#------------------------------------------------------------------------------ #$Date: 2025-01-17 01:06:06 +0200 (Fri, 17 Jan 2025) $ #$Revision: 297361 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/57/37/1573704.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_1573704 loop_ _publ_author_name 'Bonfante, Sara' 'Tanner, Theo' 'Lorber, Christian' 'Lynam, Jason Martin' 'Simonneau, Antoine' 'Slattery, John M.' _publ_section_title ; Zirconium-Mediated Carbon-Fluorine Bond Functionalisation Through Cyclohexyne “Umpolung” ; _journal_name_full 'Chemical Science' _journal_paper_doi 10.1039/D4SC08522A _journal_year 2025 _chemical_formula_moiety 'C21 H20 F3 N Zr' _chemical_formula_sum 'C21 H20 F3 N Zr' _chemical_formula_weight 434.60 _chemical_properties_physical Air-sensitive,Moisture-sensitive _space_group_crystal_system monoclinic _space_group_IT_number 14 _space_group_name_Hall '-P 2yn' _space_group_name_H-M_alt 'P 1 21/n 1' _atom_sites_solution_hydrogens geom _atom_sites_solution_primary dual _audit_creation_date 2023-01-20 _audit_creation_method ; Olex2 1.5 (compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498) ; _audit_update_record ; 2024-03-12 deposited with the CCDC. 2025-01-16 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 99.4290(10) _cell_angle_gamma 90 _cell_formula_units_Z 4 _cell_length_a 8.17660(10) _cell_length_b 15.5546(2) _cell_length_c 14.6671(2) _cell_measurement_reflns_used 8675 _cell_measurement_temperature 110.00(10) _cell_measurement_theta_max 76.2160 _cell_measurement_theta_min 4.1470 _cell_volume 1840.21(4) _computing_cell_refinement 'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)' _computing_data_collection 'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)' _computing_data_reduction 'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)' _computing_molecular_graphics 'Olex2 1.5 (Dolomanov et al., 2009)' _computing_publication_material 'Olex2 1.5 (Dolomanov et al., 2009)' _computing_structure_refinement 'SHELXL 2018/3 (Sheldrick, 2015)' _computing_structure_solution 'SHELXT 2018/2 (Sheldrick, 2018)' _diffrn_ambient_environment N~2~ _diffrn_ambient_temperature 110.00(10) _diffrn_detector 'Hybrid Pixel Array Detector' _diffrn_detector_area_resol_mean 10.0000 _diffrn_detector_type HyPix _diffrn_measured_fraction_theta_full 0.999 _diffrn_measured_fraction_theta_max 0.957 _diffrn_measurement_details ; List of Runs (angles in degrees, time in seconds): # Type Start End Width t~exp~ \w \q \k \f Frames #-------------------------------------------------------------------------- 1 \w -113.00 -56.00 0.50 0.40 -- -48.70 165.00-121.00 114 2 \w -68.00 -29.00 0.50 0.40 -- -48.70 116.00 90.00 78 3 \w -108.00 -83.00 0.50 0.40 -- -48.70-165.00-145.00 50 4 \w 34.00 59.00 0.50 0.40 -- 48.70-116.00 2.00 50 5 \w 65.00 90.00 0.50 0.40 -- 48.70-165.00-145.00 50 6 \w 69.00 118.00 0.50 1.61 -- 107.75 165.00-121.00 98 7 \w 96.00 125.00 0.50 1.61 -- 107.75-165.00-145.00 58 8 \w 79.00 105.00 0.50 1.61 -- 107.75-116.00 2.00 52 9 \w 106.00 167.00 0.50 1.61 -- 107.75 116.00 90.00 122 10 \w -118.00 -74.00 0.50 0.40 -- -48.70-125.00 60.00 88 11 \w -61.00 24.00 0.50 0.40 -- -48.70 19.00-120.00 170 12 \w -105.00 -73.00 0.50 0.40 -- -48.70-125.00 30.00 64 13 \w -118.00 -90.00 0.50 0.40 -- -48.70-125.00 150.00 56 14 \w 12.00 37.00 0.50 0.40 -- 48.70 -99.00-180.00 50 15 \w 43.00 99.00 0.50 1.61 -- 107.75-125.00 -60.00 112 16 \w 48.00 73.00 0.50 1.61 -- 107.75 -77.00-180.00 50 17 \w 39.00 106.00 0.50 1.61 -- 107.75 -99.00-180.00 134 18 \w 40.00 100.00 0.50 1.61 -- 107.75 -99.00 60.00 120 19 \w 89.00 114.00 0.50 1.61 -- 107.75 -19.00 -60.00 50 20 \w 132.00 171.00 0.50 1.61 -- 107.75 57.00 150.00 78 21 \w 91.00 130.00 0.50 1.61 -- 107.75 -77.00-180.00 78 22 \w 32.00 57.00 0.50 1.61 -- 107.75 -19.00 -60.00 50 23 \w 94.00 124.00 0.50 1.61 -- 107.75 57.00 150.00 60 24 \w 97.00 164.00 0.50 1.61 -- 107.75 57.00-180.00 134 ; _diffrn_measurement_device 'four-circle diffractometer' _diffrn_measurement_device_type 'SuperNova, Dual, Cu at home/near, HyPix' _diffrn_measurement_method '\w scans' _diffrn_orient_matrix_type 'CrysAlisPro convention (1999,Acta A55,543-557)' _diffrn_orient_matrix_UB_11 -0.0769238000 _diffrn_orient_matrix_UB_12 0.0668839000 _diffrn_orient_matrix_UB_13 0.0578794000 _diffrn_orient_matrix_UB_21 0.0357759000 _diffrn_orient_matrix_UB_22 0.0714525000 _diffrn_orient_matrix_UB_23 -0.0667467000 _diffrn_orient_matrix_UB_31 -0.1711812000 _diffrn_orient_matrix_UB_32 -0.0151058000 _diffrn_orient_matrix_UB_33 -0.0593791000 _diffrn_radiation_monochromator mirror _diffrn_radiation_probe x-ray _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_wavelength 1.54184 _diffrn_reflns_av_R_equivalents 0.0375 _diffrn_reflns_av_unetI/netI 0.0361 _diffrn_reflns_Laue_measured_fraction_full 0.999 _diffrn_reflns_Laue_measured_fraction_max 0.957 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_number 12546 _diffrn_reflns_point_group_measured_fraction_full 0.999 _diffrn_reflns_point_group_measured_fraction_max 0.957 _diffrn_reflns_theta_full 67.684 _diffrn_reflns_theta_max 76.951 _diffrn_reflns_theta_min 4.173 _diffrn_source 'micro-focus sealed X-ray tube' _diffrn_source_type 'SuperNova (Cu) X-ray Source' _exptl_absorpt_coefficient_mu 5.188 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.76005 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_colour 'clear orange' _exptl_crystal_colour_lustre clear _exptl_crystal_colour_primary orange _exptl_crystal_density_diffrn 1.569 _exptl_crystal_description block _exptl_crystal_F_000 880 _exptl_crystal_recrystallization_method 'Re-crystallisation from solvent' _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.09 _refine_diff_density_max 0.316 _refine_diff_density_min -0.475 _refine_diff_density_rms 0.070 _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.095 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 235 _refine_ls_number_reflns 3722 _refine_ls_number_restraints 0 _refine_ls_restrained_S_all 1.095 _refine_ls_R_factor_all 0.0274 _refine_ls_R_factor_gt 0.0247 _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^)+(0.0180P)^2^+1.1752P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0608 _refine_ls_wR_factor_ref 0.0621 _reflns_Friedel_coverage 0.000 _reflns_number_gt 3429 _reflns_number_total 3722 _reflns_threshold_expression 'I > 2\s(I)' _cod_data_source_file d4sc08522a2.cif _cod_data_source_block jms23002 _cod_database_code 1573704 _shelx_shelxl_version_number 2018/3 _chemical_oxdiff_usercomment 'Sara Bonfante SB36c' _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_max 0.652 _shelx_estimated_absorpt_t_min 0.357 _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups 2.a Secondary CH2 refined with riding coordinates: C5(H5A,H5B), C2(H2A,H2B), C4(H4A,H4B), C3(H3A,H3B) 2.b Aromatic/amide H refined with riding coordinates: C8(H8), C10(H10), C17(H17), C18(H18), C19(H19), C13(H13), C21(H21), C15(H15), C20(H20), C14(H14), C12(H12), C16(H16) ; _shelx_res_file ; TITL jms23002_a.res in P2(1)/n jms23002.res created by SHELXL-2018/3 at 17:08:19 on 20-Jan-2023 REM Old TITL jms23002 in P2(1)/n REM SHELXT solution in P2(1)/n: R1 0.065, Rweak 0.003, Alpha 0.028 REM 0.386 for 149 systematic absences, Orientation as input REM Formula found by SHELXT: C21 N O3 Br CELL 1.54184 8.1766 15.5546 14.6671 90 99.429 90 ZERR 4 0.0001 0.0002 0.0002 0 0.001 0 LATT 1 SYMM 0.5-X,0.5+Y,0.5-Z SFAC C H F N Zr UNIT 84 80 12 4 4 L.S. 4 0 0 PLAN 1 SIZE 0.09 0.1 0.25 TEMP -163 CONF BOND list 4 fmap 2 53 MORE -1 BOND $H ACTA REM REM REM WGHT 0.018000 1.175200 FVAR 0.47977 ZR1 5 0.458830 0.198363 0.573831 11.00000 0.01834 0.01411 = 0.01437 -0.00127 0.00262 -0.00075 F1 3 0.576052 0.164919 0.469101 11.00000 0.03650 0.02658 = 0.02529 -0.00729 0.01403 -0.00160 F2 3 0.388370 0.487613 0.890641 11.00000 0.04171 0.02761 = 0.02793 -0.01224 0.00778 0.00641 F3 3 0.232700 0.224458 0.752439 11.00000 0.04749 0.02617 = 0.03364 -0.00543 0.02402 -0.01350 N1 4 0.415743 0.305773 0.692505 11.00000 0.02250 0.01766 = 0.01712 0.00056 0.00474 -0.00099 C9 1 0.394841 0.428334 0.824305 11.00000 0.02905 0.02216 = 0.01833 -0.00656 0.00182 0.01067 C8 1 0.495851 0.443494 0.760155 11.00000 0.02330 0.01622 = 0.02510 -0.00235 0.00114 0.00116 AFIX 43 H8 2 0.557331 0.495396 0.761034 11.00000 -1.20000 AFIX 0 C11 1 0.319769 0.298168 0.756309 11.00000 0.02796 0.02017 = 0.02301 0.00033 0.00834 -0.00205 C10 1 0.300526 0.355298 0.825246 11.00000 0.03240 0.02646 = 0.01871 -0.00132 0.01048 0.00328 AFIX 43 H10 2 0.229169 0.345304 0.869157 11.00000 -1.20000 AFIX 0 C6 1 0.608259 0.388786 0.621272 11.00000 0.01877 0.01768 = 0.02368 0.00070 0.00299 -0.00141 C17 1 0.462501 0.082184 0.698528 11.00000 0.03384 0.02383 = 0.02052 0.00555 -0.00170 0.00120 AFIX 43 H17 2 0.358812 0.066805 0.715089 11.00000 -1.20000 AFIX 0 C5 1 0.710606 0.470354 0.622558 11.00000 0.02355 0.02135 = 0.03809 -0.00484 0.00985 -0.00548 AFIX 23 H5A 2 0.770566 0.480326 0.685972 11.00000 -1.20000 H5B 2 0.635715 0.519827 0.605377 11.00000 -1.20000 AFIX 0 C7 1 0.505920 0.380231 0.693159 11.00000 0.01835 0.01675 = 0.01617 -0.00052 0.00055 0.00133 C18 1 0.535769 0.044727 0.627279 11.00000 0.03731 0.01603 = 0.02622 -0.00134 -0.00359 0.00296 AFIX 43 H18 2 0.490226 -0.000520 0.587549 11.00000 -1.20000 AFIX 0 C1 1 0.603570 0.324531 0.558645 11.00000 0.02099 0.01986 = 0.01924 -0.00090 0.00387 -0.00144 C19 1 0.687644 0.086133 0.625544 11.00000 0.02848 0.02789 = 0.03662 -0.00052 0.00081 0.01034 AFIX 43 H19 2 0.763975 0.073083 0.585170 11.00000 -1.20000 AFIX 0 C13 1 0.167547 0.266194 0.539473 11.00000 0.02543 0.02409 = 0.04075 -0.00423 -0.00754 0.00485 AFIX 43 H13 2 0.137847 0.310817 0.577858 11.00000 -1.20000 AFIX 0 C21 1 0.570117 0.146045 0.740364 11.00000 0.04211 0.02113 = 0.02053 -0.00042 -0.00602 0.00562 AFIX 43 H21 2 0.553203 0.180573 0.791430 11.00000 -1.20000 AFIX 0 C2 1 0.696788 0.334977 0.478591 11.00000 0.02851 0.02783 = 0.02902 -0.00204 0.01184 -0.00582 AFIX 23 H2A 2 0.624352 0.316032 0.421326 11.00000 -1.20000 H2B 2 0.794676 0.296593 0.488521 11.00000 -1.20000 AFIX 0 C15 1 0.203061 0.134137 0.479149 11.00000 0.02664 0.02143 = 0.02699 -0.00091 -0.00511 -0.00329 AFIX 43 H15 2 0.204305 0.073625 0.470508 11.00000 -1.20000 AFIX 0 C4 1 0.835199 0.465052 0.556065 11.00000 0.02711 0.02931 = 0.04687 -0.00251 0.01552 -0.00877 AFIX 23 H4A 2 0.877434 0.523312 0.545815 11.00000 -1.20000 H4B 2 0.930368 0.428951 0.583489 11.00000 -1.20000 AFIX 0 C20 1 0.707244 0.150441 0.694108 11.00000 0.02922 0.02154 = 0.03939 0.00222 -0.00951 0.00152 AFIX 43 H20 2 0.797078 0.189714 0.706767 11.00000 -1.20000 AFIX 0 C14 1 0.146642 0.177689 0.552659 11.00000 0.02036 0.02892 = 0.02946 0.00131 0.00164 -0.00090 AFIX 43 H14 2 0.102559 0.151792 0.602049 11.00000 -1.20000 AFIX 0 C12 1 0.239667 0.277366 0.460051 11.00000 0.03606 0.02475 = 0.03653 0.01095 -0.01384 -0.00706 AFIX 43 H12 2 0.271494 0.330560 0.436378 11.00000 -1.20000 AFIX 0 C3 1 0.755327 0.426917 0.464466 11.00000 0.03451 0.03567 = 0.03749 0.00295 0.01844 -0.01038 AFIX 23 H3A 2 0.836274 0.426425 0.421125 11.00000 -1.20000 H3B 2 0.659647 0.462720 0.437139 11.00000 -1.20000 AFIX 0 C16 1 0.256501 0.195644 0.421635 11.00000 0.03272 0.03791 = 0.02053 0.00200 -0.00526 -0.00800 AFIX 43 H16 2 0.297438 0.184313 0.365842 11.00000 -1.20000 AFIX 0 HKLF 4 REM jms23002_a.res in P2(1)/n REM wR2 = 0.0621, GooF = S = 1.095, Restrained GooF = 1.095 for all data REM R1 = 0.0247 for 3429 Fo > 4sig(Fo) and 0.0274 for all 3722 data REM 235 parameters refined using 0 restraints END WGHT 0.0180 1.1751 REM Highest difference peak 0.316, deepest hole -0.475, 1-sigma level 0.070 Q1 1 0.2769 0.1574 0.4576 11.00000 0.05 0.32 ; _shelx_res_checksum 11179 _olex2_submission_special_instructions 'No special instructions were received' _oxdiff_exptl_absorpt_empirical_details ; Empirical correction (ABSPACK) includes: - Absorption correction using spherical harmonics - Frame scaling ; _oxdiff_exptl_absorpt_empirical_full_max 1.314 _oxdiff_exptl_absorpt_empirical_full_min 0.802 loop_ _space_group_symop_operation_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -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 Zr1 Zr 0.45883(2) 0.19836(2) 0.57383(2) 0.01561(7) Uani 1 1 d . . . . . F1 F 0.57605(16) 0.16492(8) 0.46910(9) 0.0285(3) Uani 1 1 d . . . . . F2 F 0.38837(17) 0.48761(9) 0.89064(9) 0.0322(3) Uani 1 1 d . . . . . F3 F 0.23270(18) 0.22446(9) 0.75244(10) 0.0338(3) Uani 1 1 d . . . . . N1 N 0.4157(2) 0.30577(11) 0.69250(12) 0.0189(3) Uani 1 1 d . . . . . C9 C 0.3948(3) 0.42833(14) 0.82430(15) 0.0234(4) Uani 1 1 d . . . . . C8 C 0.4959(2) 0.44349(13) 0.76016(15) 0.0219(4) Uani 1 1 d . . . . . H8 H 0.557331 0.495396 0.761034 0.026 Uiso 1 1 calc R U . . . C11 C 0.3198(3) 0.29817(14) 0.75631(16) 0.0232(4) Uani 1 1 d . . . . . C10 C 0.3005(3) 0.35530(15) 0.82525(15) 0.0252(4) Uani 1 1 d . . . . . H10 H 0.229169 0.345304 0.869157 0.030 Uiso 1 1 calc R U . . . C6 C 0.6083(2) 0.38879(13) 0.62127(15) 0.0201(4) Uani 1 1 d . . . . . C17 C 0.4625(3) 0.08218(15) 0.69853(15) 0.0268(5) Uani 1 1 d . . . . . H17 H 0.358812 0.066805 0.715089 0.032 Uiso 1 1 calc R U . . . C5 C 0.7106(3) 0.47035(14) 0.62256(17) 0.0271(5) Uani 1 1 d . . . . . H5A H 0.770566 0.480326 0.685972 0.033 Uiso 1 1 calc R U . . . H5B H 0.635715 0.519827 0.605377 0.033 Uiso 1 1 calc R U . . . C7 C 0.5059(2) 0.38023(13) 0.69316(13) 0.0173(4) Uani 1 1 d . . . . . C18 C 0.5358(3) 0.04473(14) 0.62728(16) 0.0275(5) Uani 1 1 d . . . . . H18 H 0.490226 -0.000520 0.587549 0.033 Uiso 1 1 calc R U . . . C1 C 0.6036(2) 0.32453(14) 0.55864(14) 0.0200(4) Uani 1 1 d . . . . . C19 C 0.6876(3) 0.08613(16) 0.62554(18) 0.0315(5) Uani 1 1 d . . . . . H19 H 0.763975 0.073083 0.585170 0.038 Uiso 1 1 calc R U . . . C13 C 0.1675(3) 0.26619(16) 0.53947(18) 0.0315(5) Uani 1 1 d . . . . . H13 H 0.137847 0.310817 0.577858 0.038 Uiso 1 1 calc R U . . . C21 C 0.5701(3) 0.14605(15) 0.74036(16) 0.0292(5) Uani 1 1 d . . . . . H21 H 0.553203 0.180573 0.791430 0.035 Uiso 1 1 calc R U . . . C2 C 0.6968(3) 0.33498(15) 0.47859(16) 0.0277(5) Uani 1 1 d . . . . . H2A H 0.624352 0.316032 0.421326 0.033 Uiso 1 1 calc R U . . . H2B H 0.794676 0.296593 0.488521 0.033 Uiso 1 1 calc R U . . . C15 C 0.2031(3) 0.13414(15) 0.47915(16) 0.0261(5) Uani 1 1 d . . . . . H15 H 0.204305 0.073625 0.470508 0.031 Uiso 1 1 calc R U . . . C4 C 0.8352(3) 0.46505(16) 0.55606(19) 0.0334(5) Uani 1 1 d . . . . . H4A H 0.877434 0.523312 0.545815 0.040 Uiso 1 1 calc R U . . . H4B H 0.930368 0.428951 0.583489 0.040 Uiso 1 1 calc R U . . . C20 C 0.7072(3) 0.15044(15) 0.69411(18) 0.0317(5) Uani 1 1 d . . . . . H20 H 0.797078 0.189714 0.706767 0.038 Uiso 1 1 calc R U . . . C14 C 0.1466(3) 0.17769(15) 0.55266(16) 0.0265(5) Uani 1 1 d . . . . . H14 H 0.102559 0.151792 0.602049 0.032 Uiso 1 1 calc R U . . . C12 C 0.2397(3) 0.27737(16) 0.46005(18) 0.0347(6) Uani 1 1 d . . . . . H12 H 0.271494 0.330560 0.436378 0.042 Uiso 1 1 calc R U . . . C3 C 0.7553(3) 0.42692(17) 0.46447(18) 0.0345(5) Uani 1 1 d . . . . . H3A H 0.836274 0.426425 0.421125 0.041 Uiso 1 1 calc R U . . . H3B H 0.659647 0.462720 0.437139 0.041 Uiso 1 1 calc R U . . . C16 C 0.2565(3) 0.19564(16) 0.42164(17) 0.0315(5) Uani 1 1 d . . . . . H16 H 0.297438 0.184313 0.365842 0.038 Uiso 1 1 calc R U . . . 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 Zr1 0.01834(10) 0.01411(10) 0.01437(10) -0.00127(6) 0.00262(6) -0.00075(5) F1 0.0365(7) 0.0266(7) 0.0253(7) -0.0073(5) 0.0140(5) -0.0016(5) F2 0.0417(7) 0.0276(7) 0.0279(7) -0.0122(6) 0.0078(6) 0.0064(6) F3 0.0475(8) 0.0262(7) 0.0336(7) -0.0054(6) 0.0240(6) -0.0135(6) N1 0.0225(8) 0.0177(9) 0.0171(8) 0.0006(6) 0.0047(7) -0.0010(6) C9 0.0290(10) 0.0222(11) 0.0183(10) -0.0066(8) 0.0018(8) 0.0107(8) C8 0.0233(10) 0.0162(10) 0.0251(11) -0.0023(8) 0.0011(8) 0.0012(7) C11 0.0280(11) 0.0202(11) 0.0230(11) 0.0003(8) 0.0083(8) -0.0020(8) C10 0.0324(11) 0.0265(11) 0.0187(10) -0.0013(8) 0.0105(8) 0.0033(9) C6 0.0188(9) 0.0177(10) 0.0237(10) 0.0007(8) 0.0030(8) -0.0014(7) C17 0.0338(11) 0.0238(11) 0.0205(10) 0.0056(9) -0.0017(9) 0.0012(9) C5 0.0236(10) 0.0213(11) 0.0381(12) -0.0048(9) 0.0098(9) -0.0055(8) C7 0.0184(9) 0.0168(9) 0.0162(9) -0.0005(7) 0.0005(7) 0.0013(7) C18 0.0373(12) 0.0160(10) 0.0262(12) -0.0013(8) -0.0036(9) 0.0030(8) C1 0.0210(9) 0.0199(10) 0.0192(10) -0.0009(8) 0.0039(8) -0.0014(7) C19 0.0285(11) 0.0279(12) 0.0366(13) -0.0005(10) 0.0008(9) 0.0103(9) C13 0.0254(11) 0.0241(12) 0.0407(14) -0.0042(10) -0.0075(10) 0.0049(8) C21 0.0421(13) 0.0211(11) 0.0205(11) -0.0004(9) -0.0060(9) 0.0056(9) C2 0.0285(11) 0.0278(12) 0.0290(12) -0.0020(9) 0.0118(9) -0.0058(9) C15 0.0266(10) 0.0214(11) 0.0270(11) -0.0009(9) -0.0051(9) -0.0033(8) C4 0.0271(11) 0.0293(12) 0.0469(15) -0.0025(11) 0.0155(10) -0.0088(9) C20 0.0292(11) 0.0215(11) 0.0394(14) 0.0022(10) -0.0095(10) 0.0015(9) C14 0.0204(10) 0.0289(12) 0.0295(12) 0.0013(9) 0.0016(8) -0.0009(8) C12 0.0361(12) 0.0247(12) 0.0365(14) 0.0110(10) -0.0138(10) -0.0071(9) C3 0.0345(12) 0.0357(14) 0.0375(13) 0.0030(11) 0.0184(10) -0.0104(10) C16 0.0327(12) 0.0379(14) 0.0205(11) 0.0020(9) -0.0053(9) -0.0080(9) loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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' F F 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zr Zr -0.1862 2.2449 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist -2 -2 -1 0.0385 2 2 1 0.0505 0 2 -1 0.0997 0 -2 1 0.1284 0 -1 -2 0.0506 -1 4 9 0.0289 2 -1 -2 0.0655 2 1 2 0.0666 -2 -1 0 0.0399 0 -1 2 0.1037 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 F1 Zr1 N1 148.46(6) . . ? F1 Zr1 C17 114.28(7) . . ? F1 Zr1 C18 82.43(7) . . ? F1 Zr1 C1 80.26(6) . . ? F1 Zr1 C19 68.63(7) . . ? F1 Zr1 C13 119.87(7) . . ? F1 Zr1 C15 86.14(7) . . ? F1 Zr1 C20 91.57(7) . . ? F1 Zr1 C14 118.01(7) . . ? F1 Zr1 C12 89.80(8) . . ? F1 Zr1 C16 69.44(7) . . ? N1 Zr1 C17 87.74(7) . . ? N1 Zr1 C18 118.03(7) . . ? N1 Zr1 C19 115.41(7) . . ? N1 Zr1 C13 68.19(7) . . ? N1 Zr1 C15 116.97(7) . . ? N1 Zr1 C20 84.31(7) . . ? N1 Zr1 C14 85.16(7) . . ? N1 Zr1 C12 88.24(8) . . ? N1 Zr1 C16 118.62(7) . . ? C17 Zr1 C19 52.50(8) . . ? C17 Zr1 C13 109.26(8) . . ? C17 Zr1 C20 52.55(8) . . ? C18 Zr1 C17 31.97(7) . . ? C18 Zr1 C19 31.66(8) . . ? C18 Zr1 C13 127.91(8) . . ? C18 Zr1 C20 52.63(7) . . ? C1 Zr1 N1 68.34(7) . . ? C1 Zr1 C17 135.78(7) . . ? C1 Zr1 C18 135.62(7) . . ? C1 Zr1 C19 104.10(8) . . ? C1 Zr1 C13 96.00(8) . . ? C1 Zr1 C15 132.26(7) . . ? C1 Zr1 C20 87.31(7) . . ? C1 Zr1 C14 127.81(7) . . ? C1 Zr1 C12 81.07(7) . . ? C1 Zr1 C16 101.41(7) . . ? C13 Zr1 C19 159.47(8) . . ? C15 Zr1 C17 91.45(7) . . ? C15 Zr1 C18 86.49(7) . . ? C15 Zr1 C19 112.96(8) . . ? C15 Zr1 C13 52.97(7) . . ? C15 Zr1 C20 138.92(8) . . ? C15 Zr1 C14 32.43(8) . . ? C15 Zr1 C12 53.18(7) . . ? C15 Zr1 C16 31.86(8) . . ? C20 Zr1 C19 31.73(8) . . ? C20 Zr1 C13 148.53(9) . . ? C14 Zr1 C17 83.82(7) . . ? C14 Zr1 C18 96.36(8) . . ? C14 Zr1 C19 128.01(8) . . ? C14 Zr1 C13 31.84(7) . . ? C14 Zr1 C20 135.37(8) . . ? C14 Zr1 C12 52.98(8) . . ? C14 Zr1 C16 52.89(8) . . ? C12 Zr1 C17 136.79(8) . . ? C12 Zr1 C18 139.43(7) . . ? C12 Zr1 C19 156.16(9) . . ? C12 Zr1 C13 31.65(9) . . ? C12 Zr1 C20 167.90(8) . . ? C16 Zr1 C17 122.80(8) . . ? C16 Zr1 C18 110.11(7) . . ? C16 Zr1 C19 125.51(8) . . ? C16 Zr1 C13 52.41(8) . . ? C16 Zr1 C20 157.05(8) . . ? C16 Zr1 C12 31.97(8) . . ? C11 N1 Zr1 127.31(14) . . ? C11 N1 C7 116.83(18) . . ? C7 N1 Zr1 115.83(13) . . ? F2 C9 C8 118.5(2) . . ? F2 C9 C10 118.0(2) . . ? C8 C9 C10 123.5(2) . . ? C9 C8 H8 120.9 . . ? C9 C8 C7 118.1(2) . . ? C7 C8 H8 120.9 . . ? F3 C11 C10 117.3(2) . . ? N1 C11 F3 114.70(18) . . ? N1 C11 C10 128.0(2) . . ? C9 C10 C11 113.3(2) . . ? C9 C10 H10 123.4 . . ? C11 C10 H10 123.4 . . ? C7 C6 C5 116.65(18) . . ? C1 C6 C5 125.4(2) . . ? C1 C6 C7 117.92(18) . . ? Zr1 C17 H17 116.9 . . ? C18 C17 Zr1 73.75(13) . . ? C18 C17 H17 126.1 . . ? C21 C17 Zr1 75.29(13) . . ? C21 C17 H17 126.1 . . ? C21 C17 C18 107.7(2) . . ? C6 C5 H5A 109.3 . . ? C6 C5 H5B 109.3 . . ? C6 C5 C4 111.83(19) . . ? H5A C5 H5B 107.9 . . ? C4 C5 H5A 109.3 . . ? C4 C5 H5B 109.3 . . ? N1 C7 C8 120.26(19) . . ? N1 C7 C6 116.37(18) . . ? C8 C7 C6 123.37(19) . . ? Zr1 C18 H18 116.8 . . ? C17 C18 Zr1 74.27(12) . . ? C17 C18 H18 126.0 . . ? C19 C18 Zr1 74.92(13) . . ? C19 C18 C17 107.9(2) . . ? C19 C18 H18 126.0 . . ? C6 C1 Zr1 121.15(15) . . ? C6 C1 C2 119.11(19) . . ? C2 C1 Zr1 119.73(15) . . ? Zr1 C19 H19 118.7 . . ? C18 C19 Zr1 73.41(12) . . ? C18 C19 H19 126.0 . . ? C18 C19 C20 108.1(2) . . ? C20 C19 Zr1 73.84(13) . . ? C20 C19 H19 126.0 . . ? Zr1 C13 H13 120.1 . . ? C14 C13 Zr1 72.62(12) . . ? C14 C13 H13 125.9 . . ? C12 C13 Zr1 73.25(13) . . ? C12 C13 H13 125.9 . . ? C12 C13 C14 108.3(2) . . ? Zr1 C21 H21 119.4 . . ? C17 C21 Zr1 73.24(12) . . ? C17 C21 H21 125.8 . . ? C17 C21 C20 108.5(2) . . ? C20 C21 Zr1 73.41(13) . . ? C20 C21 H21 125.8 . . ? C1 C2 H2A 108.6 . . ? C1 C2 H2B 108.6 . . ? C1 C2 C3 114.5(2) . . ? H2A C2 H2B 107.6 . . ? C3 C2 H2A 108.6 . . ? C3 C2 H2B 108.6 . . ? Zr1 C15 H15 116.1 . . ? C14 C15 Zr1 74.61(12) . . ? C14 C15 H15 126.1 . . ? C16 C15 Zr1 75.34(13) . . ? C16 C15 H15 126.1 . . ? C16 C15 C14 107.9(2) . . ? C5 C4 H4A 109.5 . . ? C5 C4 H4B 109.5 . . ? H4A C4 H4B 108.1 . . ? C3 C4 C5 110.64(19) . . ? C3 C4 H4A 109.5 . . ? C3 C4 H4B 109.5 . . ? Zr1 C20 H20 116.5 . . ? C19 C20 Zr1 74.43(13) . . ? C19 C20 H20 126.2 . . ? C21 C20 Zr1 75.06(13) . . ? C21 C20 C19 107.7(2) . . ? C21 C20 H20 126.2 . . ? Zr1 C14 H14 117.4 . . ? C13 C14 Zr1 75.54(13) . . ? C13 C14 C15 107.6(2) . . ? C13 C14 H14 126.2 . . ? C15 C14 Zr1 72.96(12) . . ? C15 C14 H14 126.2 . . ? Zr1 C12 H12 116.9 . . ? C13 C12 Zr1 75.09(13) . . ? C13 C12 H12 126.2 . . ? C13 C12 C16 107.7(2) . . ? C16 C12 Zr1 73.90(13) . . ? C16 C12 H12 126.2 . . ? C2 C3 H3A 109.6 . . ? C2 C3 H3B 109.6 . . ? C4 C3 C2 110.1(2) . . ? C4 C3 H3A 109.6 . . ? C4 C3 H3B 109.6 . . ? H3A C3 H3B 108.1 . . ? Zr1 C16 H16 119.2 . . ? C15 C16 Zr1 72.80(12) . . ? C15 C16 C12 108.5(2) . . ? C15 C16 H16 125.7 . . ? C12 C16 Zr1 74.13(13) . . ? C12 C16 H16 125.7 . . ? 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 Zr1 F1 2.0078(13) . ? Zr1 N1 2.4791(17) . ? Zr1 C17 2.568(2) . ? Zr1 C18 2.561(2) . ? Zr1 C1 2.321(2) . ? Zr1 C19 2.580(2) . ? Zr1 C13 2.578(2) . ? Zr1 C15 2.520(2) . ? Zr1 C20 2.573(2) . ? Zr1 C14 2.541(2) . ? Zr1 C12 2.555(2) . ? Zr1 C16 2.552(2) . ? F2 C9 1.348(2) . ? F3 C11 1.346(3) . ? N1 C11 1.321(3) . ? N1 C7 1.372(3) . ? C9 C8 1.370(3) . ? C9 C10 1.374(3) . ? C8 H8 0.9500 . ? C8 C7 1.403(3) . ? C11 C10 1.374(3) . ? C10 H10 0.9500 . ? C6 C5 1.518(3) . ? C6 C7 1.456(3) . ? C6 C1 1.354(3) . ? C17 H17 0.9500 . ? C17 C18 1.413(3) . ? C17 C21 1.400(3) . ? C5 H5A 0.9900 . ? C5 H5B 0.9900 . ? C5 C4 1.524(3) . ? C18 H18 0.9500 . ? C18 C19 1.403(4) . ? C1 C2 1.510(3) . ? C19 H19 0.9500 . ? C19 C20 1.409(4) . ? C13 H13 0.9500 . ? C13 C14 1.405(3) . ? C13 C12 1.400(4) . ? C21 H21 0.9500 . ? C21 C20 1.404(4) . ? C2 H2A 0.9900 . ? C2 H2B 0.9900 . ? C2 C3 1.533(3) . ? C15 H15 0.9500 . ? C15 C14 1.413(3) . ? C15 C16 1.392(3) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C4 C3 1.515(4) . ? C20 H20 0.9500 . ? C14 H14 0.9500 . ? C12 H12 0.9500 . ? C12 C16 1.406(4) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C16 H16 0.9500 . ? 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 Zr1 N1 C11 F3 -2.6(3) . . . . ? Zr1 N1 C11 C10 176.62(17) . . . . ? Zr1 N1 C7 C8 -177.25(14) . . . . ? Zr1 N1 C7 C6 3.2(2) . . . . ? Zr1 C17 C18 C19 67.96(16) . . . . ? Zr1 C17 C21 C20 -65.47(16) . . . . ? Zr1 C18 C19 C20 66.25(16) . . . . ? Zr1 C1 C2 C3 167.54(16) . . . . ? Zr1 C19 C20 C21 68.30(16) . . . . ? Zr1 C13 C14 C15 -66.46(15) . . . . ? Zr1 C13 C12 C16 67.30(16) . . . . ? Zr1 C21 C20 C19 -67.87(16) . . . . ? Zr1 C15 C14 C13 68.20(15) . . . . ? Zr1 C15 C16 C12 -66.08(16) . . . . ? Zr1 C12 C16 C15 65.20(16) . . . . ? F2 C9 C8 C7 177.99(17) . . . . ? F2 C9 C10 C11 -178.29(18) . . . . ? F3 C11 C10 C9 179.57(19) . . . . ? N1 C11 C10 C9 0.3(3) . . . . ? C9 C8 C7 N1 0.3(3) . . . . ? C9 C8 C7 C6 179.82(18) . . . . ? C8 C9 C10 C11 1.1(3) . . . . ? C11 N1 C7 C8 0.9(3) . . . . ? C11 N1 C7 C6 -178.63(18) . . . . ? C10 C9 C8 C7 -1.4(3) . . . . ? C6 C5 C4 C3 43.9(3) . . . . ? C6 C1 C2 C3 -13.5(3) . . . . ? C17 C18 C19 Zr1 -67.52(15) . . . . ? C17 C18 C19 C20 -1.3(3) . . . . ? C17 C21 C20 Zr1 65.36(16) . . . . ? C17 C21 C20 C19 -2.5(3) . . . . ? C5 C6 C7 N1 -179.00(18) . . . . ? C5 C6 C7 C8 1.5(3) . . . . ? C5 C6 C1 Zr1 174.46(16) . . . . ? C5 C6 C1 C2 -4.5(3) . . . . ? C5 C4 C3 C2 -61.9(3) . . . . ? C7 N1 C11 F3 179.45(17) . . . . ? C7 N1 C11 C10 -1.3(3) . . . . ? C7 C6 C5 C4 169.57(19) . . . . ? C7 C6 C1 Zr1 -6.2(3) . . . . ? C7 C6 C1 C2 174.80(18) . . . . ? C18 C17 C21 Zr1 67.19(15) . . . . ? C18 C17 C21 C20 1.7(3) . . . . ? C18 C19 C20 Zr1 -65.96(16) . . . . ? C18 C19 C20 C21 2.3(3) . . . . ? C1 C6 C5 C4 -11.1(3) . . . . ? C1 C6 C7 N1 1.6(3) . . . . ? C1 C6 C7 C8 -177.89(19) . . . . ? C1 C2 C3 C4 46.3(3) . . . . ? C13 C12 C16 Zr1 -68.11(15) . . . . ? C13 C12 C16 C15 -2.9(3) . . . . ? C21 C17 C18 Zr1 -68.23(15) . . . . ? C21 C17 C18 C19 -0.3(2) . . . . ? C14 C13 C12 Zr1 -64.67(15) . . . . ? C14 C13 C12 C16 2.6(2) . . . . ? C14 C15 C16 Zr1 68.13(15) . . . . ? C14 C15 C16 C12 2.1(3) . . . . ? C12 C13 C14 Zr1 65.08(15) . . . . ? C12 C13 C14 C15 -1.4(2) . . . . ? C16 C15 C14 Zr1 -68.62(15) . . . . ? C16 C15 C14 C13 -0.4(2) . . . . ? loop_ _exptl_oxdiff_crystal_face_indexfrac_h _exptl_oxdiff_crystal_face_indexfrac_k _exptl_oxdiff_crystal_face_indexfrac_l _exptl_oxdiff_crystal_face_x _exptl_oxdiff_crystal_face_y _exptl_oxdiff_crystal_face_z -1.9995 -1.9978 -0.9973 -0.0375 -0.1477 0.4317 1.9995 1.9978 0.9973 0.0375 0.1477 -0.4317 0.0015 1.9990 -1.0012 0.0756 0.2097 0.0290 -0.0015 -1.9990 1.0012 -0.0756 -0.2097 -0.0290 -0.0009 -1.0005 -1.9976 -0.1825 0.0618 0.1339 -1.0187 4.2805 8.6143 0.8633 -0.3056 -0.4018 1.9969 -1.0024 -1.9977 -0.3363 0.1332 -0.2081 1.9987 0.9985 1.9976 0.0286 0.0095 -0.4758 -1.9986 -0.9977 0.0010 0.0871 -0.1429 0.3571 -0.0007 -0.9990 1.9996 0.0490 -0.2049 -0.1035