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_7718419
_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         'C45 H62 Bi Br N2 O2'
_chemical_formula_sum            'C45 H62 Bi Br N2 O2'
_chemical_formula_weight         951.85
_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             2023-04-01
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-04-13 deposited with the CCDC.	2025-03-25 downloaded from the CCDC.
;
_cell_angle_alpha                102.6760(10)
_cell_angle_beta                 91.5980(10)
_cell_angle_gamma                93.5020(10)
_cell_formula_units_Z            2
_cell_length_a                   9.76170(10)
_cell_length_b                   14.1831(2)
_cell_length_c                   20.8728(2)
_cell_measurement_reflns_used    44569
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      68.1770
_cell_measurement_theta_min      2.1480
_cell_volume                     2811.63(6)
_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_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            HyPix3000
_diffrn_measured_fraction_theta_full 0.997
_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   -111.00 -28.00   0.50    0.20    --  -41.33 -27.00 -15.00  166
  2  \w    -32.00  28.00   0.50    0.20    --  -41.33  27.00 146.00  120
  3  \w    -28.00  33.00   0.50    0.20    --   41.33 -27.00 -15.00  122
  4  \w     28.00 111.00   0.50    0.20    --   41.33  27.00 146.00  166
  5  \w   -152.00 -69.00   0.50    0.60    --  -82.50 -27.00 -15.00  166
  6  \w     83.00 166.00   0.50    0.60    --   96.67  27.00 146.00  166
  7  \w    -96.00 -19.00   0.50    0.20    --  -41.33 138.00 150.00  154
  8  \w    -24.00  35.00   0.50    0.20    --  -41.33  11.00-120.00  118
  9  \w   -108.00 -24.00   0.50    0.20    --  -41.33 -43.00 150.00  168
 10  \w    -24.00  35.00   0.50    0.20    --  -41.33  11.00 -60.00  118
 11  \w    -28.00  30.00   0.50    0.20    --  -41.33  21.00 -60.00  116
 12  \w    -34.00  24.00   0.50    0.20    --   41.33 -11.00 -30.00  116
 13  \w     11.00  43.00   0.50    0.20    --   41.33  88.00 -28.29   64
 14  \w      8.00  35.00   0.50    0.20    --   41.33  94.00  55.12   54
 15  \w    -26.00  65.00   0.50    0.20    --   41.33 -65.00-120.00  182
 16  \w     41.00 100.00   0.50    0.20    --   41.33-138.00-180.00  118
 17  \w     14.00  43.00   0.50    0.20    --   41.33  78.00 130.57   58
 18  \w     13.00  43.00   0.50    0.20    --   41.33  83.00 -53.02   60
 19  \w     41.00 100.00   0.50    0.20    --   41.33-138.00   0.00  118
 20  \w      8.00  35.00   0.50    0.20    --   41.33  94.00  -8.86   54
 21  \w    -34.00  24.00   0.50    0.20    --   41.33 -11.00 -90.00  116
 22  \w    -47.00 -15.00   0.50    0.60    --  -82.50  42.00 -90.00   64
 23  \w    -47.00 -15.00   0.50    0.60    --  -82.50  42.00-120.00   64
 24  \w    -47.00 -15.00   0.50    0.60    --  -82.50  42.00 -30.00   64
 25  \w    -47.00 -15.00   0.50    0.60    --  -82.50  42.00-180.00   64
 26  \w   -153.00 -78.00   0.50    0.60    --  -82.50 -87.00 -90.00  150
 27  \w    -84.00 -15.00   0.50    0.60    --  -82.50 117.00-180.00  138
 28  \w    -47.00 -15.00   0.50    0.60    --  -82.50  42.00   0.00   64
 29  \w    -47.00 -15.00   0.50    0.60    --  -82.50  42.00-150.00   64
 30  \w     29.00  83.00   0.50    0.60    --   96.67 -68.00  90.00  108
 31  \w     22.00 106.00   0.50    0.60    --   96.67 -96.00  30.00  168
 32  \w     99.00 164.00   0.50    0.60    --   96.67 117.00 120.00  130
 33  \w     44.00 127.00   0.50    0.60    --   96.67-145.00 -60.00  166
 34  \w     75.00 164.00   0.50    0.60    --   96.67  59.00  90.00  178
 35  \w     30.00  57.00   0.50    0.60    --   96.67 -50.00-150.00   54
 36  \w     44.00 127.00   0.50    0.60    --   96.67-145.00 -90.00  166
 37  \w     22.00 106.00   0.50    0.60    --   96.67 -96.00  90.00  168
 38  \w     30.00  57.00   0.50    0.60    --   96.67 -50.00 -90.00   54
 39  \w     30.00  57.00   0.50    0.60    --   96.67 -50.00  60.00   54
 40  \w     82.00 167.00   0.50    0.60    --   96.67  25.00-150.00  170
 41  \w     29.00  68.00   0.50    0.60    --   96.67 -59.00   0.00   78
 42  \w     30.00  57.00   0.50    0.60    --   96.67 -50.00 120.00   54
 43  \w     82.00 167.00   0.50    0.60    --   96.67  25.00-180.00  170
 44  \w     81.00 164.00   0.50    0.60    --   96.67 145.00 -30.00  166
 45  \w     44.00 127.00   0.50    0.60    --   96.67-145.00 120.00  166
 46  \w     29.00  83.00   0.50    0.60    --   96.67 -68.00 150.00  108
 47  \w     30.00  57.00   0.50    0.60    --   96.67 -50.00  90.00   54
 48  \w     80.00 163.00   0.50    0.60    --   96.67  42.00  60.00  166
 49  \w     82.00 167.00   0.50    0.60    --   96.67  25.00 -60.00  170
 50  \w     22.00 106.00   0.50    0.60    --   96.67 -96.00   0.00  168
 51  \w     44.00 127.00   0.50    0.60    --   96.67-145.00  30.00  166
 52  \w     44.00 127.00   0.50    0.60    --   96.67-145.00 150.00  166
 53  \w     30.00  57.00   0.50    0.60    --   96.67 -50.00-180.00   54
 54  \w     28.00 105.00   0.50    0.60    --   96.67 -77.00 120.00  154
 55  \w     30.00  57.00   0.50    0.60    --   96.67 -50.00 150.00   54
 56  \w     29.00  68.00   0.50    0.60    --   96.67 -59.00-150.00   78
 57  \w     44.00 127.00   0.50    0.60    --   96.67-145.00-180.00  166
 58  \w     44.00 127.00   0.50    0.60    --   96.67-145.00 -30.00  166
 59  \w     82.00 167.00   0.50    0.60    --   96.67  25.00 120.00  170
 60  \w     29.00  68.00   0.50    0.60    --   96.67 -59.00 -90.00   78
 61  \w    105.00 170.00   0.50    0.60    --   96.67  96.00   0.00  130
 62  \w     29.00  68.00   0.50    0.60    --   96.67 -59.00 -60.00   78
 63  \w     22.00 106.00   0.50    0.60    --   96.67 -96.00 -60.00  168
 64  \w   -108.00 -21.00   0.50    0.20    --  -41.33 -54.00 -60.00  174
 65  \w   -109.00 -18.00   0.50    0.20    --  -41.33 -65.00-120.00  182
 66  \w   -110.00 -14.00   0.50    0.20    --  -41.33 -77.00 120.00  192
 67  \w   -110.00 -17.00   0.50    0.20    --  -41.33 -67.00  62.32  186
 68  \w   -108.00 -24.00   0.50    0.20    --  -41.33 -43.00 -90.00  168
 69  \w   -110.00 -14.00   0.50    0.20    --  -41.33 -77.00-180.00  192
 70  \w   -108.00 -21.00   0.50    0.20    --  -41.33 -54.00  90.00  174
 71  \w   -109.00 -18.00   0.50    0.20    --  -41.33 -65.00   0.00  182
 72  \w    -37.00  27.00   0.50    0.20    --  -41.33  32.00  30.00  128
 73  \w    -79.00   4.00   0.50    0.20    --  -41.33 104.00  60.00  166
 74  \w     14.00  43.00   0.50    0.20    --   41.33  80.00-169.91   58
 75  \w    -30.00  28.00   0.50    0.20    --   41.33 -21.00  60.00  116
 76  \w     13.00  43.00   0.50    0.20    --   41.33  83.00 -93.80   60
 77  \w      9.00  35.00   0.50    0.20    --   41.33  93.00 124.92   52
 78  \w      8.00  35.00   0.50    0.20    --   41.33  94.00-116.07   54
 79  \w     12.00  43.00   0.50    0.20    --   41.33  86.00 159.28   62
 80  \w     15.00 110.00   0.50    0.20    --   41.33  77.00-120.00  190
 81  \w      9.00  42.00   0.50    0.20    --   41.33  92.00-103.43   66
 82  \w     12.00  43.00   0.50    0.20    --   41.33  86.00  86.52   62
 83  \w     13.00  43.00   0.50    0.20    --   41.33  82.00  29.19   60
 84  \w   -151.00 -55.00   0.50    0.60    --  -82.50 -77.00 -30.00  192
 85  \w   -151.00 -55.00   0.50    0.60    --  -82.50 -77.00-103.63  192
 86  \w   -151.00 -56.00   0.50    0.60    --  -82.50 -74.00  44.85  190
 87  \w   -151.00 -55.00   0.50    0.60    --  -82.50 -77.00 110.14  192
 88  \w   -151.00 -55.00   0.50    0.60    --  -82.50 -77.00 150.00  192
 89  \w   -151.00 -55.00   0.50    0.60    --  -82.50 -77.00-150.00  192
 90  \w   -151.00 -55.00   0.50    0.60    --  -82.50 -77.00-180.00  192
 91  \w   -151.00 -55.00   0.50    0.60    --  -82.50 -77.00  90.00  192
 92  \w   -151.00 -55.00   0.50    0.60    --  -82.50 -77.00  11.01  192
 93  \w     73.00 165.00   0.50    0.60    --   96.67  68.00   0.00  184
 94  \w     70.00 165.00   0.50    0.60    --   96.67  75.00 -80.51  190
 95  \w     78.00 163.00   0.50    0.60    --   96.67  50.00-120.00  170
 96  \w     75.00 164.00   0.50    0.60    --   96.67  59.00 -30.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0624878000
_diffrn_orient_matrix_UB_12      0.1048828000
_diffrn_orient_matrix_UB_13      0.0101567000
_diffrn_orient_matrix_UB_21      0.1371830000
_diffrn_orient_matrix_UB_22      -0.0312063000
_diffrn_orient_matrix_UB_23      0.0240350000
_diffrn_orient_matrix_UB_31      0.0481707000
_diffrn_orient_matrix_UB_32      -0.0219221000
_diffrn_orient_matrix_UB_33      -0.0710805000
_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  0.0801
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            63630
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.214
_diffrn_reflns_theta_min         3.201
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.194
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.22531
_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    1.124
_exptl_crystal_description       plate
_exptl_crystal_F_000             960
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.310
_refine_diff_density_min         -1.241
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     458
_refine_ls_number_reflns         10196
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0424
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0759P)^2^+1.6141P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1127
_refine_ls_wR_factor_ref         0.1143
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9513
_reflns_number_total             10196
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00706b2.cif
_cod_data_source_block           sg329_new23dec
_cod_depositor_comments
'Adding full bibliography for 7718416--7718419.cif.'
_cod_database_code               7718419
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O Bi Br Si'
_chemical_oxdiff_usercomment     100K
_shelx_estimated_absorpt_t_max   0.715
_shelx_estimated_absorpt_t_min   0.156
_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(C44) = Uanis(C45) = Uanis(C43)
Uanis(C42) = Uanis(C44) = Uanis(C43) = Uanis(C45)
3.a Ternary CH refined with riding coordinates:
 C1(H1), C26(H26), C29(H29)
3.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C11(H11), C9(H9), C37(H37), C4(H4), C24(H24), C22(H22), C23(H23),
 C35(H35)
3.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C15(H15A,H15B,H15C), C30(H30A,H30B,H30C), C13(H13A,H13B,
 H13C), C39(H39A,H39B,H39C), C31(H31A,H31B,H31C), C40(H40A,H40B,H40C), C14(H14A,
 H14B,H14C), C28(H28A,H28B,H28C), C27(H27A,H27B,H27C), C19(H19A,H19B,H19C),
 C17(H17A,H17B,H17C), C41(H41A,H41B,H41C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C45(H45A,H45B,H45C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 201 electrons were 
found in a volume of 938\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C6H14] per Asymmetric Unit 
which account for 200 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              58785
_shelx_hkl_checksum              89032
_shelx_fab_checksum              79766
_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 3.841
_oxdiff_exptl_absorpt_empirical_full_min 0.578