Direct Functionalization of White Phosphorus to Cyclotetraphosphanes: Selective Formation of Four P-C Bonds.
Du, Shanshan; Yang, Jimin; Hu, Jingyuan; Chai, Zhengqi; Luo, Gen; Luo, Yi; Zhang, Wen-Xiong; Xi, Zhenfeng; Journal of the American Chemical Society 141 (2019) 6843–6847; doi:10.1021/jacs.9b02628

data_4128135
_publ_section_title
;
 Direct Functionalization of White Phosphorus to Cyclotetraphosphanes:
 Selective Formation of Four P-C Bonds.
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6843
_journal_page_last               6847
_journal_paper_doi               10.1021/jacs.9b02628
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'C36 H72 Al2 P4 Si4, 2(C16 H32 Li O4), 2(C4 H8 O)'
_chemical_formula_sum            'C76 H152 Al2 Li2 O10 P4 Si4'
_chemical_formula_weight         1530.06
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-08-31
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   16.4422(2)
_cell_length_b                   20.0536(3)
_cell_length_c                   27.5154(4)
_cell_measurement_reflns_used    61731
_cell_measurement_temperature    180.0(3)
_cell_measurement_theta_max      28.4460
_cell_measurement_theta_min      3.5920
_cell_volume                     9072.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      180.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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     26.00  75.00   0.50    2.00    --   -9.50  57.00   0.00   98
  2  \w    -33.00  -7.00   0.50    2.00    --   -9.50  57.00   0.00   52
  3  \w    -31.00  29.00   0.50    2.00    --   -9.50 -77.00-150.00  120
  4  \w    -89.00  15.00   0.50    2.00    --   -9.50 -57.00   0.00  208
  5  \w    -88.00  70.00   0.50    2.00    --   -9.50   0.00 -30.00  316
  6  \w    -68.00  34.00   0.50    2.00    --    9.80 -57.00 150.00  204
  7  \w      0.00  52.00   0.50    2.00    --    9.80 -82.00 -30.00  104
  8  \w    -25.00  52.00   0.50    2.00    --    9.80 -82.00-120.00  154
  9  \w    -21.00  73.00   0.50    2.00    --    9.80  57.00 -60.00  188
 10  \w     -6.00  52.00   0.50    2.00    --    9.80 -82.00  60.00  116
 11  \w     71.00  97.00   0.50    2.00    --    9.80  38.00-150.00   52
 12  \w    -29.00  57.00   0.50    2.00    --    9.80  38.00-150.00  172
 13  \w    -34.00  52.00   0.50    2.00    --    9.80 -82.00 120.00  172
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0274439000
_diffrn_orient_matrix_UB_12      0.0270500000
_diffrn_orient_matrix_UB_13      -0.0026498000
_diffrn_orient_matrix_UB_21      0.0112822000
_diffrn_orient_matrix_UB_22      -0.0031414000
_diffrn_orient_matrix_UB_23      0.0247785000
_diffrn_orient_matrix_UB_31      0.0313131000
_diffrn_orient_matrix_UB_32      -0.0225606000
_diffrn_orient_matrix_UB_33      -0.0066169000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0467
_diffrn_reflns_av_unetI/netI     0.0149
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            215028
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.37
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.204
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76020
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic yellowish yellow'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.120
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3344
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.412
_refine_diff_density_min         -0.784
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     450
_refine_ls_number_reflns         8895
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0826
_refine_ls_R_factor_gt           0.0738
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1083P)^2^+13.6682P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1997
_refine_ls_wR_factor_ref         0.2094
_reflns_number_gt                7711
_reflns_number_total             8895
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b02628_si_002.cif
_cod_data_source_block           2b
_cod_database_code               4128135
_chemical_oxdiff_formula         'C1 H1 Si1 P1 O1 Li1 Al1'
_reflns_odcompleteness_completeness 99.65
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C13-C12
 1.6 with sigma of 0.02
3. Rigid bond restraints
 C12, C11
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C13, C12
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C13, C14
 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(C33) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
5.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,
 H15B), C17(H17A,H17B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B),
 C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B),
  C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,
 H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B),
 C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B)
5.b Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C)
;
_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 1.411
_oxdiff_exptl_absorpt_empirical_full_min 0.581