A diazadiphospholenium cation featuring a reactive PP bond: synthesis and reversible main-group bond activation.
Wieneke, Jan; Cirigliano, Francesco; Schorpp, Marcel; Chemical communications (Cambridge, England) 61 (2025) 17601–17604; doi:10.1039/d5cc04820f

data_7135033
_publ_section_title
;
 A diazadiphospholenium cation featuring a reactive P&#xe006;P bond:
 synthesis and reversible main-group bond activation.
;
_journal_issue                   90
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              17601
_journal_page_last               17604
_journal_paper_doi               10.1039/d5cc04820f
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C76 H102 N4 P4'
_chemical_formula_sum            'C76 H102 N4 P4'
_chemical_formula_weight         1195.579
_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'
_symmetry_Int_Tables_number      61
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-11
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-08-13 deposited with the CCDC.	2025-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.3323(1)
_cell_length_b                   21.5645(1)
_cell_length_c                   29.5421(2)
_cell_measurement_reflns_used    32444
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      72.9830
_cell_measurement_theta_min      2.9760
_cell_volume                     14227.03(13)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.144a 64-bit (release 23-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.9981
_diffrn_measured_fraction_theta_max 0.9697
_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     30.00  56.00   0.50    1.30    --   63.06 -95.00-180.00   52
  2  \w     32.00  67.00   0.50    1.30    --   63.06 -95.00-120.00   70
  3  \w     30.00  70.00   0.50    1.30    --   63.06 -95.00 -30.00   80
  4  \w     38.00  75.00   0.50    1.30    --   75.67 -95.00   0.00   74
  5  \w     39.00  64.00   0.50    1.30    --   75.67 -95.00 -30.00   50
  6  \w     29.00  65.00   0.50    1.30    --   63.06 -95.00  90.00   72
  7  \w     27.00  67.00   0.50    1.30    --   63.06 -95.00 150.00   80
  8  \w     32.00  58.00   0.50    1.30    --   63.06 -95.00   0.00   52
  9  \w     40.00 101.00   0.50    1.30    --   63.06  15.00 -90.00  122
 10  \w     45.00 119.00   0.50    1.30    --   75.67  15.00 -30.00  148
 11  \w   -117.00 -74.00   0.50    1.30    --  -76.59-125.00  90.00   86
 12  \w   -103.00 -35.00   0.50    1.30    --  -76.59 125.00  60.00  136
;
_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      -0.0305877000
_diffrn_orient_matrix_UB_12      0.0433631000
_diffrn_orient_matrix_UB_13      0.0343969000
_diffrn_orient_matrix_UB_21      -0.0528137000
_diffrn_orient_matrix_UB_22      -0.0456663000
_diffrn_orient_matrix_UB_23      0.0038477000
_diffrn_orient_matrix_UB_31      0.0321246000
_diffrn_orient_matrix_UB_32      -0.0337257000
_diffrn_orient_matrix_UB_33      0.0390227000
_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  0.0244
_diffrn_reflns_av_unetI/netI     0.0202
_diffrn_reflns_Laue_measured_fraction_full 0.9981
_diffrn_reflns_Laue_measured_fraction_max 0.9697
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            61112
_diffrn_reflns_point_group_measured_fraction_full 0.9981
_diffrn_reflns_point_group_measured_fraction_max 0.9697
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         73.14
_diffrn_reflns_theta_min         2.99
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.301
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.692
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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    1.116
_exptl_crystal_description       block
_exptl_crystal_F_000             5190.625
_exptl_crystal_size_max          0.166
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.081
_refine_diff_density_max         0.2823
_refine_diff_density_min         -0.2483
_refine_diff_density_rms         0.0420
_refine_ls_d_res_high            0.8055
_refine_ls_d_res_low             14.7711
_refine_ls_goodness_of_fit_ref   1.0300
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    156
_refine_ls_number_parameters     779
_refine_ls_number_reflns         13836
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0300
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0309
_refine_ls_shift/su_max          -0.0008
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0389P)^2^+5.4174P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0790
_refine_ls_wR_factor_ref         0.0819
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              27
_reflns_limit_h_min              0
_reflns_limit_k_max              25
_reflns_limit_k_min              0
_reflns_limit_l_max              36
_reflns_limit_l_min              0
_reflns_number_gt                12235
_reflns_number_total             13836
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5cc04820f2.cif
_cod_data_source_block           JW134
_cod_depositor_comments
'Adding full bibliography for 7135028--7135034.cif.'
_cod_database_code               7135033
_chemical_oxdiff_formula         'C H N P'
_cell_oxdiff_angle_alpha         89.9967(4)
_cell_oxdiff_angle_beta          89.9722(4)
_cell_oxdiff_angle_gamma         90.0233(5)
_cell_oxdiff_length_a            22.33663(14)
_cell_oxdiff_length_b            21.56543(14)
_cell_oxdiff_length_c            29.53498(14)
_cell_oxdiff_measurement_reflns_used 32444
_cell_oxdiff_volume              14226.97(14)
_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.a Ternary CH refined with riding coordinates:
 C30(H30), C59(H59), C27(H27), C15(H15), C71(H71), C62(H62), C18(H18), C74(H74)
2.b Secondary CH2 refined with riding coordinates:
 C42(H42a,H42b), C39(H39a,H39b), C36(H36a,H36b), C33(H33a,H33b)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C67(H67), C57(H57), C47(H47), C11(H11), C51(H51), C69(H69),
 C4(H4), C55(H55), C23(H23), C6(H6), C56(H56), C68(H68), C25(H25), C13(H13),
 C24(H24), C12(H12), C48(H48), C50(H50)
2.d Idealised Me refined as rotating group:
 C31(H31a,H31b,H31c), C43(H43a,H43b,H43c), C32(H32a,H32b,H32c), C19(H19a,H19b,
 H19c), C16(H16a,H16b,H16c), C37(H37a,H37b,H37c), C44(H44a,H44b,H44c), C28(H28a,
 H28b,H28c), C17(H17a,H17b,H17c), C38(H38a,H38b,H38c), C29(H29a,H29b,H29c),
 C63(H63a,H63b,H63c), C64(H64a,H64b,H64c), C72(H72a,H72b,H72c), C60(H60a,H60b,
 H60c), C75(H75a,H75b,H75c), C76(H76a,H76b,H76c), C61(H61a,H61b,H61c), C8(H8a,
 H8b,H8c), C73(H73a,H73b,H73c), C52(H52a,H52b,H52c), C20(H20a,H20b,H20c)
;
_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 1.279
_oxdiff_exptl_absorpt_empirical_full_min 0.782