Luminescent Iridium(III) Dipyrrinato Complexes: Synthesis, X-ray Structures, DFT and Photocytotoxicity Studies of Glycosylated Derivatives
Gupta, Iti; Manav, Neha; Lone, Mohsin; Raza, Md Kausar; Chavda, Jaydeepsinh; Mori, Shigeki; Dalton Transactions  (2022) –; doi:10.1039/D1DT04218A

data_7709519
_publ_section_title
;
 Luminescent Iridium(III) Dipyrrinato Complexes: Synthesis, X-ray
 Structures, DFT and Photocytotoxicity Studies of Glycosylated Derivatives
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT04218A
_journal_year                    2022
_chemical_formula_moiety         'C41 H27 Ir N6 S2, 1(C1 H1 Cl3)'
_chemical_formula_sum            'C42 H28 Cl3 Ir N6 S2'
_chemical_formula_weight         979.37
_chemical_name_systematic        Ir-BTD-IG
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-07-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2020-08-11 deposited with the CCDC.	2022-02-15 downloaded from the CCDC.
;
_cell_angle_alpha                103.329(5)
_cell_angle_beta                 106.405(5)
_cell_angle_gamma                104.690(6)
_cell_formula_units_Z            2
_cell_length_a                   9.3922(6)
_cell_length_b                   13.6988(11)
_cell_length_c                   16.1785(6)
_cell_measurement_reflns_used    4236
_cell_measurement_temperature    100
_cell_measurement_theta_max      20.9120
_cell_measurement_theta_min      2.2800
_cell_volume                     1826.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       Apex-III
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f     -9.83 350.17   0.50    8.00  77.72 -13.22  30.17    --   720
  2  \w   -110.93 -13.43   0.50    8.00    --  -56.90 118.35  56.89  195
  3  \w     -9.50  24.50   0.50    8.00    --  -14.32 -81.06  67.81   68
  4  \f   -339.99  20.01   0.50    8.00  12.52 -13.22 -59.07    --   720
  5  \w    -75.35 -13.85   0.50    8.00    --  -14.32 119.59 172.09  123
  6  \w   -103.14  11.86   0.50    8.00    --  -13.22 -59.77 -51.73  230
  7  \w    -71.01 -11.51   0.50    8.00    --  -14.32 112.00 -33.32  119
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0063051000
_diffrn_orient_matrix_UB_12      0.0414172000
_diffrn_orient_matrix_UB_13      0.0378785000
_diffrn_orient_matrix_UB_21      -0.0789884000
_diffrn_orient_matrix_UB_22      -0.0267502000
_diffrn_orient_matrix_UB_23      -0.0053899000
_diffrn_orient_matrix_UB_31      0.0271393000
_diffrn_orient_matrix_UB_32      -0.0278234000
_diffrn_orient_matrix_UB_33      0.0295405000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1403
_diffrn_reflns_av_unetI/netI     0.1101
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            50381
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.998
_diffrn_reflns_theta_min         2.301
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.032
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.16453
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.781
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             964
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.975
_refine_diff_density_min         -2.029
_refine_diff_density_rms         0.166
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.974
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     524
_refine_ls_number_reflns         7164
_refine_ls_number_restraints     305
_refine_ls_restrained_S_all      0.993
_refine_ls_R_factor_all          0.1081
_refine_ls_R_factor_gt           0.0605
_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^)+(0.0673P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1225
_refine_ls_wR_factor_ref         0.1351
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4762
_reflns_number_total             7164
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt04218a2.cif
_cod_data_source_block           mo_8
_cod_database_code               7709519
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C41 H27 Ir1 N6 S2'
_shelx_estimated_absorpt_t_max   0.689
_shelx_estimated_absorpt_t_min   0.583
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 Cl1-C42 = Cl2-C42 = Cl3-C42
 1.78 with sigma of 0.02
 Cl11-C142 = Cl12-C142 = Cl13-C142
 1.78 with sigma of 0.02
 Cl1-Cl2 = Cl2-Cl3 = Cl3-Cl1
 2.85 with sigma of 0.04
 Cl11-Cl12 = Cl12-Cl13 = Cl13-Cl11
 2.85 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl2 \\sim Cl3 \\sim C42: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Cl11 \\sim Cl12 \\sim Cl13 \\sim C142: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim N5 \\sim S2 \\sim
N6: within 2A with sigma of 0.03 and sigma for terminal atoms of 0.06 within 2A
Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(C42)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl11) \\sim Ueq, Uanis(Cl12) \\sim Ueq, Uanis(Cl13) \\sim Ueq,
Uanis(C142) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(N5) \\sim Ueq,
Uanis(S2) \\sim Ueq, Uanis(N6) \\sim Ueq: with sigma of 0.03 and sigma for
terminal atoms of 0.06
4. Rigid body (RIGU) restrains
 Cl1, Cl2, Cl3, C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl11, Cl12, Cl13, C142
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C36, C37, C38, C39, C40, C41, N5, S2, N6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Cl11)=Sof(Cl12)=Sof(Cl13)=Sof(C142)=Sof(H142)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(C42)=Sof(H42)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C42(H42), C142(H142)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C15(H15), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23),
  C24(H24), C25(H25), C29(H29), C30(H30), C31(H31), C33(H33), C34(H34),
 C39(H39), C40(H40), C41(H41)
;
_shelx_res_checksum              50266
_shelx_hkl_checksum              64567
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.948
_oxdiff_exptl_absorpt_empirical_full_min 0.449