Access to 1,2,3-triphospholide ligands by reduction of di-<i>tert</i>-butyldiphosphatetrahedrane.
Uttendorfer, Maria K.; Hierlmeier, Gabriele; Balázs, Gábor; Wolf, Robert; Dalton transactions (Cambridge, England : 2003) 53 (2024) 10113–10119; doi:10.1039/d4dt01067a

data_7715982
_publ_section_title
;
 Access to 1,2,3-triphospholide ligands by reduction of
 di-<i>tert</i>-butyldiphosphatetrahedrane.
;
_journal_issue                   24
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10113
_journal_page_last               10119
_journal_paper_doi               10.1039/d4dt01067a
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety
'C10 H18 P3, C16 H32 Li O8, 0.5(C4 H8 O), 0.5[C4H8O]'
_chemical_formula_sum            'C30 H58 Li O9 P3'
_chemical_formula_weight         662.61
_chemical_name_systematic        '[Li([12]crown-4)2][1,2,3-P3C2tBu2].(C4H8O)'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-04
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-05 deposited with the CCDC.	2024-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   37.25924(16)
_cell_length_b                   12.33778(5)
_cell_length_c                   31.13083(16)
_cell_measurement_reflns_used    103390
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      71.5230
_cell_measurement_theta_min      2.3540
_cell_volume                     14310.73(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.91a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.91a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.91a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_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     67.00 110.00   0.50    0.35    --   60.44  30.00   0.00   86
  2  \w     78.00 124.00   0.50    0.35    --   74.67  30.00-120.00   92
  3  \w     80.00 124.00   0.50    0.35    --   74.67  30.00   0.00   88
  4  \w     62.00 105.00   0.50    0.35    --   60.44  30.00  60.00   86
  5  \w     62.00  98.00   0.50    0.35    --   60.44  30.00  90.00   72
  6  \w     75.00 123.00   0.50    0.35    --   73.92  30.00 150.00   96
  7  \w   -111.00 -63.00   0.50    0.35    --  -61.80 -30.00-180.00   96
  8  \w   -120.00 -77.00   0.50    0.35    --  -75.44 -30.00-150.00   86
  9  \w   -108.00 -69.00   0.50    0.35    --  -61.80 -30.00 120.00   78
 10  \w   -124.00 -76.00   0.50    0.35    --  -75.44 -30.00 150.00   96
 11  \w   -101.00 -29.00   0.50    0.35    --  -74.27 116.00  35.00  144
 12  \w   -106.00 -33.00   0.50    0.35    --  -75.44 125.00 120.00  146
 13  \w    -90.00 -29.00   0.50    0.35    --  -74.27 125.00 -30.00  122
 14  \w   -109.00 -34.00   0.50    0.35    --  -61.80 166.00-177.00  150
 15  \w   -123.00 -39.00   0.50    0.35    --  -75.44 166.00-177.00  168
 16  \w    -92.00 -18.00   0.50    0.35    --  -61.80 125.00-180.00  148
 17  \w   -106.00 -30.00   0.50    0.35    --  -75.44 125.00 -60.00  152
 18  \w   -102.00 -30.00   0.50    0.35    --  -75.44 116.00  35.00  144
 19  \w    -88.00 -16.00   0.50    0.35    --  -61.80 116.00  35.00  144
 20  \w   -101.00 -30.00   0.50    0.35    --  -75.44 125.00  60.00  142
 21  \w    -76.00 -30.00   0.50    0.35    --  -75.44 125.00  90.00   92
 22  \w   -106.00 -80.00   0.50    0.35    --  -75.44 125.00  90.00   52
 23  \w   -120.00 -76.00   0.50    0.35    --  -74.27-125.00  90.00   88
 24  \w   -111.00 -48.00   0.50    0.35    --  -74.27-166.00 160.00  126
 25  \w    -98.00 -48.00   0.50    0.35    --  -61.80-166.00 160.00  100
 26  \w   -119.00 -75.00   0.50    0.35    --  -74.27-125.00 -30.00   88
 27  \w     35.00  85.00   0.50    0.35    --   74.67 -95.00-120.00  100
 28  \w     76.00 105.00   0.50    0.35    --   74.67-125.00-120.00   58
 29  \w     29.00  55.00   0.50    0.35    --   74.67-125.00-120.00   52
 30  \w     15.00  87.00   0.50    0.35    --   60.44-116.00 -52.00  144
 31  \w     28.00 100.00   0.50    0.35    --   73.92-116.00 -52.00  144
 32  \w     29.00 101.00   0.50    0.35    --   74.67-116.00 -52.00  144
 33  \w     34.00  62.00   0.50    0.35    --   73.92 -95.00 -30.00   56
 34  \w     39.00 122.00   0.50    0.35    --   74.67-166.00 160.00  166
 35  \w     39.00 108.00   0.50    0.35    --   60.44-166.00 160.00  138
 36  \w     35.00  77.00   0.50    0.35    --   73.92 -95.00  60.00   84
 37  \w     21.00  71.00   0.50    0.35    --   60.44 -95.00   0.00  100
 38  \w     21.00  71.00   0.50    0.35    --   60.44 -95.00-180.00  100
 39  \w     14.00  47.00   0.50    0.35    --   60.44 -30.00 -90.00   66
 40  \w     11.00  40.00   0.50    0.35    --   60.44 -30.00   0.00   58
 41  \w     52.00 111.00   0.50    0.35    --   73.92 166.00-177.00  118
 42  \w     57.00  82.00   0.50    0.35    --   74.67 166.00-177.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0066831000
_diffrn_orient_matrix_UB_12      -0.0179153000
_diffrn_orient_matrix_UB_13      -0.0483152000
_diffrn_orient_matrix_UB_21      0.0408008000
_diffrn_orient_matrix_UB_22      0.0068239000
_diffrn_orient_matrix_UB_23      0.0076892000
_diffrn_orient_matrix_UB_31      0.0012822000
_diffrn_orient_matrix_UB_32      -0.1233420000
_diffrn_orient_matrix_UB_33      0.0074191000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0529
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            263626
_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         71.946
_diffrn_reflns_theta_min         2.372
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.914
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.294
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.91a (Rigaku Oxford Diffraction, 2020)
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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_description       block
_exptl_crystal_F_000             5728
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-hexane/THF'
_exptl_crystal_size_max          0.322
_exptl_crystal_size_mid          0.181
_exptl_crystal_size_min          0.167
_refine_diff_density_max         0.445
_refine_diff_density_min         -0.266
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     851
_refine_ls_number_reflns         13906
_refine_ls_number_restraints     352
_refine_ls_restrained_S_all      1.141
_refine_ls_R_factor_all          0.0461
_refine_ls_R_factor_gt           0.0413
_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^)+(0.0594P)^2^+5.3410P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1143
_refine_ls_wR_factor_ref         0.1178
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12302
_reflns_number_total             13906
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01067a2.cif
_cod_data_source_block           mu016_op
_cod_depositor_comments
'Adding full bibliography for 7715982--7715988.cif.'
_cod_original_cell_volume        14310.72(11)
_cod_database_code               7715982
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C30H48LiO9P3
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H16A-H18A = H18A-H20C
 2.5 with sigma of 0.02
 H6C-H8C = H8C-H5A
 2.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O16A \\sim C52A \\sim C46A \\sim C51A \\sim C45A \\sim C52B \\sim C45B \\sim
O16B \\sim C46B \\sim C47B \\sim O14A \\sim O15A \\sim O13A \\sim C48A \\sim
C50A \\sim C49A \\sim C47A \\sim O14B \\sim O15B \\sim C50B \\sim C51B \\sim
O13B \\sim C48B \\sim C49B: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 1.7A
4. Others
 Sof(O14B)=Sof(O15B)=Sof(C50B)=Sof(H50C)=Sof(H50D)=Sof(C51B)=Sof(H51C)=
 Sof(H51D)=Sof(C52B)=Sof(H52C)=Sof(H52D)=Sof(C45B)=Sof(H45C)=Sof(H45D)=
 Sof(O16B)=Sof(C46B)=Sof(H46C)=Sof(H46D)=Sof(C47B)=Sof(H47C)=Sof(H47D)=
 Sof(O13B)=Sof(C48B)=Sof(H48C)=Sof(H48D)=Sof(C49B)=Sof(H49C)=Sof(H49D)=1-FVAR(1)
 Sof(O14A)=Sof(O16A)=Sof(O15A)=Sof(O13A)=Sof(C48A)=Sof(H48A)=Sof(H48B)=
 Sof(C50A)=Sof(H50A)=Sof(H50B)=Sof(C52A)=Sof(H52A)=Sof(H52B)=Sof(C49A)=
 Sof(H49A)=Sof(H49B)=Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(C47A)=Sof(H47A)=
 Sof(H47B)=Sof(C51A)=Sof(H51A)=Sof(H51B)=Sof(C45A)=Sof(H45A)=Sof(H45B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C44(H44A,H44B), C43(H43A,H43B), C32(H32A,H32B), C42(H42A,H42B), C31(H31A,
 H31B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C25(H25A,H25B),
 C38(H38A,H38B), C27(H27A,H27B), C37(H37A,H37B), C48A(H48A,H48B), C41(H41A,
 H41B), C29(H29A,H29B), C28(H28A,H28B), C26(H26A,H26B), C30(H30A,H30B),
 C23(H23A,H23B), C39(H39A,H39B), C36(H36A,H36B), C56(H56A,H56B), C50A(H50A,
 H50B), C53(H53A,H53B), C40(H40A,H40B), C24(H24A,H24B), C22(H22A,H22B),
 C55(H55A,H55B), C21(H21A,H21B), C52A(H52A,H52B), C54(H54A,H54B), C49A(H49A,
 H49B), C46A(H46A,H46B), C47A(H47A,H47B), C51A(H51A,H51B), C45A(H45A,H45B),
 C50B(H50C,H50D), C51B(H51C,H51D), C52B(H52C,H52D), C45B(H45C,H45D), C46B(H46C,
 H46D), C47B(H47C,H47D), C48B(H48C,H48D), C49B(H49C,H49D)
5.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C9(H9A,H9B,H9C), C15(H15A,H15B,H15C), C8(H8A,H8B,H8C),
 C4(H4A,H4B,H4C), C10(H10A,H10B,H10C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C),
  C5(H5A,H5B,H5C), C14(H14A,H14B,H14C), C20(H20A,H20B,H20C), C19(H19A,H19B,H19C)
;
_smtbx_masks_special_details
;
A THF molecule per asymmetric unit was found to be disordered over a symmetry element and could thus not be modeled.
This is consistend with the compound having beeing crystallized from THF and n-hexane.
A solvent mask was used to account for this THF molecule. This is consistend with the 320 electrons found in a volume of 1164\%A^3^ in 1 void per unit cell which accounts for 0.5 molecules of THF per cell.
;
_smtbx_masks_void_probe_radius   1.5
_smtbx_masks_void_truncation_radius 1.5
_shelx_res_checksum              79584
_shelx_fab_checksum              19251
_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 2.787
_oxdiff_exptl_absorpt_empirical_full_min 0.442