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_4519026
_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         'C19 H15 N2 O3 P S'
_chemical_formula_sum            'C19 H15 N2 O3 P S'
_chemical_formula_weight         382.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/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                 95.5790(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.86710(10)
_cell_length_b                   11.72690(10)
_cell_length_c                   16.05540(10)
_cell_measurement_reflns_used    24304
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.5170
_cell_measurement_theta_min      4.4250
_cell_volume                     3535.47(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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 2014/5 (Sheldrick, 2014)'
_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 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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     -5.00  35.00   1.00    2.00    --  -42.12  19.00  30.00   40
  2  \w     -5.00  35.00   1.00    2.00    --  -42.12  19.00 -90.00   40
  3  \w     18.00 114.00   1.00    2.00    --   42.12  38.00 -90.00   96
  4  \w     27.00  96.00   1.00    2.00    --   42.12-125.00   0.00   69
  5  \w     17.00 112.00   1.00    2.00    --   42.12  57.00 -60.00   95
  6  \w     18.00 114.00   1.00    2.00    --   42.12  38.00   0.00   96
  7  \w     11.00  42.00   1.00    2.00    --   42.12  77.00  -8.30   31
  8  \w    -21.00  74.00   1.00    2.00    --   42.12 -77.00 120.00   95
  9  \w     73.00 172.00   1.00    8.00    --  101.44  68.00-109.75   99
 10  \w     77.00 172.00   1.00    8.00    --  101.44  45.00 -60.00   95
 11  \w     31.00  72.00   1.00    8.00    --  101.44 -45.00-180.00   41
 12  \w     75.00 175.00   1.00    8.00    --  101.44  30.00  60.00  100
 13  \w     28.00  57.00   1.00    8.00    --  101.44 -30.00 -60.00   29
 14  \w     77.00 172.00   1.00    8.00    --  101.44  48.00 -74.75   95
 15  \w     76.00 171.00   1.00    8.00    --  101.44  56.00 -43.33   95
 16  \w     31.00  93.00   1.00    8.00    --  101.44 -61.00-120.00   62
 17  \w     31.00  72.00   1.00    8.00    --  101.44 -45.00 120.00   41
 18  \w     97.00 175.00   1.00    8.00    --  101.44 125.00-120.00   78
 19  \w     28.00  57.00   1.00    8.00    --  101.44 -30.00   0.00   29
 20  \w     75.00 171.00   1.00    8.00    --  101.44  61.00 -60.00   96
 21  \w     77.00 172.00   1.00    8.00    --  101.44  45.00-120.00   95
 22  \w     76.00 171.00   1.00    8.00    --  101.44  58.00 -16.12   95
 23  \w     75.00 175.00   1.00    8.00    --  101.44  30.00 -30.00  100
 24  \w     75.00 171.00   1.00    8.00    --  101.44  61.00-120.00   96
 25  \w     75.00 171.00   1.00    8.00    --  101.44  61.00 -30.00   96
 26  \w     97.00 175.00   1.00    8.00    --  101.44 125.00  90.00   78
 27  \w     77.00 172.00   1.00    8.00    --  101.44  45.00 -90.00   95
 28  \w     75.00 171.00   1.00    8.00    --  101.44  61.00 -90.00   96
 29  \w     77.00 172.00   1.00    8.00    --  101.44  45.00 -30.00   95
 30  \w     28.00  57.00   1.00    8.00    --  101.44 -30.00-150.00   29
 31  \w     77.00 172.00   1.00    8.00    --  101.44  46.00 -83.43   95
 32  \w    103.00 178.00   1.00    8.00    --  101.44 114.00  53.00   75
 33  \w     74.00 171.00   1.00    8.00    --  101.44  62.00 -35.07   97
 34  \w     73.00 172.00   1.00    8.00    --  101.44  67.00-133.11   99
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Titan 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      -0.0800176000
_diffrn_orient_matrix_UB_12      -0.0282605000
_diffrn_orient_matrix_UB_13      -0.0039012000
_diffrn_orient_matrix_UB_21      -0.0114675000
_diffrn_orient_matrix_UB_22      0.0530241000
_diffrn_orient_matrix_UB_23      -0.0880369000
_diffrn_orient_matrix_UB_31      0.0141656000
_diffrn_orient_matrix_UB_32      -0.1168081000
_diffrn_orient_matrix_UB_33      -0.0390568000
_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  0.0164
_diffrn_reflns_av_unetI/netI     0.0079
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            31782
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.542
_diffrn_reflns_theta_min         4.445
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    2.676
_exptl_absorpt_correction_T_max  0.974
_exptl_absorpt_correction_T_min  0.609
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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 dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.437
_exptl_crystal_description       prism
_exptl_crystal_F_000             1584
_exptl_crystal_recrystallization_method '1:1, THF:ethanol at -30C'
_exptl_crystal_size_max          0.336
_exptl_crystal_size_mid          0.203
_exptl_crystal_size_min          0.161
_refine_diff_density_max         0.327
_refine_diff_density_min         -0.306
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         3493
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0270
_refine_ls_R_factor_gt           0.0269
_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^)+(0.0385P)^2^+3.3724P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0735
_refine_ls_wR_factor_ref         0.0736
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3476
_reflns_number_total             3493
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc1c02907_si_002.cif
_cod_data_source_block           ochdka
_cod_database_code               4519026
_nottingham_internal_coll_name   OCHDKA
_nottingham_internal_coll_number 18726
_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   13/07/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 14/07/2020
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 23/07/2020
_nottingham_internal_solution_user pcxch6
_nottingham_internal_refinement_date 23/07/2020
_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 17/02/201
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date 17/02/2021
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C19H15N2O3P1S1
_chemical_oxdiff_usercomment
'OCHDKA #18726 GVA-1800 CH/DLK fomblin micromount'
_shelx_estimated_absorpt_t_max   0.673
_shelx_estimated_absorpt_t_min   0.467
_reflns_odcompleteness_completeness 99.97
_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 N(H) groups
2. Restrained distances
 N1-H1
 0.88 with sigma of 0.02
3.a 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), C16(H16), C18(H18), C19(H19)
;
_shelx_res_checksum              68608
_shelx_hkl_checksum              84607
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id OCHDKA
_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 1.266
_oxdiff_exptl_absorpt_empirical_full_min 0.782