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_7718416
_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         'C36 H59 Bi Br N3 O Si2, 2(C7 H8)'
_chemical_formula_sum            'C50 H75 Bi Br N3 O0.99 Si2'
_chemical_formula_weight         1079.02
_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     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                 95.7800(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.4928(3)
_cell_length_b                   14.7259(2)
_cell_length_c                   34.2124(6)
_cell_measurement_reflns_used    26784
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      68.1450
_cell_measurement_theta_min      2.5840
_cell_volume                     10272.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.21a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.42.21a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.42.21a (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 0.994
_diffrn_measured_fraction_theta_max 0.984
_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    3.22    --  -41.33 -27.00  33.00  166
  2  \w    -32.00  28.00   0.50    3.22    --  -41.33  27.00-163.00  120
  3  \w    -28.00  33.00   0.50    3.22    --   41.33 -27.00  33.00  122
  4  \w     85.00 123.00   0.50   12.88    --   96.67  59.00-120.00   76
  5  \w   -152.00 -69.00   0.50   12.88    --  -82.50 -27.00  33.00  166
  6  \w     83.00 166.00   0.50   12.88    --   96.67  27.00-163.00  166
  7  \w    -61.00  26.00   0.50    3.22    --  -41.33  54.00-120.00  174
  8  \w    -79.00   4.00   0.50    3.22    --  -41.33 104.00 -30.00  166
  9  \w    -37.00  27.00   0.50    3.22    --  -41.33  32.00 -90.00  128
 10  \w    -28.00  30.00   0.50    3.22    --  -41.33  21.00-180.00  116
 11  \w     18.00 109.00   0.50    3.22    --   41.33  65.00   0.00  182
 12  \w     21.00 108.00   0.50    3.22    --   41.33  54.00 -60.00  174
 13  \w     41.00 100.00   0.50    3.22    --   41.33-138.00 120.00  118
 14  \w     41.00 100.00   0.50    3.22    --   41.33-138.00-180.00  118
 15  \w    -47.00 -15.00   0.50   12.88    --  -82.50  42.00-120.00   64
 16  \w    -47.00 -15.00   0.50   12.88    --  -82.50  42.00-180.00   64
 17  \w    -80.00  -9.00   0.50   12.88    --  -82.50  96.00-150.00  142
 18  \w    -47.00 -15.00   0.50   12.88    --  -82.50  42.00 -30.00   64
 19  \w     99.00 164.00   0.50   12.88    --   96.67 117.00  90.00  130
 20  \w     99.00 164.00   0.50   12.88    --   96.67 117.00   0.00  130
 21  \w     29.00  68.00   0.50   12.88    --   96.67 -59.00 -90.00   78
 22  \w     75.00 164.00   0.50   12.88    --   96.67  59.00 -90.00  178
 23  \w     85.00 164.00   0.50   12.88    --   96.67  59.00-120.00  158
 24  \w    135.00 164.00   0.50   12.88    --   96.67  59.00-120.00   58
 25  \w     31.00  57.00   0.50   12.88    --   96.67 -50.00 -30.00   52
 26  \w     53.00 127.00   0.50   12.88    --   96.67-145.00  30.00  148
 27  \w    116.00 142.00   0.50   12.88    --   96.67 117.00  30.00   52
 28  \w     80.00 121.00   0.50   12.88    --   96.67  42.00 150.00   82
 29  \w    136.00 162.00   0.50   12.88    --   96.67  42.00 150.00   52
 30  \w     35.00 105.00   0.50   12.88    --   96.67 -77.00-180.00  140
 31  \w     87.00 144.00   0.50   12.88    --   96.67  33.00 -30.00  114
 32  \w    114.00 159.00   0.50   12.88    --   96.67 117.00-150.00   90
 33  \w     90.00 160.00   0.50   12.88    --   96.67  59.00-150.00  140
 34  \w     30.00  55.00   0.50   12.88    --   96.67 -50.00-120.00   50
 35  \w     30.00  56.00   0.50   12.88    --   96.67 -50.00  30.00   52
 36  \w     31.00  63.00   0.50   12.88    --   96.67 -59.00  90.00   64
 37  \w     40.00  82.00   0.50   12.88    --   96.67 -68.00-120.00   84
;
_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  0.0649
_diffrn_reflns_av_unetI/netI     0.0509
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            71954
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.418
_diffrn_reflns_theta_min         2.167
_exptl_absorpt_coefficient_mu    8.365
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51477
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.21a (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    1.395
_exptl_crystal_description       block
_exptl_crystal_F_000             4399
_exptl_crystal_size_max          0.523
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.07
_refine_diff_density_max         10.766
_refine_diff_density_min         -4.153
_refine_diff_density_rms         0.333
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1082
_refine_ls_number_reflns         18574
_refine_ls_number_restraints     1604
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.1109
_refine_ls_R_factor_gt           0.0957
_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^)+(0.1484P)^2^+285.2774P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2617
_refine_ls_wR_factor_ref         0.2740
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14414
_reflns_number_total             18574
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00706b2.cif
_cod_data_source_block           sg-330
_cod_depositor_comments
'Adding full bibliography for 7718416--7718419.cif.'
_cod_database_code               7718416
_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
O1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
All non-hydrogen atoms have similar U: within 2A with sigma of 0.002 and sigma
for terminal atoms of 0.004 within 2A
3. Rigid body (RIGU) restrains
 O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4.a Ternary CH refined with riding coordinates:
 C00Z(H00Z), C012(H012), C016(H016), C01N(H01N)
4.b Secondary CH2 refined with riding coordinates:
 C00O(H00A,H00B), C01D(H01,H)
4.c Aromatic/amide H refined with riding coordinates:
 C00J(H00J), C00L(H00L), C00P(H00P), C00T(H00T), C00U(H00U), C013(H013),
 C017(H017), C01A(H01Z), C01J(H1), C01L(H3), C01M(H4), C01V(H01V), C029(H029),
 C02E(H12), C02G(H15), C02H(H20), C02I(H16), C02L(H21), C02M(H25), C02N(H22),
 C02O(H23), C02Q(H17), C02R(H27), C02S(H26), C02T(H28), C02U(H24), C02Y(H19),
 C031(H031), C032(H032), C033(H033), C034(H034), C035(H035), C039(H039),
 C03A(H03J)
4.d Idealised Me refined as rotating group:
 C00S(H00C,H00D,H00E), C00X(H00F,H00G,H00H), C00Y(H00I,H00K,H00M), C018(H01A,
 H01B,H01C), C01E(H01D,H01E,H01F), C01H(H01G,H01H,H01I), C01I(H01J,H01K,H01L),
 C01K(H2,HA,HB), C01O(H5,HC,HD), C01Q(H6,HE,HF), C01S(H7,HG,HH), C01T(H01M,H01O,
 H01P), C01U(H01Q,H01R,H01S), C01W(H01T,H01U,H01W), C01X(H01X,H01Y,HI), C01Y(H8,
 HJ,HK), C020(H02S,H02T,H02U), C021(H02V,H02W,H02X), C023(H02A,H02B,H02C),
 C024(H02D,H02E,H02F), C025(H02Y,HL,HM), C026(H02G,H02H,H02I), C027(H02Z,HN,HO),
  C028(H02,HP,HQ), C02A(H02J,H02K,H02L), C02B(H9,HR,HS), C02C(H10,HT,HU),
 C02D(H11,HV,HW), C02F(H02M,H02N,H02O), C02J(H13,HX,HY), C02K(H02P,H02Q,H02R),
 C02W(H14,HZ,H29), C02X(H18,H30,H31), C030(H03A,H03B,H03C), C037(H03G,H03H,
 H03I), C038(H03D,H03E,H03F)
;
_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   0.097
_shelx_estimated_absorpt_t_max   0.592
_shelx_res_checksum              18560
_shelx_hkl_checksum              5857