Evaluation and Development of Methodologies for the Synthesis of Thiophosphinic Acids
Winters, Karen R.; Montchamp, Jean-Luc; The Journal of Organic Chemistry  (2020) –; doi:10.1021/acs.joc.0c01151

data_4038671
_publ_section_title
;
 Evaluation and Development of Methodologies for the Synthesis of
 Thiophosphinic Acids
;
_journal_name_full               'The Journal of Organic Chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01151
_journal_year                    2020
_chemical_formula_moiety         '1(C26 H22 N O2 P)'
_chemical_formula_sum            'C26 H22 N O2 P'
_chemical_formula_weight         411.41
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-03-01
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                96.509(4)
_cell_angle_beta                 95.256(4)
_cell_angle_gamma                90.126(4)
_cell_formula_units_Z            2
_cell_length_a                   5.0456(4)
_cell_length_b                   10.0717(8)
_cell_length_c                   20.3776(17)
_cell_measurement_reflns_used    9789
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      44.956
_cell_measurement_theta_min      3.031
_cell_volume                     1024.46(14)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.98
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0344
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            44276
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.282
_diffrn_reflns_theta_min         3.028
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.158
_exptl_absorpt_correction_T_max  0.7489
_exptl_absorpt_correction_T_min  0.6843
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0678 before and 0.0480 after correction.
The Ratio of minimum to maximum transmission is 0.9137.
The \l/2 correction factor is Not present.
;
_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    1.334
_exptl_crystal_description       plate
_exptl_crystal_F_000             432
_exptl_crystal_size_max          0.402
_exptl_crystal_size_mid          0.379
_exptl_crystal_size_min          0.056
_refine_diff_density_max         0.856
_refine_diff_density_min         -0.323
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Flack x determined using 4754 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.194
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     718
_refine_ls_number_reflns         10065
_refine_ls_number_restraints     305
_refine_ls_restrained_S_all      1.241
_refine_ls_R_factor_all          0.0522
_refine_ls_R_factor_gt           0.0517
_refine_ls_shift/su_max          0.037
_refine_ls_shift/su_mean         0.006
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0309P)^2^+1.9349P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1388
_refine_ls_wR_factor_ref         0.1390
_reflns_Friedel_coverage         0.992
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                9950
_reflns_number_total             10065
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01151_si_002.cif
_cod_data_source_block           ssphenyldopo
_cod_database_code               4038671
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.939
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9918(11)
 0.0082(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C22-C26 \\sim C22A-C26A
 with sigma of 0.04
 C21-C20 \\sim C21-C22 \\sim C21-C26 \\sim C21-C22A \\sim C21-C26A
 with sigma of 0.02
 C52-C48 \\sim C52A-C48A
 with sigma of 0.04
 C47-C45 \\sim C47-C52 \\sim C47-C48 \\sim C47-C52A \\sim C47-C48A
 with sigma of 0.02
 C18-C14 \\sim C14A-C18A
 with sigma of 0.04
 C13-C11 \\sim C13-C18 \\sim C13-C14 \\sim C13-C14A \\sim C13-C18A
 with sigma of 0.02
 C31-C27 \\sim C31A-C27A
 with sigma of 0.04
 C32-C34 \\sim C32-C31 \\sim C32-C27 \\sim C32-C31A \\sim C32-C27A
 with sigma of 0.02
4. Rigid body (RIGU) restrains
 C21, C24, C22, C26, C23, C25, C22A, C23A, C24A, C25A, C26A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13, C16, C18, C14, C17, C15, C14A, C15A, C16A, C17A, C18A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C47, C50, C51, C52, C49, C48, C50A, C51A, C52A, C48A, C49A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C32, C29, C31, C28, C30, C27, C30A, C31A, C27A, C28A, C29A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=
 Sof(H25A)=Sof(C26A)=Sof(H26A)=1-FVAR(1)
 Sof(C24)=Sof(H24)=Sof(C22)=Sof(H22)=Sof(C26)=Sof(H26)=Sof(C23)=Sof(H23)=
 Sof(C25)=Sof(H25)=FVAR(1)
 Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=
 Sof(H17A)=Sof(C18A)=Sof(H18A)=1-FVAR(2)
 Sof(C16)=Sof(H16)=Sof(C18)=Sof(H18)=Sof(C14)=Sof(H14)=Sof(C17)=Sof(H17)=
 Sof(C15)=Sof(H15)=FVAR(2)
 Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=Sof(C52A)=Sof(H52A)=Sof(C48A)=
 Sof(H48A)=Sof(C49A)=Sof(H49A)=1-FVAR(3)
 Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=Sof(C49)=Sof(H49)=
 Sof(C48)=Sof(H48)=FVAR(3)
 Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=
 Sof(H28A)=Sof(C29A)=Sof(H29A)=1-FVAR(4)
 Sof(C29)=Sof(H29)=Sof(C31)=Sof(H31)=Sof(C28)=Sof(H28)=Sof(C30)=Sof(H30)=
 Sof(C27)=Sof(H27)=FVAR(4)
6.a Riding coordinates:
 N1(H1), N2(H2)
6.b Ternary CH refined with riding coordinates:
 C20(H20), C34(H34)
6.c Aromatic/amide H refined with riding coordinates:
 C36(H36), C43(H43), C42(H42), C1(H1A), C8(H8), C44(H44), C38(H38), C3(H3),
 C16(H16), C37(H37), C9(H9), C39(H39), C10(H10), C4(H4), C2(H2A), C24(H24),
 C50(H50), C29(H29), C18(H18), C51(H51), C52(H52), C31(H31), C28(H28), C22(H22),
  C30(H30), C27(H27), C26(H26), C49(H49), C48(H48), C14(H14), C17(H17),
 C23(H23), C15(H15), C25(H25), C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A),
 C26A(H26A), C14A(H14A), C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A),
 C50A(H50A), C51A(H51A), C52A(H52A), C48A(H48A), C49A(H49A), C30A(H30A),
 C31A(H31A), C27A(H27A), C28A(H28A), C29A(H29A)
6.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C19(H19A,H19B,H19C)
;
_olex2_submission_special_instructions 'No special instructions were received'