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_4126540
_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         'C70 H92 Cl Ga2 N4 P7, 0.5(C5 H12), C H2 Cl2'
_chemical_formula_sum            'C73.5 H100 Cl3 Ga2 N4 P7'
_chemical_formula_weight         1502.15
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-02-13
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.7696(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   42.77468(17)
_cell_length_b                   16.26254(7)
_cell_length_c                   22.00113(9)
_cell_measurement_reflns_used    33210
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      76.3540
_cell_measurement_theta_min      2.8950
_cell_volume                     15297.24(11)
_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      100.0(2)
_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 0.989
_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    -61.00  34.00   0.50    1.00    --  -38.50  38.00-180.00  190
  2  \w    -65.00  32.00   0.50    1.00    --  -38.50  57.00  60.00  194
  3  \w     23.00  98.00   0.50    1.00    --   43.00-125.00-180.00  150
  4  \w     23.00  98.00   0.50    1.00    --   43.00-125.00 -30.00  150
  5  \w     31.00 108.00   0.50    4.00    --  111.00 -94.00-150.00  154
  6  \w     42.00 118.00   0.50    4.00    --  111.00 -30.00-150.00  152
  7  \w    140.00 165.00   0.50    4.00    --  111.00 125.00 -90.00   50
  8  \w    138.00 164.00   0.50    4.00    --  111.00  30.00  30.00   52
  9  \w    103.00 128.00   0.50    4.00    --  111.00  30.00  30.00   50
 10  \w     52.00 108.00   0.50    4.00    --  111.00 -94.00 -90.00  112
 11  \w     88.00 173.00   0.50    4.00    --  111.00  45.00  60.00  170
 12  \w     80.00 149.00   0.50    4.00    --  111.00  77.00 -30.00  138
 13  \w     54.00  93.00   0.50    4.00    --  111.00 -94.00 -60.00   78
 14  \w     54.00 108.00   0.50    4.00    --  111.00 -94.00 120.00  108
 15  \w     45.00  71.00   0.50    4.00    --  111.00 -61.00-150.00   52
 16  \w     95.00 137.00   0.50    4.00    --  111.00 125.00 -90.00   84
 17  \w     35.00  60.00   0.50    4.00    --  111.00 -94.00-180.00   50
 18  \w     48.00  74.00   0.50    4.00    --  111.00 -94.00 -30.00   52
 19  \w    114.00 154.00   0.50    4.00    --  111.00  51.00  83.00   80
;
_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      0.0218880000
_diffrn_orient_matrix_UB_12      0.0151149000
_diffrn_orient_matrix_UB_13      0.0557694000
_diffrn_orient_matrix_UB_21      0.0042019000
_diffrn_orient_matrix_UB_22      0.0901103000
_diffrn_orient_matrix_UB_23      -0.0197861000
_diffrn_orient_matrix_UB_31      -0.0283074000
_diffrn_orient_matrix_UB_32      0.0251124000
_diffrn_orient_matrix_UB_33      0.0374752000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0225
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -53
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            48808
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.654
_diffrn_reflns_theta_min         2.907
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.537
_exptl_absorpt_correction_T_max  0.810
_exptl_absorpt_correction_T_min  0.684
_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    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             6296
_exptl_crystal_size_max          0.295
_exptl_crystal_size_mid          0.184
_exptl_crystal_size_min          0.146
_refine_diff_density_max         1.201
_refine_diff_density_min         -0.992
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     861
_refine_ls_number_reflns         15927
_refine_ls_number_restraints     164
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0352
_refine_ls_R_factor_gt           0.0341
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0469P)^2^+31.1928P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0926
_refine_ls_wR_factor_ref         0.0935
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15340
_reflns_number_total             15927
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_015.cif
_cod_data_source_block           8_1
_cod_original_cell_volume        15297.23(11)
_cod_original_formula_sum        'C73.50 H100 Cl3 Ga2 N4 P7'
_cod_database_code               4126540
_chemical_oxdiff_formula         C73.5H100Cl3Ga2N4P7
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 C72-C73 \\sim C74-C73
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
P7B \\sim C66B \\sim C65B \\sim C70B \\sim C68B \\sim C69B \\sim C67B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C59B \\sim C60B \\sim C61B \\sim C62B \\sim C63B \\sim C64B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C59A \\sim C60A \\sim C61A \\sim C62A \\sim C63A \\sim C64A \\sim C59B \\sim
C60B \\sim C61B \\sim C62B \\sim C63B \\sim C64B: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
4. Others
 Sof(P7B)=Sof(P4B)=Sof(C59B)=Sof(C60B)=Sof(H60B)=Sof(C61B)=Sof(H61B)=Sof(C62B)=
 Sof(H62B)=Sof(C63B)=Sof(H63B)=Sof(C64B)=Sof(H64B)=Sof(C65B)=Sof(C70B)=
 Sof(H70B)=Sof(C69B)=Sof(H69B)=Sof(C68B)=Sof(H68B)=Sof(C67B)=Sof(H67B)=
 Sof(C66B)=Sof(H66B)=1-FVAR(1)
 Sof(P4A)=Sof(P7A)=Sof(C59A)=Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(H61A)=Sof(C62A)=
 Sof(H62A)=Sof(C63A)=Sof(H63A)=Sof(C64A)=Sof(H64A)=Sof(C65A)=Sof(C66A)=
 Sof(H66A)=Sof(C67A)=Sof(H67A)=Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(H69A)=
 Sof(C70A)=Sof(H70A)=FVAR(1)
 Fixed Sof: H74A(0.5) H74B(0.5)
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 Secondary CH2 refined with riding coordinates:
 C73(H73A,H73B), C74(H74A,H74B), C71(H71A,H71B)
5.c 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), C60A(H60A),
 C61A(H61A), C62A(H62A), C63A(H63A), C64A(H64A), C66A(H66A), C67A(H67A),
 C68A(H68A), C69A(H69A), C70A(H70A), C60B(H60B), C61B(H61B), C62B(H62B),
 C63B(H63B), C64B(H64B), C70B(H70B), C69B(H69B), C68B(H68B), C67B(H67B),
 C66B(H66B)
5.d Fitted hexagon refined as free rotating group:
 C59B(C60B,C61B,C62B,C63B,C64B), C65B(C70B,C69B,C68B,C67B,C66B)
5.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), 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), C72(H72A,H72B,H72C)
;
_shelx_res_checksum              26380
_shelx_hkl_checksum              30741
_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 1.163
_oxdiff_exptl_absorpt_empirical_full_min 0.851