# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Li, Dan' _publ_contact_author_email dli@stu.edu.cn _publ_section_title ; When Cu4I4 Cubane Meets Cu3(Pyrazolate)3 Triangle: Dynamic Interplay between Two Classical Luminophores Functioning in a Reversiblly Thermochromic Coordination Polymer ; loop_ _publ_author_name 'Shun-Ze Zhan' 'Mian Li' 'Xiao-Ping Zhou' 'Jun-Hao Wang' 'Ju-Rong Yang' ; Dan Li ; # Attachment '- complexes.cif' data_293K _database_code_depnum_ccdc_archive 'CCDC 829986' #TrackingRef '- complexes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C45 H39 Cu7 I4 N10' _chemical_formula_sum 'C45 H39 Cu7 I4 N10' _chemical_formula_weight 1672.24 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M R-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 18.4873(4) _cell_length_b 18.4873(4) _cell_length_c 25.7549(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 7623.2(3) _cell_formula_units_Z 6 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 2809 _cell_measurement_theta_min 2.9902 _cell_measurement_theta_max 29.2522 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.16 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.186 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4764 _exptl_absorpt_coefficient_mu 5.346 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.4817 _exptl_absorpt_correction_T_max 0.5433 _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.7107 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Xcalibur, Atlas, Gemini' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6643 _diffrn_reflns_av_R_equivalents 0.0231 _diffrn_reflns_av_sigmaI/netI 0.0443 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -33 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 3.00 _diffrn_reflns_theta_max 27.50 _reflns_number_total 3741 _reflns_number_gt 2907 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0288P)^2^+18.3392P] 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_extinction_coef ? _refine_ls_number_reflns 3741 _refine_ls_number_parameters 201 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0552 _refine_ls_R_factor_gt 0.0372 _refine_ls_wR_factor_ref 0.0792 _refine_ls_wR_factor_gt 0.0709 _refine_ls_goodness_of_fit_ref 1.024 _refine_ls_restrained_S_all 1.024 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 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 Cu1 Cu 1.07637(3) 0.96283(3) 0.06095(2) 0.03275(15) Uani 1 1 d . . . Cu2 Cu 1.27045(4) 0.69905(4) 0.00541(3) 0.04572(18) Uani 1 1 d . . . Cu3 Cu 1.3333 0.6667 -0.07790(4) 0.0638(4) Uani 1 3 d S . . I1 I 1.3333 0.6667 0.08880(2) 0.03950(15) Uani 1 3 d S . . I2 I 1.38004(2) 0.82615(2) -0.053041(14) 0.04697(12) Uani 1 1 d . . . N1 N 0.9134(2) 0.8406(2) 0.07378(14) 0.0301(8) Uani 1 1 d . . . N2 N 0.9899(2) 0.8515(2) 0.06007(14) 0.0304(8) Uani 1 1 d . . . N3 N 1.1831(2) 0.7280(2) 0.02801(15) 0.0391(10) Uani 1 1 d . . . N4 N 1.3333 0.6667 -0.1572(3) 0.078(3) Uani 1 3 d S . . H4A H 1.2889 0.6685 -0.1687 0.116 Uiso 0.33 1 calc PR . . H4B H 1.3315 0.6204 -0.1687 0.116 Uiso 0.33 1 calc PR . . H4C H 1.3796 0.7111 -0.1687 0.116 Uiso 0.33 1 calc PR . . C1 C 1.1352(3) 0.8250(3) 0.04066(19) 0.0380(11) Uani 1 1 d . . . H1 H 1.1476 0.8803 0.0395 0.046 Uiso 1 1 calc R . . C2 C 1.1958(3) 0.8056(3) 0.02871(19) 0.0398(12) Uani 1 1 d . . . H2 H 1.2489 0.8491 0.0206 0.048 Uiso 1 1 calc R . . C3 C 1.1063(3) 0.6678(3) 0.0412(2) 0.0508(14) Uani 1 1 d . . . H3 H 1.0955 0.6130 0.0417 0.061 Uiso 1 1 calc R . . C4 C 1.0431(3) 0.6822(3) 0.0541(2) 0.0464(13) Uani 1 1 d . . . H4 H 0.9909 0.6377 0.0627 0.056 Uiso 1 1 calc R . . C5 C 1.0562(3) 0.7633(3) 0.05430(17) 0.0312(10) Uani 1 1 d . . . C6 C 0.9868(3) 0.7772(3) 0.06690(17) 0.0297(10) Uani 1 1 d . . . C7 C 0.9091(3) 0.7195(3) 0.08528(18) 0.0345(11) Uani 1 1 d . . . H7 H 0.8904 0.6638 0.0932 0.041 Uiso 1 1 calc R . . C8 C 0.8642(3) 0.7608(3) 0.08960(17) 0.0302(10) Uani 1 1 d . . . C9 C 0.7782(3) 0.7301(3) 0.10696(17) 0.0314(10) Uani 1 1 d . . . C10 C 0.7147(3) 0.6523(3) 0.0924(2) 0.0541(15) Uani 1 1 d . . . H10 H 0.7269 0.6177 0.0726 0.065 Uiso 1 1 calc R . . C11 C 0.6328(3) 0.6250(3) 0.1068(2) 0.0596(16) Uani 1 1 d . . . H11 H 0.5909 0.5728 0.0958 0.072 Uiso 1 1 calc R . . C12 C 0.6119(3) 0.6728(3) 0.1369(2) 0.0468(13) Uani 1 1 d . . . C13 C 0.6760(3) 0.7489(3) 0.1533(2) 0.0466(13) Uani 1 1 d . . . H13 H 0.6638 0.7818 0.1748 0.056 Uiso 1 1 calc R . . C14 C 0.7581(3) 0.7778(3) 0.13872(18) 0.0383(11) Uani 1 1 d . . . H14 H 0.7999 0.8296 0.1504 0.046 Uiso 1 1 calc R . . C15 C 0.5228(3) 0.6433(4) 0.1508(3) 0.074(2) Uani 1 1 d . . . H15A H 0.4871 0.6107 0.1228 0.111 Uiso 1 1 calc R . . H15B H 0.5157 0.6906 0.1570 0.111 Uiso 1 1 calc R . . H15C H 0.5083 0.6096 0.1816 0.111 Uiso 1 1 calc R . . 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 0.0261(3) 0.0211(3) 0.0481(4) 0.0012(2) 0.0035(3) 0.0096(2) Cu2 0.0417(4) 0.0519(4) 0.0576(4) 0.0067(3) 0.0083(3) 0.0339(3) Cu3 0.0772(6) 0.0772(6) 0.0370(6) 0.000 0.000 0.0386(3) I1 0.0433(2) 0.0433(2) 0.0318(3) 0.000 0.000 0.02167(10) I2 0.0455(2) 0.0365(2) 0.0600(2) 0.01504(16) 0.00762(16) 0.02126(16) N1 0.0229(18) 0.0228(18) 0.044(2) -0.0049(16) -0.0005(17) 0.0108(16) N2 0.0229(18) 0.0237(19) 0.044(2) 0.0019(16) 0.0028(16) 0.0109(16) N3 0.037(2) 0.038(2) 0.048(2) 0.0053(19) 0.0053(19) 0.023(2) N4 0.095(5) 0.095(5) 0.042(5) 0.000 0.000 0.048(2) C1 0.033(3) 0.026(2) 0.055(3) -0.004(2) 0.004(2) 0.014(2) C2 0.026(2) 0.038(3) 0.054(3) -0.005(2) 0.003(2) 0.015(2) C3 0.049(3) 0.038(3) 0.078(4) 0.015(3) 0.022(3) 0.031(3) C4 0.037(3) 0.028(3) 0.074(4) 0.010(2) 0.019(3) 0.016(2) C5 0.028(2) 0.026(2) 0.039(3) -0.002(2) -0.003(2) 0.013(2) C6 0.026(2) 0.023(2) 0.039(3) -0.0021(19) 0.001(2) 0.0121(19) C7 0.029(2) 0.020(2) 0.051(3) 0.003(2) 0.009(2) 0.0095(19) C8 0.025(2) 0.025(2) 0.038(3) -0.001(2) 0.003(2) 0.0111(19) C9 0.029(2) 0.024(2) 0.039(3) 0.002(2) 0.007(2) 0.011(2) C10 0.040(3) 0.039(3) 0.073(4) -0.019(3) 0.016(3) 0.011(2) C11 0.028(3) 0.037(3) 0.094(4) -0.016(3) 0.012(3) 0.002(2) C12 0.030(3) 0.038(3) 0.067(4) 0.001(3) 0.015(3) 0.013(2) C13 0.038(3) 0.042(3) 0.064(3) -0.005(3) 0.015(3) 0.023(2) C14 0.029(2) 0.031(2) 0.050(3) -0.007(2) 0.002(2) 0.011(2) C15 0.036(3) 0.053(4) 0.128(6) 0.001(4) 0.023(4) 0.018(3) _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 Cu1 N1 1.866(4) 2_765 ? Cu1 N2 1.872(3) . ? Cu2 N3 2.023(4) . ? Cu2 Cu3 2.6478(11) . ? Cu2 I1 2.6491(8) . ? Cu2 I2 2.6706(7) . ? Cu2 Cu2 2.6866(10) 3_775 ? Cu2 Cu2 2.6866(10) 2_755 ? Cu2 I2 2.8044(8) 2_755 ? Cu3 N4 2.041(8) . ? Cu3 Cu2 2.6478(11) 3_775 ? Cu3 Cu2 2.6478(11) 2_755 ? Cu3 I2 2.7024(4) . ? Cu3 I2 2.7024(4) 2_755 ? Cu3 I2 2.7024(4) 3_775 ? I1 Cu2 2.6491(8) 3_775 ? I1 Cu2 2.6491(8) 2_755 ? I2 Cu2 2.8044(8) 3_775 ? N1 C8 1.351(5) . ? N1 N2 1.370(5) . ? N1 Cu1 1.866(3) 3_675 ? N2 C6 1.357(5) . ? N3 C2 1.333(6) . ? N3 C3 1.338(6) . ? C1 C2 1.371(6) . ? C1 C5 1.375(6) . ? C3 C4 1.363(7) . ? C4 C5 1.393(6) . ? C5 C6 1.466(6) . ? C6 C7 1.377(6) . ? C7 C8 1.386(6) . ? C8 C9 1.464(6) . ? C9 C10 1.378(6) . ? C9 C14 1.383(6) . ? C10 C11 1.386(7) . ? C11 C12 1.367(7) . ? C12 C13 1.376(7) . ? C12 C15 1.498(7) . ? C13 C14 1.386(6) . ? 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 N1 Cu1 N2 170.40(16) 2_765 . ? N3 Cu2 Cu3 142.32(12) . . ? N3 Cu2 I1 108.95(11) . . ? Cu3 Cu2 I1 108.30(3) . . ? N3 Cu2 I2 106.51(11) . . ? Cu3 Cu2 I2 61.075(17) . . ? I1 Cu2 I2 115.48(2) . . ? N3 Cu2 Cu2 150.80(12) . 3_775 ? Cu3 Cu2 Cu2 59.514(16) . 3_775 ? I1 Cu2 Cu2 59.530(12) . 3_775 ? I2 Cu2 Cu2 63.13(3) . 3_775 ? N3 Cu2 Cu2 141.05(12) . 2_755 ? Cu3 Cu2 Cu2 59.514(16) . 2_755 ? I1 Cu2 Cu2 59.530(12) . 2_755 ? I2 Cu2 Cu2 111.88(2) . 2_755 ? Cu2 Cu2 Cu2 60.0 3_775 2_755 ? N3 Cu2 I2 101.35(12) . 2_755 ? Cu3 Cu2 I2 59.343(16) . 2_755 ? I1 Cu2 I2 111.13(2) . 2_755 ? I2 Cu2 I2 112.29(3) . 2_755 ? Cu2 Cu2 I2 107.84(2) 3_775 2_755 ? Cu2 Cu2 I2 58.16(2) 2_755 2_755 ? N4 Cu3 Cu2 144.14(2) . . ? N4 Cu3 Cu2 144.14(2) . 3_775 ? Cu2 Cu3 Cu2 60.97(3) . 3_775 ? N4 Cu3 Cu2 144.14(2) . 2_755 ? Cu2 Cu3 Cu2 60.97(3) . 2_755 ? Cu2 Cu3 Cu2 60.97(3) 3_775 2_755 ? N4 Cu3 I2 103.71(2) . . ? Cu2 Cu3 I2 59.88(2) . . ? Cu2 Cu3 I2 63.22(2) 3_775 . ? Cu2 Cu3 I2 112.11(4) 2_755 . ? N4 Cu3 I2 103.71(2) . 2_755 ? Cu2 Cu3 I2 63.22(2) . 2_755 ? Cu2 Cu3 I2 112.11(4) 3_775 2_755 ? Cu2 Cu3 I2 59.88(2) 2_755 2_755 ? I2 Cu3 I2 114.568(19) . 2_755 ? N4 Cu3 I2 103.71(2) . 3_775 ? Cu2 Cu3 I2 112.11(4) . 3_775 ? Cu2 Cu3 I2 59.88(2) 3_775 3_775 ? Cu2 Cu3 I2 63.22(2) 2_755 3_775 ? I2 Cu3 I2 114.568(19) . 3_775 ? I2 Cu3 I2 114.568(19) 2_755 3_775 ? Cu2 I1 Cu2 60.94(2) . 3_775 ? Cu2 I1 Cu2 60.94(2) . 2_755 ? Cu2 I1 Cu2 60.94(2) 3_775 2_755 ? Cu2 I2 Cu3 59.04(2) . . ? Cu2 I2 Cu2 58.71(3) . 3_775 ? Cu3 I2 Cu2 57.44(2) . 3_775 ? C8 N1 N2 108.7(3) . . ? C8 N1 Cu1 129.8(3) . 3_675 ? N2 N1 Cu1 120.9(3) . 3_675 ? C6 N2 N1 107.4(3) . . ? C6 N2 Cu1 133.7(3) . . ? N1 N2 Cu1 114.2(3) . . ? C2 N3 C3 115.7(4) . . ? C2 N3 Cu2 123.7(3) . . ? C3 N3 Cu2 120.6(3) . . ? C2 C1 C5 120.5(4) . . ? N3 C2 C1 123.9(5) . . ? N3 C3 C4 123.8(5) . . ? C3 C4 C5 120.4(5) . . ? C1 C5 C4 115.7(4) . . ? C1 C5 C6 124.7(4) . . ? C4 C5 C6 119.6(4) . . ? N2 C6 C7 109.2(4) . . ? N2 C6 C5 123.5(4) . . ? C7 C6 C5 127.3(4) . . ? C6 C7 C8 106.3(4) . . ? N1 C8 C7 108.4(4) . . ? N1 C8 C9 121.6(4) . . ? C7 C8 C9 130.0(4) . . ? C10 C9 C14 117.7(4) . . ? C10 C9 C8 121.0(4) . . ? C14 C9 C8 121.3(4) . . ? C9 C10 C11 120.9(5) . . ? C12 C11 C10 121.8(5) . . ? C11 C12 C13 117.2(5) . . ? C11 C12 C15 121.0(5) . . ? C13 C12 C15 121.8(5) . . ? C12 C13 C14 121.9(5) . . ? C9 C14 C13 120.4(4) . . ? _diffrn_measured_fraction_theta_max 0.960 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.960 _refine_diff_density_max 0.661 _refine_diff_density_min -1.091 _refine_diff_density_rms 0.114 data_100K _database_code_depnum_ccdc_archive 'CCDC 829987' #TrackingRef '- complexes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C45 H39 Cu7 I4 N10' _chemical_formula_sum 'C45 H39 Cu7 I4 N10' _chemical_formula_weight 1672.24 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' _symmetry_cell_setting trigonal _symmetry_space_group_name_H-M R-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 18.4690(4) _cell_length_b 18.4690(4) _cell_length_c 25.3532(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 7489.5(3) _cell_formula_units_Z 6 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 2792 _cell_measurement_theta_min 3.0056 _cell_measurement_theta_max 29.2850 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.16 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.225 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4764 _exptl_absorpt_coefficient_mu 5.441 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.4764 _exptl_absorpt_correction_T_max 0.5381 _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 100.0 _diffrn_radiation_wavelength 0.7107 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Xcalibur, Atlas, Gemini' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean 10.4098 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6667 _diffrn_reflns_av_R_equivalents 0.0377 _diffrn_reflns_av_sigmaI/netI 0.0712 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 32 _diffrn_reflns_theta_min 3.01 _diffrn_reflns_theta_max 27.49 _reflns_number_total 3672 _reflns_number_gt 2925 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0196P)^2^+0.0000P] 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_extinction_coef ? _refine_ls_number_reflns 3672 _refine_ls_number_parameters 201 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0588 _refine_ls_R_factor_gt 0.0402 _refine_ls_wR_factor_ref 0.0811 _refine_ls_wR_factor_gt 0.0705 _refine_ls_goodness_of_fit_ref 1.077 _refine_ls_restrained_S_all 1.077 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 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 I1 I 0.6667 1.3333 0.90984(2) 0.01517(15) Uani 1 3 d S . . I2 I 0.55375(2) 1.17440(2) 1.054136(13) 0.01664(11) Uani 1 1 d . . . Cu1 Cu 0.96229(4) 1.07649(4) 0.93934(2) 0.01178(16) Uani 1 1 d . . . Cu2 Cu 0.69760(4) 1.27027(4) 0.99486(3) 0.01593(17) Uani 1 1 d . . . Cu3 Cu 0.6667 1.3333 1.07857(4) 0.0219(3) Uani 1 3 d S . . C7 C 0.7177(3) 0.9077(3) 0.9150(2) 0.0142(12) Uani 1 1 d . . . H7 H 0.6605 0.8880 0.9073 0.017 Uiso 1 1 calc R . . N2 N 0.8510(3) 0.9897(3) 0.94027(16) 0.0107(9) Uani 1 1 d . . . C5 C 0.7616(3) 1.0557(3) 0.94610(19) 0.0105(11) Uani 1 1 d . . . C6 C 0.7763(3) 0.9865(3) 0.93318(18) 0.0096(11) Uani 1 1 d . . . C8 C 0.7598(3) 0.8637(3) 0.91040(19) 0.0117(11) Uani 1 1 d . . . C1 C 0.8254(3) 1.1362(3) 0.9585(2) 0.0155(12) Uani 1 1 d . . . H1 H 0.8821 1.1493 0.9585 0.019 Uiso 1 1 calc R . . N3 N 0.7263(3) 1.1823(3) 0.97191(16) 0.0139(10) Uani 1 1 d . . . C14 C 0.7773(3) 0.7567(3) 0.86021(19) 0.0125(11) Uani 1 1 d . . . H14 H 0.8302 0.7997 0.8482 0.015 Uiso 1 1 calc R . . C2 C 0.8049(3) 1.1966(3) 0.97072(19) 0.0136(12) Uani 1 1 d . . . H2 H 0.8489 1.2513 0.9787 0.016 Uiso 1 1 calc R . . C9 C 0.7293(3) 0.7763(3) 0.89277(19) 0.0143(12) Uani 1 1 d . . . C11 C 0.6232(4) 0.6318(4) 0.8920(2) 0.0252(14) Uani 1 1 d . . . H11 H 0.5696 0.5890 0.9032 0.030 Uiso 1 1 calc R . . C4 C 0.6803(3) 1.0410(4) 0.9472(2) 0.0162(12) Uani 1 1 d . . . H4 H 0.6350 0.9871 0.9389 0.019 Uiso 1 1 calc R . . C3 C 0.6654(4) 1.1048(4) 0.9604(2) 0.0200(13) Uani 1 1 d . . . H3 H 0.6091 1.0931 0.9613 0.024 Uiso 1 1 calc R . . C10 C 0.6506(4) 0.7127(4) 0.9070(2) 0.0226(14) Uani 1 1 d . . . H10 H 0.6151 0.7253 0.9273 0.027 Uiso 1 1 calc R . . N4 N 0.6667 1.3333 1.1595(3) 0.026(2) Uani 1 3 d S . . H4A H 0.6779 1.2936 1.1715 0.038 Uiso 0.33 1 calc PR . . H4B H 0.6156 1.3221 1.1715 0.038 Uiso 0.33 1 calc PR . . H4C H 0.7064 1.3844 1.1715 0.038 Uiso 0.33 1 calc PR . . C13 C 0.7486(4) 0.6745(4) 0.8450(2) 0.0211(13) Uani 1 1 d . . . H13 H 0.7826 0.6619 0.8232 0.025 Uiso 1 1 calc R . . C12 C 0.6712(4) 0.6107(4) 0.8612(2) 0.0194(13) Uani 1 1 d . . . C15 C 0.6410(4) 0.5212(4) 0.8458(3) 0.0320(16) Uani 1 1 d . . . H15A H 0.6115 0.4844 0.8756 0.048 Uiso 1 1 calc R . . H15B H 0.6889 0.5150 0.8360 0.048 Uiso 1 1 calc R . . H15C H 0.6028 0.5062 0.8156 0.048 Uiso 1 1 calc R . . N1 N 0.8400(3) 0.9125(3) 0.92617(16) 0.0119(9) Uani 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 I1 0.0169(2) 0.0169(2) 0.0117(3) 0.000 0.000 0.00846(11) I2 0.0132(2) 0.0122(2) 0.0223(2) 0.00551(15) 0.00283(15) 0.00468(16) Cu1 0.0075(3) 0.0092(3) 0.0177(3) -0.0016(3) -0.0003(3) 0.0035(3) Cu2 0.0174(4) 0.0139(4) 0.0209(3) -0.0028(3) -0.0021(3) 0.0111(3) Cu3 0.0259(5) 0.0259(5) 0.0139(6) 0.000 0.000 0.0130(2) C7 0.010(3) 0.013(3) 0.019(3) -0.002(2) 0.003(2) 0.006(2) N2 0.013(2) 0.007(2) 0.016(2) -0.0032(18) -0.0005(19) 0.008(2) C5 0.011(3) 0.012(3) 0.013(2) -0.004(2) -0.002(2) 0.009(2) C6 0.011(3) 0.010(3) 0.009(2) 0.004(2) 0.001(2) 0.006(2) C8 0.008(3) 0.011(3) 0.012(3) -0.002(2) -0.001(2) 0.002(2) C1 0.010(3) 0.018(3) 0.018(3) 0.000(2) 0.001(2) 0.006(3) N3 0.012(2) 0.014(2) 0.019(2) -0.004(2) -0.002(2) 0.009(2) C14 0.008(3) 0.009(3) 0.018(3) -0.003(2) 0.003(2) 0.002(2) C2 0.011(3) 0.011(3) 0.014(3) 0.002(2) 0.003(2) 0.002(2) C9 0.014(3) 0.014(3) 0.014(3) -0.003(2) 0.000(2) 0.006(2) C11 0.014(3) 0.012(3) 0.039(3) -0.007(3) 0.010(3) -0.002(3) C4 0.010(3) 0.013(3) 0.024(3) -0.004(2) -0.006(2) 0.006(2) C3 0.014(3) 0.017(3) 0.029(3) -0.012(3) -0.008(3) 0.007(3) C10 0.017(3) 0.023(3) 0.025(3) -0.004(3) 0.008(3) 0.008(3) N4 0.030(3) 0.030(3) 0.016(4) 0.000 0.000 0.0151(16) C13 0.026(3) 0.018(3) 0.024(3) -0.006(3) 0.006(3) 0.015(3) C12 0.015(3) 0.014(3) 0.027(3) -0.005(3) -0.005(3) 0.005(3) C15 0.017(3) 0.017(3) 0.057(4) -0.007(3) 0.011(3) 0.004(3) N1 0.014(2) 0.010(2) 0.016(2) 0.0026(19) 0.0032(19) 0.009(2) _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 I1 Cu2 2.6449(8) . ? I1 Cu2 2.6449(8) 2_775 ? I1 Cu2 2.6449(8) 3_575 ? I2 Cu2 2.6726(7) 3_575 ? I2 Cu3 2.6884(4) . ? I2 Cu2 2.7834(8) . ? Cu1 N1 1.870(4) 3_675 ? Cu1 N2 1.870(4) . ? Cu2 N3 2.030(4) . ? Cu2 Cu3 2.6176(11) . ? Cu2 Cu2 2.6542(11) 2_775 ? Cu2 Cu2 2.6542(11) 3_575 ? Cu2 I2 2.6726(7) 2_775 ? Cu3 N4 2.052(7) . ? Cu3 Cu2 2.6176(11) 3_575 ? Cu3 Cu2 2.6176(11) 2_775 ? Cu3 I2 2.6884(4) 2_775 ? Cu3 I2 2.6884(4) 3_575 ? C7 C8 1.381(7) . ? C7 C6 1.388(7) . ? N2 C6 1.364(6) . ? N2 N1 1.382(6) . ? C5 C4 1.386(7) . ? C5 C1 1.395(7) . ? C5 C6 1.470(7) . ? C8 N1 1.352(7) . ? C8 C9 1.488(7) . ? C1 C2 1.382(7) . ? N3 C3 1.337(7) . ? N3 C2 1.340(7) . ? C14 C9 1.385(7) . ? C14 C13 1.389(8) . ? C9 C10 1.384(8) . ? C11 C10 1.371(8) . ? C11 C12 1.377(8) . ? C4 C3 1.378(8) . ? C13 C12 1.384(8) . ? C12 C15 1.507(8) . ? N1 Cu1 1.870(4) 2_765 ? 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 I1 Cu2 60.23(3) . 2_775 ? Cu2 I1 Cu2 60.23(3) . 3_575 ? Cu2 I1 Cu2 60.23(3) 2_775 3_575 ? Cu2 I2 Cu3 58.45(2) 3_575 . ? Cu2 I2 Cu2 58.17(3) 3_575 . ? Cu3 I2 Cu2 57.13(2) . . ? N1 Cu1 N2 170.35(18) 3_675 . ? N3 Cu2 Cu3 142.28(12) . . ? N3 Cu2 I1 108.61(12) . . ? Cu3 Cu2 I1 108.76(3) . . ? N3 Cu2 Cu2 150.42(13) . 2_775 ? Cu3 Cu2 Cu2 59.536(17) . 2_775 ? I1 Cu2 Cu2 59.884(13) . 2_775 ? N3 Cu2 Cu2 141.52(13) . 3_575 ? Cu3 Cu2 Cu2 59.536(16) . 3_575 ? I1 Cu2 Cu2 59.884(13) . 3_575 ? Cu2 Cu2 Cu2 60.0 2_775 3_575 ? N3 Cu2 I2 106.15(13) . 2_775 ? Cu3 Cu2 I2 61.076(17) . 2_775 ? I1 Cu2 I2 115.52(3) . 2_775 ? Cu2 Cu2 I2 63.00(3) 2_775 2_775 ? Cu2 Cu2 I2 111.82(2) 3_575 2_775 ? N3 Cu2 I2 101.16(13) . . ? Cu3 Cu2 I2 59.610(16) . . ? I1 Cu2 I2 111.87(3) . . ? Cu2 Cu2 I2 108.42(2) 2_775 . ? Cu2 Cu2 I2 58.82(3) 3_575 . ? I2 Cu2 I2 112.28(3) 2_775 . ? N4 Cu3 Cu2 144.17(2) . . ? N4 Cu3 Cu2 144.17(2) . 3_575 ? Cu2 Cu3 Cu2 60.93(3) . 3_575 ? N4 Cu3 Cu2 144.17(2) . 2_775 ? Cu2 Cu3 Cu2 60.93(3) . 2_775 ? Cu2 Cu3 Cu2 60.93(3) 3_575 2_775 ? N4 Cu3 I2 103.32(2) . 2_775 ? Cu2 Cu3 I2 60.47(2) . 2_775 ? Cu2 Cu3 I2 112.48(4) 3_575 2_775 ? Cu2 Cu3 I2 63.26(2) 2_775 2_775 ? N4 Cu3 I2 103.32(2) . . ? Cu2 Cu3 I2 63.26(2) . . ? Cu2 Cu3 I2 60.47(2) 3_575 . ? Cu2 Cu3 I2 112.48(4) 2_775 . ? I2 Cu3 I2 114.858(18) 2_775 . ? N4 Cu3 I2 103.32(2) . 3_575 ? Cu2 Cu3 I2 112.48(4) . 3_575 ? Cu2 Cu3 I2 63.26(2) 3_575 3_575 ? Cu2 Cu3 I2 60.47(2) 2_775 3_575 ? I2 Cu3 I2 114.858(18) 2_775 3_575 ? I2 Cu3 I2 114.858(18) . 3_575 ? C8 C7 C6 105.8(5) . . ? C6 N2 N1 107.3(4) . . ? C6 N2 Cu1 133.6(4) . . ? N1 N2 Cu1 114.4(3) . . ? C4 C5 C1 117.3(5) . . ? C4 C5 C6 119.1(5) . . ? C1 C5 C6 123.5(5) . . ? N2 C6 C7 109.3(4) . . ? N2 C6 C5 123.7(5) . . ? C7 C6 C5 126.9(5) . . ? N1 C8 C7 109.5(5) . . ? N1 C8 C9 120.4(5) . . ? C7 C8 C9 130.1(5) . . ? C2 C1 C5 119.0(5) . . ? C3 N3 C2 117.1(5) . . ? C3 N3 Cu2 120.2(4) . . ? C2 N3 Cu2 122.6(4) . . ? C9 C14 C13 120.5(5) . . ? N3 C2 C1 123.6(5) . . ? C10 C9 C14 118.1(5) . . ? C10 C9 C8 120.6(5) . . ? C14 C9 C8 121.2(5) . . ? C10 C11 C12 121.8(6) . . ? C3 C4 C5 119.9(5) . . ? N3 C3 C4 123.2(5) . . ? C11 C10 C9 120.8(5) . . ? C12 C13 C14 121.1(5) . . ? C11 C12 C13 117.7(5) . . ? C11 C12 C15 121.3(5) . . ? C13 C12 C15 121.0(5) . . ? C8 N1 N2 108.2(4) . . ? C8 N1 Cu1 130.5(4) . 2_765 ? N2 N1 Cu1 120.7(3) . 2_765 ? _diffrn_measured_fraction_theta_max 0.958 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.958 _refine_diff_density_max 1.502 _refine_diff_density_min -0.910 _refine_diff_density_rms 0.196