Tetracationic phosphonium-bridged ladder stilbenes: redox states and electronic properties of highly charged P-heteropolycyclic materials
Senn, Sebastian; Konrad, Nele; Müller, Jens; Ballmann, Joachim; Gade, Lutz H.; Chemical Communications 62 (2026) 6391–6395; doi:10.1039/D6CC00544F

data_7135562
_publ_section_title
;
 Tetracationic phosphonium-bridged ladder stilbenes: redox states and
 electronic properties of highly charged P-heteropolycyclic materials
;
_journal_issue                   23
_journal_name_full               'Chemical Communications'
_journal_page_first              6391
_journal_page_last               6395
_journal_paper_doi               10.1039/D6CC00544F
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C54 H70 P4, 4(Br), 2[CH4O]'
_chemical_formula_sum            'C56 H78 Br4 O2 P4'
_chemical_formula_weight         1226.70
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-05
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2026-01-22 deposited with the CCDC.	2026-03-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.5950(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.0439(3)
_cell_length_b                   8.59720(10)
_cell_length_c                   30.0718(4)
_cell_measurement_reflns_used    18474
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.7830
_cell_measurement_theta_min      3.9290
_cell_volume                     5814.25(13)
_computing_cell_refinement       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.127a (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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -66.00 -24.00   1.00    5.00    --    0.00 -57.00  60.00   42
  2  \w     16.00  67.00   1.00    5.00    --    0.00  77.00   0.00   51
  3  \w    -17.00  69.00   1.00    5.00    --    0.00  57.00-150.00   86
  4  \w    -21.00  13.00   1.00    5.00    --    0.00 -57.00  60.00   34
  5  \w    -31.00  -4.00   1.00    5.00    --    0.00  77.00   0.00   27
  6  \w    -33.00  -6.00   1.00    5.00    --   10.00 108.00  85.40   27
  7  \w    -29.00  -3.00   1.00    5.00    --   22.00 118.00-160.73   26
  8  \w     -3.00  24.00   1.00   10.00    --   38.00  95.00 133.37   27
  9  \w      4.00  31.00   1.00   10.00    --   42.00  89.00  85.29   27
 10  \w      2.00  27.00   1.00   10.00    --   42.00  92.00 -93.79   25
 11  \w     11.00  36.00   1.00   10.00    --   46.00  83.00 -13.50   25
 12  \w     10.00  35.00   1.00   10.00    --   46.00  85.00-142.71   25
 13  \w     16.00  41.00   1.00   10.00    --   50.00  81.00-153.76   25
 14  \w     16.00  41.00   1.00   10.00    --   50.00  82.00  12.44   25
 15  \w     23.00 100.00   1.00   10.00    --   54.47-125.00-150.00   77
 16  \w      2.00  73.00   1.00   10.00    --   54.47 -99.00   0.00   71
 17  \w    -11.00  72.00   1.00   10.00    --   54.47 -57.00-150.00   83
 18  \w     -3.00  75.00   1.00   10.00    --   54.47 -57.00  30.00   78
 19  \w     23.00  51.00   1.00   10.00    --   54.47  77.00  90.00   28
 20  \w     26.00  53.00   1.00   10.00    --   58.00  77.00-103.23   27
 21  \w     91.00 128.00   1.00   10.00    --   58.00  77.00-103.23   37
 22  \w    101.00 128.00   1.00   10.00    --   58.00  76.00 -63.32   27
 23  \w     27.00  53.00   1.00   10.00    --   58.00  76.00 -63.32   26
 24  \w     31.00 131.00   1.00   10.00    --   62.00  77.00 -38.02  100
 25  \w     30.00  68.00   1.00   10.00    --   62.00  77.00  41.81   38
 26  \w     33.00 113.00   1.00   10.00    --   62.00  72.00   9.54   80
 27  \w     31.00 108.00   1.00   10.00    --   62.00  77.00-134.19   77
 28  \w     31.00 131.00   1.00   10.00    --   62.00  76.00 171.05  100
 29  \w     80.00 124.00   1.00   10.00    --   62.00  77.00  41.81   44
 30  \w     69.00 125.00   1.00   10.00    --   62.00  77.00  98.56   56
 31  \w     31.00  56.00   1.00   10.00    --   62.00  77.00 128.77   25
 32  \w     89.00 114.00   1.00   10.00    --   62.00  77.00 128.77   25
 33  \w     30.00  64.00   1.00   10.00    --   62.00  77.00  98.56   34
 34  \w     43.00  78.00   1.00   10.00    --   66.00  49.00 -54.93   35
 35  \w     75.00 110.00   1.00   15.00    --  108.94-111.00  90.00   35
 36  \w     84.00 173.00   1.00   15.00    --  108.94  64.00   0.00   89
 37  \w     84.00 117.00   1.00   15.00    --  108.94  64.00 -60.00   33
 38  \w    143.00 177.00   1.00   15.00    --  108.94 111.00-120.00   34
 39  \w     85.00 167.00   1.00   15.00    --  108.94  64.00-150.00   82
 40  \w     77.00 103.00   1.00   15.00    --  108.94  77.00 -30.00   26
 41  \w    112.00 177.00   1.00   15.00    --  108.94  77.00 -60.00   65
 42  \w     84.00 174.00   1.00   15.00    --  108.94  64.00 120.00   90
 43  \w     78.00 104.00   1.00   15.00    --  108.94  77.00 -60.00   26
 44  \w     41.00 133.00   1.00   15.00    --  108.94 -64.00 -30.00   92
 45  \w     37.00 109.00   1.00   15.00    --  108.94 -92.00 -60.00   72
 46  \w    109.00 177.00   1.00   15.00    --  108.94  77.00  30.00   68
 47  \w     78.00 103.00   1.00   15.00    --  108.94  77.00  30.00   25
 48  \w     77.00 157.00   1.00   15.00    --  108.94  77.00  60.00   80
 49  \w     84.00 123.00   1.00   15.00    --  108.94  64.00  30.00   39
 50  \w    114.00 166.00   1.00   15.00    --  108.94  64.00 -30.00   52
 51  \w     84.00 111.00   1.00   15.00    --  108.94  64.00 -30.00   27
 52  \w     77.00 103.00   1.00   15.00    --  108.94  77.00-150.00   26
 53  \w     77.00 163.00   1.00   15.00    --  108.94  77.00 -90.00   86
 54  \w     77.00 166.00   1.00   15.00    --  108.94  77.00-120.00   89
 55  \w     44.00 108.00   1.00   15.00    --  108.94-111.00-180.00   64
 56  \w     78.00 105.00   1.00   15.00    --  108.94  77.00 120.00   27
 57  \w     84.00 144.00   1.00   15.00    --  108.94  64.00  90.00   60
 58  \w     53.00 106.00   1.00   15.00    --  108.94-111.00 -90.00   53
 59  \w     77.00 177.00   1.00   15.00    --  108.94  77.00 150.00  100
 60  \w     77.00 165.00   1.00   15.00    --  108.94  77.00-180.00   88
 61  \w     77.00 103.00   1.00   15.00    --  108.94  77.00   0.00   26
 62  \w     84.00 110.00   1.00   15.00    --  108.94  64.00-180.00   26
 63  \w     36.00  83.00   1.00   15.00    --  108.94 -92.00-150.00   47
 64  \w    132.00 177.00   1.00   15.00    --  108.94  77.00  90.00   45
 65  \w     84.00 110.00   1.00   15.00    --  108.94  64.00  60.00   26
 66  \w     77.00 103.00   1.00   15.00    --  108.94  77.00  90.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0568561000
_diffrn_orient_matrix_UB_12      -0.0248359000
_diffrn_orient_matrix_UB_13      0.0182094000
_diffrn_orient_matrix_UB_21      0.0373887000
_diffrn_orient_matrix_UB_22      -0.0726091000
_diffrn_orient_matrix_UB_23      0.0438054000
_diffrn_orient_matrix_UB_31      0.0080906000
_diffrn_orient_matrix_UB_32      0.1617959000
_diffrn_orient_matrix_UB_33      0.0225088000
_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  0.0680
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            38736
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.970
_diffrn_reflns_theta_min         3.011
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.707
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.598
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.127a (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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.401
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2520
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.117
_refine_diff_density_min         -1.312
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         5572
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0571
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0929P)^2^+13.1958P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1541
_refine_ls_wR_factor_ref         0.1592
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4944
_reflns_number_total             5572
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00544f2.cif
_cod_data_source_block           ba_ss25
_cod_depositor_comments
'Adding full bibliography for 7135561--7135563.cif.'
_cod_database_code               7135562
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C56H78Br4O2P4
_chemical_oxdiff_usercomment     ss483
_shelx_estimated_absorpt_t_max   0.765
_shelx_estimated_absorpt_t_min   0.539
_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.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19), C22(H22), C25(H25)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12), C14(H14)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 136 electrons were 
found in a volume of 1368\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[CH4O] per Asymmetric Unit 
which account for 144 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.1
_smtbx_masks_void_truncation_radius 1.8
_shelx_res_checksum              7090
_shelx_hkl_checksum              63506
_shelx_fab_checksum              82310
_olex2_date_sample_data_collection 2025-05-03
_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
- Detector area scaling
;