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_4128134
_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         'C32 H68 Al2 P4 Si4, 2(C16 H32 Li O4)'
_chemical_formula_sum            'C64 H132 Al2 Li2 O8 P4 Si4'
_chemical_formula_weight         1333.78
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_symmetry_space_group_name_Hall  '-P 2n 2ab'
_symmetry_space_group_name_H-M   'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-04-25
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   22.2409(11)
_cell_length_b                   16.5648(11)
_cell_length_c                   22.3829(13)
_cell_measurement_reflns_used    7757
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      28.2470
_cell_measurement_theta_min      3.6780
_cell_volume                     8246.2(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XH (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_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     25.00  69.00   0.50    3.93    --   -9.20  19.00 -30.00   88
  2  \w    -10.00  33.00   0.50    3.93    --   -9.20 -82.00 120.00   86
  3  \w    -24.00   2.00   0.50    3.93    --   -9.20 -82.00  30.00   52
  4  \w    -64.00   1.00   0.50    3.93    --   -9.20  19.00 -30.00  130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0251472000
_diffrn_orient_matrix_UB_12      -0.0262754000
_diffrn_orient_matrix_UB_13      -0.0013235000
_diffrn_orient_matrix_UB_21      -0.0192780000
_diffrn_orient_matrix_UB_22      0.0326161000
_diffrn_orient_matrix_UB_23      0.0074317000
_diffrn_orient_matrix_UB_31      -0.0036236000
_diffrn_orient_matrix_UB_32      0.0090028000
_diffrn_orient_matrix_UB_33      -0.0307620000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0451
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            35200
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.75
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.214
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71355
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7e (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    1.074
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2912
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_platon_squeeze_details
;
;
_refine_diff_density_max         0.881
_refine_diff_density_min         -0.419
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     389
_refine_ls_number_reflns         7974
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.1097
_refine_ls_R_factor_gt           0.0780
_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^)+(0.1174P)^2^+7.9390P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2033
_refine_ls_wR_factor_ref         0.2225
_reflns_number_gt                5502
_reflns_number_total             7974
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b02628_si_002.cif
_cod_data_source_block           2a
_cod_database_code               4128134
_chemical_oxdiff_formula         'C1 H1 O1 P1 Li1 Al1 Si1'
_reflns_odcompleteness_completeness 97.75
_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. Uiso/Uaniso restraints and constraints
Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C13(H13a,H13b), C15(H15a,H15b), C17(H17a,H17b), C18(H18a,H18b), 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)
3.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), C11(H11a,H11b,H11c), C12(H12a,H12b,H12c),
 C14(H14a,H14b,H14c), C16(H16a,H16b,H16c)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.374
_oxdiff_exptl_absorpt_empirical_full_min 0.829