Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name J.Dilworth _publ_contact_author_address ; Inorganic Chemical Laboratory University of Oxford South Parks Road OXFORD OX1 3QR UNITED KINGDOM ; _publ_contact_author_email JON.DILWORTH@CHEMISTRY.OXFORD.AC.UK _publ_section_title ; Complexation versus thiadiazole formation for reactions of thiosemicarbazides with copper(II) ; loop_ _publ_author_name 'J. Dilworth' 'Andrew R. Cowley' 'Elena Lopez-Torres' # Attachment 'Elena_structure_1.cif' data_arc1414 _database_code_depnum_ccdc_archive 'CCDC 623527' #============================================================= # Diffractometer details #============================================================= _diffrn_measurement_device_type ; Nonius KappaCCD ; _diffrn_radiation_monochromator graphite _computing_data_collection ; KappaCCD software 'Collect' (Nonius, 2000) ; _computing_data_reduction ; KappaCCD software 'DENZO' (Otwinowski & Minor, 1996) ; _computing_cell_refinement ; KappaCCD software 'DENZO' (Otwinowski & Minor, 1996) ; #============================================================= # General computing #============================================================= _computing_structure_refinement ; CRYSTALS (Watkin et al, 2001) ; _computing_publication_material ; CRYSTALS (Watkin et al, 2001) ; _computing_structure_solution 'SIR92 (Giacovazzo et al, 1992)' _chemical_name_systematic # IUPAC name, in full ; ? ; _chemical_melting_point ? _exptl_crystal_thermal_history ; The material was crystallised at ambient temperature. A suitable crystal was cooled rapidly to 150K for single-crystal X-ray diffraction analysis. ; _refine_ls_matrix_type full _atom_sites_solution_primary direct _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_special_details ; The NH hydrogen atom was located in a difference Fourier map and its coordinates and isotropic displacement parameter subsequently refined. Other hydrogen atoms were positioned geometrically. ; #============================================================= _cell_length_a 11.8923(4) _cell_angle_alpha 90 _cell_length_b 5.5608(2) _cell_angle_beta 99.3695(14) _cell_length_c 15.7983(5) _cell_angle_gamma 90 _cell_volume 1030.81(6) _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1 ' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x,y+1/2,-z+1/2 x,-y+1/2,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source 'C ' 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 International_Tables_Vol_IV_Table_2.2B 'H ' 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 International_Tables_Vol_IV_Table_2.2B 'Cu ' 0.3201 1.2651 13.3380 3.5828 7.1676 0.2470 5.6158 11.3966 1.6735 64.8126 1.1910 International_Tables_Vol_IV_Table_2.2B 'N ' 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 International_Tables_Vol_IV_Table_2.2B 'S ' 0.1246 0.1234 6.9053 1.4679 5.2034 22.2151 1.4379 0.2536 1.5863 56.1720 0.8669 International_Tables_Vol_IV_Table_2.2B _cell_formula_units_Z 2 _chemical_formula_sum ' C18 H24 Cu1 N6 S2 ' _chemical_formula_moiety ' C18 H24 Cu1 N6 S2 ' _chemical_compound_source ; synthesis as described ; _chemical_formula_weight 452.11 _cell_measurement_reflns_used 10012 _cell_measurement_theta_min 5 _cell_measurement_theta_max 28 _cell_measurement_temperature 150 _exptl_crystal_description ' prism ' _exptl_crystal_colour ' dark brown-red ' _exptl_crystal_size_min 0.04 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_max 0.34 _exptl_crystal_density_diffrn 1.457 _exptl_crystal_density_meas ? # Non-dispersive F(000): _exptl_crystal_F_000 470 _exptl_absorpt_coefficient_mu 1.277 _diffrn_measurement_method \w _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; Denzo/Scalepack (Otwinowski & Minor, 1996) ; _exptl_absorpt_correction_T_min 0.64 _exptl_absorpt_correction_T_max 0.95 _diffrn_standards_interval_time 0 _diffrn_standards_interval_count 0 _diffrn_standards_number 0 _diffrn_standards_decay_% 0.00 _diffrn_ambient_temperature 150 _diffrn_reflns_number 10012 _reflns_number_total 2340 #2578 unique reflections including absences _diffrn_reflns_av_R_equivalents 0.040 _diffrn_reflns_theta_min 5.213 _diffrn_reflns_theta_max 27.478 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.478 _diffrn_measured_fraction_theta_full 0.994 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _reflns_limit_h_min -15 _reflns_limit_h_max 15 _reflns_limit_k_min 0 _reflns_limit_k_max 7 _reflns_limit_l_min 0 _reflns_limit_l_max 20 _refine_diff_density_min -0.36 _refine_diff_density_max 0.49 _refine_ls_number_reflns 1749 _refine_ls_number_restraints 0 _refine_ls_number_parameters 128 #_refine_ls_R_factor_ref 0.0324 _refine_ls_wR_factor_ref 0.0379 _refine_ls_goodness_of_fit_ref 1.0768 #_reflns_number_all 2340 _refine_ls_R_factor_all 0.0478 _refine_ls_wR_factor_all 0.0505 # The I/u(I) cutoff below was used for refinement as # well as the _gt R-factors: _reflns_threshold_expression I>3.00u(I) _reflns_number_gt 1749 _refine_ls_R_factor_gt 0.0324 _refine_ls_wR_factor_gt 0.0379 _refine_ls_shift/su_max 0.029236 _refine_ls_structure_factor_coef F _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 0.581 0.198 0.295 ; _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 # Uequiv = arithmetic mean of Ui # i.e. Ueqiv = (U1+U2+U3)/3 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn Cu1 Cu 0.5000 0.5000 0.5000 0.0241 1.0000 Uani S S1 S 0.49551(5) 0.33765(14) 0.62930(4) 0.0359 1.0000 Uani . C1 C 0.36263(19) 0.1971(4) 0.60169(13) 0.0262 1.0000 Uani . N1 N 0.29453(17) 0.2206(4) 0.53028(12) 0.0283 1.0000 Uani . N2 N 0.33405(16) 0.3863(3) 0.47026(11) 0.0243 1.0000 Uani . N3 N 0.33334(18) 0.0478(4) 0.66445(12) 0.0314 1.0000 Uani . C2 C 0.23080(19) -0.0830(4) 0.66256(14) 0.0264 1.0000 Uani . C3 C 0.2362(2) -0.2967(5) 0.70922(14) 0.0311 1.0000 Uani . C4 C 0.1391(2) -0.4292(5) 0.71172(16) 0.0358 1.0000 Uani . C5 C 0.0341(2) -0.3534(5) 0.66754(17) 0.0367 1.0000 Uani . C6 C 0.0291(2) -0.1422(5) 0.62086(17) 0.0362 1.0000 Uani . C7 C 0.1266(2) -0.0050(5) 0.61798(15) 0.0300 1.0000 Uani . C8 C 0.3116(2) 0.2597(5) 0.38691(14) 0.0328 1.0000 Uani . C9 C 0.2591(2) 0.6026(5) 0.46736(17) 0.0354 1.0000 Uani . H1 H 0.390(3) 0.009(5) 0.703(2) 0.035(7) 1.0000 Uiso . H31 H 0.3110 -0.3539 0.7410 0.0365 1.0000 Uiso . H41 H 0.1439 -0.5817 0.7456 0.0420 1.0000 Uiso . H51 H -0.0364 -0.4498 0.6695 0.0433 1.0000 Uiso . H61 H -0.0458 -0.0868 0.5886 0.0433 1.0000 Uiso . H71 H 0.1216 0.1479 0.5842 0.0362 1.0000 Uiso . H81 H 0.3366 0.3627 0.3416 0.0391 1.0000 Uiso . H82 H 0.3548 0.1047 0.3912 0.0391 1.0000 Uiso . H83 H 0.2281 0.2260 0.3716 0.0391 1.0000 Uiso . H91 H 0.2826 0.7235 0.4268 0.0427 1.0000 Uiso . H92 H 0.2664 0.6747 0.5260 0.0427 1.0000 Uiso . H93 H 0.1781 0.5544 0.4474 0.0427 1.0000 Uiso . 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 0.02299(19) 0.0305(2) 0.01824(18) 0.00128(16) 0.00160(12) -0.00344(16) S1 0.0266(3) 0.0567(4) 0.0225(3) 0.0100(3) -0.0020(2) -0.0117(3) C1 0.0274(11) 0.0304(12) 0.0207(10) 0.0000(9) 0.0041(8) -0.0020(9) N1 0.0297(9) 0.0342(11) 0.0207(8) 0.0035(8) 0.0031(7) -0.0107(8) N2 0.0278(9) 0.0272(10) 0.0176(8) 0.0019(7) 0.0024(7) -0.0036(8) N3 0.0273(9) 0.0441(13) 0.0215(9) 0.0092(8) -0.0002(7) -0.0044(9) C2 0.0277(11) 0.0317(11) 0.0200(9) -0.0010(9) 0.0048(8) -0.0029(9) C3 0.0310(12) 0.0374(13) 0.0231(10) 0.0042(9) -0.0014(8) -0.0014(10) C4 0.0399(13) 0.0350(13) 0.0300(12) 0.0076(10) -0.0020(10) -0.0062(11) C5 0.0303(12) 0.0423(14) 0.0358(13) 0.0070(11) 0.0000(10) -0.0106(11) C6 0.0270(11) 0.0432(14) 0.0381(13) 0.0072(11) 0.0042(9) -0.0001(11) C7 0.0282(10) 0.0328(11) 0.0297(11) 0.0067(10) 0.0064(8) 0.0000(10) C8 0.0386(13) 0.0386(13) 0.0206(10) -0.0036(10) 0.0027(9) -0.0133(11) C9 0.0291(12) 0.0331(13) 0.0444(14) 0.0036(11) 0.0076(10) 0.0027(10) _refine_ls_extinction_method None loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Cu1 . S1 . 2.2419(6) yes Cu1 . S1 2_666 2.2419(6) yes Cu1 . N2 . 2.0526(18) yes Cu1 . N2 2_666 2.0526(18) yes S1 . C1 . 1.753(2) yes C1 . N1 . 1.284(3) yes C1 . N3 . 1.381(3) yes N1 . N2 . 1.454(2) yes N2 . C8 . 1.479(3) yes N2 . C9 . 1.493(3) yes N3 . C2 . 1.416(3) yes N3 . H1 . 0.86(3) no C2 . C3 . 1.394(3) yes C2 . C7 . 1.391(3) yes C3 . C4 . 1.376(4) yes C3 . H31 . 1.000 no C4 . C5 . 1.393(4) yes C4 . H41 . 1.000 no C5 . C6 . 1.383(4) yes C5 . H51 . 1.000 no C6 . C7 . 1.395(3) yes C6 . H61 . 1.000 no C7 . H71 . 1.000 no C8 . H81 . 1.000 no C8 . H82 . 1.000 no C8 . H83 . 1.000 no C9 . H91 . 1.000 no C9 . H92 . 1.000 no C9 . H93 . 1.000 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag S1 . Cu1 . S1 2_666 179.995 yes S1 . Cu1 . N2 . 85.41(5) yes S1 2_666 Cu1 . N2 . 94.59(5) yes S1 . Cu1 . N2 2_666 94.59(5) yes S1 2_666 Cu1 . N2 2_666 85.41(5) yes N2 . Cu1 . N2 2_666 179.994 yes Cu1 . S1 . C1 . 96.14(7) yes S1 . C1 . N1 . 125.98(17) yes S1 . C1 . N3 . 114.33(16) yes N1 . C1 . N3 . 119.7(2) yes C1 . N1 . N2 . 114.38(18) yes Cu1 . N2 . N1 . 116.53(13) yes Cu1 . N2 . C8 . 112.22(14) yes N1 . N2 . C8 . 104.36(17) yes Cu1 . N2 . C9 . 107.80(14) yes N1 . N2 . C9 . 106.01(17) yes C8 . N2 . C9 . 109.63(18) yes C1 . N3 . C2 . 127.6(2) yes C1 . N3 . H1 . 113.4(20) no C2 . N3 . H1 . 117.5(20) no N3 . C2 . C3 . 117.5(2) yes N3 . C2 . C7 . 122.9(2) yes C3 . C2 . C7 . 119.6(2) yes C2 . C3 . C4 . 120.3(2) yes C2 . C3 . H31 . 119.842 no C4 . C3 . H31 . 119.839 no C3 . C4 . C5 . 120.8(2) yes C3 . C4 . H41 . 119.616 no C5 . C4 . H41 . 119.619 no C4 . C5 . C6 . 118.8(2) yes C4 . C5 . H51 . 120.605 no C6 . C5 . H51 . 120.604 no C5 . C6 . C7 . 121.2(2) yes C5 . C6 . H61 . 119.395 no C7 . C6 . H61 . 119.395 no C2 . C7 . C6 . 119.3(2) yes C2 . C7 . H71 . 120.345 no C6 . C7 . H71 . 120.348 no N2 . C8 . H81 . 109.463 no N2 . C8 . H82 . 109.468 no H81 . C8 . H82 . 109.478 no N2 . C8 . H83 . 109.465 no H81 . C8 . H83 . 109.473 no H82 . C8 . H83 . 109.480 no N2 . C9 . H91 . 109.469 no N2 . C9 . H92 . 109.465 no H91 . C9 . H92 . 109.475 no N2 . C9 . H93 . 109.468 no H91 . C9 . H93 . 109.476 no H92 . C9 . H93 . 109.474 no # Attachment 'thiadiazolium_salt.cif' data_arc1564 _database_code_depnum_ccdc_archive 'CCDC 623528' #============================================================= # Diffractometer details #============================================================= _diffrn_measurement_device_type ; Nonius KappaCCD ; _diffrn_radiation_monochromator graphite _computing_data_collection ; KappaCCD software 'Collect' (Nonius, 2000) ; _computing_data_reduction ; KappaCCD software 'DENZO' (Otwinowski & Minor, 1996) ; _computing_cell_refinement ; KappaCCD software 'DENZO' (Otwinowski & Minor, 1996) ; #============================================================= # General computing #============================================================= _computing_structure_refinement ; CRYSTALS (Watkin et al, 2001) ; _computing_publication_material ; CRYSTALS (Watkin et al, 2001) ; _computing_structure_solution 'SIR92 (Giacovazzo et al, 1992)' _chemical_name_systematic # IUPAC name, in full ; ? ; _chemical_melting_point ? _exptl_crystal_thermal_history ; The material was crystallised at ambient temperature. A suitable crystal was cooled rapidly to 150K for single-crystal X-ray diffraction analysis. ; _refine_ls_matrix_type full _atom_sites_solution_primary direct _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_special_details ; The NH hydrogen atoms were located in a difference Fouier map and their coordinates and isotropic displacement parameters subsequently refined. Other hydrogen atoms were positioned geometrically, the preferred orientations of the methyl groups having been identified previously by examination of the Fourier map. ; #============================================================= _cell_length_a 7.3900(2) _cell_angle_alpha 80.9969(10) _cell_length_b 9.9448(2) _cell_angle_beta 88.6086(10) _cell_length_c 16.1842(3) _cell_angle_gamma 85.1073(9) _cell_volume 1170.40(5) _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P -1 ' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source 'C ' 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 International_Tables_Vol_IV_Table_2.2B 'H ' 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 International_Tables_Vol_IV_Table_2.2B 'Cl ' 0.1484 0.1585 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 International_Tables_Vol_IV_Table_2.2B 'Cu ' 0.3201 1.2651 13.3380 3.5828 7.1676 0.2470 5.6158 11.3966 1.6735 64.8126 1.1910 International_Tables_Vol_IV_Table_2.2B 'N ' 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 International_Tables_Vol_IV_Table_2.2B 'S ' 0.1246 0.1234 6.9053 1.4679 5.2034 22.2151 1.4379 0.2536 1.5863 56.1720 0.8669 International_Tables_Vol_IV_Table_2.2B _cell_formula_units_Z 2 _chemical_formula_sum ' C18 H20 Cl4 Cu N6 S2 ' _chemical_formula_moiety ' 2 ( C9 H10 N3 S ), Cl4 Cu ' _chemical_compound_source ; synthesis as described ; _chemical_formula_weight 589.89 _cell_measurement_reflns_used 17872 _cell_measurement_theta_min 5 _cell_measurement_theta_max 28 _cell_measurement_temperature 150 _exptl_crystal_description ' fragment ' _exptl_crystal_colour ' green-yellow ' _exptl_crystal_size_min 0.20 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_max 0.28 _exptl_crystal_density_diffrn 1.674 _exptl_crystal_density_meas ? # Non-dispersive F(000): _exptl_crystal_F_000 598 _exptl_absorpt_coefficient_mu 1.588 _diffrn_measurement_method \w _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; Denzo/Scalepack (Otwinowski & Minor, 1996) ; _exptl_absorpt_correction_T_min 0.64 _exptl_absorpt_correction_T_max 0.73 # Sheldrick geometric definitions 0.64 0.73 _diffrn_standards_interval_time 0 _diffrn_standards_interval_count 0 _diffrn_standards_number 0 _diffrn_standards_decay_% 0.00 _diffrn_ambient_temperature 150 _diffrn_reflns_number 17872 _reflns_number_total 5319 _diffrn_reflns_av_R_equivalents 0.039 _diffrn_reflns_theta_min 5.102 _diffrn_reflns_theta_max 27.471 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.471 _diffrn_measured_fraction_theta_full 0.999 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _reflns_limit_h_min -9 _reflns_limit_h_max 9 _reflns_limit_k_min -12 _reflns_limit_k_max 12 _reflns_limit_l_min 0 _reflns_limit_l_max 20 _refine_diff_density_min -0.51 _refine_diff_density_max 0.47 _refine_ls_number_reflns 4108 _refine_ls_number_restraints 0 _refine_ls_number_parameters 288 #_refine_ls_R_factor_ref 0.0310 _refine_ls_wR_factor_ref 0.0357 _refine_ls_goodness_of_fit_ref 1.0827 #_reflns_number_all 5319 _refine_ls_R_factor_all 0.0421 _refine_ls_wR_factor_all 0.0488 # The I/u(I) cutoff below was used for refinement as # well as the _gt R-factors: _reflns_threshold_expression I>3.00u(I) _reflns_number_gt 4108 _refine_ls_R_factor_gt 0.0310 _refine_ls_wR_factor_gt 0.0357 _refine_ls_shift/su_max 0.010918 _refine_ls_structure_factor_coef F _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 0.470 0.258 0.194 ; _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 # Uequiv = arithmetic mean of Ui # i.e. Ueqiv = (U1+U2+U3)/3 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_occupancy _atom_site_adp_type S1 S 0.27840(11) 0.61735(6) -0.04778(4) 0.0383 1.0000 Uani C1 C 0.2460(3) 0.7937(2) -0.04446(14) 0.0256 1.0000 Uani N1 N 0.1835(3) 0.86723(19) -0.11398(12) 0.0249 1.0000 Uani N2 N 0.1603(3) 0.7804(2) -0.17051(13) 0.0282 1.0000 Uani N3 N 0.2873(3) 0.8412(2) 0.02515(13) 0.0287 1.0000 Uani C2 C 0.2805(3) 0.9780(2) 0.03996(13) 0.0234 1.0000 Uani C3 C 0.3529(3) 0.9989(2) 0.11513(14) 0.0286 1.0000 Uani C4 C 0.3514(4) 1.1294(3) 0.13477(15) 0.0321 1.0000 Uani C5 C 0.2774(3) 1.2412(2) 0.07955(15) 0.0293 1.0000 Uani C6 C 0.2072(3) 1.2197(2) 0.00490(15) 0.0281 1.0000 Uani C7 C 0.2067(3) 1.0892(2) -0.01602(14) 0.0245 1.0000 Uani C8 C 0.2035(4) 0.6511(3) -0.14761(16) 0.0339 1.0000 Uani C9 C 0.0886(4) 0.8421(3) -0.25265(16) 0.0376 1.0000 Uani S2 S 0.32125(10) 0.37952(6) 0.52783(4) 0.0376 1.0000 Uani C10 C 0.2829(3) 0.2064(2) 0.53171(15) 0.0264 1.0000 Uani N4 N 0.2359(3) 0.1450(2) 0.60624(12) 0.0262 1.0000 Uani N5 N 0.2323(3) 0.2379(2) 0.66093(13) 0.0297 1.0000 Uani N6 N 0.3031(3) 0.1498(2) 0.46176(13) 0.0297 1.0000 Uani C11 C 0.2757(3) 0.0154(2) 0.45029(14) 0.0246 1.0000 Uani C12 C 0.3139(4) -0.0175(3) 0.37092(14) 0.0309 1.0000 Uani C13 C 0.2881(4) -0.1457(3) 0.35342(15) 0.0363 1.0000 Uani C14 C 0.2246(4) -0.2449(3) 0.41526(16) 0.0329 1.0000 Uani C15 C 0.1890(4) -0.2124(2) 0.49444(15) 0.0314 1.0000 Uani C16 C 0.2130(4) -0.0836(2) 0.51273(14) 0.0295 1.0000 Uani C17 C 0.2750(4) 0.3609(3) 0.63148(17) 0.0338 1.0000 Uani C18 C 0.1738(4) 0.1905(3) 0.74661(18) 0.0442 1.0000 Uani Cu1 Cu 0.30019(4) 0.49458(3) 0.246194(16) 0.0213 1.0000 Uani Cl1 Cl 0.51017(8) 0.62612(6) 0.17890(4) 0.0314 1.0000 Uani Cl2 Cl 0.09623(8) 0.57443(7) 0.14666(4) 0.0351 1.0000 Uani Cl3 Cl 0.51422(8) 0.34381(6) 0.31548(4) 0.0327 1.0000 Uani Cl4 Cl 0.08536(8) 0.43548(6) 0.34298(4) 0.0304 1.0000 Uani H1 H 0.321(5) 0.786(4) 0.064(2) 0.044(9) 1.0000 Uiso H2 H 0.339(5) 0.201(4) 0.420(2) 0.048(9) 1.0000 Uiso H31 H 0.4063 0.9192 0.1551 0.0335 1.0000 Uiso H41 H 0.4036 1.1436 0.1889 0.0388 1.0000 Uiso H51 H 0.2753 1.3356 0.0938 0.0357 1.0000 Uiso H61 H 0.1554 1.2999 -0.0351 0.0331 1.0000 Uiso H71 H 0.1545 1.0753 -0.0702 0.0289 1.0000 Uiso H81 H 0.1938 0.5800 -0.1843 0.0416 1.0000 Uiso H91 H 0.0780 0.7691 -0.2879 0.0463 1.0000 Uiso H92 H 0.1729 0.9092 -0.2807 0.0463 1.0000 Uiso H93 H -0.0338 0.8903 -0.2455 0.0463 1.0000 Uiso H121 H 0.3606 0.0525 0.3261 0.0366 1.0000 Uiso H131 H 0.3151 -0.1677 0.2960 0.0437 1.0000 Uiso H141 H 0.2051 -0.3379 0.4027 0.0397 1.0000 Uiso H151 H 0.1451 -0.2834 0.5394 0.0376 1.0000 Uiso H161 H 0.1856 -0.0617 0.5702 0.0352 1.0000 Uiso H171 H 0.2797 0.4353 0.6661 0.0411 1.0000 Uiso H181 H 0.1765 0.2661 0.7805 0.0561 1.0000 Uiso H182 H 0.2576 0.1110 0.7717 0.0561 1.0000 Uiso H183 H 0.0474 0.1618 0.7463 0.0561 1.0000 Uiso 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 S1 0.0593(4) 0.0183(3) 0.0360(3) -0.0027(2) 0.0127(3) -0.0013(3) C1 0.0285(11) 0.0189(10) 0.0279(11) -0.0003(8) 0.0084(9) -0.0027(8) N1 0.0287(9) 0.0225(9) 0.0249(9) -0.0070(7) 0.0037(7) -0.0054(7) N2 0.0307(10) 0.0272(10) 0.0293(10) -0.0104(8) 0.0074(8) -0.0080(8) N3 0.0400(11) 0.0208(9) 0.0236(10) 0.0008(8) -0.0006(8) 0.0004(8) C2 0.0256(10) 0.0216(10) 0.0221(10) -0.0016(8) 0.0051(8) -0.0013(8) C3 0.0352(12) 0.0292(12) 0.0193(10) 0.0007(8) -0.0005(9) 0.0019(9) C4 0.0393(13) 0.0348(13) 0.0228(11) -0.0055(9) 0.0000(10) -0.0048(10) C5 0.0333(12) 0.0267(11) 0.0292(12) -0.0075(9) 0.0053(9) -0.0049(9) C6 0.0284(11) 0.0232(11) 0.0311(12) -0.0015(9) 0.0026(9) 0.0002(9) C7 0.0269(11) 0.0236(10) 0.0218(10) -0.0010(8) -0.0004(8) 0.0007(8) C8 0.0406(14) 0.0269(12) 0.0367(13) -0.0116(10) 0.0158(11) -0.0093(10) C9 0.0461(15) 0.0395(14) 0.0302(13) -0.0131(11) -0.0070(11) -0.0043(11) S2 0.0532(4) 0.0207(3) 0.0385(3) 0.0004(2) -0.0122(3) -0.0058(3) C10 0.0293(11) 0.0194(10) 0.0298(11) -0.0017(8) -0.0037(9) -0.0014(8) N4 0.0300(10) 0.0254(9) 0.0242(9) -0.0073(7) 0.0006(8) -0.0026(8) N5 0.0296(10) 0.0308(10) 0.0314(10) -0.0124(8) -0.0009(8) -0.0030(8) N6 0.0427(12) 0.0248(10) 0.0199(9) 0.0027(7) 0.0022(8) -0.0055(8) C11 0.0276(11) 0.0234(10) 0.0215(10) 0.0010(8) -0.0011(8) -0.0013(8) C12 0.0394(13) 0.0308(12) 0.0213(11) 0.0000(9) 0.0063(9) -0.0047(10) C13 0.0461(15) 0.0405(14) 0.0228(11) -0.0081(10) 0.0021(10) -0.0013(11) C14 0.0384(13) 0.0276(12) 0.0333(13) -0.0079(10) -0.0045(10) 0.0003(10) C15 0.0404(13) 0.0256(11) 0.0280(12) -0.0009(9) -0.0008(10) -0.0070(10) C16 0.0412(13) 0.0274(12) 0.0192(10) -0.0006(9) 0.0028(9) -0.0068(10) C17 0.0340(13) 0.0267(12) 0.0420(14) -0.0107(10) -0.0093(11) 0.0023(10) C18 0.0528(17) 0.0526(17) 0.0348(14) -0.0230(13) 0.0142(12) -0.0217(14) Cu1 0.02389(14) 0.01979(13) 0.01919(13) -0.00006(9) 0.00033(9) -0.00191(9) Cl1 0.0283(3) 0.0274(3) 0.0343(3) 0.0091(2) 0.0008(2) -0.0049(2) Cl2 0.0317(3) 0.0414(3) 0.0296(3) 0.0039(2) -0.0083(2) -0.0036(2) Cl3 0.0275(3) 0.0330(3) 0.0314(3) 0.0115(2) 0.0029(2) 0.0023(2) Cl4 0.0289(3) 0.0337(3) 0.0277(3) -0.0019(2) 0.0066(2) -0.0052(2) _refine_ls_extinction_method None loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag S1 . C1 . 1.759(2) yes S1 . C8 . 1.694(3) yes C1 . N1 . 1.313(3) yes C1 . N3 . 1.339(3) yes N1 . N2 . 1.376(3) yes N2 . C8 . 1.296(3) yes N2 . C9 . 1.466(3) yes N3 . C2 . 1.414(3) yes N3 . H1 . 0.80(4) no C2 . C3 . 1.393(3) yes C2 . C7 . 1.396(3) yes C3 . C4 . 1.382(4) yes C3 . H31 . 1.000 no C4 . C5 . 1.394(4) yes C4 . H41 . 1.000 no C5 . C6 . 1.380(3) yes C5 . H51 . 1.000 no C6 . C7 . 1.392(3) yes C6 . H61 . 1.000 no C7 . H71 . 1.000 no C8 . H81 . 1.000 no C9 . H91 . 1.000 no C9 . H92 . 1.000 no C9 . H93 . 1.000 no S2 . C10 . 1.760(2) yes S2 . C17 . 1.688(3) yes C10 . N4 . 1.317(3) yes C10 . N6 . 1.341(3) yes N4 . N5 . 1.374(3) yes N5 . C17 . 1.303(3) yes N5 . C18 . 1.460(3) yes N6 . C11 . 1.410(3) yes N6 . H2 . 0.84(4) no C11 . C12 . 1.391(3) yes C11 . C16 . 1.396(3) yes C12 . C13 . 1.378(4) yes C12 . H121 . 1.000 no C13 . C14 . 1.394(4) yes C13 . H131 . 1.000 no C14 . C15 . 1.384(4) yes C14 . H141 . 1.000 no C15 . C16 . 1.386(3) yes C15 . H151 . 1.000 no C16 . H161 . 1.000 no C17 . H171 . 1.000 no C18 . H181 . 1.000 no C18 . H182 . 1.000 no C18 . H183 . 1.000 no Cu1 . Cl1 . 2.2635(6) yes Cu1 . Cl2 . 2.2385(6) yes Cu1 . Cl3 . 2.2721(6) yes Cu1 . Cl4 . 2.2516(6) yes loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag C1 . S1 . C8 . 87.84(12) yes S1 . C1 . N1 . 114.36(18) yes S1 . C1 . N3 . 119.48(17) yes N1 . C1 . N3 . 126.2(2) yes C1 . N1 . N2 . 108.13(19) yes N1 . N2 . C8 . 118.0(2) yes N1 . N2 . C9 . 117.00(19) yes C8 . N2 . C9 . 125.0(2) yes C1 . N3 . C2 . 128.9(2) yes C1 . N3 . H1 . 117(2) no C2 . N3 . H1 . 114(2) no N3 . C2 . C3 . 116.5(2) yes N3 . C2 . C7 . 123.6(2) yes C3 . C2 . C7 . 119.9(2) yes C2 . C3 . C4 . 120.3(2) yes C2 . C3 . H31 . 119.854 no C4 . C3 . H31 . 119.854 no C3 . C4 . C5 . 120.4(2) yes C3 . C4 . H41 . 119.822 no C5 . C4 . H41 . 119.822 no C4 . C5 . C6 . 119.0(2) yes C4 . C5 . H51 . 120.501 no C6 . C5 . H51 . 120.501 no C5 . C6 . C7 . 121.6(2) yes C5 . C6 . H61 . 119.195 no C7 . C6 . H61 . 119.195 no C2 . C7 . C6 . 118.8(2) yes C2 . C7 . H71 . 120.585 no C6 . C7 . H71 . 120.585 no S1 . C8 . N2 . 111.64(18) yes S1 . C8 . H81 . 124.181 no N2 . C8 . H81 . 124.181 no N2 . C9 . H91 . 109.467 no N2 . C9 . H92 . 109.467 no H91 . C9 . H92 . 109.476 no N2 . C9 . H93 . 109.466 no H91 . C9 . H93 . 109.476 no H92 . C9 . H93 . 109.476 no C10 . S2 . C17 . 87.87(12) yes S2 . C10 . N4 . 114.25(17) yes S2 . C10 . N6 . 119.32(17) yes N4 . C10 . N6 . 126.4(2) yes C10 . N4 . N5 . 108.28(19) yes N4 . N5 . C17 . 117.6(2) yes N4 . N5 . C18 . 116.5(2) yes C17 . N5 . C18 . 125.9(2) yes C10 . N6 . C11 . 128.8(2) yes C10 . N6 . H2 . 115(2) no C11 . N6 . H2 . 116(2) no N6 . C11 . C12 . 116.5(2) yes N6 . C11 . C16 . 124.2(2) yes C12 . C11 . C16 . 119.3(2) yes C11 . C12 . C13 . 120.6(2) yes C11 . C12 . H121 . 119.700 no C13 . C12 . H121 . 119.700 no C12 . C13 . C14 . 120.5(2) yes C12 . C13 . H131 . 119.762 no C14 . C13 . H131 . 119.762 no C13 . C14 . C15 . 118.7(2) yes C13 . C14 . H141 . 120.630 no C15 . C14 . H141 . 120.630 no C14 . C15 . C16 . 121.4(2) yes C14 . C15 . H151 . 119.299 no C16 . C15 . H151 . 119.299 no C11 . C16 . C15 . 119.5(2) yes C11 . C16 . H161 . 120.268 no C15 . C16 . H161 . 120.268 no S2 . C17 . N5 . 111.97(18) yes S2 . C17 . H171 . 124.014 no N5 . C17 . H171 . 124.014 no N5 . C18 . H181 . 109.466 no N5 . C18 . H182 . 109.467 no H181 . C18 . H182 . 109.476 no N5 . C18 . H183 . 109.466 no H181 . C18 . H183 . 109.476 no H182 . C18 . H183 . 109.476 no Cl1 . Cu1 . Cl2 . 91.07(2) yes Cl1 . Cu1 . Cl3 . 92.95(2) yes Cl2 . Cu1 . Cl3 . 156.57(3) yes Cl1 . Cu1 . Cl4 . 156.43(3) yes Cl2 . Cu1 . Cl4 . 93.20(2) yes Cl3 . Cu1 . Cl4 . 92.28(2) yes loop_ _geom_hbond_atom_site_label_d _geom_hbond_atom_site_label_h _geom_hbond_atom_site_label_a _geom_hbond_site_symmetry_a _geom_hbond_distance_dh _geom_hbond_distance_ha _geom_hbond_distance_da _geom_hbond_angle_dha _geom_hbond_publ_flag N3 H1 Cl1 . 0.80(4) 2.60(4) 3.378(2) 166(3) yes N6 H2 Cl3 . 0.84(4) 2.45(4) 3.266(2) 166(3) yes