Luminescent ruffled iridium(III) porphyrin complexes containing N-heterocyclic carbene ligands: structures, spectroscopies and potent antitumor activities under dark and light irradiation conditions
Lam, Tsz Lung; Ka Chung, Tong; Yang, Chen; Kwong, Wai-Lun; Guan, Xiangguo; Li, Ming-De; Lo, Vanessa Kar-Yan; Chan, Sharon Lai-Fung; Phillips, David Lee; Lok, Chun-Nam; Che, Chi-Ming; Chemical Science  (2018) –; doi:10.1039/C8SC02920B

data_1550024
_publ_section_title
;
 Luminescent ruffled iridium(III) porphyrin complexes containing
 N-heterocyclic carbene ligands: structures, spectroscopies and potent
 antitumor activities under dark and light irradiation conditions
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC02920B
_journal_year                    2018
_chemical_formula_moiety         'C54 H24 F20 Ir N8, 0.25(C F3 O3 S)'
_chemical_formula_sum            'C54.25 H24 F20.75 Ir N8 O0.75 S0.25'
_chemical_formula_weight         1394.28
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2016-04-17
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2018-05-31 deposited with the CCDC.
2018-09-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.9405(17)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   24.7628(7)
_cell_length_b                   23.6873(7)
_cell_length_c                   39.6486(13)
_cell_measurement_reflns_used    206937
_cell_measurement_temperature    100
_cell_measurement_theta_max      45
_cell_measurement_theta_min      3
_cell_volume                     23131.5(12)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.580
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1664
_diffrn_reflns_av_unetI/netI     0.1121
_diffrn_reflns_Laue_measured_fraction_full 0.580
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            206937
_diffrn_reflns_point_group_measured_fraction_full 0.580
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         50.637
_diffrn_reflns_theta_min         1.794
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.567
_exptl_absorpt_correction_T_max  0.7500
_exptl_absorpt_correction_T_min  0.5186
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1211 before and 0.0897 after correction.
The Ratio of minimum to maximum transmission is 0.6915.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.601
_exptl_crystal_description       block
_exptl_crystal_F_000             10868
_exptl_crystal_recrystallization_method DCM/Et2O
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.726
_refine_diff_density_min         -1.193
_refine_diff_density_rms         0.160
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2885
_refine_ls_number_reflns         24295
_refine_ls_number_restraints     2218
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.1624
_refine_ls_R_factor_gt           0.1073
_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^)+(0.1130P)^2^+557.6390P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2648
_refine_ls_wR_factor_ref         0.2863
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14427
_reflns_number_total             24295
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc02920b2.cif
_cod_data_source_block           david222_0m-mon
_cod_database_code               1550024
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.897
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C17C-C18C
 1.38 with sigma of 0.02
 C20C-C19C
 1.48 with sigma of 0.02
 C8C-C9C
 1.38 with sigma of 0.02
 C47C-C46C
 1.31 with sigma of 0.02
 C47A-C46A
 1.32 with sigma of 0.02
 C9B-C8B
 1.36 with sigma of 0.02
 C7B-C8B = C9B-C10B
 1.43 with sigma of 0.02
 N6C-C47C = N5C-C46C
 1.32 with sigma of 0.02
 C9B-C8B
 1.33 with sigma of 0.02
 N7B-C51B = N8B-C52B
 1.36 with sigma of 0.02
 C52B-C51B
 1.36 with sigma of 0.02
 C17C-C19C
 2.24 with sigma of 0.04
 C20C-C18C
 2.24 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.02
4.a Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C19(H19), C14A(H14A), C51(H51), C13A(H13A), C3C(H3C), C8C(H8C),
 C18(H18), C9C(H9C), C3(H3), C13(H13), C51C(H51C), C9A(H9A), C14(H14),
 C13B(H13B), C14B(H14B), C9B(H9B), C19A(H19A), C8(H8), C18A(H18A), C47A(H47A),
 C4(H4), C9(H9), C3B(H3B), C46B(H46B), C8B(H8B), C18B(H18B), C46(H46), C47(H47),
  C52B(H52B), C8A(H8A), C19B(H19B), C4B(H4B), C13C(H13C), C14C(H14C),
 C52C(H52C), C4C(H4C), C19C(H19C), C46C(H46C), C46A(H46A), C51A(H51A),
 C52A(H52A), C47B(H47B), C51B(H51B), C4A(H4A), C47C(H47C), C52(H52), C18C(H18C)
4.b Fitted hexagon refined as free rotating group:
 C31B(C30B,C29B,C28B,C27B,C32B), C40A(C39A,C44A,C43A,C42A,C41A), C34C(C33C,
 C38C,C37C,C36C,C35C), C31C(C32C,C27C,C28C,C29C,C30C), C37A(C38A,C33A,C34A,C35A,
 C36A), C26A(C25A,C24A,C23A,C22A,C21A), C43(C42,C41,C40,C39,C44), C22C(C23C,
 C24C,C25C,C26C,C21C), C30A(C29A,C28A,C27A,C32A,C31A), C25(C26,C21,C22,C23,C24),
  C36(C37,C38,C33,C34,C35), C37B(C36B,C35B,C34B,C33B,C38B), C32(C31,C30,C29,C28,
 C27), C23B(C24B,C25B,C26B,C21B,C22B), C42C(C43C,C44C,C39C,C40C,C41C),
 C40B(C41B,C42B,C43B,C44B,C39B)
4.c Idealised Me refined as rotating group:
 C53(H53J,H53K,H53L), C48A(H48D,H48E,H48F), C48(H48J,H48K,H48L), C49(H49J,H49K,
 H49L), C49C(H49G,H49H,H49I), C49A(H49D,H49E,H49F), C54A(H54D,H54E,H54F),
 C54B(H54A,H54B,H54C), C48B(H48A,H48B,H48C), C54C(H54G,H54H,H54I), C53C(H53G,
 H53H,H53I), C48C(H48G,H48H,H48I), C49B(H49A,H49B,H49C), C54(H54J,H54K,H54L),
 C53A(H53D,H53E,H53F), C53B(H53A,H53B,H53C)
;
_olex2_submission_special_instructions 'No special instructions were received'