Selective Derivatization of a Hexaphosphane from Functionalization of White Phosphorus.
Hennersdorf, Felix; Frötschel, Julia; Weigand, Jan J.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b07704

data_4126527
_publ_section_title
;
 Selective Derivatization of a Hexaphosphane from Functionalization of
 White Phosphorus.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b07704
_journal_year                    2017
_chemical_formula_moiety         'C58 H83 Cl Ga2 N4 P6, 2(C7 H8)'
_chemical_formula_sum            'C72 H99 Cl Ga2 N4 P6'
_chemical_formula_weight         1381.26
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-06-08
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                89.4430(13)
_cell_angle_beta                 68.6438(14)
_cell_angle_gamma                88.7141(12)
_cell_formula_units_Z            2
_cell_length_a                   13.45492(19)
_cell_length_b                   15.7011(2)
_cell_length_c                   18.1283(3)
_cell_measurement_reflns_used    38349
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.4840
_cell_measurement_theta_min      2.7940
_cell_volume                     3565.86(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2850
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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   -112.00 -51.00   0.50    1.00    --  -38.50-158.00 -31.00  122
  2  \w    -70.00  35.00   0.50    1.00    --  -38.50  77.00 120.00  210
  3  \w   -109.00 -12.00   0.50    1.00    --  -38.50 -57.00 -30.00  194
  4  \w    -70.00  35.00   0.50    1.00    --  -38.50  77.00-120.00  210
  5  \w    -70.00  35.00   0.50    1.00    --  -38.50  77.00   0.00  210
  6  \w   -111.00 -16.00   0.50    1.00    --  -38.50 -38.00-150.00  190
  7  \w     87.00 178.00   0.50    4.00    --  111.00  45.00 120.00  182
  8  \w     30.00 109.00   0.50    4.00    --  111.00 -94.00 -90.00  158
  9  \w     40.00 135.00   0.50    4.00    --  111.00 -45.00-120.00  190
 10  \w     39.00 121.00   0.50    4.00    --  111.00-125.00 120.00  164
 11  \w     30.00 109.00   0.50    4.00    --  111.00 -94.00  90.00  158
 12  \w     87.00 178.00   0.50    4.00    --  111.00  30.00  60.00  182
 13  \w     80.00 178.00   0.50    4.00    --  111.00  77.00   0.00  196
 14  \w     87.00 178.00   0.50    4.00    --  111.00  30.00-180.00  182
 15  \w     66.00 178.00   0.50    4.00    --  111.00  15.00 -60.00  224
 16  \w     30.00 109.00   0.50    4.00    --  111.00 -94.00  30.00  158
 17  \w     39.00 121.00   0.50    4.00    --  111.00-125.00-180.00  164
 18  \w     40.00 135.00   0.50    4.00    --  111.00 -45.00  90.00  190
 19  \w     49.00 121.00   0.50    4.00    --  111.00-125.00   0.00  144
 20  \w     89.00 177.00   0.50    4.00    --  111.00  45.00  90.00  176
 21  \w     92.00 118.00   0.50    4.00    --  111.00-118.00 121.00   52
 22  \w     56.00  97.00   0.50    4.00    --  111.00 -94.00-120.00   82
 23  \w     40.00  91.00   0.50    4.00    --  111.00-125.00-120.00  102
 24  \w     35.00  73.00   0.50    4.00    --  111.00 -94.00 -60.00   76
 25  \w     54.00 121.00   0.50    4.00    --  111.00-125.00-150.00  134
 26  \w     55.00 103.00   0.50    4.00    --  111.00 -94.00   0.00   96
 27  \w    101.00 147.00   0.50    4.00    --  111.00  30.00   0.00   92
 28  \w     46.00  72.00   0.50    4.00    --  111.00 -94.00  60.00   52
 29  \w    134.00 176.00   0.50    4.00    --  111.00 125.00 -30.00   84
 30  \w     46.00 131.00   0.50    4.00    --  111.00 -61.00   0.00  170
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0626872000
_diffrn_orient_matrix_UB_12      -0.0233253000
_diffrn_orient_matrix_UB_13      0.0871526000
_diffrn_orient_matrix_UB_21      -0.0035840000
_diffrn_orient_matrix_UB_22      -0.0933511000
_diffrn_orient_matrix_UB_23      -0.0241308000
_diffrn_orient_matrix_UB_31      0.1057300000
_diffrn_orient_matrix_UB_32      -0.0193144000
_diffrn_orient_matrix_UB_33      0.0122172000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0210
_diffrn_reflns_av_unetI/netI     0.0193
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            51732
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.734
_diffrn_reflns_theta_min         2.617
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.868
_exptl_absorpt_correction_T_max  0.868
_exptl_absorpt_correction_T_min  0.652
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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    1.286
_exptl_crystal_description       block
_exptl_crystal_F_000             1456
_exptl_crystal_size_max          0.227
_exptl_crystal_size_mid          0.182
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.613
_refine_diff_density_min         -0.604
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.141
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     889
_refine_ls_number_reflns         14876
_refine_ls_number_restraints     74
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.0404
_refine_ls_R_factor_gt           0.0400
_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^)+(0.0181P)^2^+5.3975P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0891
_refine_ls_wR_factor_ref         0.0893
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14649
_reflns_number_total             14876
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_022.cif
_cod_data_source_block           10_1
_cod_original_cell_volume        3565.87(10)
_cod_database_code               4126527
_chemical_oxdiff_formula         'C144 H202 Cl2 Ga4 N8 P12 '
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C68A-C69A \\sim C70A-C69A \\sim C70A-C71A \\sim C66A-C71A \\sim C66A-C67A
\\sim C68A-C67A \\sim C70B-
 C71B \\sim C69B-C70B \\sim C69B-C68B \\sim C67B-C68B \\sim C67B-C66B \\sim
C66B-C71B
 with sigma of 0.001
 P4A-H4A \\sim P4B-H4B
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
C66B \\sim C67B \\sim C68B \\sim C69B \\sim C70B \\sim C71B \\sim C72B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(Cl1B)=Sof(P1B)=Sof(P2B)=Sof(P3B)=Sof(P4B)=Sof(H4B)=Sof(P5B)=Sof(P6B)=
 Sof(C66B)=Sof(C67B)=Sof(H67B)=Sof(C68B)=Sof(H68B)=Sof(C69B)=Sof(H69B)=
 Sof(C70B)=Sof(H70B)=Sof(C71B)=Sof(H71B)=Sof(C72B)=Sof(H72D)=Sof(H72E)=
 Sof(H72F)=1-FVAR(1)
 Sof(Cl1A)=Sof(P1A)=Sof(P2A)=Sof(P3A)=Sof(P4A)=Sof(H4A)=Sof(P5A)=Sof(P6A)=
 Sof(C66A)=Sof(C67A)=Sof(H67A)=Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(H69A)=
 Sof(C70A)=Sof(H70A)=Sof(C71A)=Sof(H71A)=Sof(C72A)=Sof(H72A)=Sof(H72B)=
 Sof(H72C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27), C41(H41), C44(H44), C53(H53), C56(H56)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C31(H31),
 C37(H37), C38(H38), C39(H39), C49(H49), C50(H50), C51(H51), C67A(H67A),
 C67B(H67B), C68A(H68A), C68B(H68B), C69A(H69A), C69B(H69B), C70A(H70A),
 C70B(H70B), C71A(H71A), C71B(H71B), C60(H60), C61(H61), C62(H62), C63(H63),
 C64(H64)
5.c Idealised Me refined as rotating group:
 C4(H4C,H4D,H4E), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C72A(H72A,H72B,H72C), C72B(H72D,H72E,H72F),
 C65(H65A,H65B,H65C)
;
_shelx_res_checksum              27746
_shelx_hkl_checksum              7041
_shelx_shelxl_version_number     2014/7
_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 2.717
_oxdiff_exptl_absorpt_empirical_full_min 0.844