Cyclic Alkyl(amino)iminates (CAAIs) as Strong 2σ,4π-Electron Donor Ligands for the Stabilisation of Boranes and Diboranes(4): A Synthetic and Computational Study
Huynh, Silvia; Arrowsmith, Merle; Meier, Lukas; Dietz, Maximilian; Härterich, Marcel; Michel, Maximilian; Gärtner, Annalena; Braunschweig, Holger; Dalton Transactions  (2023) –; doi:10.1039/D3DT00298E

data_7712434
_publ_section_title
;
 Cyclic Alkyl(amino)iminates (CAAIs) as Strong 2\s,4\p-Electron Donor
 Ligands for the Stabilisation of Boranes and Diboranes(4): A Synthetic
 and Computational Study
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00298E
_journal_year                    2023
_chemical_formula_moiety         'C40 H62 B Br N4'
_chemical_formula_sum            'C40 H62 B Br N4'
_chemical_formula_weight         689.65
_chemical_name_systematic        (CAAI)2BBr
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           'CIF-fill 1.2x (K.Radacki, 2005-21)'
_audit_update_record
;
2023-01-19 deposited with the CCDC.	2023-02-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.2800(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.55970(10)
_cell_length_b                   9.60350(10)
_cell_length_c                   21.56940(10)
_cell_measurement_reflns_used    34017
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.4330
_cell_measurement_theta_min      4.1270
_cell_volume                     1974.69(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.96a (Rigaku OD, 2021)'
_computing_data_collection       'BIS 2011.8 / APEX2 ver. 2014.9 (Bruker AXS)'
_computing_data_reduction        'CrysAlisPro 1.171.41.96a (Rigaku OD, 2021)'
_computing_molecular_graphics    'ShelXLe (Huebschle et all, 2011)'
_computing_publication_material  'SHELXL-2017/1 (Sheldrick, 2017)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_computing_structure_solution    'SHELXT (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 HPA
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HyPix Arc150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     58.00  89.00   0.50    0.05    --   42.00  50.00-138.16   62
   2  \w    102.00 128.00   0.50    0.05    --   83.50  50.00 -48.02   52
   3  \w     58.00  88.00   0.50    0.05    --   42.00  52.00  26.79   60
   4  \w     54.00 129.00   0.50    0.05    --   80.41  15.00 -60.00  150
   5  \w     40.00  86.00   0.50    0.05    --   80.41 -95.00  90.00   92
   6  \w     35.00  97.00   0.50    0.05    --   80.41-112.00  60.00  124
   7  \w     37.00  66.00   0.50    0.05    --   80.41-112.00  30.00   58
   8  \w     35.00  69.00   0.50    0.05    --   80.41-112.00 -30.00   68
   9  \w     35.00  97.00   0.50    0.05    --   80.41-112.00 -90.00  124
  10  \w     35.00  97.00   0.50    0.05    --   80.41-112.00-150.00  124
  11  \w     50.00  97.00   0.50    0.05    --   80.41-112.00-180.00   94
  12  \w     20.00  87.00   0.50    0.05    --   61.21-126.00-180.00  134
  13  \w     40.00  86.00   0.50    0.05    --   80.41 -95.00  60.00   92
  14  \w    -94.00 -30.00   0.50    0.05    --  -76.35 112.00  30.00  128
  15  \w    -88.00 -16.00   0.50    0.05    --  -62.16 126.00  30.00  144
  16  \w   -102.00 -34.00   0.50    0.05    --  -79.50 129.00  61.06  136
  17  \w    -94.00 -30.00   0.50    0.05    --  -76.35 112.00  60.00  128
  18  \w    -98.00 -26.00   0.50    0.05    --  -72.80 126.00  90.00  144
  19  \w    -98.00 -26.00   0.50    0.05    --  -72.80 126.00  30.00  144
  20  \w    -88.00 -16.00   0.50    0.05    --  -62.16 126.00 -60.00  144
  21  \w    -98.00 -26.00   0.50    0.05    --  -72.80 126.00-150.00  144
  22  \w    -94.00 -30.00   0.50    0.05    --  -76.35 112.00-180.00  128
  23  \w    -94.00 -30.00   0.50    0.05    --  -76.35 112.00-150.00  128
  24  \w    -94.00 -30.00   0.50    0.05    --  -76.35 112.00  90.00  128
  25  \w   -123.00 -93.00   0.50    0.05    --  -79.50 -63.00  85.99   60
  26  \w   -123.00 -93.00   0.50    0.05    --  -79.50 -60.00 111.75   60
  27  \w   -123.00 -93.00   0.50    0.05    --  -79.50 -61.00 108.37   60
  28  \w   -122.00 -91.00   0.50    0.05    --  -78.00 -61.00 101.38   62
  29  \w   -119.00 -88.00   0.50    0.05    --  -74.00 -57.00 172.53   62
  30  \w   -115.00 -85.00   0.50    0.05    --  -70.00 -55.00 119.25   60
  31  \w   -124.00 -94.00   0.50    0.05    --  -79.50 -57.00  83.44   60
  32  \w   -125.00 -94.00   0.50    0.05    --  -79.50 -55.00  87.87   62
  33  \w   -125.00 -94.00   0.50    0.05    --  -79.50 -56.00  85.59   62
  34  \w   -125.00 -95.00   0.50    0.05    --  -79.50 -54.00  22.19   60
  35  \w   -118.00 -88.00   0.50    0.05    --  -74.00 -59.00  -8.93   60
  36  \w   -104.00 -73.00   0.50    0.05    --  -58.00 -52.00 -68.61   62
  37  \w   -115.00 -85.00   0.50    0.05    --  -70.00 -58.00 -33.38   60
  38  \w   -104.00 -74.00   0.50    0.05    --  -58.00 -51.00   2.88   60
  39  \w   -108.00 -78.00   0.50    0.05    --  -62.00 -51.00 -16.14   60
  40  \w    -90.00 -57.00   0.50    0.05    --  -42.00 -44.00  17.62   66
  41  \w   -126.00 -96.00   0.50    0.05    --  -79.50 -49.00   6.48   60
  42  \w   -129.00 -92.00   0.50    0.05    --  -79.50 -30.00 -74.15   74
  43  \w   -128.00 -94.00   0.50    0.05    --  -79.50 -41.00 -85.59   68
  44  \w   -110.00 -42.00   0.50    0.05    --  -62.16 -15.00-180.00  136
  45  \w   -127.00 -95.00   0.50    0.05    --  -79.50 -48.00  37.40   64
  46  \w   -128.00 -94.00   0.50    0.05    --  -79.50 -43.00  50.43   68
  47  \w   -129.00 -71.00   0.50    0.05    --  -79.50 -20.00 156.50  116
  48  \w   -126.00 -95.00   0.50    0.05    --  -79.50 -50.00 158.61   62
  49  \w   -126.00 -90.00   0.50    0.05    --  -79.50-126.00 151.27   72
  50  \w   -123.00 -83.00   0.50    0.05    --  -79.50-140.00  36.47   80

;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-R'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  'multi-layer mirror'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0362
_diffrn_reflns_av_unetI/netI     0.0178
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            37680
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.068
_diffrn_reflns_theta_min         4.111
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R X-ray Source'
_exptl_absorpt_coefficient_mu    1.638
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.592
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.96a (Rigaku Oxford Diffraction, 2021) 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            'clear colourless'
_exptl_crystal_density_diffrn    1.160
_exptl_crystal_description       block
_exptl_crystal_F_000             740
_exptl_crystal_size_max          0.289
_exptl_crystal_size_mid          0.169
_exptl_crystal_size_min          0.164
_refine_diff_density_max         0.225
_refine_diff_density_min         -0.376
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 3459 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     431
_refine_ls_number_reflns         7493
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0229
_refine_ls_R_factor_gt           0.0228
_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^)+(0.0419P)^2^+0.3899P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0614
_refine_ls_wR_factor_ref         0.0615
_reflns_Friedel_coverage         0.879
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                7469
_reflns_number_total             7493
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00298e2.cif
_cod_data_source_block           MaDi175_SiHu_a
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               7712434
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_min   0.648
_shelx_estimated_absorpt_t_max   0.780
_shelx_res_checksum              46539
_shelx_hkl_checksum              61878