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_7712435
_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         'C26 H36 B Br N2'
_chemical_formula_sum            'C26 H36 B Br N2'
_chemical_formula_weight         467.29
_chemical_name_systematic        (CAAI)BBrPh
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2023-01-12
_audit_creation_method           'CIF-fill 1.3q (K.Radacki, 2005-22)'
_audit_update_record
;
2023-01-19 deposited with the CCDC.	2023-02-27 downloaded from the CCDC.
;
_cell_angle_alpha                86.673(2)
_cell_angle_beta                 85.097(2)
_cell_angle_gamma                75.815(2)
_cell_formula_units_Z            4
_cell_length_a                   9.3778(3)
_cell_length_b                   13.0392(3)
_cell_length_c                   20.8478(6)
_cell_measurement_reflns_used    12753
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.8060
_cell_measurement_theta_min      5.1350
_cell_volume                     2460.66(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_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 0.991
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
 List of Runs (angles in degrees, time in seconds):
 --------------------------------------------------------------------------
  1  \w   -107.00 -72.00   0.50    0.83    --  -58.00 -48.00 -92.03   70
  2  \w     16.00  66.00   0.50    0.83    --   58.30 -95.00-180.00  100
  3  \w     16.00  66.00   0.50    0.83    --   58.30 -95.00  60.00  100
  4  \w   -110.00 -75.00   0.50    0.83    --  -62.00 -51.00-118.62   70
  5  \w   -116.00 -79.00   0.50    0.83    --  -66.00 -45.00  -8.62   74
  6  \w   -120.00 -82.00   0.50    0.83    --  -70.00 -42.00-169.91   76
  7  \w   -118.00 -83.00   0.50    0.83    --  -70.00 -53.00 -31.89   70
  8  \w     28.00  79.00   0.50    0.83    --   71.06 -95.00 -90.00  102
  9  \w   -121.00 -86.00   0.50    0.83    --  -74.00 -55.00  96.77   70
 10  \w    -97.00 -32.00   0.50    0.83    --  -78.00 114.00 -29.67  130
 11  \w    -97.00 -32.00   0.50    0.83    --  -78.00 114.00 -70.04  130
 12  \w    -98.00 -32.00   0.50    0.83    --  -79.50 120.00  89.83  132
 13  \w   -126.00 -93.00   0.50    0.83    --  -79.50-120.00 -95.21   66
 14  \w    -97.00 -33.00   0.50    0.83    --  -79.50 116.00  36.09  128
 15  \w   -128.00 -93.00   0.50    0.83    --  -79.50 -49.00-138.12   70
 16  \w   -126.00 -93.00   0.50    0.83    --  -79.50-120.00  11.77   66
 17  \w   -126.00 -86.00   0.50    0.83    --  -79.50-134.00  34.99   80
 18  \w   -104.00 -33.00   0.50    0.83    --  -79.50 134.00 146.06  142
 19  \w   -127.00 -90.00   0.50    0.83    --  -79.50-127.00 -53.44   74
 20  \w     40.00  90.00   0.50    0.83    --   82.35 -95.00-150.00  100
 21  \w     40.00  90.00   0.50    0.83    --   82.35 -95.00  90.00  100
 22  \w     46.00 133.00   0.50    0.83    --   82.35  15.00  60.00  174
 23  \w     40.00  90.00   0.50    0.83    --   82.35 -95.00 150.00  100
 24  \w     40.00  90.00   0.50    0.83    --   82.35 -95.00  60.00  100
 25  \w     40.00  90.00   0.50    0.83    --   82.35 -95.00 -90.00  100
 26  \w     91.00 117.00   0.50    0.83    --   82.35  15.00 120.00   52
 27  \w     41.00  67.00   0.50    0.83    --   85.25-123.00  22.27   52
 28  \w     53.00  93.00   0.50    0.83    --   85.25-102.00  -7.58   80
 29  \w     63.00  89.00   0.50    0.83    --   85.25 -90.00-109.84   52
 30  \w    107.00 132.00   0.50    0.83    --   85.25 126.00  14.12   50
 31  \w     50.00  94.00   0.50    0.83    --   85.25-130.00 108.60   88
 32  \w     47.00  73.00   0.50    0.83    --   85.25-136.00 -54.37   52
 33  \w     68.00 129.00   0.50    0.83    --   85.25  18.00 159.54  122
 34  \w     46.00  97.00   0.50    0.83    --   85.25-115.00 145.21  102
 35  \w     67.00  93.00   0.50    0.83    --   85.25-106.00-140.06   52
 36  \w     46.00  71.00   0.50    0.83    --   85.25 -79.00  11.41   50
 37  \w     38.00  78.00   0.50    0.83    --   85.25-131.00  42.96   80
 38  \w     47.00  92.00   0.50    0.83    --   85.25 -95.00 169.99   90
 39  \w     43.00  80.00   0.50    0.83    --   85.25-104.00-157.19   74
 40  \w     45.00  87.00   0.50    0.83    --   85.25 -93.00 -77.20   84
 41  \w     50.00  76.00   0.50    0.83    --   85.25 -89.00  85.64   52
 42  \w     99.00 127.00   0.50    0.83    --   85.25  43.00 -87.46   56
 43  \w     43.00  68.00   0.50    0.83    --   85.25-125.00 144.00   50
 44  \w     99.00 128.00   0.50    0.83    --   85.25  53.00 150.80   58
 45  \w     44.00  70.00   0.50    0.83    --   85.25-107.00 -99.43   52
 46  \w     97.00 135.00   0.50    0.83    --   85.25  35.00  73.14   76
 47  \w     58.00 104.00   0.50    0.83    --   85.25-135.00  80.82   92
 48  \w     96.00 133.00   0.50    0.83    --   85.25 127.00 128.96   74
 49  \w     48.00  93.00   0.50    0.83    --   85.25-102.00 -44.38   90
 50  \w    104.00 132.00   0.50    0.83    --   85.25 121.00 151.20   56
 51  \w     67.00  93.00   0.50    0.83    --   85.25-107.00  63.04   52
 52  \w    105.00 131.00   0.50    0.83    --   85.25 116.00   6.06   52
 53  \w     40.00  65.00   0.50    0.83    --   85.25-108.00-142.27   50
 54  \w    102.00 129.00   0.50    0.83    --   85.25 138.00  62.23   54
 55  \w    103.00 128.00   0.50    0.83    --   85.25 136.00 -48.58   50
 56  \w    102.00 129.00   0.50    0.83    --   85.25  47.00-136.67   54
 57  \w     44.00  69.00   0.50    0.83    --   85.25 -92.00  95.80   50
 58  \w    110.00 135.00   0.50    0.83    --   85.25  39.00 177.79   50
 59  \w    100.00 125.00   0.50    0.83    --   85.25  41.00 -61.44   50
 60  \w     39.00  65.00   0.50    0.83    --   85.25-133.00 -35.36   52
 61  \w     61.00  87.00   0.50    0.83    --   85.25-118.00 163.81   52
 62  \w     47.00  93.00   0.50    0.83    --   85.25 -97.00 -31.88   92
 63  \w     48.00  92.00   0.50    0.83    --   85.25 -95.00-137.73   88
;
_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      -0.1101550000
_diffrn_orient_matrix_UB_12      0.0780938000
_diffrn_orient_matrix_UB_13      0.0439184000
_diffrn_orient_matrix_UB_21      0.1270951000
_diffrn_orient_matrix_UB_22      0.0106941000
_diffrn_orient_matrix_UB_23      0.0393100000
_diffrn_orient_matrix_UB_31      0.0240895000
_diffrn_orient_matrix_UB_32      0.0930585000
_diffrn_orient_matrix_UB_33      -0.0451087000
_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  0.0697
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            14301
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.075
_diffrn_reflns_theta_min         3.499
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet-R X-ray Source'
_exptl_absorpt_coefficient_mu    2.365
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48579
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 CrysAlisPro 1.171.42.68a (Rigaku Oxford Diffraction, 2022) Empirical 
 absorption correction using spherical harmonics, implemented in SCALE3 
 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       plate
_exptl_crystal_F_000             984
_exptl_crystal_preparation
;
 Crystals were grown from saturated solution. 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          0.149
_exptl_crystal_size_mid          0.038
_exptl_crystal_size_min          0.006
_refine_diff_density_max         2.414
_refine_diff_density_min         -1.140
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     558
_refine_ls_number_reflns         14301
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0884
_refine_ls_R_factor_gt           0.0775
_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^)+(0.1380P)^2^+8.0494P] where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2353
_refine_ls_wR_factor_ref         0.2428
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11911
_reflns_number_total             14301
_reflns_threshold_expression     'I > 2\s(I)'
_twin_dimensionality             triperiodic
_twin_formation_mechanism        gt
_twin_morphology                 polysynthetic
_twin_special_details
;
 Component 2 rotated by -179.9271\% 
 around [0.00 0.00 1.00] (reciprocal) or [-0.16 -0.06 0.98] (direct)
;
_cod_data_source_file            d3dt00298e2.cif
_cod_data_source_block           MaDi256_SiHu_twin1_hklf5
_cod_database_code               7712435
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.720
_shelx_estimated_absorpt_t_max   0.986
_shelx_res_checksum              76267
_shelx_hkl_checksum              35530