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_1550026
_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         'C58 H52 Ir N8, F6 P, 0.13(C H2 Cl2)'
_chemical_formula_sum            'C58.12 H52.25 Cl0.25 F6 Ir N8 P'
_chemical_formula_weight         1208.86
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2018-05-31 deposited with the CCDC.
2018-09-28 downloaded from the CCDC.
;
_cell_angle_alpha                77.893(3)
_cell_angle_beta                 84.194(2)
_cell_angle_gamma                78.728(3)
_cell_formula_units_Z            4
_cell_length_a                   12.7322(6)
_cell_length_b                   16.8417(10)
_cell_length_c                   26.2843(12)
_cell_measurement_reflns_used    9387
_cell_measurement_temperature    100
_cell_measurement_theta_max      43.87
_cell_measurement_theta_min      2.73
_cell_volume                     5393.9(5)
_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_measured_fraction_theta_full 0.415
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0726
_diffrn_reflns_av_unetI/netI     0.0850
_diffrn_reflns_Laue_measured_fraction_full 0.415
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            28233
_diffrn_reflns_point_group_measured_fraction_full 0.415
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         44.375
_diffrn_reflns_theta_min         1.722
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.745
_exptl_absorpt_correction_T_max  0.7488
_exptl_absorpt_correction_T_min  0.5526
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0870 before and 0.0664 after correction.
The Ratio of minimum to maximum transmission is 0.7380.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'dull dark red'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.489
_exptl_crystal_description       needle
_exptl_crystal_F_000             2429
_exptl_crystal_recrystallization_method DCM/Et2O
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.002
_exptl_crystal_size_min          0.002
_refine_diff_density_max         1.744
_refine_diff_density_min         -0.968
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1226
_refine_ls_number_reflns         8106
_refine_ls_number_restraints     980
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0559
_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^)+(0.0670P)^2^+50.9990P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1395
_refine_ls_wR_factor_ref         0.1526
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5880
_reflns_number_total             8106
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc02920b2.cif
_cod_data_source_block           david173_0m-p-1
_cod_database_code               1550026
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl1S-C1S = Cl2S-C1S
 1.78 with sigma of 0.02
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
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(Cl2S) \\sim Ueq, Uanis(C1S) \\sim Ueq, Uanis(Cl1S) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl1S) = Uanis(Cl2S) = Uanis(C1S)
Uanis(N4A) = Uanis(N1A) = Uanis(C49A) = Uanis(N3A) = Uanis(Ir1A) = Uanis(N2A) =
Uanis(C54A)
Uanis(N1) = Uanis(C4) = Uanis(C3) = Uanis(C2) = Uanis(C1) = Uanis(C20) =
Uanis(C19) = Uanis(N4) = Uanis(N3) = Uanis(C14) = Uanis(C15) = Uanis(C16) =
Uanis(C11) = Uanis(C10) = Uanis(C9) = Uanis(N2) = Uanis(C6) = Uanis(C5)
4. Others
 Fixed Sof: Cl1S(0.25) Cl2S(0.25) C1S(0.25) H1SA(0.25) H1SB(0.25)
5.a Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB)
5.b Aromatic/amide H refined with riding coordinates:
 C36(H36), C25(H25), C2A(H2A), C26(H26), C12A(H12A), C39A(H39A), C43A(H43A),
 C13A(H13A), C47A(H47A), C39(H39), C23A(H23A), C3(H3), C40(H40), C7(H7),
 C37A(H37A), C40A(H40A), C25A(H25A), C46(H46), C18A(H18A), C8(H8), C46A(H46A),
 C32A(H32A), C47(H47), C18(H18), C13(H13), C44A(H44A), C2(H2), C33A(H33A),
 C29(H29), C22(H22), C36A(H36A), C22A(H22A), C30(H30), C37(H37), C17(H17),
 C26A(H26A), C44(H44), C3A(H3A), C33(H33), C32(H32), C23(H23), C12(H12),
 C29A(H29A), C17A(H17A), C30A(H30A), C7A(H7A), C8A(H8A), C43(H43), C51A(H51A),
 C56(H56), C55(H55), C50A(H50A), C55A(H55A), C50(H50), C51(H51), C56A(H56A)
5.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C41A(H41D,H41E,H41F), C41(H41A,H41B,H41C), C27A(H27D,
 H27E,H27F), C48A(H48D,H48E,H48F), C48(H48A,H48B,H48C), C52A(H52D,H52E,H52F),
 C53A(H53D,H53E,H53F), C58A(H58D,H58E,H58F), C57A(H57D,H57E,H57F), C57(H57A,
 H57B,H57C), C58(H58A,H58B,H58C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C),
 C34A(H34D,H34E,H34F), C34(H34A,H34B,H34C)
;
_olex2_submission_special_instructions 'No special instructions were received'