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_4519021
_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 H18 N O2 P'
_chemical_formula_sum            'C16 H18 N O2 P'
_chemical_formula_weight         287.28
_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.r6226)
;
_cell_angle_alpha                108.1640(10)
_cell_angle_beta                 109.2100(10)
_cell_angle_gamma                94.7470(10)
_cell_formula_units_Z            8
_cell_length_a                   13.2516(2)
_cell_length_b                   14.6070(2)
_cell_length_c                   17.4270(3)
_cell_measurement_reflns_used    35435
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.5440
_cell_measurement_theta_min      3.5840
_cell_volume                     2961.45(9)
_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 0.980
_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     -7.00  19.00   1.00    3.50    --   30.00  93.00  -0.20   26
  2  \w    -12.00  13.00   1.00    3.50    --   30.00 103.00 -66.22   25
  3  \w     -1.00  24.00   1.00    3.50    --   30.00  75.00 130.61   25
  4  \w   -114.00 -23.00   1.00    3.50    --  -42.12 -38.00 120.00   91
  5  \w     20.00 109.00   1.00    3.50    --   42.12  38.00-120.00   89
  6  \w     27.00  96.00   1.00    3.50    --   42.12-125.00-180.00   69
  7  \w     29.00  96.00   1.00    3.50    --   42.12-125.00 -90.00   67
  8  \w     13.00  38.00   1.00    3.50    --   46.00  82.00-168.88   25
  9  \w     13.00  38.00   1.00    3.50    --   46.00  81.00 131.01   25
 10  \w     13.00  40.00   1.00    3.50    --   46.00  82.00  61.15   27
 11  \w     15.00  42.00   1.00    3.50    --   46.00  81.00-126.62   27
 12  \w     13.00  42.00   1.00    3.50    --   46.00  82.00 -47.24   29
 13  \w     24.00  51.00   1.00    3.50    --   54.00  74.00  23.65   27
 14  \w     65.00 127.00   1.00    3.50    --   54.00  74.00  23.65   62
 15  \w     81.00 125.00   1.00    3.50    --   58.00  72.00 -42.51   44
 16  \w     31.00  79.00   1.00    3.50    --   58.00  72.00 -42.51   48
 17  \w     27.00  54.00   1.00    3.50    --   58.00  74.00 110.41   27
 18  \w     90.00 133.00   1.00    3.50    --   62.00  74.00-124.41   43
 19  \w     33.00  60.00   1.00    3.50    --   62.00  74.00-124.41   27
 20  \w    107.00 134.00   1.00    3.50    --   66.00  73.00  45.01   27
 21  \w     37.00  64.00   1.00    3.50    --   66.00  73.00  45.01   27
 22  \w     37.00  64.00   1.00    3.50    --   66.00  73.00 -86.67   27
 23  \w    104.00 131.00   1.00    3.50    --   66.00  73.00 -86.67   27
 24  \w     35.00  61.00   1.00    3.50    --   66.00  74.00 -24.59   26
 25  \w     36.00  63.00   1.00    3.50    --   66.00  73.00 121.55   27
 26  \w     40.00  69.00   1.00    3.50    --   70.00  72.00-160.86   29
 27  \w     40.00  73.00   1.00    3.50    --   70.00  73.00 172.61   33
 28  \w     41.00  77.00   1.00    3.50    --   70.00  72.00   6.31   36
 29  \w    106.00 143.00   1.00    3.50    --   70.00  73.00 172.61   37
 30  \w     40.00  73.00   1.00    3.50    --   70.00  71.00 150.59   33
 31  \w    119.00 144.00   1.00   14.00    --   74.00  70.00-124.65   25
 32  \w     45.00  72.00   1.00   14.00    --   74.00  70.00-124.65   27
 33  \w     44.00  71.00   1.00   14.00    --   74.00  73.00  57.66   27
 34  \w     48.00  76.00   1.00   14.00    --   78.00  71.00 -89.52   28
 35  \w     53.00  79.00   1.00   14.00    --   82.00  69.00 -20.98   26
 36  \w     57.00  82.00   1.00   14.00    --   86.00  73.00  57.37   25
 37  \w     61.00  88.00   1.00   14.00    --   86.00  53.00-111.03   27
 38  \w     56.00  84.00   1.00   14.00    --   86.00  72.00 -79.56   28
 39  \w     58.00  84.00   1.00   14.00    --   86.00  65.00 179.09   26
 40  \w    114.00 158.00   1.00   14.00    --   86.00  74.00  94.65   44
 41  \w     55.00  88.00   1.00   14.00    --   86.00  74.00  94.65   33
 42  \w     62.00  89.00   1.00   14.00    --   90.00  64.00 -17.10   27
 43  \w     61.00 136.00   1.00   14.00    --   90.00  69.00  79.59   75
 44  \w     65.00  92.00   1.00   14.00    --   94.00  67.00-170.41   27
 45  \w    137.00 165.00   1.00   14.00    --   94.00  73.00 131.56   28
 46  \w     64.00  91.00   1.00   14.00    --   94.00  73.00 131.56   27
 47  \w    102.00 127.00   1.00   14.00    --  101.44 -77.00-180.00   25
 48  \w     75.00 158.00   1.00   14.00    --  101.44  61.00 120.00   83
 49  \w     27.00  86.00   1.00   14.00    --  101.44 -77.00-180.00   59
 50  \w     75.00 171.00   1.00   14.00    --  101.44  61.00 -60.00   96
 51  \w     42.00 112.00   1.00   14.00    --  101.44-125.00  90.00   70
 52  \w     76.00 151.00   1.00   14.00    --  101.44  57.00 -10.95   75
 53  \w     73.00 163.00   1.00   14.00    --  101.44  71.00  41.49   90
 54  \w     75.00 171.00   1.00   14.00    --  101.44  59.00 167.12   96
 55  \w     82.00 113.00   1.00   14.00    --  101.44-125.00 -60.00   31
 56  \w    136.00 168.00   1.00   14.00    --  101.44  61.00   0.00   32
 57  \w     76.00 103.00   1.00   14.00    --  101.44  61.00   0.00   27
 58  \w     31.00  76.00   1.00   14.00    --  101.44 -61.00  60.00   45
 59  \w     75.00 119.00   1.00   14.00    --  101.44  61.00  30.00   44
 60  \w    120.00 171.00   1.00   14.00    --  101.44  61.00-120.00   51
 61  \w     76.00 108.00   1.00   14.00    --  101.44  61.00-120.00   32
 62  \w     34.00  91.00   1.00   14.00    --  101.44 -61.00-150.00   57
 63  \w     30.00 113.00   1.00   14.00    --  101.44-125.00   0.00   83
 64  \w     28.00  53.00   1.00   14.00    --  101.44 -30.00-120.00   25
 65  \w     75.00 166.00   1.00   14.00    --  101.44  61.00-150.00   91
 66  \w     53.00  93.00   1.00   14.00    --  101.44 -61.00 -60.00   40
 67  \w     31.00 112.00   1.00   14.00    --  101.44-125.00-180.00   81
 68  \w    120.00 147.00   1.00   14.00    --  101.44  61.00 -90.00   27
 69  \w     76.00 108.00   1.00   14.00    --  101.44  61.00 -90.00   32
;
_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      -0.0721808000
_diffrn_orient_matrix_UB_12      -0.0418513000
_diffrn_orient_matrix_UB_13      -0.0977781000
_diffrn_orient_matrix_UB_21      -0.0475770000
_diffrn_orient_matrix_UB_22      -0.0932085000
_diffrn_orient_matrix_UB_23      0.0104826000
_diffrn_orient_matrix_UB_31      -0.0914209000
_diffrn_orient_matrix_UB_32      0.0493005000
_diffrn_orient_matrix_UB_33      0.0199900000
_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  0.0234
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            59544
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.525
_diffrn_reflns_theta_min         3.483
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    1.651
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.723
_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    1.289
_exptl_crystal_description       block
_exptl_crystal_F_000             1216
_exptl_crystal_recrystallization_method 'ethanol - 30C'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.168
_exptl_crystal_size_min          0.064
_refine_diff_density_max         0.404
_refine_diff_density_min         -0.404
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     763
_refine_ls_number_reflns         11523
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0302
_refine_ls_R_factor_gt           0.0281
_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^)+(0.0399P)^2^+1.0686P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0762
_refine_ls_wR_factor_ref         0.0779
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10732
_reflns_number_total             11523
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc1c02907_si_002.cif
_cod_data_source_block           ochdkc
_cod_original_cell_volume        2961.44(8)
_cod_database_code               4519021
_nottingham_internal_coll_name   OCHDKC
_nottingham_internal_coll_number 18737
_nottingham_internal_coll_client CH/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '3.50, 14.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pcxch6
_nottingham_internal_coll_date   20/07/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 06/08/2020
_nottingham_internal_process_user pcxch6
_nottingham_internal_solution_date 06/08/2020
_nottingham_internal_solution_user pcxch6
_nottingham_internal_refinement_date 20/08/2020
_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 pcxh6
_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         C16H18N1O2P
_chemical_oxdiff_usercomment
'OCHDKC #18737 GVA-1807 CH/DLK fomblin micromount'
_shelx_estimated_absorpt_t_max   0.902
_shelx_estimated_absorpt_t_min   0.673
_reflns_odcompleteness_completeness 99.95
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N4-H4 = N3-H3A = N1-H1 = N2-H2A
 0.88 with sigma of 0.02
 N4-C62B \\sim N4-C62A
 with sigma of 0.02
 C63B-C62B \\sim C63A-C62A
 with sigma of 0.02
 C64B-C63B \\sim C64A-C63A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C63A, C63B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33, C62A, C62B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C64A, C64B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C62B)=Sof(H62C)=Sof(H62D)=Sof(C63B)=Sof(H63C)=Sof(H63D)=Sof(C64B)=
 Sof(H64D)=Sof(H64E)=Sof(H64F)=1-FVAR(1)
 Sof(C62A)=Sof(H62A)=Sof(H62B)=Sof(C63A)=Sof(H63A)=Sof(H63B)=Sof(C64A)=
 Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C30(H30A,H30B), C31(H31A,H31B), C46(H46A,
 H46B), C47(H47A,H47B), C62A(H62A,H62B), C62B(H62C,H62D), C63A(H63A,H63B),
 C63B(H63C,H63D)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4A), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24), C25(H25),
  C26(H26), C27(H27), C28(H28), N3(H3A), C34(H34), C35(H35), C36(H36), C37(H37),
  C38(H38), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C50(H50),
 C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59),
  C60(H60)
5.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C32(H32A,H32B,H32C), C48(H48A,H48B,H48C), C64A(H64A,H64B,
 H64C), C64B(H64D,H64E,H64F)
;
_shelx_res_checksum              26441
_shelx_hkl_checksum              62179
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id OCHDKC
_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 1.765
_oxdiff_exptl_absorpt_empirical_full_min 0.719