#------------------------------------------------------------------------------ #$Date: 2021-09-30 00:46:04 +0300 (Thu, 30 Sep 2021) $ #$Revision: 269372 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/56/47/1564767.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_1564767 loop_ _publ_author_name 'Prima, Darya O.' 'Madiyeva, Malena' 'Burykina, Julia V.' 'Minyaev, Mikhail E.' 'Boiko, Daniil A.' 'Ananikov, Valentine P.' _publ_section_title ; Evidence for “cocktail”-type catalysis in Buchwald--Hartwig reaction. A mechanistic study ; _journal_name_full 'Catalysis Science & Technology' _journal_paper_doi 10.1039/D1CY01601F _journal_year 2021 _chemical_formula_moiety 'C54 H72 Br4 N4 Pd2, 2(C H2 Cl2)' _chemical_formula_sum 'C56 H76 Br4 Cl4 N4 Pd2' _chemical_formula_weight 1479.44 _space_group_crystal_system orthorhombic _space_group_IT_number 61 _space_group_name_Hall '-P 2ac 2ab' _space_group_name_H-M_alt 'P b c a' _atom_sites_solution_hydrogens geom _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _audit_creation_method SHELXL-2018/3 _audit_update_record ; 2021-04-25 deposited with the CCDC. 2021-09-13 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_formula_units_Z 4 _cell_length_a 14.6417(4) _cell_length_b 19.3275(6) _cell_length_c 22.4789(7) _cell_measurement_reflns_used 9430 _cell_measurement_temperature 100(2) _cell_measurement_theta_max 35.59 _cell_measurement_theta_min 2.52 _cell_volume 6361.2(3) _computing_cell_refinement 'SAINT (Bruker, 2019)' _computing_data_collection 'APEX3 (Bruker, 2019)' _computing_data_reduction 'SAINT (Bruker, 2019)' _computing_molecular_graphics 'SHELXTL (Sheldrick, Acta Cryst., 2008, A64, 112-122)' _computing_publication_material 'SHELXTL (Sheldrick, Acta Cryst., 2008, A64, 112-122)' _computing_structure_refinement 'SHELXL-2018 (Sheldrick, Acta Cryst., 2015, C71, 3-8)' _computing_structure_solution 'SHELXT, SHELXS-2013 (Sheldrick, Acta Cryst., 2015, A71, 3-8)' _diffrn_ambient_temperature 100(2) _diffrn_detector_area_resol_mean 7.31 _diffrn_measured_fraction_theta_full 0.999 _diffrn_measured_fraction_theta_max 0.999 _diffrn_measurement_device_type 'Bruker AXS D8 QUEST, Photon III detector' _diffrn_measurement_method '\f and \w shutterless scans' _diffrn_radiation_monochromator graphite _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_reflns_av_R_equivalents 0.0268 _diffrn_reflns_av_unetI/netI 0.0152 _diffrn_reflns_Laue_measured_fraction_full 0.999 _diffrn_reflns_Laue_measured_fraction_max 0.999 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_k_max 31 _diffrn_reflns_limit_k_min -31 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_limit_l_min -36 _diffrn_reflns_number 120402 _diffrn_reflns_point_group_measured_fraction_full 0.999 _diffrn_reflns_point_group_measured_fraction_max 0.999 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 34.998 _diffrn_reflns_theta_min 2.284 _diffrn_source 'sealed X-Ray tube' _diffrn_source_current 30 _diffrn_source_power 50 _diffrn_source_size '0.6 mm, fine-focus' _exptl_absorpt_coefficient_mu 3.282 _exptl_absorpt_correction_T_max 0.1649 _exptl_absorpt_correction_T_min 0.0846 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS 2016/2 (Krause et al., J. Appl. Cryst. 2015, 48, 3-10)' _exptl_crystal_colour 'pale orange' _exptl_crystal_density_diffrn 1.545 _exptl_crystal_density_method 'not measured' _exptl_crystal_description block _exptl_crystal_F_000 2960 _exptl_crystal_size_max 0.57 _exptl_crystal_size_mid 0.38 _exptl_crystal_size_min 0.18 _refine_diff_density_max 1.276 _refine_diff_density_min -1.181 _refine_diff_density_rms 0.099 _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.037 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 334 _refine_ls_number_reflns 13997 _refine_ls_number_restraints 2 _refine_ls_restrained_S_all 1.037 _refine_ls_R_factor_all 0.0371 _refine_ls_R_factor_gt 0.0304 _refine_ls_shift/su_max 0.004 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(0.0423P)^2^+6.6724P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0809 _refine_ls_wR_factor_ref 0.0849 _reflns_Friedel_coverage 0.000 _reflns_number_gt 12064 _reflns_number_total 13997 _reflns_threshold_expression 'I > 2\s(I)' _cod_data_source_file d1cy01601f2.cif _cod_data_source_block 2b _cod_database_code 1564767 _shelx_shelxl_version_number 2018/3 _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_estimated_absorpt_t_min 0.256 _shelx_estimated_absorpt_t_max 0.590 _shelx_res_file ; TITL MM2 in Pbca MM2b.res created by SHELXL-2018/3 at 11:57:49 on 30-Mar-2021 CELL 0.71073 14.6417 19.3275 22.4789 90.000 90.000 90.000 ZERR 4.00 0.0004 0.0006 0.0007 0.000 0.000 0.000 LATT 1 SYMM x+1/2, -y+1/2, -z SYMM -x, y+1/2, -z+1/2 SYMM -x+1/2, -y, z+1/2 SFAC C H N CL BR PD UNIT 224 304 16 16 16 8 TEMP -173.15 SIZE 0.18 0.38 0.57 OMIT -4 70 LIST 4 L.S. 8 FMAP 2 PLAN 25 ACTA BOND $H CONF EADP Cl1A Cl1B EADP Cl2A Cl2B EADP C28A C28B SADI 0.003 C28A Cl1A C28B Cl1B SADI 0.003 C28A Cl2A C28B Cl2B WGHT 0.042300 6.672400 FVAR 0.06077 0.82826 PD1 6 0.468292 0.588892 0.501403 11.00000 0.01175 0.01535 = 0.01601 0.00044 -0.00066 0.00094 BR1 5 0.605326 0.518291 0.528650 11.00000 0.01713 0.01877 = 0.03501 -0.00091 -0.00593 0.00182 BR2 5 0.544719 0.690928 0.535129 11.00000 0.01750 0.02094 = 0.02950 -0.00205 -0.00146 -0.00235 N1 3 0.319748 0.647606 0.425853 11.00000 0.01532 0.02053 = 0.01793 -0.00121 -0.00303 0.00417 N2 3 0.304289 0.679020 0.517349 11.00000 0.01460 0.01979 = 0.02011 -0.00433 -0.00203 0.00308 C1 1 0.359242 0.642448 0.480239 11.00000 0.01396 0.01653 = 0.01720 -0.00068 -0.00061 0.00000 C2 1 0.230400 0.706051 0.486317 11.00000 0.01711 0.02718 = 0.02792 -0.00788 -0.00592 0.00749 AFIX 43 H2 2 0.182002 0.732870 0.502459 11.00000 -1.20000 AFIX 0 C3 1 0.240302 0.687101 0.429134 11.00000 0.01867 0.02586 = 0.02594 -0.00413 -0.00667 0.00747 AFIX 43 H3 2 0.200718 0.698462 0.397105 11.00000 -1.20000 AFIX 0 C4 1 0.354703 0.621719 0.370176 11.00000 0.01854 0.02489 = 0.01612 -0.00001 -0.00136 0.00494 C5 1 0.432416 0.653832 0.345944 11.00000 0.02277 0.03294 = 0.02099 0.00743 -0.00101 0.00196 C6 1 0.462648 0.629659 0.290716 11.00000 0.03297 0.04456 = 0.02364 0.00877 0.00676 0.00514 AFIX 43 H6 2 0.515591 0.649492 0.273220 11.00000 -1.20000 AFIX 0 C7 1 0.416938 0.577488 0.261159 11.00000 0.04253 0.04592 = 0.02178 0.00187 0.00729 0.01461 AFIX 43 H7 2 0.438718 0.561907 0.223671 11.00000 -1.20000 AFIX 0 C8 1 0.339919 0.547791 0.285588 11.00000 0.03541 0.03463 = 0.02169 -0.00667 -0.00091 0.00916 AFIX 43 H8 2 0.309082 0.512212 0.264450 11.00000 -1.20000 AFIX 0 C9 1 0.306486 0.569010 0.340712 11.00000 0.02238 0.02759 = 0.02003 -0.00468 -0.00307 0.00571 C10 1 0.478256 0.714893 0.376246 11.00000 0.03106 0.04070 = 0.02763 0.01295 -0.00531 -0.01190 AFIX 13 H10 2 0.470805 0.708294 0.420101 11.00000 -1.20000 AFIX 0 C11 1 0.429340 0.782406 0.359830 11.00000 0.07102 0.03209 = 0.07340 0.01384 -0.03111 -0.01840 AFIX 137 H11A 2 0.436364 0.791147 0.317131 11.00000 -1.50000 H11B 2 0.456100 0.820803 0.382346 11.00000 -1.50000 H11C 2 0.364297 0.778413 0.369524 11.00000 -1.50000 AFIX 0 C12 1 0.580664 0.719828 0.363849 11.00000 0.03490 0.09986 = 0.04248 0.01115 -0.00146 -0.02748 AFIX 137 H12A 2 0.609824 0.675539 0.373326 11.00000 -1.50000 H12B 2 0.607369 0.756411 0.388521 11.00000 -1.50000 H12C 2 0.590476 0.730699 0.321748 11.00000 -1.50000 AFIX 0 C13 1 0.219197 0.536865 0.364716 11.00000 0.02271 0.03499 = 0.02989 -0.01155 -0.00310 -0.00152 AFIX 13 H13 2 0.213451 0.549724 0.407644 11.00000 -1.20000 AFIX 0 C14 1 0.135721 0.566037 0.331377 11.00000 0.02565 0.05564 = 0.04663 -0.02076 -0.01055 0.00666 AFIX 137 H14A 2 0.139872 0.553772 0.289161 11.00000 -1.50000 H14B 2 0.134458 0.616506 0.335492 11.00000 -1.50000 H14C 2 0.079733 0.546388 0.348269 11.00000 -1.50000 AFIX 0 C15 1 0.218113 0.457440 0.360133 11.00000 0.03816 0.03745 = 0.04366 -0.01245 -0.00643 -0.00962 AFIX 137 H15A 2 0.218796 0.443771 0.318153 11.00000 -1.50000 H15B 2 0.162785 0.439447 0.379175 11.00000 -1.50000 H15C 2 0.272067 0.438514 0.380153 11.00000 -1.50000 AFIX 0 C16 1 0.316723 0.695319 0.579599 11.00000 0.01627 0.02321 = 0.02032 -0.00606 -0.00122 0.00290 C17 1 0.342455 0.763561 0.593781 11.00000 0.01833 0.02417 = 0.02979 -0.00928 -0.00423 0.00303 C18 1 0.342658 0.780779 0.654186 11.00000 0.02889 0.03428 = 0.03356 -0.01619 -0.00756 0.00527 AFIX 43 H18 2 0.359430 0.826286 0.665840 11.00000 -1.20000 AFIX 0 C19 1 0.319025 0.733126 0.697295 11.00000 0.03672 0.04550 = 0.02446 -0.01413 -0.00349 0.01104 AFIX 43 H19 2 0.318409 0.746497 0.737961 11.00000 -1.20000 AFIX 0 C20 1 0.296245 0.666077 0.681718 11.00000 0.03577 0.03996 = 0.02157 -0.00398 0.00195 0.00871 AFIX 43 H20 2 0.281788 0.633506 0.711936 11.00000 -1.20000 AFIX 0 C21 1 0.294220 0.645628 0.622102 11.00000 0.02258 0.02916 = 0.02110 -0.00353 0.00328 0.00300 C22 1 0.367729 0.817279 0.547433 11.00000 0.02359 0.02229 = 0.04045 -0.00597 -0.00412 -0.00015 AFIX 13 H22 2 0.381273 0.792595 0.509344 11.00000 -1.20000 AFIX 0 C23 1 0.289233 0.867926 0.535989 11.00000 0.03107 0.02631 = 0.05632 -0.00210 -0.00878 0.00402 AFIX 137 H23A 2 0.308693 0.902819 0.507009 11.00000 -1.50000 H23B 2 0.272316 0.890735 0.573334 11.00000 -1.50000 H23C 2 0.236459 0.842633 0.520302 11.00000 -1.50000 AFIX 0 C24 1 0.452878 0.858551 0.565194 11.00000 0.02780 0.02435 = 0.06628 -0.01087 -0.00632 -0.00273 AFIX 137 H24A 2 0.502196 0.826523 0.575701 11.00000 -1.50000 H24B 2 0.438631 0.887937 0.599489 11.00000 -1.50000 H24C 2 0.472241 0.887577 0.531746 11.00000 -1.50000 AFIX 0 C25 1 0.266870 0.572215 0.606403 11.00000 0.03073 0.02680 = 0.02728 0.00003 0.00667 -0.00128 AFIX 13 H25 2 0.274133 0.566420 0.562451 11.00000 -1.20000 AFIX 0 C26 1 0.166602 0.558990 0.621790 11.00000 0.03988 0.04605 = 0.05678 -0.00458 0.01722 -0.00933 AFIX 137 H26A 2 0.127738 0.589880 0.598243 11.00000 -1.50000 H26B 2 0.156671 0.567835 0.664228 11.00000 -1.50000 H26C 2 0.151165 0.510784 0.612756 11.00000 -1.50000 AFIX 0 C27 1 0.329781 0.519356 0.637238 11.00000 0.05485 0.02963 = 0.04012 0.00221 -0.00251 0.00346 AFIX 137 H27A 2 0.393041 0.527174 0.624681 11.00000 -1.50000 H27B 2 0.311112 0.472394 0.626177 11.00000 -1.50000 H27C 2 0.325216 0.524872 0.680474 11.00000 -1.50000 AFIX 0 PART 1 21 CL1A 4 0.498529 0.404849 0.252697 21.00000 0.07868 0.05629 = 0.02872 -0.00155 -0.00111 0.03489 CL2A 4 0.371869 0.302939 0.301343 21.00000 0.05504 0.09213 = 0.04638 -0.01622 -0.01655 0.00158 C28A 1 0.459422 0.363514 0.317650 21.00000 0.04017 0.06948 = 0.02598 -0.00844 -0.00391 0.01293 AFIX 23 H28A 2 0.435769 0.398652 0.345749 21.00000 -1.20000 H28B 2 0.511047 0.339364 0.337086 21.00000 -1.20000 AFIX 0 PART 2 -21 CL1B 4 0.481794 0.406702 0.262827 -21.00000 0.07868 0.05629 = 0.02872 -0.00155 -0.00111 0.03489 CL2B 4 0.388709 0.281526 0.303823 -21.00000 0.05504 0.09213 = 0.04638 -0.01622 -0.01655 0.00158 C28B 1 0.454807 0.354603 0.324551 -21.00000 0.04017 0.06948 = 0.02598 -0.00844 -0.00391 0.01293 AFIX 23 H28C 2 0.420372 0.382427 0.353949 -21.00000 -1.20000 H28D 2 0.511995 0.338793 0.343717 -21.00000 -1.20000 PART 0 AFIX 0 HKLF 4 REM MM2 in Pbca REM wR2 = 0.084912, GooF = S = 1.03715, Restrained GooF = 1.03708 for all data REM R1 = 0.030368 for 12064 Fo > 4sig(Fo) and 0.037140 for all 13997 data REM 334 parameters refined using 2 restraints END WGHT 0.0423 6.6724 REM Highest difference peak 1.276, deepest hole -1.181, 1-sigma level 0.099 Q1 1 0.4709 0.5880 0.5251 11.00000 0.05 1.01 Q2 1 0.3527 0.3100 0.3204 11.00000 0.05 0.77 Q3 1 0.3811 0.3299 0.2811 11.00000 0.05 0.75 Q4 1 0.5418 0.6869 0.5730 11.00000 0.05 0.75 Q5 1 0.3594 0.2685 0.2949 11.00000 0.05 0.75 Q6 1 0.2346 0.7049 0.4569 11.00000 0.05 0.70 Q7 1 0.4634 0.5882 0.4698 11.00000 0.05 0.69 Q8 1 0.5431 0.6899 0.4988 11.00000 0.05 0.69 Q9 1 0.5431 0.6941 0.4645 11.00000 0.05 0.59 Q10 1 0.4630 0.5154 0.5329 11.00000 0.05 0.58 Q11 1 0.3016 0.6727 0.5993 11.00000 0.05 0.54 Q12 1 0.3412 0.6432 0.4506 11.00000 0.05 0.53 Q13 1 0.6132 0.5156 0.5708 11.00000 0.05 0.51 Q14 1 0.2862 0.6584 0.6533 11.00000 0.05 0.51 Q15 1 0.5961 0.5886 0.4996 11.00000 0.05 0.51 Q16 1 0.4649 0.3902 0.2916 11.00000 0.05 0.50 Q17 1 0.3343 0.7268 0.5891 11.00000 0.05 0.49 Q18 1 0.3206 0.5656 0.3125 11.00000 0.05 0.49 Q19 1 0.3241 0.5934 0.3563 11.00000 0.05 0.47 Q20 1 0.3442 0.7704 0.6244 11.00000 0.05 0.46 Q21 1 0.3243 0.6566 0.5034 11.00000 0.05 0.46 Q22 1 0.4486 0.6459 0.3195 11.00000 0.05 0.45 Q23 1 0.3388 0.6358 0.4041 11.00000 0.05 0.43 Q24 1 0.6046 0.5148 0.4716 11.00000 0.05 0.43 Q25 1 0.3897 0.6402 0.3600 11.00000 0.05 0.43 ; _shelx_res_checksum 80166 loop_ _space_group_symop_operation_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' 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 Pd1 Pd 0.46829(2) 0.58889(2) 0.50140(2) 0.01437(3) Uani 1 1 d . . . . . Br1 Br 0.60533(2) 0.51829(2) 0.52865(2) 0.02364(4) Uani 1 1 d . . . . . Br2 Br 0.54472(2) 0.69093(2) 0.53513(2) 0.02265(4) Uani 1 1 d . . . . . N1 N 0.31975(9) 0.64761(7) 0.42585(6) 0.0179(2) Uani 1 1 d . . . . . N2 N 0.30429(9) 0.67902(7) 0.51735(6) 0.0182(2) Uani 1 1 d . . . . . C1 C 0.35924(10) 0.64245(7) 0.48024(6) 0.0159(2) Uani 1 1 d . . . . . C2 C 0.23040(11) 0.70605(9) 0.48632(8) 0.0241(3) Uani 1 1 d . . . . . H2 H 0.182002 0.732870 0.502459 0.029 Uiso 1 1 calc R U . . . C3 C 0.24030(11) 0.68710(9) 0.42913(8) 0.0235(3) Uani 1 1 d . . . . . H3 H 0.200718 0.698462 0.397105 0.028 Uiso 1 1 calc R U . . . C4 C 0.35470(11) 0.62172(9) 0.37018(7) 0.0199(3) Uani 1 1 d . . . . . C5 C 0.43242(12) 0.65383(10) 0.34594(8) 0.0256(3) Uani 1 1 d . . . . . C6 C 0.46265(15) 0.62966(12) 0.29072(9) 0.0337(4) Uani 1 1 d . . . . . H6 H 0.515591 0.649492 0.273220 0.040 Uiso 1 1 calc R U . . . C7 C 0.41694(17) 0.57749(13) 0.26116(9) 0.0367(4) Uani 1 1 d . . . . . H7 H 0.438718 0.561907 0.223671 0.044 Uiso 1 1 calc R U . . . C8 C 0.33992(14) 0.54779(11) 0.28559(8) 0.0306(4) Uani 1 1 d . . . . . H8 H 0.309082 0.512212 0.264450 0.037 Uiso 1 1 calc R U . . . C9 C 0.30649(12) 0.56901(9) 0.34071(7) 0.0233(3) Uani 1 1 d . . . . . C10 C 0.47826(14) 0.71489(12) 0.37625(9) 0.0331(4) Uani 1 1 d . . . . . H10 H 0.470805 0.708294 0.420101 0.040 Uiso 1 1 calc R U . . . C11 C 0.4293(2) 0.78241(14) 0.35983(16) 0.0588(8) Uani 1 1 d . . . . . H11A H 0.436364 0.791147 0.317131 0.088 Uiso 1 1 calc R U . . . H11B H 0.456100 0.820803 0.382346 0.088 Uiso 1 1 calc R U . . . H11C H 0.364297 0.778413 0.369524 0.088 Uiso 1 1 calc R U . . . C12 C 0.58066(19) 0.7198(2) 0.36385(13) 0.0591(9) Uani 1 1 d . . . . . H12A H 0.609824 0.675539 0.373326 0.089 Uiso 1 1 calc R U . . . H12B H 0.607369 0.756411 0.388521 0.089 Uiso 1 1 calc R U . . . H12C H 0.590476 0.730699 0.321748 0.089 Uiso 1 1 calc R U . . . C13 C 0.21920(13) 0.53686(11) 0.36472(9) 0.0292(4) Uani 1 1 d . . . . . H13 H 0.213451 0.549724 0.407644 0.035 Uiso 1 1 calc R U . . . C14 C 0.13572(15) 0.56604(14) 0.33138(12) 0.0426(5) Uani 1 1 d . . . . . H14A H 0.139872 0.553772 0.289161 0.064 Uiso 1 1 calc R U . . . H14B H 0.134458 0.616506 0.335492 0.064 Uiso 1 1 calc R U . . . H14C H 0.079733 0.546388 0.348269 0.064 Uiso 1 1 calc R U . . . C15 C 0.21811(17) 0.45744(12) 0.36013(11) 0.0398(5) Uani 1 1 d . . . . . H15A H 0.218796 0.443771 0.318153 0.060 Uiso 1 1 calc R U . . . H15B H 0.162785 0.439447 0.379175 0.060 Uiso 1 1 calc R U . . . H15C H 0.272067 0.438514 0.380153 0.060 Uiso 1 1 calc R U . . . C16 C 0.31672(10) 0.69532(8) 0.57960(7) 0.0199(3) Uani 1 1 d . . . . . C17 C 0.34246(11) 0.76356(9) 0.59378(8) 0.0241(3) Uani 1 1 d . . . . . C18 C 0.34266(14) 0.78078(11) 0.65419(9) 0.0322(4) Uani 1 1 d . . . . . H18 H 0.359430 0.826286 0.665840 0.039 Uiso 1 1 calc R U . . . C19 C 0.31902(16) 0.73313(12) 0.69730(9) 0.0356(4) Uani 1 1 d . . . . . H19 H 0.318409 0.746497 0.737961 0.043 Uiso 1 1 calc R U . . . C20 C 0.29624(15) 0.66608(12) 0.68172(8) 0.0324(4) Uani 1 1 d . . . . . H20 H 0.281788 0.633506 0.711936 0.039 Uiso 1 1 calc R U . . . C21 C 0.29422(12) 0.64563(9) 0.62210(8) 0.0243(3) Uani 1 1 d . . . . . C22 C 0.36773(13) 0.81728(9) 0.54743(10) 0.0288(3) Uani 1 1 d . . . . . H22 H 0.381273 0.792595 0.509344 0.035 Uiso 1 1 calc R U . . . C23 C 0.28923(15) 0.86793(11) 0.53599(12) 0.0379(5) Uani 1 1 d . . . . . H23A H 0.308693 0.902819 0.507009 0.057 Uiso 1 1 calc R U . . . H23B H 0.272316 0.890735 0.573334 0.057 Uiso 1 1 calc R U . . . H23C H 0.236459 0.842633 0.520302 0.057 Uiso 1 1 calc R U . . . C24 C 0.45288(15) 0.85855(11) 0.56519(13) 0.0395(5) Uani 1 1 d . . . . . H24A H 0.502196 0.826523 0.575701 0.059 Uiso 1 1 calc R U . . . H24B H 0.438631 0.887937 0.599489 0.059 Uiso 1 1 calc R U . . . H24C H 0.472241 0.887577 0.531746 0.059 Uiso 1 1 calc R U . . . C25 C 0.26687(14) 0.57221(10) 0.60640(9) 0.0283(3) Uani 1 1 d . . . . . H25 H 0.274133 0.566420 0.562451 0.034 Uiso 1 1 calc R U . . . C26 C 0.16660(18) 0.55899(15) 0.62179(13) 0.0476(6) Uani 1 1 d . . . . . H26A H 0.127738 0.589880 0.598243 0.071 Uiso 1 1 calc R U . . . H26B H 0.156671 0.567835 0.664228 0.071 Uiso 1 1 calc R U . . . H26C H 0.151165 0.510784 0.612756 0.071 Uiso 1 1 calc R U . . . C27 C 0.32978(19) 0.51936(12) 0.63724(11) 0.0415(5) Uani 1 1 d . . . . . H27A H 0.393041 0.527174 0.624681 0.062 Uiso 1 1 calc R U . . . H27B H 0.311112 0.472394 0.626177 0.062 Uiso 1 1 calc R U . . . H27C H 0.325216 0.524872 0.680474 0.062 Uiso 1 1 calc R U . . . Cl1A Cl 0.4985(2) 0.40485(10) 0.25270(11) 0.0546(4) Uani 0.828(12) 1 d D . P A 1 Cl2A Cl 0.37187(18) 0.3029(2) 0.30134(7) 0.0645(5) Uani 0.828(12) 1 d D . P A 1 C28A C 0.4594(8) 0.3635(4) 0.31765(18) 0.0452(7) Uani 0.828(12) 1 d D . P A 1 H28A H 0.435769 0.398652 0.345749 0.054 Uiso 0.828(12) 1 calc R U P A 1 H28B H 0.511047 0.339364 0.337086 0.054 Uiso 0.828(12) 1 calc R U P A 1 Cl1B Cl 0.4818(9) 0.4067(6) 0.2628(4) 0.0546(4) Uani 0.172(12) 1 d D . P A 2 Cl2B Cl 0.3887(8) 0.2815(8) 0.3038(4) 0.0645(5) Uani 0.172(12) 1 d D . P A 2 C28B C 0.455(4) 0.355(2) 0.3246(7) 0.0452(7) Uani 0.172(12) 1 d D . P A 2 H28C H 0.420372 0.382427 0.353949 0.054 Uiso 0.172(12) 1 calc R U P A 2 H28D H 0.511995 0.338793 0.343717 0.054 Uiso 0.172(12) 1 calc R U P A 2 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 Pd1 0.01175(5) 0.01535(5) 0.01601(5) 0.00044(3) -0.00066(3) 0.00094(3) Br1 0.01713(7) 0.01877(7) 0.03501(9) -0.00091(6) -0.00593(6) 0.00182(5) Br2 0.01750(7) 0.02094(7) 0.02950(8) -0.00205(5) -0.00146(5) -0.00235(5) N1 0.0153(5) 0.0205(5) 0.0179(5) -0.0012(4) -0.0030(4) 0.0042(4) N2 0.0146(5) 0.0198(5) 0.0201(5) -0.0043(4) -0.0020(4) 0.0031(4) C1 0.0140(5) 0.0165(5) 0.0172(6) -0.0007(4) -0.0006(4) 0.0000(4) C2 0.0171(6) 0.0272(7) 0.0279(7) -0.0079(6) -0.0059(5) 0.0075(5) C3 0.0187(6) 0.0259(7) 0.0259(7) -0.0041(6) -0.0067(5) 0.0075(5) C4 0.0185(6) 0.0249(7) 0.0161(6) 0.0000(5) -0.0014(5) 0.0049(5) C5 0.0228(7) 0.0329(8) 0.0210(7) 0.0074(6) -0.0010(6) 0.0020(6) C6 0.0330(9) 0.0446(11) 0.0236(8) 0.0088(7) 0.0068(7) 0.0051(8) C7 0.0425(11) 0.0459(11) 0.0218(8) 0.0019(7) 0.0073(7) 0.0146(9) C8 0.0354(9) 0.0346(9) 0.0217(7) -0.0067(6) -0.0009(6) 0.0092(7) C9 0.0224(7) 0.0276(7) 0.0200(6) -0.0047(5) -0.0031(5) 0.0057(6) C10 0.0311(9) 0.0407(10) 0.0276(8) 0.0129(7) -0.0053(7) -0.0119(8) C11 0.0710(19) 0.0321(11) 0.0734(19) 0.0138(12) -0.0311(16) -0.0184(12) C12 0.0349(12) 0.100(3) 0.0425(13) 0.0112(15) -0.0015(10) -0.0275(14) C13 0.0227(7) 0.0350(9) 0.0299(8) -0.0116(7) -0.0031(6) -0.0015(6) C14 0.0257(9) 0.0556(14) 0.0466(12) -0.0208(11) -0.0105(8) 0.0067(9) C15 0.0382(11) 0.0375(11) 0.0437(12) -0.0124(9) -0.0064(9) -0.0096(9) C16 0.0163(6) 0.0232(6) 0.0203(6) -0.0061(5) -0.0012(5) 0.0029(5) C17 0.0183(6) 0.0242(7) 0.0298(8) -0.0093(6) -0.0042(6) 0.0030(5) C18 0.0289(8) 0.0343(9) 0.0336(9) -0.0162(7) -0.0076(7) 0.0053(7) C19 0.0367(10) 0.0455(11) 0.0245(8) -0.0141(8) -0.0035(7) 0.0110(9) C20 0.0358(9) 0.0400(10) 0.0216(7) -0.0040(7) 0.0019(7) 0.0087(8) C21 0.0226(7) 0.0292(8) 0.0211(7) -0.0035(6) 0.0033(5) 0.0030(6) C22 0.0236(7) 0.0223(7) 0.0404(10) -0.0060(7) -0.0041(7) -0.0001(6) C23 0.0311(9) 0.0263(8) 0.0563(13) -0.0021(8) -0.0088(9) 0.0040(7) C24 0.0278(9) 0.0244(8) 0.0663(15) -0.0109(9) -0.0063(9) -0.0027(7) C25 0.0307(8) 0.0268(8) 0.0273(8) 0.0000(6) 0.0067(6) -0.0013(7) C26 0.0399(12) 0.0460(13) 0.0568(15) -0.0046(11) 0.0172(11) -0.0093(10) C27 0.0549(14) 0.0296(9) 0.0401(11) 0.0022(8) -0.0025(10) 0.0035(9) Cl1A 0.0787(10) 0.0563(4) 0.0287(6) -0.0016(4) -0.0011(6) 0.0349(5) Cl2A 0.0550(8) 0.0921(15) 0.0464(4) -0.0162(7) -0.0165(5) 0.0016(8) C28A 0.0402(18) 0.069(3) 0.0260(13) -0.0084(14) -0.0039(18) 0.0129(17) Cl1B 0.0787(10) 0.0563(4) 0.0287(6) -0.0016(4) -0.0011(6) 0.0349(5) Cl2B 0.0550(8) 0.0921(15) 0.0464(4) -0.0162(7) -0.0165(5) 0.0016(8) C28B 0.0402(18) 0.069(3) 0.0260(13) -0.0084(14) -0.0039(18) 0.0129(17) 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' Cl Cl 0.1484 0.1585 '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' Pd Pd -0.9988 1.0072 '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 C1 Pd1 Br2 91.30(4) . . ? C1 Pd1 Br1 91.22(4) . 5_666 ? Br2 Pd1 Br1 176.920(8) . 5_666 ? C1 Pd1 Br1 178.77(4) . . ? Br2 Pd1 Br1 89.823(7) . . ? Br1 Pd1 Br1 87.642(6) 5_666 . ? Pd1 Br1 Pd1 92.357(7) 5_666 . ? C1 N1 C3 110.40(13) . . ? C1 N1 C4 127.28(12) . . ? C3 N1 C4 122.17(13) . . ? C1 N2 C2 110.42(13) . . ? C1 N2 C16 129.31(13) . . ? C2 N2 C16 120.14(13) . . ? N1 C1 N2 105.25(12) . . ? N1 C1 Pd1 127.20(11) . . ? N2 C1 Pd1 127.46(11) . . ? C3 C2 N2 107.08(14) . . ? C3 C2 H2 126.5 . . ? N2 C2 H2 126.5 . . ? C2 C3 N1 106.85(14) . . ? C2 C3 H3 126.6 . . ? N1 C3 H3 126.6 . . ? C9 C4 C5 122.96(15) . . ? C9 C4 N1 118.84(14) . . ? C5 C4 N1 118.06(15) . . ? C6 C5 C4 116.91(18) . . ? C6 C5 C10 121.19(18) . . ? C4 C5 C10 121.79(16) . . ? C7 C6 C5 121.18(19) . . ? C7 C6 H6 119.4 . . ? C5 C6 H6 119.4 . . ? C8 C7 C6 120.57(18) . . ? C8 C7 H7 119.7 . . ? C6 C7 H7 119.7 . . ? C7 C8 C9 121.24(19) . . ? C7 C8 H8 119.4 . . ? C9 C8 H8 119.4 . . ? C8 C9 C4 117.12(17) . . ? C8 C9 C13 119.38(17) . . ? C4 C9 C13 123.46(15) . . ? C5 C10 C12 113.6(2) . . ? C5 C10 C11 110.29(17) . . ? C12 C10 C11 111.2(2) . . ? C5 C10 H10 107.1 . . ? C12 C10 H10 107.1 . . ? C11 C10 H10 107.1 . . ? 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 . . ? 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 . . ? C9 C13 C15 113.12(17) . . ? C9 C13 C14 110.17(18) . . ? C15 C13 C14 108.93(17) . . ? C9 C13 H13 108.2 . . ? C15 C13 H13 108.2 . . ? C14 C13 H13 108.2 . . ? C13 C14 H14A 109.5 . . ? C13 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C13 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C13 C15 H15A 109.5 . . ? C13 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? C13 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? C21 C16 C17 123.59(15) . . ? C21 C16 N2 118.91(14) . . ? C17 C16 N2 117.18(15) . . ? C18 C17 C16 116.32(18) . . ? C18 C17 C22 120.25(17) . . ? C16 C17 C22 123.43(16) . . ? C19 C18 C17 121.48(18) . . ? C19 C18 H18 119.3 . . ? C17 C18 H18 119.3 . . ? C18 C19 C20 120.51(18) . . ? C18 C19 H19 119.7 . . ? C20 C19 H19 119.7 . . ? C19 C20 C21 120.9(2) . . ? C19 C20 H20 119.6 . . ? C21 C20 H20 119.6 . . ? C16 C21 C20 117.21(17) . . ? C16 C21 C25 123.21(15) . . ? C20 C21 C25 119.57(17) . . ? C17 C22 C23 111.71(17) . . ? C17 C22 C24 112.07(18) . . ? C23 C22 C24 108.75(16) . . ? C17 C22 H22 108.1 . . ? C23 C22 H22 108.1 . . ? C24 C22 H22 108.1 . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C21 C25 C26 110.93(17) . . ? C21 C25 C27 110.98(17) . . ? C26 C25 C27 111.18(19) . . ? C21 C25 H25 107.9 . . ? C26 C25 H25 107.9 . . ? C27 C25 H25 107.9 . . ? C25 C26 H26A 109.5 . . ? C25 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? C25 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? C25 C27 H27A 109.5 . . ? C25 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? C25 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? Cl1A C28A Cl2A 111.3(2) . . ? Cl1A C28A H28A 109.4 . . ? Cl2A C28A H28A 109.4 . . ? Cl1A C28A H28B 109.4 . . ? Cl2A C28A H28B 109.4 . . ? H28A C28A H28B 108.0 . . ? Cl1B C28B Cl2B 111.8(10) . . ? Cl1B C28B H28C 109.3 . . ? Cl2B C28B H28C 109.3 . . ? Cl1B C28B H28D 109.3 . . ? Cl2B C28B H28D 109.3 . . ? H28C C28B H28D 107.9 . . ? 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 Pd1 C1 1.9614(14) . ? Pd1 Br2 2.3908(2) . ? Pd1 Br1 2.4309(2) 5_666 ? Pd1 Br1 2.5026(2) . ? N1 C1 1.3561(19) . ? N1 C3 1.393(2) . ? N1 C4 1.442(2) . ? N2 C1 1.3575(19) . ? N2 C2 1.389(2) . ? N2 C16 1.446(2) . ? C2 C3 1.344(2) . ? C2 H2 0.9500 . ? C3 H3 0.9500 . ? C4 C9 1.405(2) . ? C4 C5 1.406(2) . ? C5 C6 1.398(3) . ? C5 C10 1.519(3) . ? C6 C7 1.381(4) . ? C6 H6 0.9500 . ? C7 C8 1.379(3) . ? C7 H7 0.9500 . ? C8 C9 1.394(2) . ? C8 H8 0.9500 . ? C9 C13 1.520(3) . ? C10 C12 1.528(3) . ? C10 C11 1.534(4) . ? C10 H10 1.0000 . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? C13 C15 1.539(3) . ? C13 C14 1.541(3) . ? C13 H13 1.0000 . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? C16 C21 1.394(2) . ? C16 C17 1.408(2) . ? C17 C18 1.398(3) . ? C17 C22 1.517(3) . ? C18 C19 1.381(3) . ? C18 H18 0.9500 . ? C19 C20 1.383(3) . ? C19 H19 0.9500 . ? C20 C21 1.397(2) . ? C20 H20 0.9500 . ? C21 C25 1.516(3) . ? C22 C23 1.531(3) . ? C22 C24 1.533(3) . ? C22 H22 1.0000 . ? C23 H23A 0.9800 . ? C23 H23B 0.9800 . ? C23 H23C 0.9800 . ? C24 H24A 0.9800 . ? C24 H24B 0.9800 . ? C24 H24C 0.9800 . ? C25 C26 1.530(3) . ? C25 C27 1.540(3) . ? C25 H25 1.0000 . ? C26 H26A 0.9800 . ? C26 H26B 0.9800 . ? C26 H26C 0.9800 . ? C27 H27A 0.9800 . ? C27 H27B 0.9800 . ? C27 H27C 0.9800 . ? Cl1A C28A 1.760(3) . ? Cl2A C28A 1.774(4) . ? C28A H28A 0.9900 . ? C28A H28B 0.9900 . ? Cl1B C28B 1.759(4) . ? Cl2B C28B 1.774(5) . ? C28B H28C 0.9900 . ? C28B H28D 0.9900 . ? 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 C3 N1 C1 N2 -0.17(17) . . . . ? C4 N1 C1 N2 175.43(15) . . . . ? C3 N1 C1 Pd1 176.49(12) . . . . ? C4 N1 C1 Pd1 -7.9(2) . . . . ? C2 N2 C1 N1 0.74(18) . . . . ? C16 N2 C1 N1 -174.96(15) . . . . ? C2 N2 C1 Pd1 -175.92(12) . . . . ? C16 N2 C1 Pd1 8.4(2) . . . . ? C1 N2 C2 C3 -1.0(2) . . . . ? C16 N2 C2 C3 175.11(15) . . . . ? N2 C2 C3 N1 0.9(2) . . . . ? C1 N1 C3 C2 -0.5(2) . . . . ? C4 N1 C3 C2 -176.32(16) . . . . ? C1 N1 C4 C9 114.92(18) . . . . ? C3 N1 C4 C9 -70.0(2) . . . . ? C1 N1 C4 C5 -69.3(2) . . . . ? C3 N1 C4 C5 105.84(18) . . . . ? C9 C4 C5 C6 -1.8(3) . . . . ? N1 C4 C5 C6 -177.39(15) . . . . ? C9 C4 C5 C10 174.54(16) . . . . ? N1 C4 C5 C10 -1.1(2) . . . . ? C4 C5 C6 C7 1.1(3) . . . . ? C10 C5 C6 C7 -175.22(19) . . . . ? C5 C6 C7 C8 0.0(3) . . . . ? C6 C7 C8 C9 -0.5(3) . . . . ? C7 C8 C9 C4 -0.1(3) . . . . ? C7 C8 C9 C13 177.51(19) . . . . ? C5 C4 C9 C8 1.3(2) . . . . ? N1 C4 C9 C8 176.86(15) . . . . ? C5 C4 C9 C13 -176.22(17) . . . . ? N1 C4 C9 C13 -0.6(2) . . . . ? C6 C5 C10 C12 -32.8(3) . . . . ? C4 C5 C10 C12 151.03(19) . . . . ? C6 C5 C10 C11 92.8(3) . . . . ? C4 C5 C10 C11 -83.4(2) . . . . ? C8 C9 C13 C15 47.4(2) . . . . ? C4 C9 C13 C15 -135.10(18) . . . . ? C8 C9 C13 C14 -74.7(2) . . . . ? C4 C9 C13 C14 102.72(19) . . . . ? C1 N2 C16 C21 -81.2(2) . . . . ? C2 N2 C16 C21 103.48(19) . . . . ? C1 N2 C16 C17 105.05(19) . . . . ? C2 N2 C16 C17 -70.3(2) . . . . ? C21 C16 C17 C18 -1.4(2) . . . . ? N2 C16 C17 C18 172.00(15) . . . . ? C21 C16 C17 C22 179.42(16) . . . . ? N2 C16 C17 C22 -7.1(2) . . . . ? C16 C17 C18 C19 0.1(3) . . . . ? C22 C17 C18 C19 179.31(18) . . . . ? C17 C18 C19 C20 1.4(3) . . . . ? C18 C19 C20 C21 -1.8(3) . . . . ? C17 C16 C21 C20 1.1(3) . . . . ? N2 C16 C21 C20 -172.21(16) . . . . ? C17 C16 C21 C25 -179.81(16) . . . . ? N2 C16 C21 C25 6.9(2) . . . . ? C19 C20 C21 C16 0.5(3) . . . . ? C19 C20 C21 C25 -178.60(19) . . . . ? C18 C17 C22 C23 -77.5(2) . . . . ? C16 C17 C22 C23 101.6(2) . . . . ? C18 C17 C22 C24 44.8(2) . . . . ? C16 C17 C22 C24 -136.06(18) . . . . ? C16 C21 C25 C26 -112.7(2) . . . . ? C20 C21 C25 C26 66.4(2) . . . . ? C16 C21 C25 C27 123.2(2) . . . . ? C20 C21 C25 C27 -57.7(2) . . . . ?