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_7135028
_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         'C64 H82 N4 P4, C4 H10 O'
_chemical_formula_sum            'C68 H92 N4 O P4'
_chemical_formula_weight         1105.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-10
_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                 99.9045(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.94331(6)
_cell_length_b                   17.65986(11)
_cell_length_c                   18.49899(10)
_cell_measurement_reflns_used    31105
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.4230
_cell_measurement_theta_min      2.5000
_cell_volume                     3199.96(3)
_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  'SHELXL 2019/3 (Sheldrick, 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 0.999
_diffrn_measured_fraction_theta_max 0.985
_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     44.00  70.00   0.50    0.32    --   63.06-150.00-133.00   52
  2  \w     54.00  79.00   0.50    0.32    --   75.94-150.00-133.00   50
  3  \w     55.00  88.00   0.50    0.32    --   63.06-123.00  28.00   66
  4  \w     32.00  71.00   0.50    0.32    --   63.06 -95.00 -60.00   78
  5  \w     44.00  69.00   0.50    0.32    --   75.94-123.00  28.00   50
  6  \w     27.00  66.00   0.50    0.32    --   63.06 -95.00 120.00   78
  7  \w     54.00 114.00   0.50    0.32    --   79.75  -1.00  22.22  120
  8  \w     52.00  77.00   0.50    0.32    --   79.75  -4.00 156.16   50
  9  \w     42.00  77.00   0.50    0.32    --   79.75  -4.00 -79.03   70
 10  \w     43.00  82.00   0.50    0.32    --   79.75  -4.00-168.53   78
 11  \w     64.00  89.00   0.50    0.32    --   75.67 150.00 -88.00   50
 12  \w     62.00  87.00   0.50    0.32    --   75.94 150.00 -88.00   50
 13  \w     50.00  78.00   0.50    0.32    --   79.75  -4.00 -35.34   56
 14  \w     80.00 119.00   0.50    0.32    --   79.75  23.00   9.62   78
 15  \w     66.00  99.00   0.50    0.32    --   79.75  22.00  79.89   66
 16  \w     66.00  97.00   0.50    0.32    --   79.75  21.00 172.99   62
 17  \w     53.00  79.00   0.50    0.32    --   79.75  19.00 165.53   52
 18  \w    101.00 126.00   0.50    0.32    --   79.75  19.00 165.53   50
 19  \w     80.00 120.00   0.50    0.32    --   79.75  20.00 102.01   80
 20  \w     90.00 115.00   0.50    0.32    --   79.75  22.00-175.85   50
 21  \w     32.00 102.00   0.50    0.32    --   63.06  15.00 -90.00  140
 22  \w    -91.00 -66.00   0.50    0.32    --  -63.65 150.00 -88.00   50
 23  \w    -83.00 -57.00   0.50    0.32    --  -73.72 150.00 -88.00   52
 24  \w    -79.00 -54.00   0.50    0.32    --  -76.59 150.00 -88.00   50
 25  \w   -113.00 -78.00   0.50    0.32    --  -78.25 136.00 -36.56   70
 26  \w   -116.00 -75.00   0.50    0.32    --  -78.25 141.00 -49.11   82
 27  \w    -82.00 -56.00   0.50    0.32    --  -78.25 135.00  14.61   52
 28  \w    -71.00 -46.00   0.50    0.32    --  -78.25 129.00  11.47   50
 29  \w   -108.00 -81.00   0.50    0.32    --  -78.25 129.00  11.47   54
 30  \w   -110.00 -84.00   0.50    0.32    --  -78.25 132.00  42.38   52
 31  \w   -117.00 -74.00   0.50    0.32    --  -78.25 143.00  53.45   86
 32  \w   -106.00 -80.00   0.50    0.32    --  -78.25 128.00  89.94   52
 33  \w    -93.00 -68.00   0.50    0.32    --  -78.25 137.00 109.68   50
 34  \w   -100.00 -52.00   0.50    0.32    --  -73.72 125.00   0.00   96
 35  \w    -84.00 -46.00   0.50    0.32    --  -78.25 123.00  -1.26   76
 36  \w    -82.00 -56.00   0.50    0.32    --  -76.59 123.00 108.00   52
 37  \w    -90.00 -65.00   0.50    0.32    --  -73.72 123.00 108.00   50
 38  \w    -82.00 -57.00   0.50    0.32    --  -63.65 123.00 108.00   50
 39  \w    -77.00 -51.00   0.50    0.32    --  -78.25 116.00  74.87   52
 40  \w   -100.00 -57.00   0.50    0.32    --  -78.25 123.00   6.12   86
 41  \w    -73.00 -48.00   0.50    0.32    --  -78.25 121.00 -14.56   50
 42  \w    -89.00 -24.00   0.50    0.32    --  -63.65 125.00-150.00  130
 43  \w    -83.00 -55.00   0.50    0.32    --  -78.25 102.00-168.68   56
 44  \w    -87.00 -61.00   0.50    0.32    --  -78.25 117.00-138.72   52
 45  \w    -81.00 -56.00   0.50    0.32    --  -78.25  98.00 -16.60   50
 46  \w    -76.00 -41.00   0.50    0.32    --  -78.25  98.00 153.65   70
 47  \w    -80.00 -50.00   0.50    0.32    --  -78.25  87.00  88.44   60
 48  \w    -63.00 -38.00   0.50    0.32    --  -78.25  64.00   1.77   50
 49  \w    -67.00 -38.00   0.50    0.32    --  -78.25  63.00 -22.58   58
 50  \w    -62.00 -36.00   0.50    0.32    --  -78.25  57.00 175.02   52
 51  \w    -67.00 -41.00   0.50    0.32    --  -73.72   0.00 -30.00   52
 52  \w   -110.00 -73.00   0.50    0.32    --  -73.72   0.00 -30.00   74
 53  \w   -111.00 -86.00   0.50    0.32    --  -78.25 -87.00  99.29   50
 54  \w   -114.00 -89.00   0.50    0.32    --  -78.25 -90.00-107.75   50
 55  \w   -110.00 -85.00   0.50    0.32    --  -76.59-150.00-133.00   50
 56  \w   -102.00 -56.00   0.50    0.32    --  -63.65-150.00-133.00   92
;
_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      0.0878361000
_diffrn_orient_matrix_UB_12      0.0312010000
_diffrn_orient_matrix_UB_13      0.0704501000
_diffrn_orient_matrix_UB_21      -0.0455859000
_diffrn_orient_matrix_UB_22      0.0810793000
_diffrn_orient_matrix_UB_23      -0.0232279000
_diffrn_orient_matrix_UB_31      -0.1222003000
_diffrn_orient_matrix_UB_32      -0.0079609000
_diffrn_orient_matrix_UB_33      0.0405777000
_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  0.0287
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            49828
_diffrn_reflns_point_group_measured_fraction_full 0.818
_diffrn_reflns_point_group_measured_fraction_max 0.791
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.080
_diffrn_reflns_theta_min         2.502
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.418
_exptl_absorpt_correction_T_max  0.805
_exptl_absorpt_correction_T_min  0.378
_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    1.147
_exptl_crystal_description       block
_exptl_crystal_F_000             1192
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.292
_refine_diff_density_min         -0.190
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 3674 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.018(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     735
_refine_ls_number_reflns         10438
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0308
_refine_ls_R_factor_gt           0.0299
_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^)+(0.0480P)^2^+0.6187P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0784
_refine_ls_wR_factor_ref         0.0790
_reflns_Friedel_coverage         0.604
_reflns_Friedel_fraction_full    0.635
_reflns_Friedel_fraction_max     0.597
_reflns_number_gt                10155
_reflns_number_total             10438
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04820f2.cif
_cod_data_source_block           jw161
_cod_depositor_comments
'Adding full bibliography for 7135028--7135034.cif.'
_cod_database_code               7135028
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N P'
_cell_oxdiff_angle_alpha         89.9225(12)
_cell_oxdiff_angle_beta          99.9106(13)
_cell_oxdiff_angle_gamma         90.0846(14)
_cell_oxdiff_length_a            9.94559(18)
_cell_oxdiff_length_b            17.6590(3)
_cell_oxdiff_length_c            18.4960(2)
_cell_oxdiff_measurement_reflns_used 31105
_cell_oxdiff_volume              3199.96(9)
_shelx_estimated_absorpt_t_max   0.883
_shelx_estimated_absorpt_t_min   0.795
_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. Restrained distances
 C15-C16 \\sim C15-C16B \\sim C15-C17 \\sim C15-C17B
 with sigma of 0.02
 C15-C16 \\sim C15-C17
 with sigma of 0.02
 C16-C17 \\sim C16B-C17B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C16 \\sim C17B \\sim C17 \\sim C16B \\sim C15: within 1A with sigma of 0.02 and
sigma for terminal atoms of 0.01 within 1A
4. Others
 Sof(H15A)=Sof(C16B)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17B)=Sof(H17D)=
 Sof(H17E)=Sof(H17F)=1-FVAR(1)
 Sof(H15)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(H17C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C30(H30), C27(H27), C50(H50), C59(H59), C18(H18), C15(H15A), C15(H15),
 C47(H47), C62(H62)
5.b Secondary CH2 refined with riding coordinates:
 C65(H65A,H65B), C67(H67A,H67B)
5.c Aromatic/amide H refined with riding coordinates:
 C35(H35), C36(H36), C39(H39), C38(H38), C6(H6), C3(H3), C7(H7), C23(H23),
 C13(H13), C12(H12), C25(H25), C4(H4), C11(H11), C45(H45), C24(H24), C44(H44),
 C43(H43), C55(H55), C56(H56), C57(H57)
5.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C28(H28A,H28B,H28C), C60(H60A,H60B,H60C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C29(H29A,H29B,H29C), C40(H40A,H40B,H40C), C8(H8A,
 H8B,H8C), C63(H63A,H63B,H63C), C48(H48A,H48B,H48C), C64(H64A,H64B,H64C),
 C51(H51A,H51B,H51C), C19(H19A,H19B,H19C), C61(H61A,H61B,H61C), C49(H49A,H49B,
 H49C), C16(H16A,H16B,H16C), C52(H52A,H52B,H52C), C68(H68A,H68B,H68C), C66(H66A,
 H66B,H66C), C17(H17A,H17B,H17C), C16B(H16D,H16E,H16F), C17B(H17D,H17E,H17F)
;
_shelx_res_checksum              26377
_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 1.497
_oxdiff_exptl_absorpt_empirical_full_min 0.777