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_7718418
_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         'C90 H122 Bi2 Br4 N8 O2, 2(C7 H8)'
_chemical_formula_sum            'C104 H138 Bi2 Br4 N8 O2'
_chemical_formula_weight         2269.82
_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     iterative
_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                90
_cell_angle_beta                 102.8870(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.7082(2)
_cell_length_b                   19.7308(2)
_cell_length_c                   18.4697(2)
_cell_measurement_reflns_used    40681
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      68.1230
_cell_measurement_theta_min      3.2800
_cell_volume                     5224.98(11)
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_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    -75.00  28.00   0.50    1.40    --  -40.33  98.00-168.00  206
  2  \w     -6.00  75.00   0.50    1.40    --   40.33 -98.00  84.00  162
  3  \w    -81.00  -9.00   0.50    5.61    --  -82.50  98.00-168.00  144
  4  \w     23.00 106.00   0.50    5.61    --   96.67 -98.00  84.00  166
  5  \w    106.00 170.00   0.50    5.61    --   96.67  98.00-168.00  128
  6  \w    -31.00  30.00   0.50    1.40    --  -40.33  25.00-180.00  122
  7  \w    -43.00  26.00   0.50    1.40    --  -40.33  38.00-150.00  138
  8  \w   -106.00 -25.00   0.50    1.40    --  -40.33 -38.00-120.00  162
  9  \w    -56.00  26.00   0.50    1.40    --  -40.33  50.00  60.00  164
 10  \w    -31.00  30.00   0.50    1.40    --  -40.33  25.00 120.00  122
 11  \w    -24.00  35.00   0.50    1.40    --  -40.33  12.00  90.00  118
 12  \w    -96.00 -19.00   0.50    1.40    --  -40.33 138.00-180.00  154
 13  \w    -24.00  35.00   0.50    1.40    --  -40.33  12.00-150.00  118
 14  \w    -35.00  24.00   0.50    1.40    --   40.33 -12.00 -60.00  118
 15  \w    -47.00 -15.00   0.50    5.61    --  -82.50  42.00 -30.00   64
 16  \w    -47.00 -15.00   0.50    5.61    --  -82.50  42.00 -60.00   64
 17  \w   -153.00 -78.00   0.50    5.61    --  -82.50 -87.00 -30.00  150
 18  \w   -156.00 -85.00   0.50    5.61    --  -82.50 -98.00  84.00  142
 19  \w   -156.00 -58.00   0.50    5.61    --  -82.50 -17.00 120.00  196
 20  \w    -47.00 -15.00   0.50    5.61    --  -82.50  42.00  30.00   64
 21  \w   -157.00 -83.00   0.50    5.61    --  -82.50 -96.00  90.00  148
 22  \w     30.00 109.00   0.50    5.61    --   96.67-117.00-120.00  158
 23  \w     22.00 106.00   0.50    5.61    --   96.67 -96.00  30.00  168
 24  \w     78.00 163.00   0.50    5.61    --   96.67  50.00 -60.00  170
 25  \w     44.00 127.00   0.50    5.61    --   96.67-145.00-120.00  166
 26  \w     30.00  57.00   0.50    5.61    --   96.67 -50.00  90.00   54
 27  \w     29.00  68.00   0.50    5.61    --   96.67 -59.00 -60.00   78
 28  \w     83.00 164.00   0.50    5.61    --   96.67  33.00 -90.00  162
 29  \w     29.00  68.00   0.50    5.61    --   96.67 -59.00-150.00   78
 30  \w     30.00  57.00   0.50    5.61    --   96.67 -50.00 -90.00   54
 31  \w     29.00  83.00   0.50    5.61    --   96.67 -68.00 120.00  108
 32  \w     30.00  57.00   0.50    5.61    --   96.67 -50.00 120.00   54
 33  \w    105.00 170.00   0.50    5.61    --   96.67  96.00-150.00  130
 34  \w     29.00  83.00   0.50    5.61    --   96.67 -68.00  90.00  108
 35  \w     99.00 164.00   0.50    5.61    --   96.67 117.00 120.00  130
 36  \w     28.00 105.00   0.50    5.61    --   96.67 -77.00 -90.00  154
 37  \w     29.00  68.00   0.50    5.61    --   96.67 -59.00  60.00   78
 38  \w     30.00  57.00   0.50    5.61    --   96.67 -50.00 150.00   54
 39  \w     99.00 164.00   0.50    5.61    --   96.67 117.00 150.00  130
 40  \w   -109.00 -13.00   0.50    1.40    --  -40.33 -77.00-150.00  192
 41  \w    -31.00  30.00   0.50    1.40    --  -40.33  25.00   0.00  122
 42  \w   -108.00 -17.00   0.50    1.40    --  -40.33 -64.00  90.00  182
 43  \w   -109.00 -13.00   0.50    1.40    --  -40.33 -77.00-120.00  192
 44  \w   -109.00 -13.00   0.50    1.40    --  -40.33 -77.00 -60.00  192
 45  \w   -109.00 -13.00   0.50    1.40    --  -40.33 -77.00  30.00  192
 46  \w   -109.00 -13.00   0.50    1.40    --  -40.33 -77.00-180.00  192
 47  \w     21.00 107.00   0.50    1.40    --   40.33  50.00  60.00  172
 48  \w     14.00 109.00   0.50    1.40    --   40.33  77.00  90.00  190
 49  \w     14.00 109.00   0.50    1.40    --   40.33  77.00   0.00  190
 50  \w     14.00 109.00   0.50    1.40    --   40.33  77.00 -30.00  190
 51  \w     14.00 109.00   0.50    1.40    --   40.33  77.00-180.00  190
 52  \w     70.00 144.00   0.50    5.61    --   96.67  77.00-180.00  148
 53  \w     70.00 165.00   0.50    5.61    --   96.67  77.00  60.00  190
 54  \w     80.00 163.00   0.50    5.61    --   96.67  42.00   0.00  166
;
_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  0.0592
_diffrn_reflns_av_unetI/netI     0.0300
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            66659
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.303
_diffrn_reflns_theta_min         3.323
_exptl_absorpt_coefficient_mu    8.698
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67806
_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    1.443
_exptl_crystal_description       block
_exptl_crystal_F_000             2280
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         4.418
_refine_diff_density_min         -1.848
_refine_diff_density_rms         0.154
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     508
_refine_ls_number_reflns         9506
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0490
_refine_ls_R_factor_gt           0.0447
_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^)+(0.0776P)^2^+18.8683P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1181
_refine_ls_wR_factor_ref         0.1227
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8614
_reflns_number_total             9506
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00706b2.cif
_cod_data_source_block           sg_356_23decnew
_cod_depositor_comments
'Adding full bibliography for 7718416--7718419.cif.'
_cod_database_code               7718418
_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. Uiso/Uaniso restraints and constraints
Uanis(C12) = Uanis(C13) = Uanis(C11) = Uanis(C14)
Uanis(C15) = Uanis(C17) = Uanis(C16) = Uanis(C18)
Uanis(C44) = Uanis(C43) = Uanis(C45)
3.a Ternary CH refined with riding coordinates:
 C25(H25), C40(H40), C28(H28), C43(H43)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
3.c Aromatic/amide H refined with riding coordinates:
 C31(H31), C33(H33), C2(H2), C32(H32), C10(H10), C3(H3), C21(H21), C8(H8),
 C23(H23), C37(H37), C36(H36), C38(H38), C22(H22), C51(H51), C47(H47), C50(H50),
  C49(H49), C48(H48)
3.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C26(H26A,H26B,
 H26C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C29(H29A,H29B,H29C), C27(H27A,
 H27B,H27C), C30(H30A,H30B,H30C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C),
 C17(H17A,H17B,H17C), C52(H52A,H52B,H52C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C)
;
_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
_shelx_estimated_absorpt_t_min   0.376
_shelx_estimated_absorpt_t_max   0.670
_shelx_res_checksum              8772
_shelx_hkl_checksum              40432