.190543 0.254780 0.098655 11.00000 0.02142 0.01517 = 0.02028 0.00215 0.00350 -0.00221 IR 6 0.151738 0.109806 0.175027 11.00000 0.01322 0.01182 = 0.01512 -0.00094 0.00257 -0.00043 H20 2 0.414799 0.225693 0.204949 11.00000 0.02662 H21 2 0.191142 0.320590 0.220449 11.00000 0.02098 H24 2 -0.019933 -0.023529 0.234031 11.00000 0.00973 H26 2 0.192292 -0.118795 0.202687 11.00000 0.02094 HKLF 4 REM mo_VPX73D_0m in P2(1)/c REM R1 = 0.0236 for 5219 Fo > 4sig(Fo) and 0.0313 for all 6081 data REM 282 parameters refined using 4 restraints END WGHT 0.0245 0.1666 REM Highest difference peak 1.359, deepest hole -0.609, 1-sigma level 0.131 Q1 1 -0.0179 0.1074 0.1195 11.00000 0.05 1.36 Q2 1 0.1245 0.0364 0.1784 11.00000 0.05 1.24 Q3 1 0.1972 0.1091 0.2094 11.00000 0.05 1.24 Q4 1 0.1071 0.1081 0.1413 11.00000 0.05 1.11 Q5 1 0.1492 0.1845 0.1761 11.00000 0.05 1.11 Q6 1 0.2226 0.0496 0.1986 11.00000 0.05 0.74 Q7 1 0.2214 0.2578 0.1344 11.00000 0.05 0.73 Q8 1 0.2560 0.1110 0.1678 11.00000 0.05 0.64 Q9 1 0.1466 0.3249 0.0992 11.00000 0.05 0.61 Q10 1 0.0550 0.1099 0.1827 11.00000 0.05 0.59 ; _shelx_res_checksum 13331 loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.0125(3) 0.0112(2) 0.11499(12) 0.0150(6) Uani 1 1 d . . . . . C3 C -0.1806(4) -0.0724(3) 0.05323(13) 0.0201(6) Uani 1 1 d . . . . . H3 H -0.2829 -0.0907 0.0340 0.024 Uiso 1 1 calc R U . . . C4 C -0.0445(4) -0.1216(3) 0.04332(13) 0.0192(6) Uani 1 1 d . . . . . H4 H -0.0313 -0.1798 0.0155 0.023 Uiso 1 1 calc R U . . . C6 C -0.2742(3) 0.0833(3) 0.11705(13) 0.0186(6) Uani 1 1 d . . . . . C7 C -0.3604(4) 0.0012(3) 0.15289(14) 0.0253(7) Uani 1 1 d . . . . . H7A H -0.2886 -0.0219 0.1867 0.038 Uiso 1 1 calc R U . . . H7B H -0.3965 -0.0712 0.1315 0.038 Uiso 1 1 calc R U . . . H7C H -0.4515 0.0439 0.1635 0.038 Uiso 1 1 calc R U . . . C8 C -0.3879(4) 0.1263(3) 0.06623(14) 0.0312(8) Uani 1 1 d . . . . . H8A H -0.4370 0.0564 0.0457 0.047 Uiso 1 1 calc R U . . . H8B H -0.3299 0.1733 0.0416 0.047 Uiso 1 1 calc R U . . . H8C H -0.4699 0.1767 0.0787 0.047 Uiso 1 1 calc R U . . . C9 C -0.2084(4) 0.1934(3) 0.15005(14) 0.0260(7) Uani 1 1 d . . . . . H9A H -0.2954 0.2398 0.1616 0.039 Uiso 1 1 calc R U . . . H9B H -0.1511 0.2438 0.1265 0.039 Uiso 1 1 calc R U . . . H9C H -0.1363 0.1676 0.1833 0.039 Uiso 1 1 calc R U . . . C10 C 0.2414(3) -0.0907(3) 0.08226(13) 0.0183(6) Uani 1 1 d . . . . . H10A H 0.3004 -0.0457 0.1141 0.022 Uiso 1 1 calc R U . . . H10B H 0.2716 -0.0571 0.0474 0.022 Uiso 1 1 calc R U . . . C11 C 0.2909(3) -0.2218(3) 0.08703(12) 0.0159(6) Uani 1 1 d . . . . . C13 C 0.4792(3) -0.3595(3) 0.07118(12) 0.0158(6) Uani 1 1 d . . . . . C14 C 0.3977(3) -0.4535(3) 0.09256(12) 0.0174(6) Uani 1 1 d . . . . . H14 H 0.4368 -0.5337 0.0932 0.021 Uiso 1 1 calc R U . . . C15 C 0.2596(3) -0.4273(3) 0.11262(13) 0.0193(6) Uani 1 1 d . . . . . H15 H 0.2029 -0.4890 0.1283 0.023 Uiso 1 1 calc R U . . . C16 C 0.2035(3) -0.3088(3) 0.10974(12) 0.0162(6) Uani 1 1 d . . . . . H16 H 0.1079 -0.2886 0.1230 0.019 Uiso 1 1 calc R U . . . C17 C 0.6334(3) -0.3791(3) 0.04929(13) 0.0181(6) Uani 1 1 d . . . . . H17A H 0.6216 -0.3550 0.0094 0.022 Uiso 1 1 calc R U . . . H17B H 0.7164 -0.3281 0.0706 0.022 Uiso 1 1 calc R U . . . C19 C 0.8328(4) -0.5182(3) 0.04072(15) 0.0276(7) Uani 1 1 d . . . . . H19A H 0.8373 -0.4853 0.0033 0.041 Uiso 1 1 calc R U . . . H19B H 0.8571 -0.6045 0.0410 0.041 Uiso 1 1 calc R U . . . H19C H 0.9100 -0.4767 0.0683 0.041 Uiso 1 1 calc R U . . . C20 C 0.3538(4) 0.1849(3) 0.22994(13) 0.0220(7) Uani 1 1 d D . . . . C21 C 0.2176(4) 0.2423(3) 0.24027(13) 0.0210(6) Uani 1 1 d D . . . . C22 C 0.1314(4) 0.2169(3) 0.28968(13) 0.0268(7) Uani 1 1 d . . . . . H22A H 0.0285 0.2593 0.2837 0.032 Uiso 1 1 calc R U . . . H22B H 0.1940 0.2498 0.3241 0.032 Uiso 1 1 calc R U . . . C23 C 0.1024(4) 0.0816(3) 0.29831(14) 0.0252(7) Uani 1 1 d . . . . . H23B H 0.1917 0.0478 0.3245 0.030 Uiso 1 1 calc R U . . . H23A H 0.0052 0.0714 0.3155 0.030 Uiso 1 1 calc R U . . . C24 C 0.0853(4) 0.0123(3) 0.24323(13) 0.0188(6) Uani 1 1 d D . . . . C25 C 0.2168(4) -0.0435(3) 0.22412(13) 0.0189(6) Uani 1 1 d D . . . . C26 C 0.3826(4) -0.0377(3) 0.25543(13) 0.0249(7) Uani 1 1 d . . . . . H26A H 0.4553 -0.0762 0.2325 0.030 Uiso 1 1 calc R U . . . H26B H 0.3877 -0.0841 0.2907 0.030 Uiso 1 1 calc R U . . . C27 C 0.4388(4) 0.0928(3) 0.26951(14) 0.0270(7) Uani 1 1 d . . . . . H27B H 0.4219 0.1121 0.3082 0.032 Uiso 1 1 calc R U . . . H27A H 0.5535 0.0981 0.2681 0.032 Uiso 1 1 calc R U . . . N2 N -0.1452(3) 0.0101(2) 0.09657(10) 0.0156(5) Uani 1 1 d . . . . . N5 N 0.0728(3) -0.0706(2) 0.08175(10) 0.0145(5) Uani 1 1 d . . . . . N12 N 0.4269(3) -0.2454(2) 0.06805(10) 0.0156(5) Uani 1 1 d . . . . . O18 O 0.6788(2) -0.50112(19) 0.05464(10) 0.0248(5) Uani 1 1 d . . . . . Br Br 0.19054(4) 0.25478(3) 0.09866(2) 0.01891(7) Uani 1 1 d . . . . . Ir Ir 0.15174(2) 0.10981(2) 0.17503(2) 0.01334(4) Uani 1 1 d . . . . . H20 H 0.415(4) 0.226(3) 0.2049(12) 0.027(9) Uiso 1 1 d D . . . . H21 H 0.191(4) 0.321(2) 0.2204(12) 0.021(8) Uiso 1 1 d D . . . . H24 H -0.020(2) -0.024(2) 0.2340(11) 0.010(7) Uiso 1 1 d D . . . . H26 H 0.192(4) -0.119(2) 0.2027(13) 0.021(9) Uiso 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 C1 0.0162(14) 0.0130(13) 0.0165(14) 0.0027(10) 0.0043(11) -0.0028(11) C3 0.0177(16) 0.0192(14) 0.0222(16) -0.0013(12) -0.0015(13) -0.0028(12) C4 0.0219(16) 0.0162(14) 0.0184(15) -0.0035(11) 0.0000(12) -0.0013(12) C6 0.0132(15) 0.0208(15) 0.0224(16) -0.0003(12) 0.0046(12) 0.0028(11) C7 0.0205(17) 0.0297(18) 0.0276(17) 0.0013(14) 0.0098(14) 0.0002(13) C8 0.0291(19) 0.039(2) 0.0265(18) 0.0039(15) 0.0064(15) 0.0167(15) C9 0.0174(16) 0.0235(16) 0.038(2) -0.0072(14) 0.0076(14) 0.0027(13) C10 0.0122(14) 0.0178(15) 0.0263(16) -0.0040(12) 0.0074(12) 0.0000(11) C11 0.0164(15) 0.0160(14) 0.0153(14) -0.0029(11) 0.0021(11) 0.0013(11) C13 0.0153(15) 0.0193(14) 0.0126(14) -0.0018(11) 0.0013(11) 0.0017(11) C14 0.0192(15) 0.0151(14) 0.0173(15) -0.0018(11) 0.0005(12) 0.0018(11) C15 0.0161(15) 0.0170(14) 0.0241(16) 0.0004(12) 0.0014(13) -0.0040(11) C16 0.0146(14) 0.0173(14) 0.0173(14) -0.0002(11) 0.0048(11) 0.0018(11) C17 0.0160(15) 0.0175(14) 0.0205(15) -0.0011(11) 0.0017(12) 0.0031(11) C19 0.0178(16) 0.0316(18) 0.0341(19) -0.0012(15) 0.0059(14) 0.0081(13) C20 0.0234(17) 0.0217(16) 0.0200(16) -0.0025(12) 0.0007(13) -0.0093(13) C21 0.0287(18) 0.0150(14) 0.0189(15) -0.0033(12) 0.0021(13) -0.0048(13) C22 0.040(2) 0.0219(16) 0.0199(16) -0.0043(12) 0.0079(15) -0.0008(14) C23 0.0295(19) 0.0256(16) 0.0226(17) -0.0021(13) 0.0109(14) 0.0018(14) C24 0.0199(16) 0.0172(14) 0.0206(15) 0.0006(11) 0.0072(13) -0.0028(12) C25 0.0206(16) 0.0167(15) 0.0200(15) 0.0036(12) 0.0048(12) -0.0004(12) C26 0.0254(17) 0.0263(17) 0.0234(17) 0.0097(13) 0.0050(13) 0.0064(14) C27 0.0199(17) 0.0351(19) 0.0246(17) 0.0028(14) -0.0008(14) -0.0020(14) N2 0.0117(12) 0.0158(12) 0.0193(13) -0.0001(9) 0.0028(10) 0.0003(9) N5 0.0121(12) 0.0134(11) 0.0185(12) -0.0023(9) 0.0042(10) -0.0001(9) N12 0.0148(12) 0.0164(12) 0.0151(12) -0.0016(9) 0.0009(10) 0.0010(9) O18 0.0170(11) 0.0197(11) 0.0398(14) -0.0001(10) 0.0113(10) 0.0060(9) Br 0.02142(16) 0.01517(13) 0.02028(15) 0.00215(11) 0.00350(12) -0.00221(11) Ir 0.01322(6) 0.01182(6) 0.01512(6) -0.00094(4) 0.00257(4) -0.00043(4) 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' Br Br -0.2901 2.4595 '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' 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 N2 C1 N5 104.3(2) . . ? N2 C1 Ir 133.0(2) . . ? N5 C1 Ir 122.7(2) . . ? C4 C3 N2 107.8(3) . . ? C4 C3 H3 126.1 . . ? N2 C3 H3 126.1 . . ? C3 C4 N5 106.1(3) . . ? C3 C4 H4 126.9 . . ? N5 C4 H4 126.9 . . ? N2 C6 C9 111.8(2) . . ? N2 C6 C7 107.8(2) . . ? C9 C6 C7 110.9(3) . . ? N2 C6 C8 108.4(2) . . ? C9 C6 C8 108.2(3) . . ? C7 C6 C8 109.8(3) . . ? C6 C7 H7A 109.5 . . ? C6 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C6 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C6 C8 H8A 109.5 . . ? C6 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C6 C8 H8C 109.5 . . ? 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 . . ? N5 C10 C11 114.4(2) . . ? N5 C10 H10A 108.7 . . ? C11 C10 H10A 108.7 . . ? N5 C10 H10B 108.7 . . ? C11 C10 H10B 108.7 . . ? H10A C10 H10B 107.6 . . ? N12 C11 C16 123.3(3) . . ? N12 C11 C10 114.2(2) . . ? C16 C11 C10 122.6(3) . . ? N12 C13 C14 123.0(3) . . ? N12 C13 C17 114.7(3) . . ? C14 C13 C17 122.3(3) . . ? C15 C14 C13 118.5(3) . . ? C15 C14 H14 120.8 . . ? C13 C14 H14 120.8 . . ? C14 C15 C16 119.3(3) . . ? C14 C15 H15 120.4 . . ? C16 C15 H15 120.4 . . ? C11 C16 C15 118.3(3) . . ? C11 C16 H16 120.9 . . ? C15 C16 H16 120.9 . . ? O18 C17 C13 110.5(2) . . ? O18 C17 H17A 109.5 . . ? C13 C17 H17A 109.5 . . ? O18 C17 H17B 109.5 . . ? C13 C17 H17B 109.5 . . ? H17A C17 H17B 108.1 . . ? O18 C19 H19A 109.5 . . ? O18 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? O18 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? C21 C20 C27 122.5(3) . . ? C21 C20 Ir 70.81(18) . . ? C27 C20 Ir 112.9(2) . . ? C21 C20 H20 116(2) . . ? C27 C20 H20 117(2) . . ? Ir C20 H20 105(2) . . ? C20 C21 C22 125.3(3) . . ? C20 C21 Ir 72.06(17) . . ? C22 C21 Ir 109.9(2) . . ? C20 C21 H21 116.7(18) . . ? C22 C21 H21 115.7(18) . . ? Ir C21 H21 103.1(18) . . ? C21 C22 C23 113.2(3) . . ? C21 C22 H22A 108.9 . . ? C23 C22 H22A 108.9 . . ? C21 C22 H22B 108.9 . . ? C23 C22 H22B 108.9 . . ? H22A C22 H22B 107.7 . . ? C24 C23 C22 111.7(3) . . ? C24 C23 H23B 109.3 . . ? C22 C23 H23B 109.3 . . ? C24 C23 H23A 109.3 . . ? C22 C23 H23A 109.3 . . ? H23B C23 H23A 107.9 . . ? C25 C24 C23 121.7(3) . . ? C25 C24 Ir 69.66(17) . . ? C23 C24 Ir 114.7(2) . . ? C25 C24 H24 119.8(17) . . ? C23 C24 H24 111.6(17) . . ? Ir C24 H24 112.1(17) . . ? C24 C25 C26 123.5(3) . . ? C24 C25 Ir 70.96(17) . . ? C26 C25 Ir 113.5(2) . . ? C24 C25 H26 115(2) . . ? C26 C25 H26 114.1(19) . . ? Ir C25 H26 111.8(19) . . ? C25 C26 C27 112.9(3) . . ? C25 C26 H26A 109.0 . . ? C27 C26 H26A 109.0 . . ? C25 C26 H26B 109.0 . . ? C27 C26 H26B 109.0 . . ? H26A C26 H26B 107.8 . . ? C20 C27 C26 113.0(3) . . ? C20 C27 H27B 109.0 . . ? C26 C27 H27B 109.0 . . ? C20 C27 H27A 109.0 . . ? C26 C27 H27A 109.0 . . ? H27B C27 H27A 107.8 . . ? C1 N2 C3 110.3(2) . . ? C1 N2 C6 128.9(2) . . ? C3 N2 C6 120.8(2) . . ? C1 N5 C4 111.5(2) . . ? C1 N5 C10 123.9(2) . . ? C4 N5 C10 124.2(2) . . ? C11 N12 C13 117.7(3) . . ? C17 O18 C19 111.1(2) . . ? C1 Ir C25 92.48(11) . . ? C1 Ir C24 94.62(11) . . ? C25 Ir C24 39.37(11) . . ? C1 Ir C21 159.49(12) . . ? C25 Ir C21 96.99(12) . . ? C24 Ir C21 81.56(12) . . ? C1 Ir C20 163.35(12) . . ? C25 Ir C20 81.24(12) . . ? C24 Ir C20 90.26(12) . . ? C21 Ir C20 37.13(12) . . ? C1 Ir Br 87.15(8) . . ? C25 Ir Br 151.86(8) . . ? C24 Ir Br 168.65(8) . . ? C21 Ir Br 92.86(8) . . ? C20 Ir Br 91.19(8) . . ? loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 N2 1.357(4) . ? C1 N5 1.363(4) . ? C1 Ir 2.050(3) . ? C3 C4 1.341(4) . ? C3 N2 1.389(4) . ? C3 H3 0.9500 . ? C4 N5 1.382(4) . ? C4 H4 0.9500 . ? C6 N2 1.513(4) . ? C6 C9 1.520(4) . ? C6 C7 1.520(4) . ? C6 C8 1.524(4) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 N5 1.459(4) . ? C10 C11 1.515(4) . ? C10 H10A 0.9900 . ? C10 H10B 0.9900 . ? C11 N12 1.340(4) . ? C11 C16 1.384(4) . ? C13 N12 1.342(4) . ? C13 C14 1.395(4) . ? C13 C17 1.510(4) . ? C14 C15 1.375(4) . ? C14 H14 0.9500 . ? C15 C16 1.398(4) . ? C15 H15 0.9500 . ? C16 H16 0.9500 . ? C17 O18 1.410(3) . ? C17 H17A 0.9900 . ? C17 H17B 0.9900 . ? C19 O18 1.421(4) . ? C19 H19A 0.9800 . ? C19 H19B 0.9800 . ? C19 H19C 0.9800 . ? C20 C21 1.384(4) . ? C20 C27 1.510(4) . ? C20 Ir 2.182(3) . ? C20 H20 0.967(18) . ? C21 C22 1.520(4) . ? C21 Ir 2.166(3) . ? C21 H21 1.001(17) . ? C22 C23 1.541(4) . ? C22 H22A 0.9900 . ? C22 H22B 0.9900 . ? C23 C24 1.524(4) . ? C23 H23B 0.9900 . ? C23 H23A 0.9900 . ? C24 C25 1.421(4) . ? C24 Ir 2.117(3) . ? C24 H24 0.980(17) . ? C25 C26 1.507(4) . ? C25 Ir 2.100(3) . ? C25 H26 0.988(17) . ? C26 C27 1.548(4) . ? C26 H26A 0.9900 . ? C26 H26B 0.9900 . ? C27 H27B 0.9900 . ? C27 H27A 0.9900 . ? Br Ir 2.5054(3) . ?