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_7719884
_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         'C33 H25 Ir N7, F6 P, 0.375[CH2Cl2]'
_chemical_formula_sum            'C33.38 H25.75 Cl0.75 F6 Ir N7 P'
_chemical_formula_weight         888.68
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2dlrf6
_audit_creation_date             2022-10-12
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-11-28 deposited with the CCDC.	2025-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.8150(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.48790(10)
_cell_length_b                   18.7654(4)
_cell_length_c                   41.0127(6)
_cell_measurement_reflns_used    28236
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.4060
_cell_measurement_theta_min      4.3100
_cell_volume                     6517.98(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_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 0.997
_diffrn_measured_fraction_theta_max 0.958
_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     49.00 119.00   0.50    0.08    --   45.98 163.00-166.00  140
  2  \w     87.00 116.00   0.50    0.08    --   45.98 125.00 -30.00   58
  3  \w     75.00 118.00   0.50    0.08    --   45.98 125.00   0.00   86
  4  \w    103.00 128.00   0.50    0.28    --  102.69 116.00  44.00   50
  5  \w     91.00 171.00   0.50    0.28    --  102.69  45.00 -30.00  160
  6  \w    -27.00  24.00   0.50    0.08    --   45.98 -19.00 -90.00  102
  7  \w     32.00 118.00   0.50    0.08    --   45.98-163.00 167.00  172
  8  \w     48.00  73.00   0.50    0.08    --   45.98-116.00 -43.00   50
  9  \w     31.00  64.00   0.50    0.28    --  102.69 -61.00  90.00   66
 10  \w     35.00 103.00   0.50    0.28    --  102.69 -94.00 150.00  136
 11  \w     60.00  85.00   0.50    0.28    --  102.69-163.00 167.00   50
 12  \w     82.00 109.00   0.50    0.28    --  102.69-116.00 -43.00   54
 13  \w     30.00  77.00   0.50    0.28    --  102.69-116.00 -43.00   94
 14  \w     52.00  78.00   0.50    0.28    --  102.69 -94.00   0.00   52
 15  \w   -118.00 -32.00   0.50    0.08    --  -45.98 163.00-166.00  172
 16  \w    -72.00 -30.00   0.50    0.28    -- -102.69  61.00   0.00   84
 17  \w    -64.00 -30.00   0.50    0.28    -- -102.69  61.00  30.00   68
 18  \w    -72.00 -32.00   0.50    0.28    -- -102.69  61.00 -30.00   80
 19  \w   -109.00 -50.00   0.50    0.28    -- -102.69 116.00  44.00  118
 20  \w    -89.00  -6.00   0.50    0.08    --  -45.98 116.00  44.00  166
 21  \w   -104.00 -31.00   0.50    0.28    -- -102.69  77.00 120.00  146
 22  \w    -72.00 -34.00   0.50    0.08    --  -45.98 -37.00 -30.00   76
 23  \w   -174.00 -93.00   0.50    0.28    -- -102.69 -45.00 150.00  162
 24  \w   -119.00 -88.00   0.50    0.08    --  -45.98 -37.00 -30.00   62
 25  \w   -127.00 -87.00   0.50    0.28    -- -102.69 -61.00-120.00   80
 26  \w   -140.00 -81.00   0.50    0.28    -- -102.69-116.00 -43.00  118
 27  \w   -118.00 -73.00   0.50    0.08    --  -45.98-125.00   0.00   90
 28  \w   -104.00 -79.00   0.50    0.08    --  -45.98-125.00  30.00   50
 29  \w   -118.00 -48.00   0.50    0.08    --  -45.98-163.00 167.00  140
 30  \w   -126.00-101.00   0.50    0.28    -- -102.69-163.00 167.00   50
;
_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      -0.0259510000
_diffrn_orient_matrix_UB_12      0.0811479000
_diffrn_orient_matrix_UB_13      0.0017247000
_diffrn_orient_matrix_UB_21      -0.0504273000
_diffrn_orient_matrix_UB_22      0.0011303000
_diffrn_orient_matrix_UB_23      -0.0367808000
_diffrn_orient_matrix_UB_31      -0.1727783000
_diffrn_orient_matrix_UB_32      -0.0124958000
_diffrn_orient_matrix_UB_33      0.0078547000
_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  0.0570
_diffrn_reflns_av_unetI/netI     0.0421
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -51
_diffrn_reflns_number            64395
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.567
_diffrn_reflns_theta_min         2.590
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.595
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88805
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.811
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3470
_exptl_crystal_recrystallization_method
'grown from the evaporation of a dichloromethane and ether solution'
_exptl_crystal_size_max          0.112
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.066
_refine_diff_density_max         1.949
_refine_diff_density_min         -2.196
_refine_diff_density_rms         0.146
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.159
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     867
_refine_ls_number_reflns         12976
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.159
_refine_ls_R_factor_all          0.0563
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0151P)^2^+58.5742P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1111
_refine_ls_wR_factor_ref         0.1134
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11849
_reflns_number_total             12976
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01745a2.cif
_cod_data_source_block           mxm589rm
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7719884
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ir C40 h28 N6 O P6 F12'
_chemical_oxdiff_usercomment     'Lee Cameron for Ryan Morris'
_shelx_estimated_absorpt_t_max   0.570
_shelx_estimated_absorpt_t_min   0.413
_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:
 C51(H51), C12(H12), C13(H13), C56(H56), C10(H10), C4(H4), C54(H54), C46(H46),
 C42(H42), C64(H64), C43(H43), C24(H24), C57(H57), C23(H23), C21(H21), C32(H32),
  C53(H53), C31(H31), C20(H20), C65(H65), C15(H15), C48(H48), C14(H14),
 C30(H30), C59(H59), C18(H18), C52(H52), C45(H45), C7(H7), C47(H47), C19(H19),
 C29(H29), C38(H38), C41(H41), C26(H26), C62(H62), C25(H25), C5(H5), C63(H63),
 C37(H37), C58(H58), C8(H8), C9(H9), C40(H40)
2.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C34(H34A,H34B,H34C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              82742
_shelx_fab_checksum              83248
_olex2_exptl_crystal_mounting_method
'crystal was 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 1.175
_oxdiff_exptl_absorpt_empirical_full_min 0.859