A Boron–Boron Double Transborylation Strategy for the Synthesis of gem-Diborylalkanes
Docherty, Jamie H.; Nicholson, Kieran; Dominey, Andrew P.; Thomas, Stephen P.; ACS Catalysis  (2020) 4686–; doi:10.1021/acscatal.0c00869

data_4517537
_publ_section_title
;
 A Boron--Boron Double Transborylation Strategy for the Synthesis of
 gem-Diborylalkanes
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              4686
_journal_paper_doi               10.1021/acscatal.0c00869
_journal_year                    2020
_chemical_formula_moiety         'C22 H34 B2 O2'
_chemical_formula_sum            'C22 H34 B2 O2'
_chemical_formula_weight         352.11
_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     dual
_audit_creation_date             2019-10-18
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.6000(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.0776(2)
_cell_length_b                   6.63350(10)
_cell_length_c                   21.5511(3)
_cell_measurement_reflns_used    12507
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      75.9730
_cell_measurement_theta_min      4.5890
_cell_volume                     2103.57(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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    -82.00  15.00   1.00   10.00    --  -41.67 101.00 -84.00   97
  2  \w      7.00  83.00   1.00   10.00    --   41.67-101.00 171.00   76
  3  \w    104.00 178.00   1.00   30.00    --  111.00 101.00 -84.00   74
  4  \w     32.00 107.00   1.00   30.00    --  111.00-101.00 171.00   75
  5  \w   -114.00 -19.00   1.00   10.00    --  -41.67 -38.00 120.00   95
  6  \w   -114.00 -19.00   1.00   10.00    --  -41.67 -38.00-150.00   95
  7  \w   -114.00 -19.00   1.00   10.00    --  -41.67 -38.00 -60.00   95
  8  \w     15.00 112.00   1.00   10.00    --   41.67  57.00  60.00   97
  9  \w     37.00 142.00   1.00   30.00    --  111.00 -77.00-180.00  105
 10  \w     30.00 107.00   1.00   30.00    --  111.00 -94.00-120.00   77
 11  \w     36.00 135.00   1.00   30.00    --  111.00 -30.00 150.00   99
 12  \w     97.00 178.00   1.00   30.00    --  111.00 125.00-120.00   81
 13  \w     87.00 178.00   1.00   30.00    --  111.00  45.00 -30.00   91
 14  \w     97.00 178.00   1.00   30.00    --  111.00 125.00   0.00   81
 15  \w     30.00 107.00   1.00   30.00    --  111.00 -94.00   0.00   77
 16  \w     31.00 156.00   1.00   30.00    --  111.00 -15.00   0.00  125
 17  \w     30.00 107.00   1.00   30.00    --  111.00 -94.00 120.00   77
 18  \w     36.00 109.00   1.00   30.00    --  111.00-111.00 -58.63   73
 19  \w     87.00 178.00   1.00   30.00    --  111.00  30.00  30.00   91
 20  \w     66.00 178.00   1.00   30.00    --  111.00  15.00-120.00  112
 21  \w    103.00 178.00   1.00   30.00    --  111.00  77.00  60.00   75
 22  \w     30.00 107.00   1.00   30.00    --  111.00 -94.00-180.00   77
 23  \w     39.00 112.00   1.00   30.00    --  111.00-125.00-180.00   73
 24  \w     41.00 139.00   1.00   30.00    --  111.00 -61.00 -30.00   98
 25  \w     39.00 112.00   1.00   30.00    --  111.00-125.00-120.00   73
 26  \w     58.00 111.00   1.00   30.00    --  111.00-125.00   0.00   53
 27  \w     80.00 123.00   1.00   30.00    --  111.00-138.00 148.30   43
 28  \w     50.00 106.00   1.00   30.00    --  111.00 -94.00 -30.00   56
 29  \w     80.00 106.00   1.00   30.00    --  111.00-101.00 149.70   26
 30  \w     45.00  71.00   1.00   30.00    --  111.00 -94.00-150.00   26
 31  \w     41.00 129.00   1.00   30.00    --  111.00 -45.00 -60.00   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0423284000
_diffrn_orient_matrix_UB_12      -0.1057117000
_diffrn_orient_matrix_UB_13      -0.0502392000
_diffrn_orient_matrix_UB_21      -0.0913571000
_diffrn_orient_matrix_UB_22      0.0158527000
_diffrn_orient_matrix_UB_23      -0.0485455000
_diffrn_orient_matrix_UB_31      0.0287543000
_diffrn_orient_matrix_UB_32      0.2061460000
_diffrn_orient_matrix_UB_33      -0.0220239000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0783
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            33239
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.058
_diffrn_reflns_theta_min         4.204
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.512
_exptl_absorpt_correction_T_max  0.95644
_exptl_absorpt_correction_T_min  0.95644
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.54a (Rigaku Oxford Diffraction, 2019)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.112
_exptl_crystal_description       needle
_exptl_crystal_F_000             768
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of pentane and hexane  by slow cooling to 233 K'
_exptl_crystal_size_max          0.442
_exptl_crystal_size_mid          0.044
_exptl_crystal_size_min          0.041
_refine_diff_density_max         0.277
_refine_diff_density_min         -0.425
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     307
_refine_ls_number_reflns         4385
_refine_ls_number_restraints     79
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0744
_refine_ls_R_factor_gt           0.0664
_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^)+(0.1149P)^2^+0.8068P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1790
_refine_ls_wR_factor_ref         0.1880
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3775
_reflns_number_total             4385
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00869_si_001.cif
_cod_data_source_block           se19005b
_cod_database_code               4517537
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H32 B2 O2'
_chemical_oxdiff_usercomment     '@ 120 K JD1 1.071'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C15-C20 \\sim C15-C20A
 with sigma of 0.02
 C22-C21 \\sim C22-C21A
 with sigma of 0.02
 C20-C21 \\sim C20A-C21A
 with sigma of 0.02
 C15-C21 \\sim C15-C21A
 with sigma of 0.04
 C22-C20 \\sim C22-C20A
 with sigma of 0.04
 C18-C17 \\sim C18-C17A
 with sigma of 0.02
 C17-C16 \\sim C17A-C16
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C17A) = Uanis(C17)
Uanis(C13A) = Uanis(C13)
4. Rigid body (RIGU) restrains
 O1A, O2A, C9, C10A, C11A, C12, C13A, C14A, B1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H15A)=Sof(C20A)=Sof(H20C)=Sof(H20D)=Sof(C21A)=Sof(H21C)=Sof(H21D)=
 Sof(H22C)=Sof(H22D)=1-FVAR(1)
 Sof(H15)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H22A)=
 Sof(H22B)=FVAR(1)
 Sof(H16C)=Sof(H16D)=Sof(C17A)=Sof(H17C)=Sof(H17D)=Sof(H18C)=Sof(H18D)=1-FVAR(2)
 Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H18A)=Sof(H18B)=FVAR(2)
 Sof(O1A)=Sof(O2A)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(H11D)=
 Sof(H11E)=Sof(H11F)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=
 Sof(H14D)=Sof(H14E)=Sof(H14F)=1-FVAR(3)
 Sof(O1)=Sof(O2)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=
 Sof(H14B)=Sof(H14C)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C15(H15), C15(H15A), C19(H19)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C16(H16A,H16B), C16(H16C,H16D), C17(H17A,H17B), C17A(H17C,H17D),
 C18(H18A,H18B), C18(H18C,H18D), C20(H20A,H20B), C20A(H20C,H20D), C21(H21A,
 H21B), C21A(H21C,H21D), C22(H22A,H22B), C22(H22C,H22D)
6.c Me refined with riding coordinates:
 C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F), C11(H11A,H11B,H11C), C11A(H11D,
 H11E,H11F), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F), C14(H14A,H14B,H14C),
 C14A(H14D,H14E,H14F)
6.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8)
;
_shelx_res_checksum              68975
_shelx_hkl_checksum              32220
_olex2_date_sample_data_collection 2019-10-17
_olex2_date_sample_submission    2019-10-17
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil.'
_olex2_submission_original_sample_id JD11.071
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.711
_oxdiff_exptl_absorpt_empirical_full_min 0.489