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_4519023
_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         'C18 H16 N O3 P'
_chemical_formula_sum            'C18 H16 N O3 P'
_chemical_formula_weight         325.29
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                108.405(4)
_cell_angle_beta                 96.291(3)
_cell_angle_gamma                90.405(3)
_cell_formula_units_Z            4
_cell_length_a                   8.4872(3)
_cell_length_b                   11.6741(5)
_cell_length_c                   16.8354(6)
_cell_measurement_reflns_used    4724
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.0710
_cell_measurement_theta_min      3.9770
_cell_volume                     1571.67(11)
_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 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_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     -4.00  23.00   1.00    2.00    --   30.00  88.00 -59.56   27
  2  \w    -12.00  13.00   1.00    2.00    --   30.00 104.00 121.48   25
  3  \w      3.00  30.00   1.00    2.00    --   34.00  76.00-172.53   27
  4  \w     -2.00  23.00   1.00    2.00    --   34.00  91.00 147.06   25
  5  \w     19.00  59.00   1.00    2.00    --   41.87  38.00-150.00   40
  6  \w     27.00  95.00   1.00    2.00    --   41.87-125.00-120.00   68
  7  \w     19.00 104.00   1.00    2.00    --   41.87  38.00  60.00   85
  8  \w    -27.00  66.00   1.00    2.00    --   41.87 -57.00   0.00   93
  9  \w     14.00  39.00   1.00    2.00    --   46.00  80.00  32.47   25
 10  \w     13.00  39.00   1.00    2.00    --   46.00  81.00-124.63   26
 11  \w     13.00  38.00   1.00    2.00    --   46.00  82.00 170.36   25
 12  \w     14.00  41.00   1.00    2.00    --   46.00  80.00  -9.66   27
 13  \w     25.00  73.00   1.00    2.00    --   54.00  74.00 107.18   48
 14  \w     79.00 116.00   1.00    2.00    --   54.00  74.00 107.18   37
 15  \w     29.00  62.00   1.00    2.00    --   58.00  73.00 -66.37   33
 16  \w     71.00 131.00   1.00    2.00    --   58.00  73.00 -66.37   60
 17  \w     34.00  61.00   1.00    2.00    --   62.00  73.00-107.00   27
 18  \w     34.00  61.00   1.00    2.00    --   62.00  72.00  30.43   27
 19  \w     36.00  70.00   1.00    2.00    --   66.00  74.00 -58.88   34
 20  \w     35.00  64.00   1.00    2.00    --   66.00  74.00  57.66   29
 21  \w     36.00  64.00   1.00    2.00    --   66.00  74.00 147.37   28
 22  \w     96.00 143.00   1.00    2.00    --   70.00  73.00 119.85   47
 23  \w     40.00  72.00   1.00    2.00    --   70.00  73.00 119.85   32
 24  \w    106.00 135.00   1.00    2.00    --   70.00  73.00 -18.49   29
 25  \w     40.00  73.00   1.00    2.00    --   70.00  73.00 -18.49   33
 26  \w     48.00  82.00   1.00    8.00    --   74.00  60.00 103.09   34
 27  \w     44.00  71.00   1.00    8.00    --   74.00  73.00-157.02   27
 28  \w     45.00  72.00   1.00    8.00    --   74.00  69.00 176.52   27
 29  \w     49.00  76.00   1.00    8.00    --   78.00  69.00  23.60   27
 30  \w     49.00  76.00   1.00    8.00    --   78.00  69.00-128.64   27
 31  \w    113.00 157.00   1.00    8.00    --   86.00  72.00 115.09   44
 32  \w     57.00  82.00   1.00    8.00    --   86.00  72.00 115.09   25
 33  \w    103.00 166.00   1.00    8.00    --   94.00  72.00-123.25   63
 34  \w     64.00  95.00   1.00    8.00    --   94.00  72.00-123.25   31
 35  \w     66.00 156.00   1.00    8.00    --   94.00  65.00  56.82   90
 36  \w     33.00 113.00   1.00    8.00    --  101.44-125.00-180.00   80
 37  \w     82.00 113.00   1.00    8.00    --  101.44-125.00 -60.00   31
 38  \w     35.00  70.00   1.00    8.00    --  101.44 -45.00 -60.00   35
 39  \w     76.00 169.00   1.00    8.00    --  101.44  61.00 -60.00   93
 40  \w     75.00 164.00   1.00    8.00    --  101.44  61.00-180.00   89
 41  \w     31.00  93.00   1.00    8.00    --  101.44 -61.00  30.00   62
 42  \w     77.00 104.00   1.00    8.00    --  101.44  45.00  30.00   27
 43  \w     32.00  90.00   1.00    8.00    --  101.44 -61.00-150.00   58
 44  \w    114.00 144.00   1.00    8.00    --  101.44  61.00 -90.00   30
 45  \w     75.00 103.00   1.00    8.00    --  101.44  61.00 -90.00   28
 46  \w    103.00 171.00   1.00    8.00    --  101.44  59.00  -6.13   68
 47  \w     75.00 101.00   1.00    8.00    --  101.44  59.00  -6.13   26
 48  \w     34.00  93.00   1.00    8.00    --  101.44 -61.00 150.00   59
 49  \w     79.00 149.00   1.00    8.00    --  101.44  61.00 150.00   70
 50  \w    146.00 171.00   1.00    8.00    --  101.44  61.00 -30.00   25
 51  \w     76.00 103.00   1.00    8.00    --  101.44  61.00 -30.00   27
 52  \w     29.00 110.00   1.00    8.00    --  101.44-125.00   0.00   81
 53  \w    111.00 163.00   1.00    8.00    --  101.44  61.00  30.00   52
 54  \w     77.00 106.00   1.00    8.00    --  101.44  61.00  30.00   29
 55  \w     71.00 112.00   1.00    8.00    --  101.44  72.00 119.93   41
 56  \w     35.00 112.00   1.00    8.00    --  101.44-125.00  60.00   77
 57  \w     76.00 158.00   1.00    8.00    --  101.44  61.00  90.00   82
 58  \w     75.00 130.00   1.00    8.00    --  101.44  61.00-150.00   55
;
_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      -0.1332442000
_diffrn_orient_matrix_UB_12      -0.0835849000
_diffrn_orient_matrix_UB_13      -0.0605253000
_diffrn_orient_matrix_UB_21      -0.1096633000
_diffrn_orient_matrix_UB_22      0.1074068000
_diffrn_orient_matrix_UB_23      0.0133682000
_diffrn_orient_matrix_UB_31      0.0602801000
_diffrn_orient_matrix_UB_32      0.0292892000
_diffrn_orient_matrix_UB_33      -0.0747637000
_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  0.0653
_diffrn_reflns_av_unetI/netI     0.0497
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            27235
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.391
_diffrn_reflns_theta_min         3.995
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    1.678
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.628
_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    1.375
_exptl_crystal_description       plate
_exptl_crystal_F_000             680
_exptl_crystal_recrystallization_method 'Recrystalised from ethanol at -30C'
_exptl_crystal_size_max          0.255
_exptl_crystal_size_mid          0.177
_exptl_crystal_size_min          0.028
_refine_diff_density_max         0.464
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     498
_refine_ls_number_reflns         6105
_refine_ls_number_restraints     264
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0600
_refine_ls_R_factor_gt           0.0388
_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^)+(0.0374P)^2^+0.2319P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0852
_refine_ls_wR_factor_ref         0.0953
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4613
_reflns_number_total             6105
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc1c02907_si_002.cif
_cod_data_source_block           ochdki
_cod_database_code               4519023
_nottingham_internal_coll_name   OCHDKI
_nottingham_internal_coll_number 18862
_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 'GVA, PL13110002'
_nottingham_internal_process_date 03/12/2020
_nottingham_internal_process_user pcxch6
_nottingham_internal_solution_date 14/12/2020
_nottingham_internal_solution_user pcxch6
_nottingham_internal_refinement_date 14/12/2020
_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         'C18 H16 N1 O3 P1'
_chemical_oxdiff_usercomment
'OCHDKI #18862 GVA-1858 CH/DLK in fomblin film on a micromount'
_shelx_estimated_absorpt_t_max   0.955
_shelx_estimated_absorpt_t_min   0.674
_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 N(H) groups
2. Restrained distances
 N1-H1
 0.88 with sigma of 0.02
 N2-H2A
 0.88 with sigma of 0.02
 O6A-C33 \\sim O6B-C33
 with sigma of 0.02
 O3A-C16A \\sim O3B-C16B
 with sigma of 0.02
 C36A-C34A \\sim C36B-C34B
 with sigma of 0.04
 O6A-C34A \\sim O6B-C34B
 with sigma of 0.02
 C33-C36A \\sim C33-C36B
 with sigma of 0.02
 C17A-C16A \\sim C17B-C16B
 with sigma of 0.02
 C35A-C36A \\sim C35B-C36B
 with sigma of 0.02
 C35A-C34A \\sim C35B-C34B
 with sigma of 0.02
 C18A-C17A \\sim C18B-C17B
 with sigma of 0.02
 C15-C16A \\sim C15-C16B
 with sigma of 0.04
 O3A-C15 \\sim O3B-C15
 with sigma of 0.02
 O6A-C35A \\sim O6B-C35B
 with sigma of 0.04
 C15-C18A \\sim C15-C18B
 with sigma of 0.02
 C33-C35A \\sim C33-C35B
 with sigma of 0.04
 O3A-C17A \\sim O3B-C17B
 with sigma of 0.04
 C33-C34A \\sim C33-C34B
 with sigma of 0.04
 C15-C17A \\sim C15-C17B
 with sigma of 0.04
 C18A-C16A \\sim C18B-C16B
 with sigma of 0.04
3. Restrained planarity
 C33, O6B, C34B, C35B, C36B
 with sigma of 0.1
 C15, O3B, C16B, C17B, C18B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C33 \\sim O6B \\sim C34B \\sim C35B \\sim C36B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C15 \\sim O3B \\sim C16B \\sim C17B \\sim C18B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
O3A \\sim C15 \\sim C16A \\sim C17A \\sim C18A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
O6A \\sim C33 \\sim C34A \\sim C35A \\sim C36A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 O6A, C33, C34A, C35A, C36A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3A, C15, C16A, C17A, C18A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33, O6B, C34B, C35B, C36B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C15, O3B, C16B, C17B, C18B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O6B)=Sof(C34B)=Sof(H34B)=Sof(C35B)=Sof(H35B)=Sof(C36B)=Sof(H36B)=1-FVAR(1)
 Sof(O6A)=Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35A)=Sof(C36A)=Sof(H36A)=FVAR(1)
 Sof(O3B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(H18B)=1-FVAR(2)
 Sof(O3A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C32(H32A,H32B)
7.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), C16A(H16A), C17A(H17A), C18A(H18A), C20(H20), C21(H21), C22(H22),
 C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30),
 C34A(H34A), C36A(H36A), C16B(H16B), C17B(H17B), C18B(H18B), C34B(H34B),
 C35B(H35B), C36B(H36B)
;
_shelx_res_checksum              26293
_shelx_hkl_checksum              6557
_olex2_date_sample_data_collection 2020-12-14
_olex2_date_sample_submission    2020-12-03
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id OCHDKI
_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 1.184
_oxdiff_exptl_absorpt_empirical_full_min 0.837