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_7709520
_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         'C35 H25 Ir N4 S'
_chemical_formula_sum            'C35 H25 Ir N4 S'
_chemical_formula_weight         725.85
_chemical_name_systematic        Ir-thia-IG
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-06-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-08-11 deposited with the CCDC.	2022-02-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.517(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.5183(4)
_cell_length_b                   9.2894(3)
_cell_length_c                   20.2339(6)
_cell_measurement_reflns_used    8060
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.3790
_cell_measurement_theta_min      2.1160
_cell_volume                     2723.73(14)
_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  (Sheldrick, 2015)'
_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   -138.17  61.83   0.50    1.00  13.02 -13.22 -30.17    --   400
  2  \w    -94.73 -12.73   0.50    1.00    --  -35.64 116.35  -4.95  164
  3  \w   -103.14  11.86   0.50    1.00    --  -13.22 -59.77-123.73  230
  4  \w    -52.42  21.58   0.50    1.00    --  -13.22  83.74 -29.95  148
  5  \f   -101.99  62.01   0.50    1.00  12.52 -13.22 -59.07    --   328
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Bruker D8 venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0106435000
_diffrn_orient_matrix_UB_12      -0.0073705000
_diffrn_orient_matrix_UB_13      0.0344993000
_diffrn_orient_matrix_UB_21      -0.0472909000
_diffrn_orient_matrix_UB_22      0.0091508000
_diffrn_orient_matrix_UB_23      0.0059372000
_diffrn_orient_matrix_UB_31      -0.0068116000
_diffrn_orient_matrix_UB_32      -0.0754647000
_diffrn_orient_matrix_UB_33      -0.0027005000
_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  0.0835
_diffrn_reflns_av_unetI/netI     0.0604
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            49498
_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         27.999
_diffrn_reflns_theta_min         2.017
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.012
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20630
_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            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.770
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1424
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.047
_refine_diff_density_min         -2.022
_refine_diff_density_rms         0.170
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.976
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     407
_refine_ls_number_reflns         6571
_refine_ls_number_restraints     272
_refine_ls_restrained_S_all      0.957
_refine_ls_R_factor_all          0.0589
_refine_ls_R_factor_gt           0.0345
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0302P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0623
_refine_ls_wR_factor_ref         0.0675
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5033
_reflns_number_total             6571
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt04218a2.cif
_cod_data_source_block           mo_sam6
_cod_database_code               7709520
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C35 H25 Ir N4 S1'
_shelx_estimated_absorpt_t_max   0.634
_shelx_estimated_absorpt_t_min   0.108
_reflns_odcompleteness_completeness 70.06
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     41.25
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Shared sites
{C32, C132}
3. Uiso/Uaniso restraints and constraints
S1 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim S101 \\sim C132 \\sim C133
\\sim C134 \\sim C135: within 2A with sigma of 0.015 and sigma for terminal
atoms of 0.03 within 2A
Uanis(S1) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34)
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(S101) \\sim Ueq, Uanis(C132) \\sim Ueq,
Uanis(C133) \\sim Ueq, Uanis(C134) \\sim Ueq, Uanis(C135) \\sim Ueq: with sigma
of 0.015 and sigma for terminal atoms of 0.03
Uanis(C32) = Uanis(C132)
4. Rigid body (RIGU) restrains
 S1, C32, C33, C34, C35, S101, C132, C133, C134, C135
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{S1, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{S101, C132, C133, C134, C135}
6. Others
 Sof(S101)=Sof(C132)=Sof(C133)=Sof(H133)=Sof(C134)=Sof(H134)=Sof(C135)=
 Sof(H135)=1-FVAR(1)
 Sof(S1)=Sof(C32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=FVAR(1)
7.a 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),
 C35(H35), C133(H133), C134(H134), C135(H135)
;
_shelx_res_checksum              80122
_shelx_hkl_checksum              19696
_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 2.884
_oxdiff_exptl_absorpt_empirical_full_min 0.637