Synthesis of symmetrical and unsymmetrical cyclic diborenes via NHC-directed C–H borylation
Mihm, Cornelius; Kar, Sourav; Sachs, Andreas; Duwe, Dario; Dewhurst, Rian D.; Braunschweig, Holger; Chemical Science 16 (2025) 11637–11643; doi:10.1039/D5SC03150H

data_1574723
_publ_section_title
;
 Synthesis of symmetrical and unsymmetrical cyclic diborenes via
 NHC-directed C--H borylation
;
_journal_issue                   25
_journal_name_full               'Chemical Science'
_journal_page_first              11637
_journal_page_last               11643
_journal_paper_doi               10.1039/D5SC03150H
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C31 H43 B N4'
_chemical_formula_sum            'C31 H43 B N4'
_chemical_formula_weight         482.50
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-11-04
_audit_creation_method           'CIF-fill 1.5k (K.Radacki, 2005-24)'
_audit_update_record
;
2025-04-29 deposited with the CCDC.	2025-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                97.5520(10)
_cell_angle_beta                 101.3590(10)
_cell_angle_gamma                101.8450(10)
_cell_formula_units_Z            4
_cell_length_a                   14.1122(2)
_cell_length_b                   14.2169(2)
_cell_length_c                   16.8130(2)
_cell_measurement_reflns_used    33549
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.8140
_cell_measurement_theta_min      3.2020
_cell_volume                     3184.39(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.89a (Rigaku OD, 2023)'
_computing_data_collection
;
 CrysAlisPro system (CCD 42.102a 64-bit (release 15-09-2023))
;
_computing_data_reduction        'CrysAlisPro 1.171.43.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'ShelXLe (Huebschle et all, 2011)'
_computing_publication_material  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 HPA
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HyPix Arc150'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details
;
 List of Runs (angles in degrees, time in seconds):
 --------------------------------------------------------------------------
  1  \w     40.00  90.00   0.50    0.10    --   82.26 -95.00  60.00  100
  2  \w   -107.00 -72.00   0.50    0.10    --  -58.00 -50.00 -52.68   70
  3  \w     61.00  90.00   0.50    0.10    --   85.25 -96.00  96.24   58
  4  \w   -128.00 -90.00   0.50    0.10    --  -78.00 -42.00-153.80   76
  5  \w   -117.00 -77.00   0.50    0.10    --  -66.00 -38.00 154.87   80
  6  \w     40.00  96.00   0.50    0.10    --   85.25-118.00 -75.08  112
  7  \w     72.00  99.00   0.50    0.10    --   85.25-121.00-106.67   54
  8  \w     56.00  90.00   0.50    0.10    --   82.26-112.00  30.00   68
  9  \w   -124.00 -92.00   0.50    0.10    --  -79.50 -63.00 104.40   64
 10  \w     41.00  66.00   0.50    0.10    --   85.25-137.00 179.20   50
 11  \w     40.00  72.00   0.50    0.10    --   85.25-123.00 119.05   64
 12  \w    -99.00 -64.00   0.50    0.10    --  -50.00 -47.00 -20.35   70
 13  \w     53.00  93.00   0.50    0.10    --   82.26-112.00-150.00   80
 14  \w   -101.00 -61.00   0.50    0.10    --  -50.00 -39.00  82.57   80
 15  \w     54.00  92.00   0.50    0.10    --   85.25 -94.00 169.09   76
 16  \w   -107.00 -72.00   0.50    0.10    --  -58.00 -49.00 -92.27   70
 17  \w    -92.00 -35.00   0.50    0.10    --  -79.50 102.00 -80.51  114
 18  \w     52.00  93.00   0.50    0.10    --   85.25 -98.00 -71.15   82
 19  \w     37.00  63.00   0.50    0.10    --   82.26-112.00-180.00   52
 20  \w     59.00  91.00   0.50    0.10    --   85.25 -92.00 -31.21   64
 21  \w     44.00  93.00   0.50    0.10    --   85.25 -97.00-113.95   98
 22  \w     44.00  85.00   0.50    0.10    --   85.25-100.00 133.25   82
 23  \w     41.00  66.00   0.50    0.10    --   82.26-112.00 120.00   50
 24  \w     45.00  91.00   0.50    0.10    --   85.25 -92.00 140.66   92
 25  \w   -106.00 -71.00   0.50    0.10    --  -58.00 -52.00-129.58   70
 26  \w   -127.00 -89.00   0.50    0.10    --  -79.50-128.00  21.23   76
 27  \w    -98.00 -32.00   0.50    0.10    --  -79.50 120.00-178.98  132
 28  \w     32.00  98.00   0.50    0.10    --   78.00-115.00 129.33  132
 29  \w     39.00  67.00   0.50    0.10    --   85.25-133.00   3.34   56
 30  \w     35.00 100.00   0.50    0.10    --   82.00-127.00 -71.44  130
 31  \w     46.00 133.00   0.50    0.10    --   82.26  15.00  60.00  174
 32  \w   -125.00 -91.00   0.50    0.10    --  -79.50 -61.00  -9.83   68
 33  \w     37.00  93.00   0.50    0.10    --   82.26-112.00 -30.00  112
 34  \w     43.00  92.00   0.50    0.10    --   85.25 -99.00   0.39   98
 35  \w   -125.00 -94.00   0.50    0.10    --  -79.50-119.00 158.47   62
 36  \w     42.00  92.00   0.50    0.10    --   85.25-100.00  36.88  100
 37  \w   -126.00 -96.00   0.50    0.10    --  -79.50-116.00 -59.20   60
 38  \w     29.00  79.00   0.50    0.10    --   71.26 -95.00-180.00  100
 39  \w     38.00  68.00   0.50    0.10    --   85.25-121.00-106.67   60
 40  \w    100.00 131.00   0.50    0.10    --   85.25  47.00-158.26   62
 41  \w    -91.00 -28.00   0.50    0.10    --  -74.00 110.00 -20.20  126
 42  \w     40.00  99.00   0.50    0.10    --   85.25-136.00 107.15  118
 43  \w   -103.00 -68.00   0.50    0.10    --  -54.00 -50.00  30.98   70
 44  \w     98.00 133.00   0.50    0.10    --   85.25  40.00 -75.03   70
 45  \w     91.00 133.00   0.50    0.10    --   82.26  15.00 120.00   84
 46  \w     75.00 136.00   0.50    0.10    --   85.25  20.00 161.10  122
 47  \w     46.00  71.00   0.50    0.10    --   85.25 -78.00 -57.22   50
 48  \w    104.00 130.00   0.50    0.10    --   85.25  62.00  26.24   52
 49  \w    102.00 130.00   0.50    0.10    --   85.25  50.00 174.58   56
 50  \w    110.00 136.00   0.50    0.10    --   85.25  40.00  68.45   52
 51  \w     98.00 124.00   0.50    0.10    --   85.25  40.00 -50.59   52
 52  \w     46.00 133.00   0.50    0.10    --   82.26  15.00-120.00  174
 53  \w     69.00 136.00   0.50    0.10    --   85.25  18.00  41.33  134
 54  \w     97.00 131.00   0.50    0.10    --   82.26  15.00 -90.00   68
 55  \w     49.00  75.00   0.50    0.10    --   85.25 -79.00-173.95   52
 56  \w     48.00  74.00   0.50    0.10    --   85.25 -79.00  22.55   52
 57  \w    105.00 130.00   0.50    0.10    --   82.26  15.00-150.00   50
 58  \w    100.00 125.00   0.50    0.10    --   85.25 120.00 106.57   50
 59  \w    101.00 127.00   0.50    0.10    --   82.26  15.00 -60.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-R'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
;
 CrysAlisPro convention (1999,Acta A55,543-557)
;
_diffrn_orient_matrix_UB_11      -0.0783706000
_diffrn_orient_matrix_UB_12      -0.0009188000
_diffrn_orient_matrix_UB_13      0.0522071000
_diffrn_orient_matrix_UB_21      0.0452069000
_diffrn_orient_matrix_UB_22      -0.0704166000
_diffrn_orient_matrix_UB_23      0.0494808000
_diffrn_orient_matrix_UB_31      0.0703965000
_diffrn_orient_matrix_UB_32      0.0877813000
_diffrn_orient_matrix_UB_33      0.0620512000
_diffrn_radiation_monochromator  'multi-layer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0504
_diffrn_reflns_av_unetI/netI     0.0362
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            63837
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.477
_diffrn_reflns_theta_min         2.725
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet-R X-ray Source'
_exptl_absorpt_coefficient_mu    0.446
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.823
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
 CrysAlisPro 1.171.43.89a (Rigaku Oxford Diffraction, 2023) Numerical 
 absorption correction based on gaussian integration over a multifaceted 
 crystal model Empirical absorption correction using spherical harmonics, 
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.006
_exptl_crystal_description       plate
_exptl_crystal_F_000             1048
_exptl_crystal_preparation
;
 For data collection the crystal was immersed in a film of perfluoropolyether 
 oil, mounted on a polyimide loop and transferred to stream of cold nitrogen 
 (Oxford Cryostream 800).
;
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.050
_refine_diff_density_max         0.293
_refine_diff_density_min         -0.350
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     667
_refine_ls_number_reflns         12833
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.0680
_refine_ls_R_factor_gt           0.0530
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0819P)^2^+0.8971P] where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1428
_refine_ls_wR_factor_ref         0.1602
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10012
_reflns_number_total             12833
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03150h2.cif
_cod_data_source_block           borylene_6
_cod_depositor_comments
'Adding full bibliography for 1574720--1574725.cif.'
_cod_database_code               1574723
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.924
_shelx_estimated_absorpt_t_max   0.978
_shelx_res_checksum              72
_shelx_fab_checksum              81237