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_4126543
_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 P12, 2(C11 H10)'
_chemical_formula_sum            'C80 H102 Ga2 N4 P12'
_chemical_formula_weight         1630.73
_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             2016-03-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                97.8684(13)
_cell_angle_beta                 96.0384(15)
_cell_angle_gamma                91.5449(13)
_cell_formula_units_Z            1
_cell_length_a                   10.5072(2)
_cell_length_b                   14.02953(19)
_cell_length_c                   14.6568(3)
_cell_measurement_reflns_used    13978
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3110
_cell_measurement_theta_min      3.0440
_cell_volume                     2126.48(7)
_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 5.2850
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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     23.00  81.00   0.50    2.00    --   42.75 -99.00 -60.00  116
  2  \w     30.00  64.00   0.50    2.00    --   42.75-125.00 -90.00   68
  3  \w     49.00 119.00   0.50    8.00    --  111.00 -61.00  30.00  140
  4  \w    108.00 135.00   0.50    8.00    --  111.00 -61.00 120.00   54
  5  \w     79.00 106.00   0.50    8.00    --  111.00 -94.00 150.00   54
  6  \w     70.00 104.00   0.50    8.00    --  111.00 -94.00  60.00   68
  7  \w     53.00 135.00   0.50    8.00    --  111.00 -30.00  60.00  164
  8  \w     96.00 168.00   0.50    8.00    --  111.00  61.00  90.00  144
  9  \w    132.00 168.00   0.50    8.00    --  111.00  77.00 120.00   72
 10  \w     95.00 159.00   0.50    8.00    --  111.00 125.00 120.00  128
 11  \w     96.00 158.00   0.50    8.00    --  111.00 125.00  90.00  124
 12  \w     94.00 130.00   0.50    8.00    --  111.00 125.00  30.00   72
 13  \w    113.00 141.00   0.50    8.00    --  111.00  45.00 -90.00   56
 14  \w    137.00 178.00   0.50    8.00    --  111.00  45.00-180.00   82
 15  \w     91.00 171.00   0.50    8.00    --  111.00  61.00-150.00  160
 16  \w     54.00  81.00   0.50    8.00    --  111.00 -94.00 -60.00   54
 17  \w     53.00 120.00   0.50    8.00    --  111.00-125.00 -90.00  134
 18  \w     83.00 121.00   0.50    8.00    --  111.00-125.00-180.00   76
 19  \w     44.00 117.00   0.50    8.00    --  111.00-125.00 -30.00  146
 20  \w     46.00 101.00   0.50    8.00    --  111.00-126.00 -56.00  110
 21  \w     42.00 121.00   0.50    8.00    --  111.00-125.00  60.00  158
 22  \w     49.00 106.00   0.50    8.00    --  111.00 -61.00 120.00  114
 23  \w     37.00  64.00   0.50    8.00    --  111.00 -94.00  60.00   54
 24  \w     38.00  97.00   0.50    8.00    --  111.00 -94.00 -30.00  118
 25  \w     26.00  83.00   0.50    2.00    --   42.75-125.00  90.00  114
 26  \w      1.00  31.00   0.50    2.00    --  -38.50  57.00-180.00   60
 27  \w    -58.00  -5.00   0.50    2.00    --  -38.50  57.00-180.00  106
 28  \w   -125.00  48.00   0.50    2.00    --  -38.50   0.00   0.00  346
;
_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      -0.0245482000
_diffrn_orient_matrix_UB_12      -0.0017603000
_diffrn_orient_matrix_UB_13      0.1015583000
_diffrn_orient_matrix_UB_21      -0.1407798000
_diffrn_orient_matrix_UB_22      -0.0323200000
_diffrn_orient_matrix_UB_23      -0.0320075000
_diffrn_orient_matrix_UB_31      0.0368039000
_diffrn_orient_matrix_UB_32      -0.1061236000
_diffrn_orient_matrix_UB_33      -0.0076252000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0209
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            21233
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.544
_diffrn_reflns_theta_min         3.062
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.240
_exptl_absorpt_correction_T_max  0.898
_exptl_absorpt_correction_T_min  0.734
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.273
_exptl_crystal_description       block
_exptl_crystal_F_000             852
_exptl_crystal_size_max          0.142
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.044
_refine_diff_density_max         1.596
_refine_diff_density_min         -0.800
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     486
_refine_ls_number_reflns         8836
_refine_ls_number_restraints     706
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0565
_refine_ls_R_factor_gt           0.0534
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0857P)^2^+4.2893P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1577
_refine_ls_wR_factor_ref         0.1613
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8152
_reflns_number_total             8836
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_010.cif
_cod_data_source_block           5_3
_cod_original_cell_volume        2126.49(6)
_cod_database_code               4126543
_chemical_oxdiff_formula         C72H82Ga2N4P12
_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, {H62,H30,H36} of C62
 At 1.5 times of:
  {H26A,H26B,H26C} of C26, {H28A,H28B,H28C} of C28, {H29A,H29B,H29C} of C29,
  {H14A,H14B,H14C} of C14, {H25A,H25B,H25C} of C25, {H16A,H16B,H16C} of C16,
  {H13A,H13B,H13C} of C13, {H17A,H17B,H17C} of C17, {H52A,H52B,H52C} of C52,
  {H41A,H41B,H41C} of C41, {H63A,H63B,H63C} of C63, {H35A,H35B,H35C} of C35,
  {H4A,H4B,H4C} of C4, {H5A,H5B,H5C} of C5
2. Restrained distances
 C42-C52 = C63-C53 = C35-C30
 1.4 with sigma of 0.02
 C36-H36 = C30-H30
 0.98 with sigma of 0.02
 C58-C63 \\sim C63-C54
 with sigma of 0.01
 C34_$1-C33 \\sim C33-C31 \\sim C34-C30 \\sim C30-C32 \\sim C37-C39 \\sim
C39-C40_$1 \\sim C40-C36 ~
 C36-C38
 with sigma of 0.01
 C36-C39 \\sim C40_$1-C38 \\sim C40-C37
 with sigma of 0.01
 C31-H30 \\sim H30-C34_$1 \\sim C40_$1-H36 \\sim H36-C37
 with sigma of 0.01
 C31-C30 \\sim C32-C31 \\sim C33-C32 \\sim C34-C33 \\sim C40-C39 \\sim C39-C38
\\sim C38-C37 \\sim C37-C36
 \\sim C58-C53 \\sim C54-C53 \\sim C55-C54 \\sim C56-C55 \\sim C57-C56 \\sim
C58-C57 \\sim C59-C58 \\sim C60-
 C59 \\sim C61-C60 \\sim C62-C61 \\sim C62-C57 \\sim C47-C42 \\sim C43-C42
\\sim C44-C43 \\sim C45-C44 ~
 C46-C45 \\sim C47-C46 \\sim C48-C47 \\sim C49-C48 \\sim C50-C49 \\sim C51-C50
\\sim C51-C46 \\sim C34-
 C34_$1 \\sim C30-C34_$1 \\sim C40_$1-C36 \\sim C40-C40_$1
 with sigma of 0.01
3. Restrained planarity
 C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63
 with sigma of 0.1
 C42, C43, C44, C45, C46, C47, C48, C49, C50, C51, C52
 with sigma of 0.1
 C36_$1, C36, H36, C37_$1, C37, C38_$1, C38, C39, C39_$1, C40, C40_$1, C41,
 C41_$1
 with sigma of 0.1
 C30, H30, C31, C34_$1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim
C50 \\sim C51: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim
C61 \\sim C62: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim
C38 \\sim C39 \\sim C40 \\sim C41: within 2A with sigma of 0.008 and sigma for
terminal atoms of 0.016
5. Same fragment restrains
{C42, C43, C44, C45, C46, C47, C48, C49, C50, C51, C52} sigma for 1-2: 0.02,
1-3: 0.02
as
{C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63}
{C36, C37, C38, C39, C40, C41} sigma for 1-2: 0.02, 1-3: 0.02
as
{C30, C31, C32, C33, C34, C35}
6. Others
 Sof(C36)=Sof(C37)=Sof(H37)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=Sof(C40)=1-
 FVAR(1)
 Sof(H36)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=0.5*(1-FVAR(2))
 Sof(H30)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=0.5*FVAR(2)
 Sof(C30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=Sof(C34)=FVAR(1)
 Sof(C53)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55)=Sof(C56)=Sof(H56)=Sof(C57)=
 Sof(C58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=Sof(C61)=Sof(H61)=Sof(C62)=
 Sof(H62)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=0.5*(1-FVAR(3))
 Sof(C42)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45)=Sof(C46)=
 Sof(C47)=Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50)=Sof(C51)=
 Sof(H51)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=0.5*FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C43(H43),
 C44(H44), C45(H45), C48(H48), C49(H49), C50(H50), C51(H51), C54(H54), C55(H55),
  C56(H56), C59(H59), C60(H60), C61(H61), C62(H62), C31(H31), C32(H32),
 C33(H33), C37(H37), C38(H38), C39(H39)
7.c Fitted hexagon refined as free rotating group:
 C42(C43,C44,C45,C46,C47)
7.d Idealised Me refined with riding coordinates:
 C52(H52A,H52B,H52C), C63(H63A,H63B,H63C), C41(H41A,H41B,H41C)
7.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), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              46326
_shelx_hkl_checksum              96624
_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 1.689
_oxdiff_exptl_absorpt_empirical_full_min 0.876