Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2003 data_global _publ_contact_author_email lhanton@alkali.otago.ac.nz _publ_contact_author_name 'Hanton, Lyall R.' _journal_name_full 'J.Chem.Soc.,Dalton Trans.' _journal_coden_Cambridge 222 _journal_year ? _journal_volume ? _journal_page_first ? _publ_requested_category FM loop_ _publ_author_name J.J.M.Amoore L.R.Hanton M.D.Spicer data_Cu3LI3 _database_code_CSD 197840 _audit_creation_date 2002-11-07T09:37:03-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.2 _audit_conform_dict_location ftp://ftp.iucr.org/pub/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_name_common Cu3LI3 _chemical_formula_moiety 'C12 H14 Cu3 I3 N4 S1' _chemical_formula_sum 'C12 H14 Cu3 I3 N4 S1' _chemical_formula_weight 817.66 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.3841(2) _cell_length_b 9.2406(2) _cell_length_c 13.7990(4) _cell_angle_alpha 87.9370(10) _cell_angle_beta 86.2090(10) _cell_angle_gamma 67.2040(10) _cell_volume 983.34(4) _cell_formula_units_Z 2 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used 3848 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.485 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.15 _exptl_crystal_density_diffrn 2.761 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 752 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 8.031 _exptl_absorpt_correction_type none #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_source 'Enraf Nonius FR590' _diffrn_ambient_temperature 123(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_detector 'CCD plate' _diffrn_orient_matrix_type 'by Nonius Collect from scalepack cell' _diffrn_orient_matrix_UB_11 0.0302574 _diffrn_orient_matrix_UB_12 -0.1042021 _diffrn_orient_matrix_UB_13 0.0335516 _diffrn_orient_matrix_UB_21 -0.0600601 _diffrn_orient_matrix_UB_22 0.0538704 _diffrn_orient_matrix_UB_23 0.0614467 _diffrn_orient_matrix_UB_31 -0.1107708 _diffrn_orient_matrix_UB_32 -0.0046361 _diffrn_orient_matrix_UB_33 -0.019341 _diffrn_measurement_device '95mm CCD camera on \k-goniostat' _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method 'CCD; rotation images; thick slices' _diffrn_reflns_av_R_equivalents 0.0262 _diffrn_reflns_av_unetI/netI 0.0457 _diffrn_reflns_number 7319 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.95 _diffrn_reflns_theta_max 27.52 _diffrn_reflns_theta_full 27.52 _diffrn_measured_fraction_theta_full 0.991 _diffrn_measured_fraction_theta_max 0.991 _reflns_number_total 4480 _reflns_number_gt 3606 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Collect (Nonius BV, 1997-2000)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0190P)^2^+1.7510P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 4480 _refine_ls_number_parameters 242 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0446 _refine_ls_R_factor_gt 0.0295 _refine_ls_wR_factor_ref 0.0628 _refine_ls_wR_factor_gt 0.0589 _refine_ls_goodness_of_fit_ref 1.045 _refine_ls_restrained_S_all 1.045 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_diff_density_max 1.194 _refine_diff_density_min -1.274 _refine_diff_density_rms 0.158 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# 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 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' I I -0.4742 1.8119 '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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 1.1441(6) -0.1598(6) 0.0810(4) 0.0314(12) Uani 1 1 d . . . H1A H 1.2412 -0.2399 0.1128 0.047 Uiso 1 1 calc R . . H1B H 1.1373 -0.0552 0.0976 0.047 Uiso 1 1 calc R . . H1C H 1.162 -0.1731 0.0105 0.047 Uiso 1 1 calc R . . C2 C 0.9789(6) -0.1768(5) 0.1148(3) 0.0233(10) Uani 1 1 d . . . C3 C 0.8466(7) -0.0610(6) 0.1687(4) 0.0276(11) Uani 1 1 d . . . C4 C 0.6786(6) -0.2044(5) 0.1689(3) 0.0235(11) Uani 1 1 d . . . C5 C 0.8105(6) -0.3222(5) 0.1177(3) 0.0195(10) Uani 1 1 d . . . C6 C -0.2070(6) 0.5300(5) 0.0915(4) 0.0217(10) Uani 1 1 d . . . C7 C -0.1897(7) 0.4197(6) 0.2834(3) 0.0221(10) Uani 1 1 d . . . C8 C -0.1293(6) 0.5248(5) 0.3376(3) 0.0184(10) Uani 1 1 d . . . C9 C 0.2417(7) 0.3667(5) 0.5967(3) 0.0220(10) Uani 1 1 d . . . C10 C 0.0238(6) 0.2939(5) 0.5577(3) 0.0218(10) Uani 1 1 d . . . C11 C 0.0918(6) 0.5992(5) 0.3782(3) 0.0212(10) Uani 1 1 d . . . C12 C 0.2755(6) 0.5820(6) 0.3635(4) 0.0308(12) Uani 1 1 d . . . H12A H 0.3518 0.4728 0.3763 0.046 Uiso 1 1 calc R . . H12B H 0.298 0.6511 0.4081 0.046 Uiso 1 1 calc R . . H12C H 0.2977 0.6106 0.2963 0.046 Uiso 1 1 calc R . . Cu1 Cu 0.49827(8) 0.11271(7) 0.26196(4) 0.02754(15) Uani 1 1 d . . . Cu2 Cu 0.35688(7) 0.09561(6) 0.45966(4) 0.02366(14) Uani 1 1 d . . . Cu3 Cu 0.18285(7) 0.34367(7) 0.22138(4) 0.02708(15) Uani 1 1 d . . . I1 I 0.64010(4) 0.14716(3) 0.42401(2) 0.02195(8) Uani 1 1 d . . . I2 I 0.22126(4) 0.04860(3) 0.30582(2) 0.02333(9) Uani 1 1 d . . . I3 I 0.45453(4) 0.33612(4) 0.13030(2) 0.02618(9) Uani 1 1 d . . . N1 N 0.6972(5) -0.0741(4) 0.1955(3) 0.0236(9) Uani 1 1 d . . . N2 N 0.9595(5) -0.3073(4) 0.0903(3) 0.0225(9) Uani 1 1 d . . . N3 N 0.1896(5) 0.2759(4) 0.5441(3) 0.0204(8) Uani 1 1 d . . . N4 N 0.0377(5) 0.5058(4) 0.3252(3) 0.0177(8) Uani 1 1 d . . . S1 S -0.08249(15) 0.36001(13) 0.16421(8) 0.0205(2) Uani 1 1 d . . . H3 H 0.865(7) 0.043(6) 0.187(4) 0.050(17) Uiso 1 1 d . . . H4 H 0.570(6) -0.211(5) 0.184(3) 0.024(13) Uiso 1 1 d . . . H6A H -0.164(8) 0.497(7) 0.024(5) 0.07(2) Uiso 1 1 d . . . H6B H -0.314(5) 0.538(4) 0.099(3) 0.001(10) Uiso 1 1 d . . . H7A H -0.173(8) 0.330(7) 0.319(4) 0.057(19) Uiso 1 1 d . . . H7B H -0.308(6) 0.466(5) 0.273(3) 0.019(12) Uiso 1 1 d . . . H9 H 0.354(6) 0.354(5) 0.588(3) 0.027(14) Uiso 1 1 d . . . H10 H -0.026(6) 0.238(6) 0.523(4) 0.028(14) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.032(3) 0.034(3) 0.032(3) -0.008(2) 0.008(2) -0.017(2) C2 0.025(3) 0.023(2) 0.022(3) -0.001(2) -0.001(2) -0.010(2) C3 0.031(3) 0.023(3) 0.027(3) -0.006(2) 0.003(2) -0.010(2) C4 0.022(3) 0.022(2) 0.023(3) -0.002(2) 0.000(2) -0.004(2) C5 0.022(2) 0.020(2) 0.015(2) -0.0001(18) -0.0039(19) -0.0064(18) C6 0.015(3) 0.027(3) 0.023(3) 0.000(2) -0.005(2) -0.007(2) C7 0.023(3) 0.026(3) 0.018(2) -0.004(2) 0.003(2) -0.011(2) C8 0.022(2) 0.019(2) 0.012(2) 0.0039(17) 0.0017(19) -0.0056(18) C9 0.021(3) 0.028(3) 0.016(2) -0.0007(19) -0.001(2) -0.009(2) C10 0.024(3) 0.021(2) 0.017(2) -0.0046(19) -0.001(2) -0.005(2) C11 0.023(2) 0.018(2) 0.020(2) -0.0007(19) -0.004(2) -0.0049(18) C12 0.020(3) 0.030(3) 0.043(3) -0.013(2) -0.001(2) -0.009(2) Cu1 0.0285(3) 0.0213(3) 0.0273(3) -0.0045(3) 0.0038(3) -0.0041(2) Cu2 0.0232(3) 0.0233(3) 0.0223(3) -0.0059(2) 0.0016(2) -0.0065(2) Cu3 0.0213(3) 0.0276(3) 0.0312(4) -0.0092(3) 0.0059(3) -0.0085(2) I1 0.02556(17) 0.02359(16) 0.01916(16) 0.00063(12) 0.00128(13) -0.01265(13) I2 0.02804(17) 0.02301(16) 0.02027(16) 0.00049(12) -0.00374(13) -0.01099(13) I3 0.02067(17) 0.03156(18) 0.02451(17) 0.00530(13) 0.00023(13) -0.00883(13) N1 0.025(2) 0.019(2) 0.023(2) -0.0056(16) 0.0061(17) -0.0047(16) N2 0.023(2) 0.026(2) 0.020(2) -0.0028(17) -0.0037(17) -0.0105(17) N3 0.022(2) 0.022(2) 0.016(2) -0.0063(16) 0.0002(16) -0.0061(16) N4 0.018(2) 0.0156(18) 0.017(2) -0.0028(15) 0.0020(16) -0.0041(15) S1 0.0224(6) 0.0192(6) 0.0198(6) -0.0037(5) -0.0006(5) -0.0076(4) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 C2 1.497(7) . ? C2 N2 1.336(6) . ? C2 C3 1.399(7) . ? C3 N1 1.332(6) . ? C4 N1 1.340(6) . ? C4 C5 1.387(6) . ? C5 N2 1.338(6) . ? C5 C6 1.488(6) 1_645 ? C6 C5 1.488(6) 1_465 ? C6 S1 1.821(5) . ? C7 C8 1.497(6) . ? C7 S1 1.818(5) . ? C8 N4 1.342(6) . ? C8 C9 1.391(6) 2_566 ? C9 N3 1.339(6) . ? C9 C8 1.391(6) 2_566 ? C10 N3 1.336(6) . ? C10 C11 1.381(6) 2_566 ? C11 N4 1.371(6) . ? C11 C10 1.381(6) 2_566 ? C11 C12 1.486(7) . ? Cu1 N1 2.069(4) . ? Cu1 I3 2.6323(7) . ? Cu1 I2 2.6392(7) . ? Cu1 I1 2.6855(7) . ? Cu1 Cu3 2.7565(8) . ? Cu1 Cu2 2.9256(9) . ? Cu2 N3 2.052(4) . ? Cu2 I2 2.5993(6) . ? Cu2 I1 2.6101(7) . ? Cu2 Cu2 2.6545(11) 2_656 ? Cu2 I1 2.7040(7) 2_656 ? Cu3 N4 2.071(3) . ? Cu3 S1 2.3574(13) . ? Cu3 I3 2.5055(7) . ? Cu3 I2 2.8348(7) . ? I1 Cu2 2.7040(7) 2_656 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N2 C2 C3 120.2(5) . . ? N2 C2 C1 117.5(4) . . ? C3 C2 C1 122.3(4) . . ? N1 C3 C2 122.1(5) . . ? N1 C4 C5 121.6(5) . . ? N2 C5 C4 121.0(4) . . ? N2 C5 C6 117.3(4) . 1_645 ? C4 C5 C6 121.7(4) . 1_645 ? C5 C6 S1 114.0(3) 1_465 . ? C8 C7 S1 115.3(3) . . ? N4 C8 C9 121.0(4) . 2_566 ? N4 C8 C7 118.4(4) . . ? C9 C8 C7 120.5(4) 2_566 . ? N3 C9 C8 121.9(4) . 2_566 ? N3 C10 C11 122.9(4) . 2_566 ? N4 C11 C10 119.9(4) . 2_566 ? N4 C11 C12 118.0(4) . . ? C10 C11 C12 122.1(4) 2_566 . ? N1 Cu1 I3 101.24(11) . . ? N1 Cu1 I2 112.00(11) . . ? I3 Cu1 I2 114.64(2) . . ? N1 Cu1 I1 102.29(11) . . ? I3 Cu1 I1 115.00(2) . . ? I2 Cu1 I1 110.59(2) . . ? N1 Cu1 Cu3 139.99(11) . . ? I3 Cu1 Cu3 55.356(18) . . ? I2 Cu1 Cu3 63.34(2) . . ? I1 Cu1 Cu3 116.73(2) . . ? N1 Cu1 Cu2 123.12(11) . . ? I3 Cu1 Cu2 135.41(2) . . ? I2 Cu1 Cu2 55.403(18) . . ? I1 Cu1 Cu2 55.243(18) . . ? Cu3 Cu1 Cu2 88.36(2) . . ? N3 Cu2 I2 113.60(10) . . ? N3 Cu2 I1 107.56(11) . . ? I2 Cu2 I1 114.35(2) . . ? N3 Cu2 Cu2 116.48(11) . 2_656 ? I2 Cu2 Cu2 128.05(3) . 2_656 ? I1 Cu2 Cu2 61.80(2) . 2_656 ? N3 Cu2 I1 98.42(11) . 2_656 ? I2 Cu2 I1 101.95(2) . 2_656 ? I1 Cu2 I1 120.09(2) . 2_656 ? Cu2 Cu2 I1 58.29(2) 2_656 2_656 ? N3 Cu2 Cu1 128.16(11) . . ? I2 Cu2 Cu1 56.701(18) . . ? I1 Cu2 Cu1 57.703(19) . . ? Cu2 Cu2 Cu1 99.65(3) 2_656 . ? I1 Cu2 Cu1 132.87(2) 2_656 . ? N4 Cu3 S1 86.95(10) . . ? N4 Cu3 I3 126.37(11) . . ? S1 Cu3 I3 130.44(4) . . ? N4 Cu3 Cu1 121.08(10) . . ? S1 Cu3 Cu1 137.74(4) . . ? I3 Cu3 Cu1 59.805(19) . . ? N4 Cu3 I2 104.56(10) . . ? S1 Cu3 I2 88.14(3) . . ? I3 Cu3 I2 112.23(2) . . ? Cu1 Cu3 I2 56.311(19) . . ? Cu2 I1 Cu1 67.05(2) . . ? Cu2 I1 Cu2 59.91(2) . 2_656 ? Cu1 I1 Cu2 104.70(2) . 2_656 ? Cu2 I2 Cu1 67.90(2) . . ? Cu2 I2 Cu3 93.51(2) . . ? Cu1 I2 Cu3 60.345(18) . . ? Cu3 I3 Cu1 64.84(2) . . ? C3 N1 C4 117.0(4) . . ? C3 N1 Cu1 119.6(3) . . ? C4 N1 Cu1 123.1(3) . . ? C2 N2 C5 118.1(4) . . ? C10 N3 C9 116.8(4) . . ? C10 N3 Cu2 119.5(3) . . ? C9 N3 Cu2 123.1(3) . . ? C8 N4 C11 117.4(4) . . ? C8 N4 Cu3 115.3(3) . . ? C11 N4 Cu3 127.1(3) . . ? C7 S1 C6 100.4(2) . . ? C7 S1 Cu3 90.72(17) . . ? C6 S1 Cu3 119.09(17) . . ?