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_4126536
_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 H84 Ga2 N4 O P6, 2(C6 H6)'
_chemical_formula_sum            'C70 H96 Ga2 N4 O P6'
_chemical_formula_weight         1334.76
_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             2016-08-21
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                89.8954(12)
_cell_angle_beta                 69.1188(14)
_cell_angle_gamma                88.7239(12)
_cell_formula_units_Z            2
_cell_length_a                   13.1634(2)
_cell_length_b                   15.5274(2)
_cell_length_c                   18.2175(3)
_cell_measurement_reflns_used    30078
_cell_measurement_temperature    100.02(11)
_cell_measurement_theta_max      76.3110
_cell_measurement_theta_min      3.5870
_cell_volume                     3478.04(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      100.02(11)
_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 0.990
_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   -109.00 -12.00   0.50    7.50    --  -38.50 -57.00-150.00  194
  2  \w    -94.00  -2.00   0.50    7.50    --  -38.50 125.00-180.00  184
  3  \w   -112.00  -7.00   0.50    7.50    --  -38.50 -77.00 120.00  210
  4  \w    -61.00  34.00   0.50    7.50    --  -38.50  38.00   0.00  190
  5  \w   -111.00 -16.00   0.50    7.50    --  -38.50 -38.00   0.00  190
  6  \w   -111.00 -16.00   0.50    7.50    --  -38.50 -38.00 -90.00  190
  7  \w     23.00  98.00   0.50    7.50    --   42.50-125.00   0.00  150
  8  \w     66.00 178.00   0.50   30.00    --  111.00  15.00  60.00  224
  9  \w     30.00 109.00   0.50   30.00    --  111.00 -94.00  90.00  158
 10  \w     37.00 142.00   0.50   30.00    --  111.00 -77.00 -90.00  210
 11  \w     87.00 178.00   0.50   30.00    --  111.00  45.00 -30.00  182
 12  \w     87.00 178.00   0.50   30.00    --  111.00  30.00-150.00  182
 13  \w     39.00 121.00   0.50   30.00    --  111.00-125.00  90.00  164
 14  \w     87.00 178.00   0.50   30.00    --  111.00  30.00 -60.00  182
 15  \w     39.00 121.00   0.50   30.00    --  111.00-125.00 -60.00  164
 16  \w     87.00 178.00   0.50   30.00    --  111.00  30.00 120.00  182
 17  \w     94.00 178.00   0.50   30.00    --  111.00 125.00 -30.00  168
 18  \w     39.00 121.00   0.50   30.00    --  111.00-125.00   0.00  164
 19  \w     39.00 121.00   0.50   30.00    --  111.00-125.00-150.00  164
 20  \w     30.00 109.00   0.50   30.00    --  111.00 -94.00-120.00  158
 21  \w     41.00 139.00   0.50   30.00    --  111.00 -61.00 -90.00  196
 22  \w     87.00 178.00   0.50   30.00    --  111.00  30.00  60.00  182
 23  \w     30.00 109.00   0.50   30.00    --  111.00 -94.00 120.00  158
 24  \w     39.00 121.00   0.50   30.00    --  111.00-125.00-180.00  164
 25  \w     40.00 135.00   0.50   30.00    --  111.00 -45.00 -60.00  190
 26  \w     30.00 109.00   0.50   30.00    --  111.00 -94.00 150.00  158
 27  \w     37.00 142.00   0.50   30.00    --  111.00 -77.00 -30.00  210
 28  \w     30.00 109.00   0.50   30.00    --  111.00 -94.00-180.00  158
 29  \w     40.00 135.00   0.50   30.00    --  111.00 -45.00 120.00  190
;
_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      0.0126108000
_diffrn_orient_matrix_UB_12      -0.0505037000
_diffrn_orient_matrix_UB_13      -0.0755760000
_diffrn_orient_matrix_UB_21      0.1199423000
_diffrn_orient_matrix_UB_22      0.0259585000
_diffrn_orient_matrix_UB_23      -0.0356172000
_diffrn_orient_matrix_UB_31      0.0339638000
_diffrn_orient_matrix_UB_32      -0.0813915000
_diffrn_orient_matrix_UB_33      0.0348134000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0291
_diffrn_reflns_av_unetI/netI     0.0248
_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       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            57836
_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         76.743
_diffrn_reflns_theta_min         2.596
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.588
_exptl_absorpt_correction_T_max  0.957
_exptl_absorpt_correction_T_min  0.809
_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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_description       plate
_exptl_crystal_F_000             1408
_exptl_crystal_size_max          0.123
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.017
_refine_diff_density_max         0.693
_refine_diff_density_min         -0.597
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     895
_refine_ls_number_reflns         14510
_refine_ls_number_restraints     267
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0402
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0350P)^2^+2.8348P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0868
_refine_ls_wR_factor_ref         0.0892
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13332
_reflns_number_total             14510
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_026.cif
_cod_data_source_block           13_2
_cod_database_code               4126536
_chemical_oxdiff_formula         C70H94Ga2N4OP6
_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, All O(H) groups, All P(H,H) groups
2. Restrained distances
 P4A-H4D = P4B-H4E
 1.34 with sigma of 0.01
 H1B-P4B = H1A-P4A
 -4 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C65A \\sim C66A \\sim C67A \\sim C68A \\sim C69A \\sim C70A \\sim C65B \\sim
C66B \\sim C67B \\sim C68B \\sim C69B \\sim C70B: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
Uanis(C66B) \\sim Ueq, Uanis(C65B) \\sim Ueq, Uanis(C67B) \\sim Ueq,
Uanis(C70B) \\sim Ueq, Uanis(C68B) \\sim Ueq, Uanis(C69B) \\sim Ueq,
Uanis(C66A) \\sim Ueq, Uanis(C68A) \\sim Ueq, Uanis(C67A) \\sim Ueq,
Uanis(C69A) \\sim Ueq, Uanis(C70A) \\sim Ueq, Uanis(C65A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(P3B)=Sof(P1B)=Sof(P2B)=Sof(P6B)=Sof(O1B)=Sof(H1B)=Sof(P4B)=Sof(H4E)=
 Sof(P5B)=1-FVAR(1)
 Sof(P1A)=Sof(P2A)=Sof(P3A)=Sof(P4A)=Sof(P5A)=Sof(P6A)=Sof(O1A)=Sof(H1A)=
 Sof(H4D)=FVAR(1)
 Sof(C65B)=Sof(H14)=Sof(C66B)=Sof(H12)=Sof(C67B)=Sof(H19)=Sof(C68B)=Sof(H16)=
 Sof(C69B)=Sof(H18)=Sof(C70B)=Sof(H0AB)=1-FVAR(2)
 Sof(C65A)=Sof(H02Q)=Sof(C66A)=Sof(H02P)=Sof(C67A)=Sof(H02R)=Sof(C68A)=
 Sof(H029)=Sof(C69A)=Sof(H02S)=Sof(C70A)=Sof(H02T)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C12(H01T), C15(H00Y), C24(H01G), C27(H01Q), C41(H00X), C44(H01H), C53(H00P),
 C56(H019)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H010), C8(H016), C9(H01R), C10(H018), C20(H01I), C21(H01Z), C22(H01P),
 C31(H00V), C37(H014), C38(H00Z), C39(H011), C49(H013), C50(H01S), C51(H00S),
 C59(H9AA), C60(H8AA), C61(H023), C62(H026), C63(H025), C64(H0BA), C65A(H02Q),
 C66A(H02P), C67A(H02R), C68A(H029), C69A(H02S), C70A(H02T), C65B(H14),
 C66B(H12), C67B(H19), C68B(H16), C69B(H18), C70B(H0AB)
5.c Idealised Me refined as rotating group:
 C4(H01U,H01V,H01W), C5(H01M,H01N,H01O), C13(H02G,H02H,H02I), C14(H5AA,HM,HN),
 C16(H02J,H02K,H02L), C17(H1AA,HE,HF), C25(H02M,H02N,H02O), C26(H02D,H02E,H02F),
  C28(H2AA,HG,HH), C29(H01,HA,HB), C33(H01D,H01E,H01F), C34(H01A,H01B,H01C),
 C42(H6AA,HO,HP), C43(H00A,H00B,H00C), C45(H4AA,HK,HL), C46(H0AA,HC,HD),
 C54(H01J,H01K,H01L), C55(H,H01X,H01Y), C57(H02A,H02B,H02C), C58(H3AA,HI,HJ)
5.d Idealised tetrahedral OH refined as rotating group:
 O1A(H1A), O1B(H1B)
;
_shelx_res_checksum              42785
_shelx_hkl_checksum              99133
_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 2.122
_oxdiff_exptl_absorpt_empirical_full_min 0.784