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_7135031
_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 P2, 0.625[C6H14]'
_chemical_formula_sum            'C67.76 H90.76 N4 P2'
_chemical_formula_weight         1023.26
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-13
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-08-13 deposited with the CCDC.	2025-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                85.4330(10)
_cell_angle_beta                 87.2380(10)
_cell_angle_gamma                68.4110(10)
_cell_formula_units_Z            4
_cell_length_a                   12.09990(10)
_cell_length_b                   14.60520(10)
_cell_length_c                   41.8681(4)
_cell_measurement_reflns_used    57715
_cell_measurement_temperature    288(5)
_cell_measurement_theta_max      74.7480
_cell_measurement_theta_min      3.2270
_cell_volume                     6856.66(11)
_computing_cell_refinement       'CrysAlisPro 1.171.44.100a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.44.100a (Rigaku OD, 2025)'
_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      air
_diffrn_ambient_temperature      288(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.979
_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     42.00  68.00   0.50    1.00    --   62.87-132.00 153.00   52
  2  \w     40.00  66.00   0.50    1.00    --   62.87-138.00 -22.00   52
  3  \w    -68.00 -23.00   0.50    1.00    --  -63.67 138.00  38.00   90
  4  \w    -95.00 -68.00   0.50    1.00    --  -63.67 132.00-137.00   54
  5  \w    -64.00 -21.00   0.50    1.00    --  -63.67 132.00-137.00   86
  6  \w   -115.00 -90.00   0.50    1.00    --  -73.66-132.00 153.00   50
  7  \w   -105.00 -69.00   0.50    1.00    --  -73.66 132.00-137.00   72
  8  \w   -114.00 -80.00   0.50    1.00    --  -73.66-138.00 -22.00   68
  9  \w   -109.00 -72.00   0.50    1.00    --  -73.66 138.00  38.00   74
 10  \w     70.00 106.00   0.50    1.00    --   75.39-132.00 153.00   72
 11  \w     73.00 108.00   0.50    1.00    --   75.39 138.00  38.00   70
 12  \w     46.00  71.00   0.50    1.00    --   75.95-132.00 153.00   50
 13  \w     49.00  74.00   0.50    1.00    --   75.95-138.00 -22.00   50
 14  \w   -118.00 -93.00   0.50    1.00    --  -76.59-132.00 153.00   50
 15  \w   -116.00 -91.00   0.50    1.00    --  -76.59-138.00 -22.00   50
 16  \w   -102.00 -71.00   0.50    1.00    --  -76.59 132.00-137.00   62
 17  \w   -111.00 -73.00   0.50    1.00    --  -76.59 138.00  38.00   76
 18  \w     21.00  76.00   0.50    1.00    --   62.87-125.00-180.00  110
 19  \w     27.00  79.00   0.50    1.00    --   62.87   0.00-150.00  104
 20  \w     34.00  60.00   0.50    1.00    --   62.87 -95.00   0.00   52
 21  \w     31.00  68.00   0.50    1.00    --   62.87 -95.00-150.00   74
 22  \w     28.00  56.00   0.50    1.00    --   62.87 -95.00  60.00   56
 23  \w     37.00  87.00   0.50    1.00    --   62.87  15.00 120.00  100
 24  \w     45.00 106.00   0.50    1.00    --   62.87  15.00-120.00  122
 25  \w    -81.00 -22.00   0.50    1.00    --  -63.67 125.00-180.00  118
 26  \w   -106.00 -69.00   0.50    1.00    --  -63.67 -15.00 -30.00   74
 27  \w    -60.00 -33.00   0.50    1.00    --  -63.67 -15.00 -30.00   54
 28  \w   -104.00 -56.00   0.50    1.00    --  -63.67 -15.00 -90.00   96
 29  \w    -90.00 -26.00   0.50    1.00    --  -63.67 125.00 -60.00  128
 30  \w     38.00  84.00   0.50    1.00    --   75.39 -95.00 150.00   92
 31  \w     49.00  77.00   0.50    1.00    --   75.39 -95.00-120.00   56
 32  \w     38.00  63.00   0.50    1.00    --   75.39 -95.00 -60.00   50
 33  \w     49.00  75.00   0.50    1.00    --   75.39 -95.00   0.00   52
 34  \w     48.00  73.00   0.50    1.00    --   75.39-138.00 -22.00   50
 35  \w    -91.00 -66.00   0.50    1.00    --  -78.25 102.00 148.03   50
 36  \w   -116.00 -90.00   0.50    1.00    --  -78.25 -45.00  25.22   52
 37  \w   -112.00 -87.00   0.50    1.00    --  -78.25 -82.00 174.85   50
 38  \w   -103.00 -77.00   0.50    1.00    --  -78.25 121.00 -16.26   52
 39  \w   -109.00 -81.00   0.50    1.00    --  -78.25 -85.00 157.40   56
 40  \w   -109.00 -59.00   0.50    1.00    --  -78.25 130.00-125.62  100
 41  \w   -109.00 -82.00   0.50    1.00    --  -78.25 130.00-118.56   54
 42  \w   -110.00 -82.00   0.50    1.00    --  -78.25 -91.00 -43.58   56
 43  \w    -97.00 -71.00   0.50    1.00    --  -78.25 119.00   6.43   52
 44  \w    -75.00 -50.00   0.50    1.00    --  -78.25  89.00-174.20   50
 45  \w   -102.00 -50.00   0.50    1.00    --  -78.25 122.00  33.24  104
 46  \w    -61.00 -36.00   0.50    1.00    --  -78.25  56.00 -24.98   50
 47  \w    -62.00 -37.00   0.50    1.00    --  -78.25  57.00 -35.75   50
 48  \w   -120.00 -94.00   0.50    1.00    --  -78.25 -43.00 174.76   52
 49  \w    -76.00 -51.00   0.50    1.00    --  -78.25  98.00-116.18   50
 50  \w    -66.00 -41.00   0.50    1.00    --  -78.25  60.00  26.63   50
 51  \w   -113.00 -88.00   0.50    1.00    --  -78.25 -85.00  53.68   50
 52  \w    -66.00 -37.00   0.50    1.00    --  -78.25  61.00  64.44   58
 53  \w    -63.00 -38.00   0.50    1.00    --  -78.25  58.00  83.64   50
 54  \w    -85.00 -60.00   0.50    1.00    --  -78.25 112.00  86.19   50
 55  \w   -101.00 -76.00   0.50    1.00    --  -78.25 130.00 154.68   50
 56  \w    -87.00 -62.00   0.50    1.00    --  -78.25 113.00   6.30   50
 57  \w   -116.00 -64.00   0.50    1.00    --  -78.25 141.00 -51.71  104
 58  \w   -116.00 -86.00   0.50    1.00    --  -78.25 141.00-102.03   60
 59  \w    -77.00 -43.00   0.50    1.00    --  -78.25  87.00 -45.85   68
 60  \w   -113.00 -80.00   0.50    1.00    --  -78.25 136.00  -0.80   66
 61  \w   -106.00 -81.00   0.50    1.00    --  -78.25 -83.00 -42.82   50
 62  \w    -63.00 -38.00   0.50    1.00    --  -78.25  60.00 131.02   50
 63  \w    -77.00 -52.00   0.50    1.00    --  -78.25 113.00 175.80   50
 64  \w    -69.00 -44.00   0.50    1.00    --  -78.25  64.00  40.00   50
 65  \w    -82.00 -55.00   0.50    1.00    --  -78.25 116.00  48.48   54
 66  \w    -61.00 -36.00   0.50    1.00    --  -78.25  56.00-129.33   50
 67  \w     61.00 125.00   0.50    1.00    --   79.75  21.00 -68.44  128
 68  \w     75.00 100.00   0.50    1.00    --   79.75-114.00 -47.13   50
 69  \w     66.00  96.00   0.50    1.00    --   79.75  22.00 120.32   60
 70  \w     41.00  66.00   0.50    1.00    --   79.75-114.00 -47.13   50
 71  \w     48.00  93.00   0.50    1.00    --   79.75-112.00  21.76   90
 72  \w     57.00 117.00   0.50    1.00    --   79.75   7.00 114.67  120
 73  \w     85.00 116.00   0.50    1.00    --   79.75   9.00-113.43   62
 74  \w     59.00 111.00   0.50    1.00    --   79.75-131.00-130.13  104
 75  \w     46.00  78.00   0.50    1.00    --   79.75   9.00-113.43   64
 76  \w     49.00  76.00   0.50    1.00    --   79.75  -4.00 146.67   54
 77  \w     56.00  95.00   0.50    1.00    --   79.75-110.00  14.10   78
 78  \w     51.00  76.00   0.50    1.00    --   79.75  18.00 101.51   50
 79  \w     57.00  82.00   0.50    1.00    --   79.75  -4.00  25.66   50
 80  \w     62.00 124.00   0.50    1.00    --   79.75  21.00  22.86  124
 81  \w     64.00  98.00   0.50    1.00    --   79.75-129.00-166.04   68
 82  \w     56.00 109.00   0.50    1.00    --   79.75-128.00 -62.77  106
 83  \w     73.00  98.00   0.50    1.00    --   79.75  21.00  95.81   50
 84  \w     70.00 108.00   0.50    1.00    --   79.75-126.00 176.87   76
 85  \w     62.00  87.00   0.50    1.00    --   79.75  21.00 174.36   50
 86  \w     98.00 124.00   0.50    1.00    --   79.75  17.00  -2.89   52
 87  \w     37.00  65.00   0.50    1.00    --   79.75-126.00 176.87   56
 88  \w     84.00 116.00   0.50    1.00    --   79.75  -2.00-154.71   64
 89  \w     41.00  74.00   0.50    1.00    --   79.75  -2.00-154.71   66
 90  \w     38.00 107.00   0.50    1.00    --   79.75-130.00 -85.10  138
 91  \w     77.00 113.00   0.50    1.00    --   79.75  22.00 -31.05   72
 92  \w     66.00 102.00   0.50    1.00    --   79.75  23.00-154.53   72
 93  \w     96.00 121.00   0.50    1.00    --   79.75  20.00 115.72   50
 94  \w     86.00 111.00   0.50    1.00    --   79.75  22.00-137.12   50
 95  \w     41.00  67.00   0.50    1.00    --   79.75  -4.00 -75.85   52
;
_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      -0.0158379000
_diffrn_orient_matrix_UB_12      0.0092494000
_diffrn_orient_matrix_UB_13      -0.0365524000
_diffrn_orient_matrix_UB_21      0.1246373000
_diffrn_orient_matrix_UB_22      0.0049986000
_diffrn_orient_matrix_UB_23      -0.0051468000
_diffrn_orient_matrix_UB_31      0.0545092000
_diffrn_orient_matrix_UB_32      -0.1132040000
_diffrn_orient_matrix_UB_33      -0.0007428000
_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  0.0253
_diffrn_reflns_av_unetI/netI     0.0152
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       52
_diffrn_reflns_limit_l_min       -52
_diffrn_reflns_number            194965
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.261
_diffrn_reflns_theta_min         3.177
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.852
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.311
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.100a (Rigaku Oxford Diffraction, 2025)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.991
_exptl_crystal_description       block
_exptl_crystal_F_000             2221
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.293
_exptl_crystal_size_min          0.124
_refine_diff_density_max         0.532
_refine_diff_density_min         -0.299
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1357
_refine_ls_number_reflns         27739
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0651
_refine_ls_R_factor_gt           0.0560
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1205P)^2^+0.3547P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1762
_refine_ls_wR_factor_ref         0.1846
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22003
_reflns_number_total             27739
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04820f2.cif
_cod_data_source_block           jw_005
_cod_depositor_comments
'Adding full bibliography for 7135028--7135034.cif.'
_cod_original_cell_volume        6856.67(11)
_cod_database_code               7135031
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C79H117N4P2
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.772
_diffrn_oxdiff_digest_od_ed
;

;
_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
2. Restrained distances
 C68B-C69B \\sim C68B-C67 \\sim C68A-C67 \\sim C68A-C70A \\sim C68A-C69A \\sim
C70-C63 \\sim C70-C69 ~
 C70-C68
 with sigma of 0.02
 C68-C69 \\sim C1B-C1A
 with sigma of 0.02
 C68-C1A \\sim C1A-C70
 with sigma of 0.02
 C1B-C69 \\sim C69-C70
 with sigma of 0.02
3. Others
 Sof(C68B)=Sof(H68B)=Sof(C69B)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70B)=
 Sof(H70A)=Sof(H70B)=Sof(H70C)=1-FVAR(1)
 Sof(C68A)=Sof(H68E)=Sof(C70A)=Sof(H70D)=Sof(H70E)=Sof(H70F)=Sof(C69A)=
 Sof(H69G)=Sof(H69H)=Sof(H69I)=FVAR(1)
 Sof(C70)=Sof(H70)=Sof(C69)=Sof(H69D)=Sof(H69E)=Sof(H69F)=Sof(C68)=Sof(H68A)=
 Sof(H68C)=Sof(H68D)=1-FVAR(2)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=
 Sof(C1C)=Sof(H1C)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C33(H33), C80(H80), C21(H21), C114(H114), C01O(H01O), C83(H83), C102(H102),
 C18(H18), C30(H30), C02F(H02F), C52(H52), C70(H70), C68B(H68B), C49(H49),
 C99(H99), C111(H111), C68A(H68E), C1C(H1C)
4.b Aromatic/amide H refined with riding coordinates:
 C60(H60), C6(H6), C56(H56), C7(H7), C41(H41), C11(H11), C57(H57), C59(H59),
 C91(H91), C10(H10), C40(H40), C90(H90), C37(H37), C76(H76), C87(H87), C16(H16),
  C15(H15), C14(H14), C96(H96), C26(H26), C38(H38), C95(H95), C47(H47),
 C88(H88), C46(H46), C77(H77), C78(H78), C97(H97), C45(H45), C02K(H02K),
 C28(H28), C02P(H02P), C27(H27), C02X(H02X), C64(H64), C66(H66), C65(H65),
 C107(H107), C109(H109), C108(H108)
4.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C61(H61A,H61B,H61C), C81(H81A,H81B,H81C), C92(H92A,H92B,
 H92C), C42(H42A,H42B,H42C), C34(H34A,H34B,H34C), C22(H22A,H22B,H22C),
 C115(H11A,H11B,H11C), C35(H35A,H35B,H35C), C032(H03A,H03B,H03C), C23(H23A,H23B,
 H23C), C035(H03D,H03E,H03F), C82(H82A,H82B,H82C), C53(H53A,H53B,H53C),
 C116(H11D,H11E,H11F), C84(H84A,H84B,H84C), C19(H19A,H19B,H19C), C103(H10A,H10B,
 H10C), C85(H85A,H85B,H85C), C03F(H03G,H03H,H03I), C20(H20A,H20B,H20C),
 C104(H10D,H10E,H10F), C03J(H03J,H03K,H03L), C54(H54A,H54B,H54C), C112(H11G,
 H11H,H11I), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C100(H10G,H10H,H10I),
 C113(H11J,H11K,H11L), C50(H50A,H50B,H50C), C69B(H69A,H69B,H69C), C69(H69D,H69E,
 H69F), C68(H68A,H68C,H68D), C101(H10J,H10K,H10L), C51(H51A,H51B,H51C),
 C70B(H70A,H70B,H70C), C70A(H70D,H70E,H70F), C69A(H69G,H69H,H69I), C1A(H1AA,
 H1AB,H1AC), C1B(H1BA,H1BB,H1BC)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 136 electrons were 
found in a volume of 1506\%A^3^ in 4 voids per unit cell. 
This is consistent with the presence of 
2.5 [C6H14] per Unit Cell 
which account for 125 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              18236
_shelx_fab_checksum              70086
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_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 1.391
_oxdiff_exptl_absorpt_empirical_full_min 0.561