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_4519024
_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 Cl N O P S'
_chemical_formula_sum            'C19 H15 Cl N O P S'
_chemical_formula_weight         371.80
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                 105.7350(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.19340(10)
_cell_length_b                   10.76950(10)
_cell_length_c                   13.88080(10)
_cell_measurement_reflns_used    18978
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.9860
_cell_measurement_theta_min      5.2370
_cell_volume                     1754.48(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'PILATUS3 R 200K Hybrid Pixel Array Detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_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    -24.00   1.00   0.50    0.50    --    0.00  -3.00-133.00   50
  2  \w     98.00 150.00   0.50    0.50    --   98.00  -3.00-133.00  104
  3  \w     29.00  59.00   0.50    0.50    --   98.00   3.00  46.00   60
  4  \w     16.00  42.00   0.50    0.50    --    0.00  38.00  30.00   52
  5  \w    -45.00 -19.00   0.50    0.50    --    0.00 -77.00 150.00   52
  6  \w    -44.00 -18.00   0.50    0.50    --    0.00 -77.00-180.00   52
  7  \w    -12.00  32.00   0.50    0.50    --    0.00 -82.00-150.00   88
  8  \w     -1.00  25.00   0.50    0.50    --    0.00  38.00-150.00   52
  9  \w    -23.00   2.00   0.50    0.50    --    0.00 -38.00-150.00   50
 10  \w      7.00  32.00   0.50    0.50    --    0.00 -82.00 -60.00   50
 11  \w    -14.00  32.00   0.50    0.50    --    0.00 -19.00 150.00   92
 12  \w    -20.00   6.00   0.50    0.50    --    0.00  38.00  30.00   52
 13  \w    -22.00  30.00   0.50    0.50    --    0.00 -82.00  90.00  104
 14  \w     49.00  74.00   0.50    0.50    --    0.00  38.00  60.00   50
 15  \w    -23.00  41.00   0.50    0.50    --    0.00  38.00  60.00  128
 16  \w     -7.00  31.00   0.50    0.50    --    0.00 -77.00 150.00   76
 17  \w    -59.00 -33.00   0.50    0.50    --    0.00 -38.00-150.00   52
 18  \w    -42.00  -3.00   0.50    0.50    --    0.00 -77.00-120.00   78
 19  \w     77.00 103.00   0.50    0.50    --   98.00  54.00  58.19   52
 20  \w     68.00  94.00   0.50    0.50    --   98.00  74.00-102.82   52
 21  \w     72.00  98.00   0.50    0.50    --   98.00  61.00-150.00   52
 22  \w     74.00 100.00   0.50    0.50    --   98.00  51.00 150.19   52
 23  \w    153.00 178.00   0.50    0.50    --   98.00  69.00-178.74   50
 24  \w    142.00 168.00   0.50    0.50    --   98.00  61.00 120.00   52
 25  \w    162.00 187.00   0.50    0.50    --   98.00  45.00-180.00   50
 26  \w     73.00  99.00   0.50    0.50    --   98.00  61.00  75.60   52
 27  \w     72.00  98.00   0.50    0.50    --   98.00  61.00  60.00   52
 28  \w     75.00 101.00   0.50    0.50    --   98.00  55.00  54.12   52
 29  \w     67.00  93.00   0.50    0.50    --   98.00  75.00 -61.21   52
 30  \w     70.00  96.00   0.50    0.50    --   98.00  69.00-178.74   52
 31  \w    162.00 187.00   0.50    0.50    --   98.00  61.00 150.00   50
 32  \w     68.00  94.00   0.50    0.50    --   98.00  74.00 -38.18   52
 33  \w     76.00 101.00   0.50    0.50    --   98.00  45.00-150.00   50
 34  \w     72.00  97.00   0.50    0.50    --   98.00  61.00 150.00   50
 35  \w     10.00 121.00   0.50    0.50    --   98.00 -61.00 150.00  222
 36  \w     72.00  97.00   0.50    0.50    --   98.00  61.00 120.00   50
 37  \w     77.00 113.00   0.50    0.50    --   98.00  45.00 120.00   72
 38  \w     70.00  96.00   0.50    0.50    --   98.00  73.00 -53.73   52
 39  \w     72.00  97.00   0.50    0.50    --   98.00  61.00-180.00   50
 40  \w    127.00 152.00   0.50    0.50    --   98.00  61.00  90.00   50
 41  \w     80.00 113.00   0.50    0.50    --   98.00 -61.00-150.00   66
 42  \w     75.00 146.00   0.50    0.50    --   98.00  30.00-150.00  142
 43  \w     76.00 107.00   0.50    0.50    --   98.00  30.00 120.00   62
 44  \w     78.00 124.00   0.50    0.50    --   98.00  30.00 150.00   92
 45  \w     73.00  99.00   0.50    0.50    --   98.00  61.00  30.00   52
 46  \w     11.00 131.00   0.50    0.50    --   98.00 -82.00  90.00  240
 47  \w     77.00 103.00   0.50    0.50    --   98.00  45.00 150.00   52
 48  \w     75.00 101.00   0.50    0.50    --   98.00  45.00-120.00   52
 49  \w     72.00  98.00   0.50    0.50    --   98.00  61.00  90.00   52
 50  \w     76.00 158.00   0.50    0.50    --   98.00  45.00  30.00  164
 51  \w     76.00 187.00   0.50    0.50    --   98.00  45.00  60.00  222
 52  \w     76.00 101.00   0.50    0.50    --   98.00  45.00  90.00   50
 53  \w     80.00 109.00   0.50    0.50    --   98.00  30.00-180.00   58
 54  \w     69.00  94.00   0.50    0.50    --   98.00  71.00-125.80   50
 55  \w     72.00  97.00   0.50    0.50    --   98.00  61.00-120.00   50
 56  \w     75.00 101.00   0.50    0.50    --   98.00  45.00-180.00   52
 57  \w     67.00  93.00   0.50    0.50    --   98.00  75.00 -15.06   52
 58  \w      9.00 127.00   0.50    0.50    --   98.00 -82.00 150.00  236
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'XtalLAB PRO MM007, PILATUS3 R 200K'
_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      -0.0919879000
_diffrn_orient_matrix_UB_12      -0.0041903000
_diffrn_orient_matrix_UB_13      -0.1010051000
_diffrn_orient_matrix_UB_21      -0.0936511000
_diffrn_orient_matrix_UB_22      0.0041200000
_diffrn_orient_matrix_UB_23      0.0553630000
_diffrn_orient_matrix_UB_31      -0.0000061000
_diffrn_orient_matrix_UB_32      0.1429679000
_diffrn_orient_matrix_UB_33      -0.0045493000
_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  0.0345
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            26862
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.433
_diffrn_reflns_theta_min         4.287
_diffrn_source                   'rotating anode'
_diffrn_source_type              'MicroMax 007 HF'
_exptl_absorpt_coefficient_mu    3.941
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.581
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_description       block
_exptl_crystal_F_000             768
_exptl_crystal_recrystallization_method '1:1 THF:ethanol -30C'
_exptl_crystal_size_max          0.292
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.058
_refine_diff_density_max         0.298
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         3568
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0287
_refine_ls_R_factor_gt           0.0278
_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^)+(0.0354P)^2^+0.9034P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0725
_refine_ls_wR_factor_ref         0.0732
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3433
_reflns_number_total             3568
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc1c02907_si_002.cif
_cod_data_source_block           ochdke
_cod_database_code               4519024
_nottingham_internal_coll_name   OCHDKE
_nottingham_internal_coll_number 18757
_nottingham_internal_coll_client CH/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time 0.50
_nottingham_internal_coll_frame_width 0.50
_nottingham_internal_coll_user   pcxch6
_nottingham_internal_coll_date   29/07/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'XtalLAB PRO, A00000876'
_nottingham_internal_process_date 03/08/2020
_nottingham_internal_process_user pcxch6
_nottingham_internal_solution_date 27/11/2020
_nottingham_internal_solution_user pcxch6
_nottingham_internal_refinement_date 27/11/2020
_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         C19H15Cl1N1O1P1S1
_chemical_oxdiff_usercomment
'OCHDKE #18757 MM-720 for CH/DLK fomblin micromount'
_shelx_estimated_absorpt_t_max   0.804
_shelx_estimated_absorpt_t_min   0.392
_reflns_odcompleteness_completeness 99.94
_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              1497
_shelx_hkl_checksum              90876
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id OCHDKE
_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 2.551
_oxdiff_exptl_absorpt_empirical_full_min 0.593