data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _publ_contact_author 'David L. Davies' _publ_contact_author_email dld3@le.ac.uk loop_ _publ_author_name _publ_author_address D.L.Davies ;Department of Chemistry, University of Leicester, Leicester, LE1 7RH ; M.P.Lowe ;Department of Chemistry, University of Leicester, Leicester, LE1 7RH ; K.S.Ryder ;Department of Chemistry, University of Leicester, Leicester, LE1 7RH ; S.Singh ;Department of Chemistry, University of Leicester, Leicester, LE1 7RH ; _publ_section_title ; Tuning emission wavelength and redox properties through position of the substituent in iridium(III) cyclometallated complexes. ; _publ_contact_author_name 'David L. Davies' data_09045 _database_code_depnum_ccdc_archive 'CCDC 795652' #TrackingRef '- 09045Dalton.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '(C40 H36 Cl2 Ir2 N8 O4)8(H2 O)' _chemical_formula_sum 'C40 H52 Cl2 Ir2 N8 O12' _chemical_formula_weight 1292.20 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' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ir Ir -1.4442 7.9887 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Fddd loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+3/4, -y+3/4, z' '-x+3/4, y, -z+3/4' 'x, -y+3/4, -z+3/4' 'x, y+1/2, z+1/2' '-x+3/4, -y+5/4, z+1/2' '-x+3/4, y+1/2, -z+5/4' 'x, -y+5/4, -z+5/4' 'x+1/2, y, z+1/2' '-x+5/4, -y+3/4, z+1/2' '-x+5/4, y, -z+5/4' 'x+1/2, -y+3/4, -z+5/4' 'x+1/2, y+1/2, z' '-x+5/4, -y+5/4, z' '-x+5/4, y+1/2, -z+3/4' 'x+1/2, -y+5/4, -z+3/4' '-x, -y, -z' 'x-3/4, y-3/4, -z' 'x-3/4, -y, z-3/4' '-x, y-3/4, z-3/4' '-x, -y+1/2, -z+1/2' 'x-3/4, y-1/4, -z+1/2' 'x-3/4, -y+1/2, z-1/4' '-x, y-1/4, z-1/4' '-x+1/2, -y, -z+1/2' 'x-1/4, y-3/4, -z+1/2' 'x-1/4, -y, z-1/4' '-x+1/2, y-3/4, z-1/4' '-x+1/2, -y+1/2, -z' 'x-1/4, y-1/4, -z' 'x-1/4, -y+1/2, z-3/4' '-x+1/2, y-1/4, z-3/4' _cell_length_a 15.880(10) _cell_length_b 19.871(12) _cell_length_c 29.233(18) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 9224(10) _cell_formula_units_Z 8 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 994 _cell_measurement_theta_min 2.479 _cell_measurement_theta_max 27.383 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.42 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.861 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 5056 _exptl_absorpt_coefficient_mu 5.949 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.462 _exptl_absorpt_correction_T_max 0.862 _exptl_absorpt_process_details ; absorption correction based on 10369 reflections(SADABS);Rint 0.2781 before correction and 0.0548 after. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Apex 2000 CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16881 _diffrn_reflns_av_R_equivalents 0.0681 _diffrn_reflns_av_sigmaI/netI 0.0330 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -36 _diffrn_reflns_limit_l_max 35 _diffrn_reflns_theta_min 2.48 _diffrn_reflns_theta_max 25.99 _reflns_number_total 2271 _reflns_number_gt 1815 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Disordered H2O was omitted using the SQUEEZE option of PLATON.The solvent accessible voids are 2023.8 3 with an estimated 1276e/cell to be added. Sixty four solvent H2O molecules/unit cell accounting for 1024e were included in the formula, FWt, (000) and density calculations. PLATON Reference: Spek, A.L. (1990), Acta Cryst. A46,C-34. 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^)+(0.0537P)^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 constrained _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2271 _refine_ls_number_parameters 129 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0445 _refine_ls_R_factor_gt 0.0308 _refine_ls_wR_factor_ref 0.0824 _refine_ls_wR_factor_gt 0.0777 _refine_ls_goodness_of_fit_ref 1.043 _refine_ls_restrained_S_all 1.043 _refine_ls_shift/su_max 0.001 _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 Ir1 Ir -0.007847(15) 0.8750 0.8750 0.02174(12) Uani 1 2 d S . . Cl1 Cl -0.1250 0.79026(8) 0.8750 0.0277(4) Uani 1 2 d S . . O1 O 0.2636(4) 0.6685(3) 0.9323(2) 0.085(2) Uani 1 1 d . . . N1 N -0.0012(2) 0.8803(2) 0.94398(17) 0.0265(10) Uani 1 1 d . . . N2 N 0.0577(3) 0.8385(2) 0.96349(15) 0.0340(11) Uani 1 1 d . . . C1 C 0.0820(3) 0.8055(2) 0.88621(17) 0.0238(11) Uani 1 1 d . . . C2 C 0.1267(4) 0.7661(3) 0.8546(2) 0.0382(13) Uani 1 1 d . . . H2 H 0.1172 0.7721 0.8228 0.046 Uiso 1 1 calc R . . C3 C 0.1852(4) 0.7179(3) 0.8695(2) 0.0445(16) Uani 1 1 d . . . H3 H 0.2119 0.6894 0.8478 0.053 Uiso 1 1 calc R . . C4 C 0.2044(4) 0.7117(3) 0.9157(2) 0.0502(18) Uani 1 1 d . . . C5 C 0.1630(5) 0.7524(3) 0.9477(2) 0.0501(17) Uani 1 1 d . . . H5 H 0.1758 0.7494 0.9794 0.060 Uiso 1 1 calc R . . C6 C 0.1036(4) 0.7968(3) 0.9321(2) 0.0349(14) Uani 1 1 d . . . C7 C 0.2767(8) 0.6092(5) 0.9081(5) 0.134(6) Uani 1 1 d . . . H7A H 0.3092 0.6189 0.8804 0.201 Uiso 1 1 calc R . . H7B H 0.2223 0.5895 0.8997 0.201 Uiso 1 1 calc R . . H7C H 0.3080 0.5773 0.9273 0.201 Uiso 1 1 calc R . . C8 C 0.0623(5) 0.8505(3) 1.00881(19) 0.0482(17) Uani 1 1 d . . . H8 H 0.0988 0.8287 1.0299 0.058 Uiso 1 1 calc R . . C9 C 0.0053(4) 0.8994(3) 1.0191(2) 0.0436(16) Uani 1 1 d . . . H9 H -0.0059 0.9182 1.0483 0.052 Uiso 1 1 calc R . . C10 C -0.0333(4) 0.9163(3) 0.97782(17) 0.0288(12) Uani 1 1 d . . . H10 H -0.0765 0.9490 0.9745 0.035 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 Ir1 0.02757(16) 0.01854(17) 0.01911(17) -0.00113(11) 0.000 0.000 Cl1 0.0310(8) 0.0182(8) 0.0339(10) 0.000 0.0017(8) 0.000 O1 0.113(5) 0.066(4) 0.076(4) -0.031(3) -0.042(3) 0.058(3) N1 0.031(2) 0.019(2) 0.030(3) -0.0033(19) 0.0031(17) -0.0004(19) N2 0.046(3) 0.035(3) 0.021(2) -0.001(2) -0.004(2) 0.014(2) C1 0.025(3) 0.020(2) 0.026(3) -0.005(2) -0.003(2) 0.004(2) C2 0.045(3) 0.038(3) 0.032(3) -0.006(3) -0.008(3) 0.004(3) C3 0.046(3) 0.044(4) 0.043(4) -0.020(3) -0.004(3) 0.019(3) C4 0.064(5) 0.043(4) 0.044(4) -0.007(3) -0.014(3) 0.025(3) C5 0.069(4) 0.041(4) 0.040(4) -0.009(3) -0.017(3) 0.024(3) C6 0.046(4) 0.030(3) 0.028(3) -0.006(2) -0.005(2) 0.009(2) C7 0.156(10) 0.063(7) 0.184(13) -0.062(7) -0.099(10) 0.069(7) C8 0.078(5) 0.048(4) 0.018(3) -0.003(3) -0.007(3) 0.025(3) C9 0.064(4) 0.046(4) 0.021(3) -0.005(3) 0.000(3) 0.013(3) C10 0.038(3) 0.026(3) 0.023(3) -0.003(2) 0.010(2) 0.007(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 Ir1 C1 2.014(5) 4_566 ? Ir1 C1 2.014(5) . ? Ir1 N1 2.022(5) . ? Ir1 N1 2.022(5) 4_566 ? Ir1 Cl1 2.5093(16) . ? Ir1 Cl1 2.5093(16) 2_465 ? Cl1 Ir1 2.5093(16) 2_465 ? O1 C4 1.362(7) . ? O1 C7 1.392(10) . ? N1 C10 1.323(6) . ? N1 N2 1.375(6) . ? N2 C8 1.348(7) . ? N2 C6 1.436(7) . ? C1 C6 1.395(8) . ? C1 C2 1.403(7) . ? C2 C3 1.403(8) . ? C2 H2 0.9500 . ? C3 C4 1.389(8) . ? C3 H3 0.9500 . ? C4 C5 1.403(9) . ? C5 C6 1.369(8) . ? C5 H5 0.9500 . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 C9 1.363(8) . ? C8 H8 0.9500 . ? C9 C10 1.393(8) . ? C9 H9 0.9500 . ? C10 H10 0.9500 . ? 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 C1 Ir1 C1 89.7(3) 4_566 . ? C1 Ir1 N1 95.13(18) 4_566 . ? C1 Ir1 N1 80.60(18) . . ? C1 Ir1 N1 80.60(18) 4_566 4_566 ? C1 Ir1 N1 95.13(18) . 4_566 ? N1 Ir1 N1 174.0(2) . 4_566 ? C1 Ir1 Cl1 170.44(14) 4_566 . ? C1 Ir1 Cl1 93.73(16) . . ? N1 Ir1 Cl1 94.23(11) . . ? N1 Ir1 Cl1 90.20(11) 4_566 . ? C1 Ir1 Cl1 93.73(16) 4_566 2_465 ? C1 Ir1 Cl1 170.44(14) . 2_465 ? N1 Ir1 Cl1 90.20(11) . 2_465 ? N1 Ir1 Cl1 94.23(11) 4_566 2_465 ? Cl1 Ir1 Cl1 84.30(8) . 2_465 ? Ir1 Cl1 Ir1 95.70(8) . 2_465 ? C4 O1 C7 117.0(6) . . ? C10 N1 N2 106.2(5) . . ? C10 N1 Ir1 139.0(4) . . ? N2 N1 Ir1 114.7(3) . . ? C8 N2 N1 109.7(5) . . ? C8 N2 C6 134.6(5) . . ? N1 N2 C6 115.4(4) . . ? C6 C1 C2 116.1(5) . . ? C6 C1 Ir1 114.5(4) . . ? C2 C1 Ir1 129.3(4) . . ? C3 C2 C1 120.7(5) . . ? C3 C2 H2 119.6 . . ? C1 C2 H2 119.6 . . ? C4 C3 C2 120.5(5) . . ? C4 C3 H3 119.7 . . ? C2 C3 H3 119.7 . . ? O1 C4 C3 123.8(6) . . ? O1 C4 C5 116.6(6) . . ? C3 C4 C5 119.6(6) . . ? C6 C5 C4 118.2(6) . . ? C6 C5 H5 120.9 . . ? C4 C5 H5 120.9 . . ? C5 C6 C1 124.7(5) . . ? C5 C6 N2 120.5(5) . . ? C1 C6 N2 114.7(5) . . ? O1 C7 H7A 109.5 . . ? O1 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? O1 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? N2 C8 C9 107.8(5) . . ? N2 C8 H8 126.1 . . ? C9 C8 H8 126.1 . . ? C8 C9 C10 105.9(5) . . ? C8 C9 H9 127.1 . . ? C10 C9 H9 127.1 . . ? N1 C10 C9 110.4(5) . . ? N1 C10 H10 124.8 . . ? C9 C10 H10 124.8 . . ? 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 C1 Ir1 Cl1 Ir1 -78.5(9) 4_566 . . 2_465 ? C1 Ir1 Cl1 Ir1 170.62(14) . . . 2_465 ? N1 Ir1 Cl1 Ir1 89.78(11) . . . 2_465 ? N1 Ir1 Cl1 Ir1 -94.23(11) 4_566 . . 2_465 ? Cl1 Ir1 Cl1 Ir1 0.0 2_465 . . 2_465 ? C1 Ir1 N1 C10 86.2(6) 4_566 . . . ? C1 Ir1 N1 C10 175.0(6) . . . . ? N1 Ir1 N1 C10 130.3(5) 4_566 . . . ? Cl1 Ir1 N1 C10 -91.9(5) . . . . ? Cl1 Ir1 N1 C10 -7.6(5) 2_465 . . . ? C1 Ir1 N1 N2 -87.6(4) 4_566 . . . ? C1 Ir1 N1 N2 1.2(4) . . . . ? N1 Ir1 N1 N2 -43.5(3) 4_566 . . . ? Cl1 Ir1 N1 N2 94.3(3) . . . . ? Cl1 Ir1 N1 N2 178.6(3) 2_465 . . . ? C10 N1 N2 C8 -1.4(7) . . . . ? Ir1 N1 N2 C8 174.4(4) . . . . ? C10 N1 N2 C6 -177.1(5) . . . . ? Ir1 N1 N2 C6 -1.3(6) . . . . ? C1 Ir1 C1 C6 94.4(4) 4_566 . . . ? N1 Ir1 C1 C6 -0.9(4) . . . . ? N1 Ir1 C1 C6 174.9(4) 4_566 . . . ? Cl1 Ir1 C1 C6 -94.6(4) . . . . ? Cl1 Ir1 C1 C6 -16.8(12) 2_465 . . . ? C1 Ir1 C1 C2 -84.1(5) 4_566 . . . ? N1 Ir1 C1 C2 -179.4(5) . . . . ? N1 Ir1 C1 C2 -3.6(5) 4_566 . . . ? Cl1 Ir1 C1 C2 87.0(5) . . . . ? Cl1 Ir1 C1 C2 164.7(6) 2_465 . . . ? C6 C1 C2 C3 4.1(8) . . . . ? Ir1 C1 C2 C3 -177.4(5) . . . . ? C1 C2 C3 C4 -4.6(10) . . . . ? C7 O1 C4 C3 -30.5(14) . . . . ? C7 O1 C4 C5 151.0(10) . . . . ? C2 C3 C4 O1 -176.5(7) . . . . ? C2 C3 C4 C5 1.9(11) . . . . ? O1 C4 C5 C6 179.4(7) . . . . ? C3 C4 C5 C6 0.9(11) . . . . ? C4 C5 C6 C1 -1.2(11) . . . . ? C4 C5 C6 N2 178.4(6) . . . . ? C2 C1 C6 C5 -1.3(9) . . . . ? Ir1 C1 C6 C5 -180.0(5) . . . . ? C2 C1 C6 N2 179.1(5) . . . . ? Ir1 C1 C6 N2 0.4(7) . . . . ? C8 N2 C6 C5 6.7(11) . . . . ? N1 N2 C6 C5 -179.0(6) . . . . ? C8 N2 C6 C1 -173.7(7) . . . . ? N1 N2 C6 C1 0.6(7) . . . . ? N1 N2 C8 C9 1.0(8) . . . . ? C6 N2 C8 C9 175.6(6) . . . . ? N2 C8 C9 C10 -0.2(8) . . . . ? N2 N1 C10 C9 1.2(6) . . . . ? Ir1 N1 C10 C9 -172.9(4) . . . . ? C8 C9 C10 N1 -0.7(8) . . . . ? loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 -0.125 0.375 -0.125 263 160 ' ' 2 0.125 0.625 0.125 263 160 ' ' 3 -0.125 0.875 0.375 263 160 ' ' 4 0.125 0.125 0.625 263 160 ' ' 5 0.375 0.875 -0.125 263 160 ' ' 6 0.375 0.375 0.375 263 160 ' ' 7 0.625 0.125 0.125 263 160 ' ' 8 0.625 0.625 0.625 263 160 ' ' _platon_squeeze_details ; Disordered H2O was omitted using the SQUEEZE option of PLATON.The solvent accessible voids are 2023.8 3 with an estimated 1276e/cell to be added. Sixty four solvent H2O molecules/unit cell accounting for 1024e were included in the formula, FWt, (000) and density calculations. PLATON Reference: Spek, A.L. (1990), Acta Cryst. A46,C-34. ; _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.99 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 2.180 _refine_diff_density_min -1.265 _refine_diff_density_rms 0.183