Transformation of CO<sub>2</sub> and isocyanates mediated by <i>N</i>-borane-substituted cyclic phosphine imides (BCPIs) <i>via</i> λ<sup>5</sup>-oxazaphosphetanes.
Nagai, Shun; Ogoshi, Sensuke; Hoshimoto, Yoichi; Organic & biomolecular chemistry 23 (2024) 202–206; doi:10.1039/d4ob01565g

data_7160235
_publ_section_title
;
 Transformation of CO<sub>2</sub> and isocyanates mediated by
 <i>N</i>-borane-substituted cyclic phosphine imides (BCPIs) <i>via</i>
 &#x3bb;<sup>5</sup>-oxazaphosphetanes.
;
_journal_issue                   1
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              202
_journal_page_last               206
_journal_paper_doi               10.1039/d4ob01565g
_journal_volume                  23
_journal_year                    2024
_chemical_formula_moiety         '2(C4 H8 O), C54 H54 B2 N4'
_chemical_formula_sum            'C62 H70 B2 N4 O2'
_chemical_formula_weight         924.84
_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_block_doi                 10.5517/ccdc.csd.cc2f6qs5
_audit_creation_date             2023-02-02
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-09 deposited with the CCDC.	2024-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.160(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.7952(3)
_cell_length_b                   19.5207(4)
_cell_length_c                   20.9941(4)
_cell_measurement_reflns_used    29121
_cell_measurement_temperature    123.15
_cell_measurement_theta_max      77.3120
_cell_measurement_theta_min      3.4890
_cell_volume                     5222.47(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/4 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      123.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_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     42.00 124.00   0.50    1.44    --   50.04  23.00 -26.00  164
  2  \w     13.00  58.00   0.50    1.44    --   50.04 -23.00 167.00   90
  3  \w    -55.00 -29.00   0.50    1.44    --  -53.16  23.00 -26.00   52
  4  \w   -100.00 -48.00   0.50    1.44    --  -53.16 -23.00 167.00  104
  5  \w     75.00 100.00   0.50    1.44    --   66.50  23.00 -26.00   50
  6  \w     34.00  59.00   0.50    1.44    --   66.50 -23.00 167.00   50
  7  \w   -163.00-137.00   0.50    1.44    -- -105.75 -23.00 167.00   52
  8  \w   -113.00 -38.00   0.50    1.44    -- -105.75  23.00 -26.00  150
  9  \w     90.00 120.00   0.50    1.44    --   50.04 125.00-150.00   60
 10  \w   -124.00 -74.00   0.50    1.44    --  -53.16-125.00 -30.00  100
 11  \w     -5.00  72.00   0.50    1.44    --   66.50 -37.00 -30.00  154
 12  \w   -100.00 -34.00   0.50    1.44    -- -105.75  37.00 150.00  132
 13  \w   -118.00 -41.00   0.50    1.44    -- -105.75  57.00-120.00  154
 14  \w   -173.00 -99.00   0.50    1.44    -- -105.75 -19.00  90.00  148
 15  \w   -138.00-105.00   0.50    1.44    -- -105.75 -19.00-180.00   66
 16  \w    -68.00 -42.00   0.50    1.44    -- -105.75 125.00   0.00   52
 17  \w   -106.00 -79.00   0.50    1.44    -- -105.75 125.00   0.00   54
 18  \w   -105.00 -35.00   0.50    1.44    -- -105.75  19.00  60.00  140
 19  \w   -112.00 -60.00   0.50    1.44    -- -105.75  57.00 150.00  104
 20  \w    -99.00 -62.00   0.50    1.44    -- -105.75 125.00 -30.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1104253000
_diffrn_orient_matrix_UB_12      0.0078792000
_diffrn_orient_matrix_UB_13      0.0229013000
_diffrn_orient_matrix_UB_21      0.0491048000
_diffrn_orient_matrix_UB_22      0.0223683000
_diffrn_orient_matrix_UB_23      0.0664665000
_diffrn_orient_matrix_UB_31      -0.0029878000
_diffrn_orient_matrix_UB_32      0.0752665000
_diffrn_orient_matrix_UB_33      -0.0220764000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            9444
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.247
_diffrn_reflns_theta_min         4.143
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.536
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63130
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (Rigaku Oxford Diffraction, 2019)
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    1.176
_exptl_crystal_description       plate
_exptl_crystal_F_000             1984
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.378
_refine_diff_density_min         -0.447
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     660
_refine_ls_number_reflns         9444
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0865
_refine_ls_R_factor_gt           0.0793
_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^)+(0.1113P)^2^+9.7025P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2191
_refine_ls_wR_factor_ref         0.2258
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8419
_reflns_number_total             9444
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01565g2.cif
_cod_data_source_block           compound_8a
_cod_depositor_comments
'Adding full bibliography for 7160230--7160235.cif.'
_cod_database_code               7160235
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C244 H292 B12 N24 O1 '
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.948
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9919(5)
 0.0081(5)
2. 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
3. Restrained distances
 C5-C4 \\sim C5-C4A
 with sigma of 0.02
 C3-C4 \\sim C3-C4A
 with sigma of 0.02
 C70-C69 \\sim C70-C69A
 with sigma of 0.02
 C68-C69 \\sim C68-C69A
 with sigma of 0.02
4. Others
 Sof(H5BC)=Sof(H5BD)=Sof(H3BC)=Sof(H3BD)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=1-FVAR(1)
 Sof(H5AA)=Sof(H5AB)=Sof(H3AA)=Sof(H3AB)=Sof(C4)=Sof(H4A)=Sof(H4B)=FVAR(1)
 Sof(H70C)=Sof(H70D)=Sof(H68C)=Sof(H68D)=Sof(C69A)=Sof(H69C)=Sof(H69D)=1-FVAR(2)
 Sof(H70A)=Sof(H70B)=Sof(H68A)=Sof(H68B)=Sof(C69)=Sof(H69A)=Sof(H69B)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C27(H27), C39(H39), C36(H36), C24(H24)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C67(H67A,H67B), C5(H5AA,H5AB), C5(H5BC,H5BD), C70(H70A,H70B),
 C70(H70C,H70D), C3(H3AA,H3AB), C3(H3BC,H3BD), C68(H68A,H68B), C68(H68C,H68D),
 C69(H69A,H69B), C4(H4A,H4B), C4A(H4AA,H4AB), C69A(H69C,H69D)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C14(H14), C7(H7), C58(H58), C13(H13), C22(H22), C62(H62), C61(H61),
 C55(H55), C64(H64), C63(H63), C20(H20), C34(H34), C33(H33), C56(H56), C21(H21),
  C32(H32), C57(H57), C49(H49), C43(H43), C50(H50), C52(H52), C45(H45),
 C46(H46), C51(H51), C44(H44)
5.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C28(H28A,H28B,H28C), C38(H38A,H38B,H38C), C41(H41A,H41B,
 H41C), C40(H40A,H40B,H40C), C37(H37A,H37B,H37C), C26(H26A,H26B,H26C), C25(H25A,
 H25B,H25C)
;
_shelx_res_checksum              5520
_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 1.562
_oxdiff_exptl_absorpt_empirical_full_min 0.648