A tridentate and dianionic N-heterocyclic olefin (NHO) with two unsymmetrically-tethered aryloxide sidearms on bismuth: a fortuitous followed by systematic discovery.
Goswami, Santu; Sarkar, Subham; Guha Roy, Anisha; Mallick, Dibyendu; Mukherjee, Debabrata; Dalton transactions (Cambridge, England : 2003) 54 (2025) 8142–8151; doi:10.1039/d5dt00706b

data_7718417
_publ_section_title
;
 A tridentate and dianionic N-heterocyclic olefin (NHO) with two
 unsymmetrically-tethered aryloxide sidearms on bismuth: a fortuitous
 followed by systematic discovery.
;
_journal_issue                   20
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              8142
_journal_page_last               8151
_journal_paper_doi               10.1039/d5dt00706b
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C68 H96 Bi2 I2 N4 O4, 2(C4 H8 O)'
_chemical_formula_sum            'C76 H112 Bi2 I2 N4 O6'
_chemical_formula_weight         1849.45
_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
_audit_creation_date             2024-05-30
_audit_creation_method
;FinalCif V123 by Daniel Kratzert, Freiburg 2024, 
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2024-06-17 deposited with the CCDC.	2025-03-25 downloaded from the CCDC.
;
_cell_angle_alpha                98.2010(10)
_cell_angle_beta                 106.435(2)
_cell_angle_gamma                99.4120(10)
_cell_formula_units_Z            1
_cell_length_a                   10.8140(2)
_cell_length_b                   13.8767(2)
_cell_length_c                   15.9783(3)
_cell_measurement_reflns_used    37499
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      68.1830
_cell_measurement_theta_min      2.8580
_cell_volume                     2223.14(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.991
_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   -108.00 -18.00   0.50    0.92    --  -40.33 -61.00-125.00  180
  2  \w    -62.00  27.00   0.50    0.92    --  -40.33  61.00  12.00  178
  3  \w   -150.00 -60.00   0.50    3.69    --  -82.50 -61.00-125.00  180
  4  \w    -71.00 -15.00   0.50    3.69    --  -82.50  61.00  12.00  112
  5  \w     29.00  71.00   0.50    3.69    --   96.67 -61.00-125.00   84
  6  \w     75.00 164.00   0.50    3.69    --   96.67  61.00  12.00  178
  7  \w    -56.00  26.00   0.50    0.92    --  -40.33  50.00 120.00  164
  8  \w    -78.00   4.00   0.50    0.92    --  -40.33 104.00 150.00  164
  9  \w    -43.00  26.00   0.50    0.92    --  -40.33  38.00-150.00  138
 10  \w     18.00 108.00   0.50    0.92    --   40.33  61.00  12.00  180
 11  \w     41.00  99.00   0.50    0.92    --   40.33-138.00 -60.00  116
 12  \w    -35.00  24.00   0.50    0.92    --   40.33 -12.00 -30.00  118
 13  \w     18.00  79.00   0.50    0.92    --   40.33-104.00  60.00  122
 14  \w     10.00  43.00   0.50    0.92    --   40.33  87.00  32.73   66
 15  \w    -30.00  31.00   0.50    0.92    --   40.33 -25.00 -90.00  122
 16  \w    -27.00  63.00   0.50    0.92    --   40.33 -61.00-125.00  180
 17  \w    -35.00  24.00   0.50    0.92    --   40.33 -12.00-150.00  118
 18  \w     14.00 109.00   0.50    0.92    --   40.33  77.00 150.00  190
 19  \w    -35.00  24.00   0.50    0.92    --   40.33 -12.00  60.00  118
 20  \w   -153.00 -78.00   0.50    3.69    --  -82.50 -87.00 -60.00  150
 21  \w    -80.00  -9.00   0.50    3.69    --  -82.50  96.00 -30.00  142
 22  \w   -156.00 -58.00   0.50    3.69    --  -82.50 -17.00   0.00  196
 23  \w   -149.00 -78.00   0.50    3.69    --  -82.50-117.00   0.00  142
 24  \w     28.00 105.00   0.50    3.69    --   96.67 -77.00   0.00  154
 25  \w     83.00 164.00   0.50    3.69    --   96.67  33.00  60.00  162
 26  \w    105.00 170.00   0.50    3.69    --   96.67  96.00 -30.00  130
 27  \w     29.00  83.00   0.50    3.69    --   96.67 -68.00 120.00  108
 28  \w     29.00  68.00   0.50    3.69    --   96.67 -59.00 120.00   78
 29  \w     44.00 127.00   0.50    3.69    --   96.67-145.00  60.00  166
 30  \w    105.00 170.00   0.50    3.69    --   96.67  96.00  60.00  130
 31  \w     83.00 164.00   0.50    3.69    --   96.67  33.00-180.00  162
 32  \w     30.00  57.00   0.50    3.69    --   96.67 -50.00   0.00   54
 33  \w     30.00 109.00   0.50    3.69    --   96.67-117.00 120.00  158
 34  \w     28.00 105.00   0.50    3.69    --   96.67 -77.00 -60.00  154
 35  \w     30.00  57.00   0.50    3.69    --   96.67 -50.00-120.00   54
 36  \w     71.00 170.00   0.50    3.69    --   96.67  17.00 -30.00  198
 37  \w     73.00 165.00   0.50    3.69    --   96.67  68.00 120.00  184
 38  \w     22.00 106.00   0.50    3.69    --   96.67 -96.00 120.00  168
 39  \w     44.00 127.00   0.50    3.69    --   96.67-145.00 120.00  166
 40  \w     30.00  57.00   0.50    3.69    --   96.67 -50.00 -30.00   54
 41  \w     22.00 106.00   0.50    3.69    --   96.67 -96.00-120.00  168
 42  \w     30.00 109.00   0.50    3.69    --   96.67-117.00-120.00  158
 43  \w     30.00  57.00   0.50    3.69    --   96.67 -50.00 120.00   54
 44  \w     27.00 127.00   0.50    3.69    --   96.67 -87.00-120.00  200
 45  \w    105.00 170.00   0.50    3.69    --   96.67  96.00-150.00  130
 46  \w     44.00 127.00   0.50    3.69    --   96.67-145.00-120.00  166
 47  \w    105.00 170.00   0.50    3.69    --   96.67  96.00  30.00  130
 48  \w     44.00 127.00   0.50    3.69    --   96.67-145.00   0.00  166
 49  \w     30.00  57.00   0.50    3.69    --   96.67 -50.00 -60.00   54
 50  \w     70.00 165.00   0.50    3.69    --   96.67  77.00  90.00  190
 51  \w   -109.00 -13.00   0.50    0.92    --  -40.33 -77.00  30.00  192
 52  \w   -108.00 -17.00   0.50    0.92    --  -40.33 -64.00  60.00  182
 53  \w   -107.00 -21.00   0.50    0.92    --  -40.33 -50.00 -60.00  172
 54  \w   -109.00 -13.00   0.50    0.92    --  -40.33 -77.00 150.00  192
 55  \w     17.00 108.00   0.50    0.92    --   40.33  64.00-150.00  182
 56  \w      9.00  43.00   0.50    0.92    --   40.33  90.00   0.60   68
 57  \w      9.00  43.00   0.50    0.92    --   40.33  89.00 115.36   68
 58  \w     13.00  43.00   0.50    0.92    --   40.33  79.00 -72.44   60
 59  \w      9.00  43.00   0.50    0.92    --   40.33  89.00 154.50   68
 60  \w      9.00  43.00   0.50    0.92    --   40.33  90.00 -27.72   68
 61  \w      8.00  35.00   0.50    0.92    --   40.33  93.00 157.37   54
 62  \w     21.00 107.00   0.50    0.92    --   40.33  50.00 -30.00  172
 63  \w      9.00  43.00   0.50    0.92    --   40.33  89.00  96.03   68
 64  \w      8.00  42.00   0.50    0.92    --   40.33  92.00-120.92   68
 65  \w     17.00 108.00   0.50    0.92    --   40.33  64.00  90.00  182
 66  \w     17.00 108.00   0.50    0.92    --   40.33  64.00-120.00  182
 67  \w   -151.00 -77.00   0.50    3.69    --  -82.50 -74.00  69.59  148
 68  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00-120.00  192
 69  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00  60.00  192
 70  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00 120.00  192
 71  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00 -60.00  192
 72  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00  30.00  192
 73  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00-150.00  192
 74  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00   0.00  192
 75  \w   -151.00 -56.00   0.50    3.69    --  -82.50 -74.00 153.96  190
 76  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00 -90.00  192
 77  \w   -151.00 -56.00   0.50    3.69    --  -82.50 -76.00 132.11  190
 78  \w   -150.00 -58.00   0.50    3.69    --  -82.50 -68.00 -90.00  184
 79  \w   -152.00 -56.00   0.50    3.69    --  -82.50 -75.00-137.00  192
 80  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00 -30.00  192
 81  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00-180.00  192
 82  \w   -151.00 -55.00   0.50    3.69    --  -82.50 -77.00  90.00  192
 83  \w   -151.00 -56.00   0.50    3.69    --  -82.50 -74.00-168.86  190
 84  \w     70.00 165.00   0.50    3.69    --   96.67  77.00 -90.00  190
 85  \w     75.00 164.00   0.50    3.69    --   96.67  59.00 -30.00  178
 86  \w     73.00 165.00   0.50    3.69    --   96.67  68.00-180.00  184
 87  \w     70.00 165.00   0.50    3.69    --   96.67  77.00-120.00  190
 88  \w     73.00 165.00   0.50    3.69    --   96.67  68.00  -6.67  184
 89  \w     70.00 165.00   0.50    3.69    --   96.67  77.00  60.00  190
 90  \w     73.00 165.00   0.50    3.69    --   96.67  68.00 150.00  184
 91  \w     70.00 165.00   0.50    3.69    --   96.67  77.00  30.00  190
 92  \w     73.00 165.00   0.50    3.69    --   96.67  68.00 -60.00  184
 93  \w     78.00 163.00   0.50    3.69    --   96.67  50.00-150.00  170
 94  \w     70.00 165.00   0.50    3.69    --   96.67  77.00-150.00  190
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0930
_diffrn_reflns_av_unetI/netI     0.0428
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            58543
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.456
_diffrn_reflns_theta_min         2.943
_exptl_absorpt_coefficient_mu    13.468
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.21086
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.115a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.381
_exptl_crystal_description       needle
_exptl_crystal_F_000             916
_exptl_crystal_size_max          0.275
_exptl_crystal_size_mid          0.078
_exptl_crystal_size_min          0.045
_refine_diff_density_max         4.469
_refine_diff_density_min         -1.876
_refine_diff_density_rms         0.174
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     419
_refine_ls_number_reflns         8098
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.0487
_refine_ls_R_factor_gt           0.0458
_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^)+(0.1003P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1230
_refine_ls_wR_factor_ref         0.1257
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7347
_reflns_number_total             8098
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00706b2.cif
_cod_data_source_block           sg_423a_27feb
_cod_depositor_comments
'Adding full bibliography for 7718416--7718419.cif.'
_cod_database_code               7718417
_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.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C36(H36A,H36B), C37(H37A,H37B), C35(H35A,H35B), C38(H38A,H38B)
2.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C11(H11), C4(H4), C9(H9), C24(H24), C3(H3)
2.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C20(H20A,H20B,H20C), C33(H33A,H33B,H33C), C13(H13A,H13B,
 H13C), C15(H15A,H15B,H15C), C34(H34A,H34B,H34C), C14(H14A,H14B,H14C), C28(H28A,
 H28B,H28C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C29(H29A,H29B,H29C),
 C19(H19A,H19B,H19C), C30(H30A,H30B,H30C)
;
_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
;
_shelx_shelxl_version_number     2018/3
_smtbx_masks_special_details
;
A solvent mask was calculated and 82 electrons were 
found in a volume of 480\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
0.4[C4H8O], 0.6[C4H8O] per Asymmetric Unit 
which account for 80 electrons 
per unit cell.
;
_shelx_estimated_absorpt_t_min   0.119
_shelx_estimated_absorpt_t_max   0.582
_shelx_res_checksum              49930
_shelx_hkl_checksum              60874
_shelx_fab_checksum              21997