Concise Synthesis of Phospholene and Its P-Stereogenic Derivatives.
Hu, Wei; Li, Er-Qing; Duan, Zheng; Mathey, François; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00545

data_4038398
_publ_section_title
;
 Concise Synthesis of Phospholene and Its P-Stereogenic Derivatives.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00545
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         '0.5(C44 H38 Au2 Cl2 O2 P2)'
_chemical_formula_sum            'C22 H19 Au Cl O P'
_chemical_formula_weight         562.76
_space_group_crystal_system      tetragonal
_space_group_IT_number           90
_space_group_name_Hall           'P 4ab 2ab'
_space_group_name_H-M_alt        'P 4 21 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2020-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   25.9881(4)
_cell_length_b                   25.9881(4)
_cell_length_c                   13.3080(3)
_cell_measurement_reflns_used    7265
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.3800
_cell_measurement_theta_min      3.7110
_cell_volume                     8988.0(3)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -99.00 -52.00   0.50    4.00    --  -33.50 -57.00  30.00   94
  2  \w    -58.00  -2.00   0.50    4.00    --  -33.50  77.00 -60.00  112
  3  \w    -69.00 -41.00   0.50    4.00    --  -33.50 178.00 -90.00   56
  4  \w     73.00 100.00   0.50    4.00    --   36.47 178.00-150.00   54
  5  \w    -31.00  47.00   0.50    4.00    --   36.47 -57.00  60.00  156
  6  \w     58.00  95.00   0.50    4.00    --   36.47 178.00  30.00   74
  7  \w     40.00 110.00   0.50   15.00    --  108.00 -94.00-180.00  140
  8  \w    126.00 162.00   0.50   15.00    --  108.00 111.00-120.00   72
  9  \w     38.00  78.00   0.50   15.00    --  108.00 -94.00  30.00   80
 10  \w     63.00 172.00   0.50   15.00    --  108.00  15.00 -90.00  218
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0529129000
_diffrn_orient_matrix_UB_12      -0.0264213000
_diffrn_orient_matrix_UB_13      0.0086724000
_diffrn_orient_matrix_UB_21      0.0247267000
_diffrn_orient_matrix_UB_22      -0.0519572000
_diffrn_orient_matrix_UB_23      -0.0276231000
_diffrn_orient_matrix_UB_31      0.0102234000
_diffrn_orient_matrix_UB_32      -0.0107514000
_diffrn_orient_matrix_UB_33      0.1120718000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0352
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            19672
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.080
_diffrn_reflns_theta_max         67.080
_diffrn_reflns_theta_min         3.321
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.119
_exptl_absorpt_correction_T_max  0.489
_exptl_absorpt_correction_T_min  0.176
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.664
_exptl_crystal_description       prism
_exptl_crystal_F_000             4320
_exptl_crystal_size_max          0.237
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.066
_refine_diff_density_max         1.394
_refine_diff_density_min         -0.686
_refine_diff_density_rms         0.110
_refine_ls_abs_structure_details
;
 Flack x determined using 2720 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.023(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     399
_refine_ls_number_reflns         8017
_refine_ls_number_restraints     32
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0476
_refine_ls_R_factor_gt           0.0414
_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^)+(0.0730P)^2^+3.3659P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1155
_refine_ls_wR_factor_ref         0.1200
_reflns_Friedel_coverage         0.776
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                7085
_reflns_number_total             8017
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00545_si_003.cif
_cod_data_source_block           20200112
_cod_original_cell_volume        8987.9(3)
_cod_database_code               4038398
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C44H39O5Cl2Au2P2
_reflns_odcompleteness_completeness 99.80
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C22-O1
 1.5 with sigma of 0.02
3. Rigid bond restraints
 C23, C28
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C23) \\sim Ueq, Uanis(C28) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C22) \\sim Ueq, Uanis(C20) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5.a Riding coordinates:
 C20(H20)
5.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C36(H36A,H36B)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C5(H5), C4(H4), C3(H3), C2(H2), C10(H10), C9(H9), C8(H8), C7(H7),
 C15(H15), C17(H17), C18(H18), C21(H21), C24(H24), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C37(H37), C42(H42),
 C43(H43), C39(H39), C40(H40)
5.d Fitted hexagon refined as free rotating group:
 C1(C6,C5,C4,C3,C2), C12(C11,C10,C9,C8,C7), C16(C17,C18,C19,C20,C21), C23(C24,
 C25,C26,C27,C28), C33(C34,C29,C30,C31,C32), C42(C43,C38,C39,C40,C41)
5.e Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              27117
_shelx_hkl_checksum              94046
_shelx_fab_checksum              20572
_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 1.298
_oxdiff_exptl_absorpt_empirical_full_min 0.852