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_4126529
_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 H82 Ga2 N4 P6, 0.5(C7 H8)'
_chemical_formula_sum            'C61.5 H86 Ga2 N4 P6'
_chemical_formula_weight         1206.60
_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   geom
_audit_creation_date             2016-02-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                81.3033(9)
_cell_angle_beta                 74.9836(9)
_cell_angle_gamma                79.5858(9)
_cell_formula_units_Z            4
_cell_length_a                   14.19345(14)
_cell_length_b                   18.9626(2)
_cell_length_c                   24.9591(3)
_cell_measurement_reflns_used    63930
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4930
_cell_measurement_theta_min      2.8340
_cell_volume                     6342.70(12)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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     13.00  53.00   0.50    2.00    --   42.50 -77.00 -60.00   80
  2  \w     42.00 138.00   0.50    8.00    --  111.00 -61.00-120.00  192
  3  \w    102.00 142.00   0.50    8.00    --  111.00 -77.00 -30.00   80
  4  \w    105.00 145.00   0.50    8.00    --  111.00 -15.00  30.00   80
  5  \w     98.00 155.00   0.50    8.00    --  111.00  45.00  30.00  114
  6  \w    139.00 165.00   0.50    8.00    --  111.00  45.00 -30.00   52
  7  \w    128.00 178.00   0.50    8.00    --  111.00  15.00 -60.00  100
  8  \w    127.00 174.00   0.50    8.00    --  111.00  94.00-160.00   94
  9  \w     90.00 137.00   0.50    8.00    --  111.00  45.00 -90.00   94
 10  \w     91.00 168.00   0.50    8.00    --  111.00  45.00   0.00  154
 11  \w    102.00 139.00   0.50    8.00    --  111.00 -61.00  90.00   74
 12  \w     93.00 127.00   0.50    8.00    --  111.00 -30.00  30.00   68
 13  \w     74.00 121.00   0.50    8.00    --  111.00  15.00 -60.00   94
 14  \w     81.00 121.00   0.50    8.00    --  111.00  77.00  30.00   80
 15  \w     74.00 101.00   0.50    2.00    --   42.50  38.00  90.00   54
 16  \w     45.00 134.00   0.50    8.00    --  111.00 -45.00  60.00  178
 17  \w     76.00 121.00   0.50    8.00    --  111.00-125.00 150.00   90
 18  \w     60.00 121.00   0.50    8.00    --  111.00-125.00  60.00  122
 19  \w     91.00 117.00   0.50    8.00    --  111.00-125.00   0.00   52
 20  \w     79.00 121.00   0.50    8.00    --  111.00-125.00 -60.00   84
 21  \w     88.00 121.00   0.50    8.00    --  111.00-125.00-120.00   66
 22  \w     71.00  97.00   0.50    8.00    --  111.00 -77.00 -30.00   52
 23  \w     57.00  99.00   0.50    8.00    --  111.00 -94.00  60.00   84
 24  \w     60.00 125.00   0.50    8.00    --  111.00 -77.00 120.00  130
 25  \w     58.00  94.00   0.50    2.00    --   42.50-125.00 120.00   72
 26  \w     45.00  72.00   0.50    8.00    --  111.00-125.00   0.00   54
 27  \w     30.00 109.00   0.50    8.00    --  111.00 -94.00-120.00  158
 28  \w     64.00 135.00   0.50    8.00    --  111.00 -30.00-150.00  142
 29  \w     53.00  79.00   0.50    8.00    --  111.00 -30.00  30.00   52
 30  \w     33.00  86.00   0.50    8.00    --  111.00 -15.00  30.00  106
 31  \w     39.00  68.00   0.50    8.00    --  111.00-125.00-120.00   58
 32  \w    -21.00   6.00   0.50    2.00    --   42.50 -77.00 -60.00   54
 33  \w    -61.00  32.00   0.50    2.00    --  -38.50  57.00  90.00  186
 34  \w    -21.00  28.00   0.50    2.00    --   42.50 -57.00 150.00   98
 35  \w   -109.00 -12.00   0.50    2.00    --  -38.50 -57.00 -60.00  194
 36  \w    -98.00  -8.00   0.50    2.00    --  -38.50 -77.00-150.00  180
 37  \w     96.00 121.00   0.50    8.00    --  111.00-123.00-130.87   50
 38  \w    -65.00  32.00   0.50    2.00    --  -38.50  57.00 -90.00  194
 39  \w   -109.00 -12.00   0.50    2.00    --  -38.50 -57.00  60.00  194
 40  \w     12.00 117.00   0.50    2.00    --   43.00  77.00 -60.00  210
 41  \w     12.00 117.00   0.50    2.00    --   43.00  77.00-150.00  210
 42  \w     12.00 117.00   0.50    2.00    --   43.00  77.00 150.00  210
 43  \w     12.00 117.00   0.50    2.00    --   43.00  77.00  90.00  210
 44  \w     12.00 117.00   0.50    2.00    --   43.00  77.00  30.00  210
 45  \w     83.00 139.00   0.50    8.00    --  111.00  61.00  30.00  112
 46  \w     83.00 178.00   0.50    8.00    --  111.00  61.00-150.00  190
 47  \w     83.00 112.00   0.50    8.00    --  111.00  61.00 120.00   58
;
_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      0.0596937000
_diffrn_orient_matrix_UB_12      -0.0437446000
_diffrn_orient_matrix_UB_13      -0.0482108000
_diffrn_orient_matrix_UB_21      -0.0298001000
_diffrn_orient_matrix_UB_22      -0.0700172000
_diffrn_orient_matrix_UB_23      0.0352720000
_diffrn_orient_matrix_UB_31      -0.0919857000
_diffrn_orient_matrix_UB_32      0.0095201000
_diffrn_orient_matrix_UB_33      -0.0237789000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0215
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            104946
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.676
_diffrn_reflns_theta_min         2.383
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.771
_exptl_absorpt_correction_T_max  0.828
_exptl_absorpt_correction_T_min  0.583
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (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            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.264
_exptl_crystal_description       block
_exptl_crystal_F_000             2540
_exptl_crystal_size_max          0.288
_exptl_crystal_size_mid          0.138
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.612
_refine_diff_density_min         -0.529
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1387
_refine_ls_number_reflns         26412
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0256
_refine_ls_R_factor_gt           0.0246
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0311P)^2^+3.5484P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0637
_refine_ls_wR_factor_ref         0.0644
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25395
_reflns_number_total             26412
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_006.cif
_cod_data_source_block           3
_cod_original_formula_sum        'C61.50 H86 Ga2 N4 P6'
_cod_database_code               4126529
_chemical_oxdiff_formula         C62H84Ga2N4P6
_chemical_oxdiff_usercomment     Toluene
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C65A-C59A
 1.51 with sigma of 0.01
 C60A-C65A \\sim C65A-C64A
 with sigma of 0.01
3. Restrained planarity
 C65B, C59B, C64B, C60B, C63B, C61B, C62B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C60A \\sim C61A \\sim C62A \\sim C63A \\sim C64A \\sim C59A \\sim C65A: within
2A with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C60B) = Uanis(C63B)
Uanis(C61B) = Uanis(C64B)
Uanis(C62B) = Uanis(C59B)
5. Others
 Fixed Sof: C59B(0.5) C64B(0.5) H64B(0.5) C63B(0.5) H63B(0.5) C62B(0.5)
 H62B(0.5) C61B(0.5) H61B(0.5) C60B(0.5) H60B(0.5) C65B(0.5) H65A(0.5)
 H65B(0.5) H65C(0.5) C60A(0.5) H60A(0.5) C61A(0.5) H61A(0.5) C62A(0.5)
 H62A(0.5) C63A(0.5) H63A(0.5) C64A(0.5) H64A(0.5) C59A(0.5) C65A(0.5)
 H65D(0.5) H65E(0.5) H65F(0.5)
6.a Ternary CH refined with riding coordinates:
 C6(HB), C8(H1BE), C9(H7), C12(H10), C18(H1BF), C53A(H53A), C1D(H1BH),
 C41A(H41A), C1G(H1BI), C1I(H1C), C15A(H15A), C41B(H41B), C15B(H15B), C1R(H1K),
 C53B(H53B), C1X(H1N)
6.b Aromatic/amide H refined with riding coordinates:
 C2B(H2B), C1(H1BA), C2(H1BB), C3(H1BC), C7(H1BD), C8B(H8B), C13(H11),
 C8A(H8A), C2A(H2A), C10A(H10A), C15(H13), C16(H14), C1C(H1BG), C9A(H9A),
 C1E(H17), C1F(H1B), C1H(H1BJ), C1J(H1BK), C1K(H1BL), C51A(H51A), C51B(H51B),
 C9B(H9B), C10B(H10B), C1O(H1H), C1P(H1J), C1T(H1BY), C1V(H1M), C23(H1R),
 C64B(H64B), C63B(H63B), C62B(H62B), C61B(H61B), C60B(H60B), C60A(H60A),
 C61A(H61A), C62A(H62A), C63A(H63A), C64A(H64A)
6.c Fitted hexagon refined as free rotating group:
 C59B(C64B,C63B,C62B,C61B,C60B), C60A(C61A,C62A,C63A,C64A,C59A)
6.d Idealised Me refined as rotating group:
 C5A(H5AA,H5AB,H5AC), C33A(H33A,H33B,H33C), C4B(H4BA,H4BB,H4BC), C4A(H4AA,H4AB,
 H4AC), C33B(H33D,H33E,H33F), C5B(H5BA,H5BB,H5BC), C42A(H42A,H42B,H42C),
 C1L(H1BM,H1BN,H1BO), C1M(H1DA,H1DB,H1DC), C1N(H1BP,H1BQ,H1BR), C1Q(H1BS,H1BT,
 H1BU), C1S(H1BV,H1BW,H1BX), C29A(H29A,H29B,H29C), C1U(H2BA,H2BB,H2BC),
 C13A(H13A,H13B,H13C), C14A(H14A,H14B,H14C), C1W(H1BZ,H,HA), C1Y(H2BD,H2BE,
 H2BF), C1Z(H0AA,HC,HD), C20(H1AA,HE,HF), C21(H1OA,H1OB,H1OC), C55A(H55A,H55B,
 H55C), C46A(H46A,H46B,H46C), C22(H1PA,H1PB,H1PC), C13B(H13D,H13E,H13F),
 C14B(H14D,H14E,H14F), C16A(H16A,H16B,H16C), C42B(H42D,H42E,H42F), C24(H1UA,
 H1UB,H1UC), C25(H1VA,H1VB,H1VC), C26(H1WA,H1WB,H1WC), C27(H1XA,H1XB,H1XC),
 C58A(H58A,H58B,H58C), C29B(H29D,H29E,H29F), C46B(H46D,H46E,H46F), C55B(H55D,
 H55E,H55F), C16B(H16D,H16E,H16F), C28(H22A,H22B,H22C), C29(H23A,H23B,H23C),
 C58B(H58D,H58E,H58F), C65B(H65A,H65B,H65C), C65A(H65D,H65E,H65F)
;
_shelx_res_checksum              4009
_shelx_hkl_checksum              63247
_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 1.324
_oxdiff_exptl_absorpt_empirical_full_min 0.764