#------------------------------------------------------------------------------ #$Date: 2024-07-13 03:14:13 +0300 (Sat, 13 Jul 2024) $ #$Revision: 293399 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/57/21/1572127.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_1572127 loop_ _publ_author_name 'Shehzad, Aamir' 'Cui, Chaonan' 'Cheng, Ran' 'Luo, Zhixun' _publ_section_title ; Electrocatalytic Nitrogen Reduction to Ammonia by Atomically Precise Cu6 Nanoclusters Supported on Graphene Oxide ; _journal_name_full Nanoscale _journal_paper_doi 10.1039/D4NR01984A _journal_year 2024 _chemical_formula_moiety 'C42 H54 Cu6 N12 S6' _chemical_formula_sum 'C42 H54 Cu6 N12 S6' _chemical_formula_weight 1300.57 _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 2024-03-27 _audit_creation_method ; Olex2 1.5 (compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928) ; _audit_update_record ; 2024-04-07 deposited with the CCDC. 2024-07-12 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 99.3973(11) _cell_angle_gamma 90 _cell_formula_units_Z 2 _cell_length_a 11.88670(14) _cell_length_b 13.06844(17) _cell_length_c 16.4807(2) _cell_measurement_reflns_used 10120 _cell_measurement_temperature 170.0(4) _cell_measurement_theta_max 76.3600 _cell_measurement_theta_min 4.2270 _cell_volume 2525.77(5) _computing_cell_refinement 'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)' _computing_data_collection 'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)' _computing_data_reduction 'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)' _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 170.0(4) _diffrn_detector 'Hybrid Pixel Array Detector' _diffrn_detector_area_resol_mean 10.0000 _diffrn_detector_type HyPix _diffrn_measured_fraction_theta_full 1.000 _diffrn_measured_fraction_theta_max 0.963 _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 76.00 110.00 0.50 0.20 -- 108.85-125.00-180.00 68 2 \w 64.00 90.00 0.50 0.20 -- 108.85-125.00-150.00 52 3 \w -13.00 78.00 0.50 0.05 -- 46.54-100.00 60.00 182 4 \w 70.00 101.00 0.50 0.20 -- 108.85-100.00 60.00 62 5 \w 40.00 108.00 0.50 0.20 -- 108.85 -77.00 60.00 136 6 \w 37.00 73.00 0.50 0.20 -- 108.85 -61.00 60.00 72 7 \w 42.00 67.00 0.50 0.20 -- 108.85 -61.00 120.00 50 8 \w 38.00 69.00 0.50 0.20 -- 108.85 -61.00 150.00 62 9 \w 144.00 178.00 0.50 0.20 -- 108.85 15.00 150.00 68 10 \w 92.00 169.00 0.50 0.20 -- 108.85 100.00 165.00 154 11 \w 92.00 178.00 0.50 0.20 -- 108.85 61.00 120.00 172 12 \w 91.00 126.00 0.50 0.20 -- 108.85 15.00 150.00 70 13 \w 24.00 118.00 0.50 0.05 -- 46.54 77.00 150.00 188 14 \w -23.00 3.00 0.50 0.05 -- -46.54 19.00-180.00 52 15 \w -66.00 -36.00 0.50 0.20 -- -104.50 61.00-180.00 60 16 \w -61.00 -34.00 0.50 0.20 -- -104.50 61.00-120.00 54 17 \w -62.00 -34.00 0.50 0.20 -- -104.50 61.00 -60.00 56 18 \w -64.00 -31.00 0.50 0.20 -- -104.50 61.00 -30.00 66 19 \w -68.00 -35.00 0.50 0.20 -- -104.50 61.00 0.00 66 20 \w -66.00 -40.00 0.50 0.20 -- -104.50 61.00 30.00 52 21 \w -39.00 25.00 0.50 0.05 -- -46.54 38.00 -60.00 128 22 \w -132.00-100.00 0.50 0.20 -- -104.50 -30.00 60.00 64 23 \w -162.00-136.00 0.50 0.20 -- -104.50 -30.00 60.00 52 24 \w -154.00-129.00 0.50 0.20 -- -104.50-100.00 60.00 50 25 \w -29.00 -4.00 0.50 0.05 -- -46.54 100.00 165.00 50 26 \w -94.00 -69.00 0.50 0.20 -- -104.50 100.00 165.00 50 ; _diffrn_measurement_device 'four-circle diffractometer' _diffrn_measurement_device_type 'XtaLAB Synergy R, HyPix' _diffrn_measurement_method '\w scans' _diffrn_orient_matrix_type 'CrysAlisPro convention (1999,Acta A55,543-557)' _diffrn_orient_matrix_UB_11 0.0263590000 _diffrn_orient_matrix_UB_12 0.0442223000 _diffrn_orient_matrix_UB_13 0.0876986000 _diffrn_orient_matrix_UB_21 0.0524918000 _diffrn_orient_matrix_UB_22 -0.1030411000 _diffrn_orient_matrix_UB_23 0.0317227000 _diffrn_orient_matrix_UB_31 0.1175387000 _diffrn_orient_matrix_UB_32 0.0363450000 _diffrn_orient_matrix_UB_33 -0.0166022000 _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 0.0451 _diffrn_reflns_av_unetI/netI 0.0432 _diffrn_reflns_Laue_measured_fraction_full 1.000 _diffrn_reflns_Laue_measured_fraction_max 0.963 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_number 16989 _diffrn_reflns_point_group_measured_fraction_full 1.000 _diffrn_reflns_point_group_measured_fraction_max 0.963 _diffrn_reflns_theta_full 67.684 _diffrn_reflns_theta_max 77.485 _diffrn_reflns_theta_min 4.273 _diffrn_source 'Rotating-anode X-ray tube' _diffrn_source_type 'PhotonJet R (Cu) X-ray Source' _exptl_absorpt_coefficient_mu 5.426 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.69780 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro 1.171.42.96a (Rigaku Oxford Diffraction, 2023) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_colour red _exptl_crystal_colour_primary red _exptl_crystal_density_diffrn 1.710 _exptl_crystal_description block _exptl_crystal_F_000 1320 _exptl_crystal_size_max 0.21 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.12 _refine_diff_density_max 0.462 _refine_diff_density_min -0.424 _refine_diff_density_rms 0.080 _refine_ls_extinction_coef 0.00015(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_extinction_method 'SHELXL-2018/3 (Sheldrick 2018)' _refine_ls_goodness_of_fit_ref 1.053 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 302 _refine_ls_number_reflns 5169 _refine_ls_number_restraints 0 _refine_ls_restrained_S_all 1.053 _refine_ls_R_factor_all 0.0364 _refine_ls_R_factor_gt 0.0322 _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^)+(0.0444P)^2^+0.9067P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0852 _refine_ls_wR_factor_ref 0.0885 _reflns_Friedel_coverage 0.000 _reflns_number_gt 4575 _reflns_number_total 5169 _reflns_threshold_expression 'I > 2\s(I)' _cod_data_source_file d4nr01984a2.cif _cod_data_source_block tx15462_auto _cod_original_cell_volume 2525.76(5) _cod_database_code 1572127 _shelx_shelxl_version_number 2018/3 _chemical_oxdiff_formula CHNOPClSAuCu _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. ; _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups At 1.5 times of: All C(H,H,H) groups 2.a Secondary CH2 refined with riding coordinates: C5(H5A,H5B), C6(H6A,H6B), C12(H12A,H12B), C13(H13A,H13B), C19(H19A,H19B), C20(H20A,H20B) 2.b Aromatic/amide H refined with riding coordinates: C2(H2), C4(H4), C9(H9), C11(H11), C16(H16), C18(H18) 2.c Idealised Me refined as rotating group: C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C21(H21A,H21B,H21C) ; _shelx_res_file ; TITL tx15462_auto_a.res in P2(1)/n tx15462_auto.res created by SHELXL-2018/3 at 10:02:01 on 27-Mar-2024 REM Old TITL TX15462_auto in P2(1)/n REM SHELXT solution in P2(1)/n: R1 0.102, Rweak 0.006, Alpha 0.030 REM 0.306 for 221 systematic absences, Orientation as input REM Formula found by SHELXT: C14 N4 S1 Cl Cu3 CELL 1.54184 11.886701 13.068443 16.480665 90 99.3973 90 ZERR 2 0.00014 0.00017 0.000203 0 0.0011 0 LATT 1 SYMM 0.5-X,0.5+Y,0.5-Z SFAC C H Cu N S UNIT 84 108 12 24 12 L.S. 4 PLAN 5 TEMP -103 CONF MORE -1 BOND $H fmap 2 ACTA REM REM REM WGHT 0.044400 0.906700 EXTI 0.000147 FVAR 0.34764 CU1 3 0.646928 0.568656 0.021726 11.00000 0.02935 0.02784 = 0.02702 -0.00363 -0.00078 0.00562 CU2 3 0.561853 0.401345 0.091402 11.00000 0.02474 0.02879 = 0.02933 -0.00268 0.00074 0.00209 CU3 3 0.440640 0.574462 0.095327 11.00000 0.02524 0.02900 = 0.02788 -0.00408 -0.00514 0.00312 S1 5 0.705413 0.501966 0.147176 11.00000 0.02285 0.03261 = 0.02714 -0.00454 -0.00393 0.00382 S2 5 0.411000 0.710952 0.009298 11.00000 0.02609 0.03169 = 0.02590 -0.00204 -0.00253 0.00692 S3 5 0.297714 0.463777 0.100745 11.00000 0.02361 0.03001 = 0.02992 -0.00376 0.00086 0.00479 N1 4 0.457189 0.325040 0.157373 11.00000 0.02283 0.03186 = 0.02791 -0.00316 0.00032 0.00190 N2 4 0.271515 0.295783 0.187060 11.00000 0.02892 0.03705 = 0.04451 -0.00073 0.00996 0.00492 N3 4 0.548780 0.625296 0.196568 11.00000 0.02442 0.03145 = 0.02556 -0.00374 -0.00224 -0.00180 N4 4 0.734784 0.626999 0.274609 11.00000 0.02528 0.05004 = 0.03402 -0.01193 -0.00399 -0.00090 N5 4 0.638583 0.724632 0.032268 11.00000 0.02799 0.02726 = 0.03279 -0.00393 -0.00133 0.00541 N6 4 0.535764 0.880677 0.024800 11.00000 0.03359 0.02901 = 0.04077 0.00172 0.00378 0.00796 C1 1 0.346996 0.351141 0.154353 11.00000 0.02658 0.03011 = 0.02576 -0.00585 0.00187 0.00219 C2 1 0.309798 0.208346 0.224880 11.00000 0.03274 0.03831 = 0.04482 0.00291 0.01282 0.00301 AFIX 43 H2 2 0.257621 0.168242 0.249281 11.00000 -1.20000 AFIX 0 C3 1 0.420700 0.173271 0.230386 11.00000 0.03410 0.03513 = 0.02663 -0.00316 0.00469 0.00308 C4 1 0.492170 0.236844 0.194965 11.00000 0.02433 0.03306 = 0.02717 -0.00129 0.00026 0.00374 AFIX 43 H4 2 0.569575 0.217148 0.197368 11.00000 -1.20000 AFIX 0 C5 1 0.463062 0.072127 0.266830 11.00000 0.03818 0.03782 = 0.03023 0.00198 0.00554 0.00368 AFIX 23 H5A 2 0.411350 0.047499 0.304018 11.00000 -1.20000 H5B 2 0.539813 0.081264 0.299813 11.00000 -1.20000 AFIX 0 C6 1 0.469043 -0.008207 0.199435 11.00000 0.04196 0.03242 = 0.03523 0.00251 0.01088 0.00401 AFIX 23 H6A 2 0.507899 0.022074 0.156393 11.00000 -1.20000 H6B 2 0.515274 -0.067000 0.223661 11.00000 -1.20000 AFIX 0 C7 1 0.351941 -0.046417 0.160000 11.00000 0.04988 0.04414 = 0.04272 -0.00303 0.01109 -0.00485 AFIX 137 H7A 2 0.360371 -0.096772 0.117339 11.00000 -1.50000 H7B 2 0.306066 0.011313 0.135239 11.00000 -1.50000 H7C 2 0.313943 -0.078410 0.202014 11.00000 -1.50000 AFIX 0 C8 1 0.540978 0.778625 0.023922 11.00000 0.02807 0.02833 = 0.02385 -0.00062 0.00005 0.00699 C9 1 0.634559 0.931169 0.035695 11.00000 0.03687 0.02685 = 0.04062 0.00190 0.00710 0.00627 AFIX 43 H9 2 0.632465 1.003821 0.036714 11.00000 -1.20000 AFIX 0 C10 1 0.740939 0.883246 0.045693 11.00000 0.03543 0.02935 = 0.02676 0.00056 0.00248 0.00470 C11 1 0.736057 0.777406 0.042452 11.00000 0.02851 0.03179 = 0.03622 -0.00302 -0.00175 0.00656 AFIX 43 H11 2 0.805687 0.740435 0.047750 11.00000 -1.20000 AFIX 0 C12 1 0.851968 0.940391 0.057746 11.00000 0.03981 0.03141 = 0.03343 0.00375 0.00484 0.00262 AFIX 23 H12A 2 0.836039 1.014783 0.055442 11.00000 -1.20000 H12B 2 0.893442 0.923542 0.012043 11.00000 -1.20000 AFIX 0 C13 1 0.927999 0.915533 0.139187 11.00000 0.03946 0.04316 = 0.03182 0.00162 0.00159 -0.00378 AFIX 23 H13A 2 0.890546 0.939604 0.185114 11.00000 -1.20000 H13B 2 0.937389 0.840424 0.144367 11.00000 -1.20000 AFIX 0 C14 1 1.045067 0.965432 0.145729 11.00000 0.04226 0.05216 = 0.04202 0.00387 -0.00078 -0.00591 AFIX 137 H14A 2 1.085202 0.937173 0.103358 11.00000 -1.50000 H14B 2 1.089279 0.951722 0.200210 11.00000 -1.50000 H14C 2 1.035972 1.039477 0.137824 11.00000 -1.50000 AFIX 0 C15 1 0.657339 0.593587 0.212519 11.00000 0.02319 0.03199 = 0.02320 -0.00320 -0.00223 0.00037 C16 1 0.515942 0.696242 0.247198 11.00000 0.02763 0.03172 = 0.02655 -0.00254 0.00146 -0.00121 AFIX 43 H16 2 0.439880 0.721098 0.236018 11.00000 -1.20000 AFIX 0 C17 1 0.588004 0.734433 0.314652 11.00000 0.03080 0.03197 = 0.02713 -0.00400 0.00406 -0.00634 C18 1 0.698966 0.696478 0.324638 11.00000 0.02939 0.05003 = 0.03040 -0.01477 -0.00406 -0.00552 AFIX 43 H18 2 0.752418 0.721267 0.369529 11.00000 -1.20000 AFIX 0 C19 1 0.551581 0.811139 0.373445 11.00000 0.03615 0.03468 = 0.03120 -0.00834 0.00764 -0.00597 AFIX 23 H19A 2 0.473225 0.834655 0.351885 11.00000 -1.20000 H19B 2 0.602713 0.871333 0.376947 11.00000 -1.20000 AFIX 0 C20 1 0.554403 0.766770 0.459201 11.00000 0.06603 0.04209 = 0.03285 -0.00565 0.01609 -0.00513 AFIX 23 H20A 2 0.496854 0.711606 0.456676 11.00000 -1.20000 H20B 2 0.630316 0.736140 0.478173 11.00000 -1.20000 AFIX 0 C21 1 0.530574 0.847007 0.520846 11.00000 0.06590 0.05752 = 0.03926 -0.01916 0.01849 -0.01506 AFIX 137 H21A 2 0.457369 0.880214 0.500863 11.00000 -1.50000 H21B 2 0.591454 0.898374 0.527540 11.00000 -1.50000 H21C 2 0.527522 0.814216 0.573920 11.00000 -1.50000 AFIX 0 HKLF 4 REM tx15462_auto_a.res in P2(1)/n REM wR2 = 0.0885, GooF = S = 1.053, Restrained GooF = 1.053 for all data REM R1 = 0.0322 for 4575 Fo > 4sig(Fo) and 0.0364 for all 5169 data REM 302 parameters refined using 0 restraints END WGHT 0.0444 0.9066 REM Highest difference peak 0.462, deepest hole -0.424, 1-sigma level 0.080 Q1 1 0.3562 0.5189 0.1090 11.00000 0.05 0.40 Q2 1 0.5002 0.3635 0.1385 11.00000 0.05 0.38 Q3 1 0.6526 0.6635 0.0297 11.00000 0.05 0.36 Q4 1 0.4752 0.7455 -0.0010 11.00000 0.05 0.36 Q5 1 0.4852 0.5621 0.0467 11.00000 0.05 0.36 ; _shelx_res_checksum 6989 _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 1.518 _oxdiff_exptl_absorpt_empirical_full_min 0.700 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 Cu1 Cu 0.64693(3) 0.56866(3) 0.02173(2) 0.02867(10) Uani 1 1 d . . . . . Cu2 Cu 0.56185(3) 0.40135(3) 0.09140(2) 0.02803(10) Uani 1 1 d . . . . . Cu3 Cu 0.44064(3) 0.57446(3) 0.09533(2) 0.02843(10) Uani 1 1 d . . . . . S1 S 0.70541(4) 0.50197(4) 0.14718(3) 0.02843(13) Uani 1 1 d . . . . . S2 S 0.41100(4) 0.71095(4) 0.00930(3) 0.02865(13) Uani 1 1 d . . . . . S3 S 0.29771(4) 0.46378(4) 0.10074(3) 0.02824(13) Uani 1 1 d . . . . . N1 N 0.45719(15) 0.32504(15) 0.15737(11) 0.0280(4) Uani 1 1 d . . . . . N2 N 0.27151(17) 0.29578(17) 0.18706(14) 0.0364(5) Uani 1 1 d . . . . . N3 N 0.54878(16) 0.62530(15) 0.19657(11) 0.0279(4) Uani 1 1 d . . . . . N4 N 0.73478(17) 0.62700(19) 0.27461(13) 0.0374(5) Uani 1 1 d . . . . . N5 N 0.63858(16) 0.72463(15) 0.03227(12) 0.0301(4) Uani 1 1 d . . . . . N6 N 0.53576(18) 0.88068(16) 0.02480(14) 0.0347(4) Uani 1 1 d . . . . . C1 C 0.34700(19) 0.35114(18) 0.15435(13) 0.0277(4) Uani 1 1 d . . . . . C2 C 0.3098(2) 0.2083(2) 0.22488(17) 0.0379(5) Uani 1 1 d . . . . . H2 H 0.257621 0.168242 0.249281 0.045 Uiso 1 1 calc R U . . . C3 C 0.4207(2) 0.17327(19) 0.23039(14) 0.0320(5) Uani 1 1 d . . . . . C4 C 0.49217(19) 0.23684(18) 0.19496(13) 0.0286(5) Uani 1 1 d . . . . . H4 H 0.569575 0.217148 0.197368 0.034 Uiso 1 1 calc R U . . . C5 C 0.4631(2) 0.0721(2) 0.26683(15) 0.0354(5) Uani 1 1 d . . . . . H5A H 0.411350 0.047499 0.304018 0.043 Uiso 1 1 calc R U . . . H5B H 0.539813 0.081264 0.299813 0.043 Uiso 1 1 calc R U . . . C6 C 0.4690(2) -0.0082(2) 0.19944(15) 0.0360(5) Uani 1 1 d . . . . . H6A H 0.507899 0.022074 0.156393 0.043 Uiso 1 1 calc R U . . . H6B H 0.515274 -0.067000 0.223661 0.043 Uiso 1 1 calc R U . . . C7 C 0.3519(3) -0.0464(2) 0.16000(18) 0.0452(6) Uani 1 1 d . . . . . H7A H 0.360371 -0.096772 0.117339 0.068 Uiso 1 1 calc R U . . . H7B H 0.306066 0.011313 0.135239 0.068 Uiso 1 1 calc R U . . . H7C H 0.313943 -0.078410 0.202014 0.068 Uiso 1 1 calc R U . . . C8 C 0.54098(19) 0.77863(18) 0.02392(13) 0.0272(4) Uani 1 1 d . . . . . C9 C 0.6346(2) 0.93117(19) 0.03570(16) 0.0347(5) Uani 1 1 d . . . . . H9 H 0.632465 1.003821 0.036714 0.042 Uiso 1 1 calc R U . . . C10 C 0.7409(2) 0.88325(19) 0.04569(14) 0.0308(5) Uani 1 1 d . . . . . C11 C 0.7361(2) 0.77741(19) 0.04245(15) 0.0330(5) Uani 1 1 d . . . . . H11 H 0.805687 0.740435 0.047750 0.040 Uiso 1 1 calc R U . . . C12 C 0.8520(2) 0.94039(19) 0.05775(15) 0.0350(5) Uani 1 1 d . . . . . H12A H 0.836039 1.014783 0.055442 0.042 Uiso 1 1 calc R U . . . H12B H 0.893442 0.923542 0.012043 0.042 Uiso 1 1 calc R U . . . C13 C 0.9280(2) 0.9155(2) 0.13919(16) 0.0386(6) Uani 1 1 d . . . . . H13A H 0.890546 0.939604 0.185114 0.046 Uiso 1 1 calc R U . . . H13B H 0.937389 0.840424 0.144367 0.046 Uiso 1 1 calc R U . . . C14 C 1.0451(2) 0.9654(3) 0.14573(18) 0.0463(6) Uani 1 1 d . . . . . H14A H 1.085202 0.937173 0.103358 0.070 Uiso 1 1 calc R U . . . H14B H 1.089279 0.951722 0.200210 0.070 Uiso 1 1 calc R U . . . H14C H 1.035972 1.039477 0.137824 0.070 Uiso 1 1 calc R U . . . C15 C 0.65734(18) 0.59359(18) 0.21252(13) 0.0268(4) Uani 1 1 d . . . . . C16 C 0.51594(19) 0.69624(18) 0.24720(14) 0.0290(4) Uani 1 1 d . . . . . H16 H 0.439880 0.721098 0.236018 0.035 Uiso 1 1 calc R U . . . C17 C 0.5880(2) 0.73443(19) 0.31465(14) 0.0300(5) Uani 1 1 d . . . . . C18 C 0.6990(2) 0.6965(2) 0.32464(15) 0.0376(6) Uani 1 1 d . . . . . H18 H 0.752418 0.721267 0.369529 0.045 Uiso 1 1 calc R U . . . C19 C 0.5516(2) 0.8111(2) 0.37345(15) 0.0338(5) Uani 1 1 d . . . . . H19A H 0.473225 0.834655 0.351885 0.041 Uiso 1 1 calc R U . . . H19B H 0.602713 0.871333 0.376947 0.041 Uiso 1 1 calc R U . . . C20 C 0.5544(3) 0.7668(2) 0.45920(16) 0.0461(7) Uani 1 1 d . . . . . H20A H 0.496854 0.711606 0.456676 0.055 Uiso 1 1 calc R U . . . H20B H 0.630316 0.736140 0.478173 0.055 Uiso 1 1 calc R U . . . C21 C 0.5306(3) 0.8470(3) 0.52085(19) 0.0531(8) Uani 1 1 d . . . . . H21A H 0.457369 0.880214 0.500863 0.080 Uiso 1 1 calc R U . . . H21B H 0.591454 0.898374 0.527540 0.080 Uiso 1 1 calc R U . . . H21C H 0.527522 0.814216 0.573920 0.080 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 Cu1 0.02935(18) 0.02784(19) 0.02702(18) -0.00363(13) -0.00078(13) 0.00562(13) Cu2 0.02474(17) 0.02879(19) 0.02933(18) -0.00268(13) 0.00074(13) 0.00209(12) Cu3 0.02524(17) 0.02900(19) 0.02788(18) -0.00408(13) -0.00514(13) 0.00312(12) S1 0.0228(2) 0.0326(3) 0.0271(3) -0.0045(2) -0.00393(19) 0.0038(2) S2 0.0261(3) 0.0317(3) 0.0259(2) -0.0020(2) -0.00253(19) 0.0069(2) S3 0.0236(2) 0.0300(3) 0.0299(3) -0.0038(2) 0.00086(19) 0.0048(2) N1 0.0228(8) 0.0319(10) 0.0279(9) -0.0032(8) 0.0003(7) 0.0019(7) N2 0.0289(10) 0.0370(11) 0.0445(12) -0.0007(9) 0.0100(9) 0.0049(9) N3 0.0244(9) 0.0314(10) 0.0256(8) -0.0037(8) -0.0022(7) -0.0018(7) N4 0.0253(9) 0.0500(13) 0.0340(10) -0.0119(9) -0.0040(8) -0.0009(9) N5 0.0280(9) 0.0273(10) 0.0328(10) -0.0039(8) -0.0013(7) 0.0054(7) N6 0.0336(10) 0.0290(10) 0.0408(11) 0.0017(9) 0.0038(8) 0.0080(8) C1 0.0266(10) 0.0301(11) 0.0258(10) -0.0059(9) 0.0019(8) 0.0022(9) C2 0.0327(12) 0.0383(14) 0.0448(14) 0.0029(11) 0.0128(10) 0.0030(10) C3 0.0341(12) 0.0351(13) 0.0266(10) -0.0032(9) 0.0047(9) 0.0031(10) C4 0.0243(10) 0.0331(12) 0.0272(10) -0.0013(9) 0.0003(8) 0.0037(9) C5 0.0382(13) 0.0378(14) 0.0302(11) 0.0020(10) 0.0055(10) 0.0037(10) C6 0.0420(13) 0.0324(13) 0.0352(12) 0.0025(10) 0.0109(10) 0.0040(10) C7 0.0499(15) 0.0441(15) 0.0427(14) -0.0030(12) 0.0111(12) -0.0049(13) C8 0.0281(10) 0.0283(11) 0.0239(10) -0.0006(8) 0.0000(8) 0.0070(8) C9 0.0369(12) 0.0269(12) 0.0406(13) 0.0019(10) 0.0071(10) 0.0063(9) C10 0.0354(12) 0.0294(12) 0.0268(10) 0.0006(9) 0.0025(9) 0.0047(9) C11 0.0285(11) 0.0318(12) 0.0362(12) -0.0030(10) -0.0017(9) 0.0066(9) C12 0.0398(13) 0.0314(12) 0.0334(12) 0.0038(9) 0.0048(10) 0.0026(10) C13 0.0395(13) 0.0432(15) 0.0318(12) 0.0016(10) 0.0016(10) -0.0038(11) C14 0.0423(14) 0.0522(17) 0.0420(14) 0.0039(13) -0.0008(11) -0.0059(13) C15 0.0232(10) 0.0320(11) 0.0232(10) -0.0032(8) -0.0022(8) 0.0004(8) C16 0.0276(10) 0.0317(12) 0.0266(10) -0.0025(9) 0.0015(8) -0.0012(9) C17 0.0308(11) 0.0320(12) 0.0271(10) -0.0040(9) 0.0041(9) -0.0063(9) C18 0.0294(11) 0.0500(15) 0.0304(11) -0.0148(11) -0.0041(9) -0.0055(10) C19 0.0362(12) 0.0347(13) 0.0312(11) -0.0083(10) 0.0076(9) -0.0060(10) C20 0.0660(19) 0.0421(15) 0.0329(13) -0.0057(11) 0.0161(13) -0.0051(13) C21 0.0659(19) 0.0575(19) 0.0393(14) -0.0192(13) 0.0185(14) -0.0151(15) 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' Cu Cu -1.9646 0.5888 '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' S S 0.3331 0.5567 '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 Cu2 Cu1 Cu2 92.407(14) . 3_665 ? Cu2 Cu1 Cu3 56.762(12) . . ? Cu2 Cu1 Cu3 64.532(11) 3_665 . ? Cu2 Cu1 Cu3 68.274(13) . 3_665 ? Cu3 Cu1 Cu2 56.873(11) 3_665 3_665 ? Cu3 Cu1 Cu3 93.533(13) 3_665 . ? S1 Cu1 Cu2 138.91(2) . 3_665 ? S1 Cu1 Cu2 52.009(17) . . ? S1 Cu1 Cu3 113.84(2) . 3_665 ? S1 Cu1 Cu3 77.387(18) . . ? S1 Cu1 S3 131.06(2) . 3_665 ? S3 Cu1 Cu2 113.92(2) 3_665 . ? S3 Cu1 Cu2 78.066(17) 3_665 3_665 ? S3 Cu1 Cu3 51.847(17) 3_665 3_665 ? S3 Cu1 Cu3 139.87(2) 3_665 . ? N5 Cu1 Cu2 137.07(6) . . ? N5 Cu1 Cu2 82.58(5) . 3_665 ? N5 Cu1 Cu3 83.28(6) . . ? N5 Cu1 Cu3 135.55(6) . 3_665 ? N5 Cu1 S1 108.65(6) . . ? N5 Cu1 S3 106.68(6) . 3_665 ? Cu1 Cu2 Cu1 87.592(14) . 3_665 ? Cu3 Cu2 Cu1 64.807(13) . . ? Cu3 Cu2 Cu1 59.469(11) . 3_665 ? S1 Cu2 Cu1 52.558(17) . . ? S1 Cu2 Cu1 135.05(2) . 3_665 ? S1 Cu2 Cu3 82.585(19) . . ? S1 Cu2 S2 119.36(2) . 3_665 ? S2 Cu2 Cu1 79.947(17) 3_665 3_665 ? S2 Cu2 Cu1 95.91(2) 3_665 . ? S2 Cu2 Cu3 134.43(2) 3_665 . ? N1 Cu2 Cu1 82.85(5) . 3_665 ? N1 Cu2 Cu1 155.82(6) . . ? N1 Cu2 Cu3 91.30(6) . . ? N1 Cu2 S1 124.09(6) . . ? N1 Cu2 S2 104.15(6) . 3_665 ? Cu1 Cu3 Cu1 86.466(13) 3_665 . ? Cu2 Cu3 Cu1 63.657(12) . 3_665 ? Cu2 Cu3 Cu1 58.431(12) . . ? S2 Cu3 Cu1 79.366(18) . . ? S2 Cu3 Cu1 95.358(19) . 3_665 ? S2 Cu3 Cu2 132.48(2) . . ? S3 Cu3 Cu1 134.03(2) . . ? S3 Cu3 Cu1 52.457(16) . 3_665 ? S3 Cu3 Cu2 82.573(19) . . ? S3 Cu3 S2 119.34(2) . . ? N3 Cu3 Cu1 83.59(5) . . ? N3 Cu3 Cu1 154.72(6) . 3_665 ? N3 Cu3 Cu2 91.44(6) . . ? N3 Cu3 S2 105.50(6) . . ? N3 Cu3 S3 123.80(6) . . ? Cu2 S1 Cu1 75.43(2) . . ? C15 S1 Cu1 102.46(8) . . ? C15 S1 Cu2 110.42(8) . . ? Cu3 S2 Cu2 85.57(2) . 3_665 ? C8 S2 Cu2 101.40(7) . 3_665 ? C8 S2 Cu3 105.41(8) . . ? Cu3 S3 Cu1 75.70(2) . 3_665 ? C1 S3 Cu1 99.73(7) . 3_665 ? C1 S3 Cu3 111.44(8) . . ? C1 N1 Cu2 122.03(16) . . ? C4 N1 Cu2 119.71(15) . . ? C4 N1 C1 117.4(2) . . ? C1 N2 C2 116.7(2) . . ? C15 N3 Cu3 121.12(15) . . ? C15 N3 C16 117.29(19) . . ? C16 N3 Cu3 121.48(15) . . ? C15 N4 C18 116.4(2) . . ? C8 N5 Cu1 124.45(16) . . ? C11 N5 Cu1 118.12(15) . . ? C11 N5 C8 117.3(2) . . ? C9 N6 C8 117.0(2) . . ? N1 C1 S3 118.08(17) . . ? N2 C1 S3 117.66(17) . . ? N2 C1 N1 124.2(2) . . ? N2 C2 H2 118.0 . . ? N2 C2 C3 123.9(2) . . ? C3 C2 H2 118.0 . . ? C2 C3 C5 124.8(2) . . ? C4 C3 C2 114.7(2) . . ? C4 C3 C5 120.5(2) . . ? N1 C4 C3 123.0(2) . . ? N1 C4 H4 118.5 . . ? C3 C4 H4 118.5 . . ? C3 C5 H5A 109.4 . . ? C3 C5 H5B 109.4 . . ? C3 C5 C6 111.3(2) . . ? H5A C5 H5B 108.0 . . ? C6 C5 H5A 109.4 . . ? C6 C5 H5B 109.4 . . ? C5 C6 H6A 109.1 . . ? C5 C6 H6B 109.1 . . ? H6A C6 H6B 107.8 . . ? C7 C6 C5 112.7(2) . . ? C7 C6 H6A 109.1 . . ? C7 C6 H6B 109.1 . . ? C6 C7 H7A 109.5 . . ? C6 C7 H7B 109.5 . . ? C6 C7 H7C 109.5 . . ? H7A C7 H7B 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? N5 C8 S2 118.22(17) . . ? N6 C8 S2 117.48(17) . . ? N6 C8 N5 124.3(2) . . ? N6 C9 H9 118.2 . . ? N6 C9 C10 123.7(2) . . ? C10 C9 H9 118.2 . . ? C9 C10 C12 123.5(2) . . ? C11 C10 C9 114.3(2) . . ? C11 C10 C12 122.2(2) . . ? N5 C11 C10 123.4(2) . . ? N5 C11 H11 118.3 . . ? C10 C11 H11 118.3 . . ? C10 C12 H12A 109.0 . . ? C10 C12 H12B 109.0 . . ? C10 C12 C13 113.1(2) . . ? H12A C12 H12B 107.8 . . ? C13 C12 H12A 109.0 . . ? C13 C12 H12B 109.0 . . ? C12 C13 H13A 109.2 . . ? C12 C13 H13B 109.2 . . ? H13A C13 H13B 107.9 . . ? C14 C13 C12 112.0(2) . . ? C14 C13 H13A 109.2 . . ? C14 C13 H13B 109.2 . . ? C13 C14 H14A 109.5 . . ? C13 C14 H14B 109.5 . . ? C13 C14 H14C 109.5 . . ? H14A C14 H14B 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? N3 C15 S1 119.15(16) . . ? N4 C15 S1 116.00(17) . . ? N4 C15 N3 124.9(2) . . ? N3 C16 H16 118.6 . . ? N3 C16 C17 122.9(2) . . ? C17 C16 H16 118.6 . . ? C16 C17 C18 114.6(2) . . ? C16 C17 C19 123.6(2) . . ? C18 C17 C19 121.8(2) . . ? N4 C18 C17 123.9(2) . . ? N4 C18 H18 118.1 . . ? C17 C18 H18 118.1 . . ? C17 C19 H19A 109.2 . . ? C17 C19 H19B 109.2 . . ? C17 C19 C20 112.2(2) . . ? H19A C19 H19B 107.9 . . ? C20 C19 H19A 109.2 . . ? C20 C19 H19B 109.2 . . ? C19 C20 H20A 109.1 . . ? C19 C20 H20B 109.1 . . ? H20A C20 H20B 107.9 . . ? C21 C20 C19 112.3(3) . . ? C21 C20 H20A 109.1 . . ? C21 C20 H20B 109.1 . . ? C20 C21 H21A 109.5 . . ? C20 C21 H21B 109.5 . . ? C20 C21 H21C 109.5 . . ? H21A C21 H21B 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? 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 Cu1 Cu2 2.7388(5) . ? Cu1 Cu2 2.8771(5) 3_665 ? Cu1 Cu3 2.9088(5) . ? Cu1 Cu3 2.7654(5) 3_665 ? Cu1 S1 2.2468(6) . ? Cu1 S3 2.2629(6) 3_665 ? Cu1 N5 2.050(2) . ? Cu2 Cu3 2.6887(5) . ? Cu2 S1 2.2302(6) . ? Cu2 S2 2.2775(6) 3_665 ? Cu2 N1 2.0411(19) . ? Cu3 S2 2.2700(6) . ? Cu3 S3 2.2441(6) . ? Cu3 N3 2.0438(18) . ? S1 C15 1.767(2) . ? S2 C8 1.762(2) . ? S3 C1 1.767(2) . ? N1 C1 1.347(3) . ? N1 C4 1.342(3) . ? N2 C1 1.333(3) . ? N2 C2 1.345(3) . ? N3 C15 1.340(3) . ? N3 C16 1.347(3) . ? N4 C15 1.333(3) . ? N4 C18 1.342(3) . ? N5 C8 1.346(3) . ? N5 C11 1.335(3) . ? N6 C8 1.335(3) . ? N6 C9 1.333(3) . ? C2 H2 0.9500 . ? C2 C3 1.385(3) . ? C3 C4 1.384(3) . ? C3 C5 1.504(3) . ? C4 H4 0.9500 . ? C5 H5A 0.9900 . ? C5 H5B 0.9900 . ? C5 C6 1.538(4) . ? C6 H6A 0.9900 . ? C6 H6B 0.9900 . ? C6 C7 1.521(4) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C9 H9 0.9500 . ? C9 C10 1.397(3) . ? C10 C11 1.385(3) . ? C10 C12 1.501(4) . ? C11 H11 0.9500 . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C12 C13 1.526(4) . ? C13 H13A 0.9900 . ? C13 H13B 0.9900 . ? C13 C14 1.525(4) . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C16 H16 0.9500 . ? C16 C17 1.381(3) . ? C17 C18 1.394(4) . ? C17 C19 1.506(3) . ? C18 H18 0.9500 . ? C19 H19A 0.9900 . ? C19 H19B 0.9900 . ? C19 C20 1.523(4) . ? C20 H20A 0.9900 . ? C20 H20B 0.9900 . ? C20 C21 1.519(4) . ? C21 H21A 0.9800 . ? C21 H21B 0.9800 . ? C21 H21C 0.9800 . ? 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 Cu1 S1 C15 N3 49.93(19) . . . . ? Cu1 S1 C15 N4 -129.29(18) . . . . ? Cu1 S3 C1 N1 53.54(18) 3_665 . . . ? Cu1 S3 C1 N2 -124.43(17) 3_665 . . . ? Cu1 N5 C8 S2 4.2(3) . . . . ? Cu1 N5 C8 N6 -174.84(17) . . . . ? Cu1 N5 C11 C10 176.26(19) . . . . ? Cu2 S1 C15 N3 -29.0(2) . . . . ? Cu2 S1 C15 N4 151.81(17) . . . . ? Cu2 S2 C8 N5 -47.89(18) 3_665 . . . ? Cu2 S2 C8 N6 131.18(17) 3_665 . . . ? Cu2 N1 C1 S3 -7.3(2) . . . . ? Cu2 N1 C1 N2 170.48(18) . . . . ? Cu2 N1 C4 C3 -170.19(17) . . . . ? Cu3 S2 C8 N5 40.62(18) . . . . ? Cu3 S2 C8 N6 -140.32(17) . . . . ? Cu3 S3 C1 N1 -24.81(19) . . . . ? Cu3 S3 C1 N2 157.22(16) . . . . ? Cu3 N3 C15 S1 -2.8(3) . . . . ? Cu3 N3 C15 N4 176.30(19) . . . . ? Cu3 N3 C16 C17 -177.98(18) . . . . ? N2 C2 C3 C4 1.3(4) . . . . ? N2 C2 C3 C5 -175.2(2) . . . . ? N3 C16 C17 C18 2.2(4) . . . . ? N3 C16 C17 C19 -177.9(2) . . . . ? N6 C9 C10 C11 0.7(4) . . . . ? N6 C9 C10 C12 179.9(2) . . . . ? C1 N1 C4 C3 -0.3(3) . . . . ? C1 N2 C2 C3 -0.9(4) . . . . ? C2 N2 C1 S3 177.54(19) . . . . ? C2 N2 C1 N1 -0.3(4) . . . . ? C2 C3 C4 N1 -0.7(3) . . . . ? C2 C3 C5 C6 99.6(3) . . . . ? C3 C5 C6 C7 -73.4(3) . . . . ? C4 N1 C1 S3 -176.95(16) . . . . ? C4 N1 C1 N2 0.9(3) . . . . ? C4 C3 C5 C6 -76.8(3) . . . . ? C5 C3 C4 N1 176.0(2) . . . . ? C8 N5 C11 C10 0.8(3) . . . . ? C8 N6 C9 C10 0.3(4) . . . . ? C9 N6 C8 S2 -179.84(18) . . . . ? C9 N6 C8 N5 -0.8(4) . . . . ? C9 C10 C11 N5 -1.2(4) . . . . ? C9 C10 C12 C13 119.5(3) . . . . ? C10 C12 C13 C14 173.8(2) . . . . ? C11 N5 C8 S2 179.34(17) . . . . ? C11 N5 C8 N6 0.3(3) . . . . ? C11 C10 C12 C13 -61.4(3) . . . . ? C12 C10 C11 N5 179.6(2) . . . . ? C15 N3 C16 C17 -1.7(3) . . . . ? C15 N4 C18 C17 -0.3(4) . . . . ? C16 N3 C15 S1 -179.11(17) . . . . ? C16 N3 C15 N4 0.0(4) . . . . ? C16 C17 C18 N4 -1.2(4) . . . . ? C16 C17 C19 C20 114.3(3) . . . . ? C17 C19 C20 C21 173.6(2) . . . . ? C18 N4 C15 S1 -179.9(2) . . . . ? C18 N4 C15 N3 0.9(4) . . . . ? C18 C17 C19 C20 -65.9(3) . . . . ? C19 C17 C18 N4 178.9(3) . . . . ?