Methylated regioisomers of Re(I) and Ir(III) tetrazole complexes: photophysical properties and optical imaging of brain tissue
Dallerba, Elena; Cameron, Lee; Armstrong, Blake I.; Ellison, Gaewyn; Turner, Eva; Innes, Evelyn; Strickling, Georgia L.; Pangiarella, Joel Ethan; O'Conghaile, Peter; Nesbit, Michael; Moggach, Stephen A.; Raiteri, Paolo; Stagni, Stefano; Pearson, Emma; Hackett, Mark; Massi, Massimiliano; Dalton Transactions  (2025) –; doi:10.1039/D5DT01745A

data_7719877
_publ_section_title
;
 Methylated regioisomers of Re(I) and Ir(III) tetrazole complexes:
 photophysical properties and optical imaging of brain tissue
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT01745A
_journal_year                    2025
_chemical_formula_moiety         'C29 H23 Ir N7, F6 P, C3 H6 O'
_chemical_formula_sum            'C32 H29 F6 Ir N7 O P'
_chemical_formula_weight         864.79
_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
_audit_block_doi                 10.5517/ccdc.csd.cc2dlrb3
_audit_creation_date             2022-10-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-11-28 deposited with the CCDC.	2025-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.9730(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.67480(10)
_cell_length_b                   13.09290(10)
_cell_length_c                   20.61330(10)
_cell_measurement_reflns_used    51553
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.4390
_cell_measurement_theta_min      3.9970
_cell_volume                     3093.28(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL n/a (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     24.00 118.00   0.50    0.05    --   46.32  77.00-120.00  188
  2  \w     24.00 118.00   0.50    0.05    --   46.32  77.00 -60.00  188
  3  \w     24.00 118.00   0.50    0.05    --   46.32  77.00 -90.00  188
  4  \w     24.00 118.00   0.50    0.05    --   46.32  77.00   0.00  188
  5  \w     24.00 118.00   0.50    0.05    --   46.32  77.00  60.00  188
  6  \w     24.00 118.00   0.50    0.05    --   46.32  77.00 120.00  188
  7  \w     24.00 118.00   0.50    0.05    --   46.32  77.00 150.00  188
  8  \w     31.00 118.00   0.50    0.05    --   46.32  59.00 148.00  174
  9  \w     34.00 119.00   0.50    0.05    --   46.32  38.00 120.00  170
 10  \w     34.00 119.00   0.50    0.05    --   46.32  38.00  30.00  170
 11  \w     34.00 121.00   0.50    0.05    --   46.32  19.00 -30.00  174
 12  \w     34.00 119.00   0.50    0.05    --   46.32  38.00 -90.00  170
 13  \w     24.00 118.00   0.50    0.05    --   46.32  77.00-180.00  188
 14  \w    -28.00  26.00   0.50    0.05    --   46.32 -19.00  30.00  108
 15  \w    -25.00  62.00   0.50    0.05    --   46.32 -59.00   8.00  174
 16  \w     30.00 105.00   0.50    0.05    --  102.29 -94.00  90.00  150
 17  \w     13.00  94.00   0.50    0.05    --   46.32-125.00  30.00  162
 18  \w     30.00 111.00   0.50    0.05    --  102.29-125.00 -30.00  162
 19  \w    -26.00  43.00   0.50    0.05    --   46.32 -38.00-180.00  138
 20  \w     30.00 105.00   0.50    0.05    --  102.29 -94.00-150.00  150
 21  \w     30.00  68.00   0.50    0.05    --  102.29 -59.00   8.00   76
 22  \w     30.00 105.00   0.50    0.05    --  102.29 -77.00 120.00  150
 23  \w     30.00 105.00   0.50    0.05    --  102.29 -77.00  90.00  150
 24  \w     30.00  71.00   0.50    0.05    --  102.29 -61.00  30.00   82
 25  \w     30.00 105.00   0.50    0.05    --  102.29 -77.00 -30.00  150
 26  \w     90.00 176.00   0.50    0.05    --  102.29  30.00 -60.00  172
 27  \w     86.00 174.00   0.50    0.05    --  102.29  61.00  60.00  176
 28  \w     87.00 174.00   0.50    0.05    --  102.29  59.00 148.00  174
 29  \w    -26.00  29.00   0.50    0.05    --  -46.32  19.00 -90.00  110
 30  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00-180.00   82
 31  \w   -105.00 -30.00   0.50    0.05    -- -102.29  77.00-180.00  150
 32  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00 -60.00   82
 33  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00 -90.00   82
 34  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00 -30.00   82
 35  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00   0.00   82
 36  \w    -62.00  26.00   0.50    0.05    --  -46.32  59.00 148.00  176
 37  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00 120.00   82
 38  \w    -68.00 -30.00   0.50    0.05    -- -102.29  59.00 148.00   76
 39  \w   -174.00 -80.00   0.50    0.05    -- -102.29 -77.00 -60.00  188
 40  \w   -174.00 -80.00   0.50    0.05    -- -102.29 -77.00 -90.00  188
 41  \w   -174.00 -86.00   0.50    0.05    -- -102.29 -61.00-120.00  176
 42  \w   -174.00 -86.00   0.50    0.05    -- -102.29 -61.00 -90.00  176
 43  \w   -174.00 -86.00   0.50    0.05    -- -102.29 -61.00 -30.00  176
 44  \w   -174.00 -87.00   0.50    0.05    -- -102.29 -59.00   8.00  174
 45  \w   -174.00 -86.00   0.50    0.05    -- -102.29 -61.00  60.00  176
 46  \w   -174.00 -90.00   0.50    0.05    -- -102.29 -45.00  30.00  168
 47  \w   -174.00 -86.00   0.50    0.05    -- -102.29 -61.00  90.00  176
 48  \w   -174.00 -90.00   0.50    0.05    -- -102.29 -45.00 120.00  168
 49  \w   -118.00 -31.00   0.50    0.05    --  -46.32 -57.00  60.00  174
 50  \w   -118.00 -31.00   0.50    0.05    --  -46.32 -59.00   8.00  174
 51  \w   -174.00 -90.00   0.50    0.05    -- -102.29 -45.00 -60.00  168
 52  \w   -176.00 -89.00   0.50    0.05    -- -102.29 -15.00 -90.00  174
 53  \w   -176.00 -90.00   0.50    0.05    -- -102.29 -30.00-120.00  172
 54  \w   -174.00 -90.00   0.50    0.05    -- -102.29 -45.00-150.00  168
 55  \w   -176.00 -90.00   0.50    0.05    -- -102.29 -30.00-150.00  172
 56  \w   -174.00 -90.00   0.50    0.05    -- -102.29 -45.00-180.00  168
 57  \w   -118.00 -73.00   0.50    0.05    --  -46.32-125.00-180.00   90
 58  \w   -118.00 -73.00   0.50    0.05    --  -46.32-125.00  90.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1010773000
_diffrn_orient_matrix_UB_12      0.0168026000
_diffrn_orient_matrix_UB_13      -0.0372296000
_diffrn_orient_matrix_UB_21      0.0532223000
_diffrn_orient_matrix_UB_22      0.0804583000
_diffrn_orient_matrix_UB_23      0.0516058000
_diffrn_orient_matrix_UB_31      0.0708779000
_diffrn_orient_matrix_UB_32      -0.0841868000
_diffrn_orient_matrix_UB_33      0.0417630000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0584
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            90926
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.341
_diffrn_reflns_theta_min         4.021
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.528
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40257
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.104a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.857
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1696
_exptl_crystal_recrystallization_method
'grown from the slow evaporation of acetone from an acetone and water solution'
_exptl_crystal_size_max          0.242
_exptl_crystal_size_mid          0.148
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.999
_refine_diff_density_min         -1.429
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     436
_refine_ls_number_reflns         6336
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0226
_refine_ls_R_factor_gt           0.0214
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0298P)^2^+3.3763P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0542
_refine_ls_wR_factor_ref         0.0550
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6033
_reflns_number_total             6336
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01745a2.cif
_cod_data_source_block           mxm542rm_auto
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               7719877
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C29 H23 Ir1 N7'
_chemical_oxdiff_usercomment     'Lee Cameron'
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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.a Aromatic/amide H refined with riding coordinates:
 C19(H19), C14(H14), C8(H8), C10(H10), C11(H11), C4(H4), C5(H5), C6(H6),
 C28(H28), C25(H25), C16(H16), C20(H20), C9(H9), C17(H17), C27(H27), C15(H15),
 C26(H26), C21(H21), C7(H7), C22(H22)
2.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              57651
_olex2_exptl_crystal_mounting_method
'mounted on a glass fibre using silicon oil'
_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 1.937
_oxdiff_exptl_absorpt_empirical_full_min 0.702