Catalyst-free Hydrophosphinylation of Isocyanates and Isothiocyanates under Low-Added-Solvent Conditions
Huke, Cameron D.; Taylor, Laurence J.; Argent, Stephen P.; Kays, Deborah L.; ACS Sustainable Chemistry & Engineering 9 (2021) 10704–10709; doi:10.1021/acssuschemeng.1c02907

data_4519027
_publ_section_title
;
 Catalyst-free Hydrophosphinylation of Isocyanates and Isothiocyanates
 under Low-Added-Solvent Conditions
;
_journal_issue                   32
_journal_name_full               'ACS Sustainable Chemistry &amp; Engineering'
_journal_page_first              10704
_journal_page_last               10709
_journal_paper_doi               10.1021/acssuschemeng.1c02907
_journal_volume                  9
_journal_year                    2021
_chemical_formula_moiety         'C16 H16 N O P S'
_chemical_formula_sum            'C16 H16 N O P S'
_chemical_formula_weight         301.33
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-02-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6257)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.0600(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.07790(10)
_cell_length_b                   16.1069(2)
_cell_length_c                   10.53440(10)
_cell_measurement_reflns_used    8213
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.5290
_cell_measurement_theta_min      4.9610
_cell_volume                     1506.31(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.2349
_diffrn_detector_type            'Agilent Diffraction Atlas S2 detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_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    -53.00 -15.00   1.00    2.00    --  -41.70 -57.00-150.00   38
  2  \w    -79.00 -15.00   1.00    2.00    --  -41.70 -57.00 120.00   64
  3  \w     -1.00  35.00   1.00    2.00    --  -41.70  19.00-150.00   36
  4  \w     -5.00  28.00   1.00    2.00    --  -41.70  19.00 150.00   33
  5  \w     -5.00  34.00   1.00    2.00    --  -41.70  19.00-180.00   39
  6  \w    -32.00  66.00   1.00    2.00    --   41.70 -38.00   0.00   98
  7  \w     38.00  75.00   1.00    2.00    --   41.70-125.00-180.00   37
  8  \w     45.00  81.00   1.00    2.00    --   41.70  57.00-150.00   36
  9  \w     15.00  43.00   1.00    2.00    --   41.70  57.00-150.00   28
 10  \w     35.00  71.00   1.00    8.00    --  104.05 -45.00 -90.00   36
 11  \w     33.00  71.00   1.00    8.00    --  104.05 -45.00 -60.00   38
 12  \w     34.00  65.00   1.00    8.00    --  104.05 -61.00 120.00   31
 13  \w     78.00 104.00   1.00    8.00    --  104.05  45.00 150.00   26
 14  \w     50.00  76.00   1.00    8.00    --  104.05 -61.00-180.00   26
 15  \w     36.00  67.00   1.00    8.00    --  104.05 -45.00 120.00   31
 16  \w     72.00  98.00   1.00    8.00    --  104.05  73.00-179.68   26
 17  \w     29.00  55.00   1.00    8.00    --  104.05 -30.00-120.00   26
 18  \w    141.00 174.00   1.00    8.00    --  104.05 125.00 -60.00   33
 19  \w     98.00 124.00   1.00    8.00    --  104.05 125.00 -60.00   26
 20  \w     28.00  55.00   1.00    8.00    --  104.05 -30.00 150.00   27
 21  \w     78.00 111.00   1.00    8.00    --  104.05  45.00-120.00   33
 22  \w     31.00  70.00   1.00    8.00    --  104.05 -45.00-150.00   39
 23  \w     35.00  60.00   1.00    8.00    --  104.05 -45.00-180.00   25
 24  \w     75.00 101.00   1.00    8.00    --  104.05  61.00-120.00   26
 25  \w     75.00 103.00   1.00    8.00    --  104.05  61.00 150.00   28
 26  \w     75.00 101.00   1.00    8.00    --  104.05  61.00-180.00   26
 27  \w     75.00 101.00   1.00    8.00    --  104.05  61.00-150.00   26
 28  \w    108.00 176.00   1.00    8.00    --  104.05  61.00-150.00   68
 29  \w     32.00  93.00   1.00    8.00    --  104.05 -61.00   0.00   61
 30  \w    103.00 164.00   1.00    8.00    --  104.05  45.00 120.00   61
 31  \w     82.00 109.00   1.00    8.00    --  104.05  45.00-150.00   27
 32  \w     74.00 157.00   1.00    8.00    --  104.05  64.00-112.35   83
 33  \w     81.00 108.00   1.00    8.00    --  104.05  58.00-157.94   27
 34  \w     74.00 173.00   1.00    8.00    --  104.05  65.00 159.83   99
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Atlas S2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1537291000
_diffrn_orient_matrix_UB_12      0.0419463000
_diffrn_orient_matrix_UB_13      -0.0498740000
_diffrn_orient_matrix_UB_21      0.0364798000
_diffrn_orient_matrix_UB_22      0.0084417000
_diffrn_orient_matrix_UB_23      -0.1357867000
_diffrn_orient_matrix_UB_31      -0.0718573000
_diffrn_orient_matrix_UB_32      -0.0855489000
_diffrn_orient_matrix_UB_33      -0.0377846000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0195
_diffrn_reflns_av_unetI/netI     0.0153
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            12627
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.837
_diffrn_reflns_theta_min         4.982
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    2.862
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.863
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       irregular
_exptl_crystal_F_000             632
_exptl_crystal_recrystallization_method 'Recrystalised from ethanol at -30C'
_exptl_crystal_size_max          0.196
_exptl_crystal_size_mid          0.172
_exptl_crystal_size_min          0.076
_refine_diff_density_max         0.322
_refine_diff_density_min         -0.266
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         2952
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0257
_refine_ls_R_factor_gt           0.0246
_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^)+(0.0313P)^2^+0.5828P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0638
_refine_ls_wR_factor_ref         0.0646
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2809
_reflns_number_total             2952
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc1c02907_si_002.cif
_cod_data_source_block           ochdkh
_cod_database_code               4519027
_nottingham_internal_coll_name   OCHDKH
_nottingham_internal_coll_number 18861
_nottingham_internal_coll_client CH/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '8.00, 2.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pcxch6
_nottingham_internal_coll_date   27/11/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVB, PL13110001'
_nottingham_internal_process_date 30/11/2020
_nottingham_internal_process_user pcxch6
_nottingham_internal_solution_date 30/11/2020
_nottingham_internal_solution_user pcxch6
_nottingham_internal_refinement_date 30/11/2020
_nottingham_internal_refinement_user pcxch6
_nottingham_internal_self_archive_date 16/02/2021
_nottingham_internal_self_validation_date 16/02/2021
_nottingham_internal_self_validation_user pcxch6
_nottingham_internal_validation_date 17/02/2021
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date 17/02/2021
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C16 H16 N1 O1 P1 S1'
_chemical_oxdiff_usercomment
'OCHDKH #18861 GVB-1858 for CH/DLK in fomblin film on a micromount'
_shelx_estimated_absorpt_t_max   0.812
_shelx_estimated_absorpt_t_min   0.604
_reflns_odcompleteness_completeness 99.96
_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 N(H) groups
2. Restrained distances
 N1-H1
 0.88 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C15(H15)
3.c X=CH2 refined with riding coordinates:
 C16(H16A,H16B)
;
_shelx_res_checksum              61363
_shelx_hkl_checksum              40150
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id OCHDKH
_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 1.414
_oxdiff_exptl_absorpt_empirical_full_min 0.683