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_7712430
_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 N7'
_chemical_formula_sum            'C40 H62 B N7'
_chemical_formula_weight         651.77
_chemical_name_systematic        (CAAI)2BN3
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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
_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                 96.8590(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.52340(10)
_cell_length_b                   12.29820(10)
_cell_length_c                   33.6499(2)
_cell_measurement_reflns_used    51107
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.0920
_cell_measurement_theta_min      3.8130
_cell_volume                     3912.89(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'BIS 2011.8 / APEX2 ver. 2014.9 (Bruker AXS)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_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 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 HPA
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HyPix Arc150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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     72.00 103.00   0.50    0.05    --   54.00  51.00-117.76   62
   2  \w     99.00 128.00   0.50    0.05    --   85.25  50.00-125.70   58
   3  \w     99.00 133.00   0.50    0.05    --   85.25  53.00-115.49   68
   4  \w     96.00 131.00   0.50    0.05    --   82.31  15.00-150.00   70
   5  \w     99.00 124.00   0.50    0.05    --   85.25  47.00 -85.43   50
   6  \w     96.00 122.00   0.50    0.05    --   85.25  12.00 -22.19   52
   7  \w     62.00  88.00   0.50    0.05    --   85.25  12.00 -22.19   52
   8  \w     68.00 134.00   0.50    0.05    --   85.25  18.00  23.96  132
   9  \w    107.00 133.00   0.50    0.05    --   82.31  15.00  60.00   52
  10  \w     73.00 135.00   0.50    0.05    --   85.25  12.00 151.02  124
  11  \w     51.00 105.00   0.50    0.05    --   85.25-138.00 -74.78  108
  12  \w     82.00 107.00   0.50    0.05    --   85.25-137.00 -94.71   50
  13  \w     82.00 107.00   0.50    0.05    --   85.25-137.00-179.77   50
  14  \w     39.00  71.00   0.50    0.05    --   85.25-137.00 -94.71   64
  15  \w     37.00  62.00   0.50    0.05    --   85.25-128.00 -29.44   50
  16  \w     77.00 102.00   0.50    0.05    --   85.25-128.00 -29.44   50
  17  \w     60.00 102.00   0.50    0.05    --   85.25-128.00  30.16   84
  18  \w     50.00  76.00   0.50    0.05    --   85.25-135.00  61.57   52
  19  \w     62.00  87.00   0.50    0.05    --   58.61-126.00 150.00   50
  20  \w     21.00  56.00   0.50    0.05    --   58.61-126.00 150.00   70
  21  \w     45.00  72.00   0.50    0.05    --   85.25-119.00  57.13   54
  22  \w     43.00  69.00   0.50    0.05    --   85.25-117.00 166.87   52
  23  \w     43.00  94.00   0.50    0.05    --   85.25-119.00 138.48  102
  24  \w     37.00  63.00   0.50    0.05    --   85.25-113.00  72.41   52
  25  \w     67.00  97.00   0.50    0.05    --   85.25-113.00  72.41   60
  26  \w     52.00  97.00   0.50    0.05    --   82.31-112.00 120.00   90
  27  \w     45.00  71.00   0.50    0.05    --   85.25-124.00 -10.24   52
  28  \w     44.00  70.00   0.50    0.05    --   85.25-119.00-123.99   52
  29  \w     37.00  73.00   0.50    0.05    --   85.25-123.00-164.24   72
  30  \w     35.00  97.00   0.50    0.05    --   82.31-112.00-120.00  124
  31  \w     72.00  97.00   0.50    0.05    --   82.31-112.00  30.00   50
  32  \w     72.00  97.00   0.50    0.05    --   82.31-112.00  90.00   50
  33  \w     42.00  68.00   0.50    0.05    --   82.31-112.00 150.00   52
  34  \w     70.00  97.00   0.50    0.05    --   82.31-112.00 150.00   54
  35  \w     72.00  97.00   0.50    0.05    --   85.25-111.00  44.53   50
  36  \w     41.00  71.00   0.50    0.05    --   85.25-109.00  74.29   60
  37  \w     39.00  64.00   0.50    0.05    --   85.25-108.00 177.01   50
  38  \w     69.00  95.00   0.50    0.05    --   85.25-107.00 164.20   52
  39  \w     51.00  97.00   0.50    0.05    --   82.31-112.00   0.00   92
  40  \w     41.00  91.00   0.50    0.05    --   85.25-106.00  92.29  100
  41  \w     42.00  81.00   0.50    0.05    --   85.25-108.00  23.16   78
  42  \w     41.00  66.00   0.50    0.05    --   85.25-105.00  33.45   50
  43  \w     46.00  94.00   0.50    0.05    --   85.25-107.00 -40.56   96
  44  \w     64.00  94.00   0.50    0.05    --   85.25-102.00 -26.51   60
  45  \w     54.00  80.00   0.50    0.05    --   85.25-112.00 -42.34   52
  46  \w     47.00  94.00   0.50    0.05    --   85.25-100.00 -58.60   94
  47  \w     70.00  95.00   0.50    0.05    --   85.25-104.00 -92.52   50
  48  \w     49.00  90.00   0.50    0.05    --   85.25 -97.00 -97.50   82
  49  \w     44.00  70.00   0.50    0.05    --   82.31-112.00-150.00   52
  50  \w     37.00  63.00   0.50    0.05    --   58.61 -95.00-120.00   52
  51  \w     42.00  95.00   0.50    0.05    --   85.25-104.00-167.62  106
  52  \w     46.00  71.00   0.50    0.05    --   85.25 -81.00 164.15   50
  53  \w     44.00  69.00   0.50    0.05    --   85.25 -92.00  37.81   50
  54  \w     40.00  71.00   0.50    0.05    --   71.30 -95.00 -30.00   62
  55  \w     51.00  77.00   0.50    0.05    --   85.25 -81.00-100.18   52
  56  \w     64.00  90.00   0.50    0.05    --   85.25 -95.00-119.26   52
  57  \w     47.00  78.00   0.50    0.05    --   85.25 -78.00-173.37   62
  58  \w     46.00  74.00   0.50    0.05    --   85.25 -76.00 -46.47   56
  59  \w     46.00  74.00   0.50    0.05    --   85.25 -74.00 121.23   56
  60  \w    107.00 132.00   0.50    0.05    --   85.25 109.00 148.91   50
  61  \w    104.00 133.00   0.50    0.05    --   85.25 112.00  88.02   58
  62  \w     99.00 132.00   0.50    0.05    --   85.25 121.00 -72.33   66
  63  \w     99.00 125.00   0.50    0.05    --   85.25 132.00-158.83   52
  64  \w    -55.00 -29.00   0.50    0.05    --  -76.37 112.00 120.00   52
  65  \w    -95.00 -58.00   0.50    0.05    --  -76.37 112.00 120.00   74
  66  \w    -97.00 -35.00   0.50    0.05    --  -76.37 112.00   0.00  124
  67  \w    -56.00 -28.00   0.50    0.05    --  -76.37 112.00-150.00   56
  68  \w    -95.00 -69.00   0.50    0.05    --  -76.37 112.00-150.00   52
  69  \w    -72.00 -46.00   0.50    0.05    --  -79.50  98.00-113.11   52
  70  \w   -124.00 -91.00   0.50    0.05    --  -79.50 -61.00   7.39   66
  71  \w   -122.00 -93.00   0.50    0.05    --  -79.50 -51.00 115.55   58
  72  \w   -117.00 -84.00   0.50    0.05    --  -70.00 -57.00 152.41   66
  73  \w   -127.00-102.00   0.50    0.05    --  -79.50 -56.00  54.34   50
  74  \w   -100.00 -68.00   0.50    0.05    --  -54.00 -48.00 -21.12   64
  75  \w   -109.00 -79.00   0.50    0.05    --  -62.00 -48.00 -57.75   60
  76  \w   -105.00 -80.00   0.50    0.05    --  -58.00 -51.00 -80.71   50
  77  \w   -119.00 -93.00   0.50    0.05    --  -74.00 -50.00-165.66   52
  78  \w   -106.00 -76.00   0.50    0.05    --  -62.00 -47.00  42.92   60
  79  \w   -128.00-103.00   0.50    0.05    --  -79.50-120.00  80.73   50
  80  \w   -125.00 -97.00   0.50    0.05    --  -79.50-114.00 128.99   56

;
_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  0.0257
_diffrn_reflns_av_unetI/netI     0.0142
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            84051
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.322
_diffrn_reflns_theta_min         2.645
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R X-ray Source'
_exptl_absorpt_coefficient_mu    0.500
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77418
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021) Empirical 
absorption correction using spherical harmonics, implemented in SCALE3 
ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.106
_exptl_crystal_description       block
_exptl_crystal_F_000             1424
_exptl_crystal_size_max          0.271
_exptl_crystal_size_mid          0.194
_exptl_crystal_size_min          0.115
_refine_diff_density_max         0.216
_refine_diff_density_min         -0.210
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     449
_refine_ls_number_reflns         8054
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0365
_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^)+(0.0495P)^2^+1.0884P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0941
_refine_ls_wR_factor_ref         0.0963
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7378
_reflns_number_total             8054
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00298e2.cif
_cod_data_source_block           MaMi042_SiHu_a
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7712430
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.877
_shelx_estimated_absorpt_t_max   0.942
_shelx_res_checksum              68065
_shelx_hkl_checksum              77718