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_4126519
_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 Ga2 N4 P7, 0.5(C4 H8 O)'
_chemical_formula_sum            'C60 H87 Ga2 N4 O0.5 P7'
_chemical_formula_weight         1228.56
_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   mixed
_audit_creation_date             2017-06-09
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.2483(16)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   39.9525(9)
_cell_length_b                   14.8160(2)
_cell_length_c                   21.8877(3)
_cell_measurement_reflns_used    19649
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4190
_cell_measurement_theta_min      3.6680
_cell_volume                     12749.4(4)
_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      100.00(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 0.982
_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    -94.00  -2.00   0.50    7.00    --  -38.50 125.00  30.00  184
  2  \w   -111.00 -16.00   0.50    7.00    --  -38.50 -38.00  90.00  190
  3  \w   -113.00 -48.00   0.50    7.00    --  -38.50-161.00 -99.00  130
  4  \w   -112.00  -7.00   0.50    7.00    --  -38.50 -77.00 -90.00  210
  5  \w     41.00 139.00   0.50   28.00    --  111.00 -61.00-120.00  196
  6  \w     30.00 109.00   0.50   28.00    --  111.00 -94.00  60.00  158
  7  \w     87.00 178.00   0.50   28.00    --  111.00  30.00  30.00  182
  8  \w     30.00 109.00   0.50   28.00    --  111.00 -94.00 -90.00  158
  9  \w     94.00 178.00   0.50   28.00    --  111.00 125.00 -60.00  168
 10  \w     30.00 109.00   0.50   28.00    --  111.00 -94.00-150.00  158
 11  \w     36.00 135.00   0.50   28.00    --  111.00 -30.00 -60.00  198
 12  \w     87.00 178.00   0.50   28.00    --  111.00  45.00  60.00  182
 13  \w     41.00 139.00   0.50   28.00    --  111.00 -61.00  30.00  196
 14  \w     30.00 109.00   0.50   28.00    --  111.00 -94.00 -30.00  158
 15  \w     36.00 135.00   0.50   28.00    --  111.00 -30.00-150.00  198
 16  \w   -109.00 -42.00   0.50    7.00    --  -38.50 -57.00   0.00  134
;
_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      0.0037547000
_diffrn_orient_matrix_UB_12      0.0623693000
_diffrn_orient_matrix_UB_13      0.0571568000
_diffrn_orient_matrix_UB_21      -0.0385911000
_diffrn_orient_matrix_UB_22      -0.0061494000
_diffrn_orient_matrix_UB_23      -0.0010443000
_diffrn_orient_matrix_UB_31      0.0056651000
_diffrn_orient_matrix_UB_32      -0.0828978000
_diffrn_orient_matrix_UB_33      0.0430609000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0583
_diffrn_reflns_av_unetI/netI     0.0471
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       50
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            48269
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.932
_diffrn_reflns_theta_min         2.248
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.002
_exptl_absorpt_correction_T_max  0.952
_exptl_absorpt_correction_T_min  0.619
_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            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       needle
_exptl_crystal_F_000             5168
_exptl_crystal_size_max          0.305
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.017
_refine_diff_density_max         0.883
_refine_diff_density_min         -0.715
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     775
_refine_ls_number_reflns         13231
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0476
_refine_ls_R_factor_gt           0.0408
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0618P)^2^+7.2960P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1053
_refine_ls_wR_factor_ref         0.1113
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11469
_reflns_number_total             13231
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_030.cif
_cod_data_source_block           17
_cod_original_formula_sum        'C60 H87 Ga2 N4 O0.50 P7'
_cod_database_code               4126519
_chemical_oxdiff_formula         'C480 H696 Ga16 N32 O8 P56 '
_reflns_odcompleteness_completeness 99.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H59A,H59B} of C59, {H60A,H60B} of C60, {H62A,H62B} of C62,
   {H61A,H61B} of C61
 At 1.5 times of:
  All C(H,H,H) groups, {H7A,H7B} of C59
2. Restrained distances
 P7B-H7B = P7A-H7A
 1.3 with sigma of 0.02
 C62-C61 \\sim C61-C60 \\sim C59-C60 \\sim O1-C59 \\sim O1-C62
 with sigma of 0.01
 C60-C62 \\sim C61-C59
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O1 \\sim C59 \\sim C60 \\sim C61 \\sim C62: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04
P1B \\sim P2B \\sim P3B \\sim P4B \\sim P5B \\sim P6B \\sim P7B: within 2.5A
with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(P1B)=Sof(P2B)=Sof(P3B)=Sof(P4B)=Sof(P5B)=Sof(P6B)=Sof(P7B)=Sof(H7B)=1-
 FVAR(1)
 Sof(P1A)=Sof(P2A)=Sof(P3A)=Sof(P4A)=Sof(P5A)=Sof(P6A)=Sof(P7A)=Sof(H7A)=FVAR(1)
 Fixed Sof: O1(0.5) C59(0.5) H59A(0.5) H59B(0.5) C60(0.5) H60A(0.5) H60B(0.5)
 C61(0.5) H61A(0.5) H61B(0.5) C62(0.5) H62A(0.5) H62B(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:
 C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B)
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)
5.d 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)
;
_shelx_res_checksum              64533
_shelx_hkl_checksum              77754
_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 2.443
_oxdiff_exptl_absorpt_empirical_full_min 0.704