Isolation of arylhalodiphosphenes: periodic trends in R–PP–X bonding (X = Cl, Br, I)
Wenger, John S.; Gaschik, Nina; Rowe, William J.; Crumpton, Agamemnon E.; van IJzendoorn, Bono; Mehta, Meera; Chemical Science  (2026) –; doi:10.1039/D6SC00723F

data_1576678
_publ_section_title
;
 Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond,
 length as m-dash]P-X bonding (X = Cl, Br, I).
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              7475
_journal_page_last               7485
_journal_paper_doi               10.1039/d6sc00723f
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C72 H89 Cl2 P, C6 H14'
_chemical_formula_sum            'C78 H103 Cl2 P'
_chemical_formula_weight         1142.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-12-04 deposited with the CCDC.	2026-02-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.4906(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.40239(7)
_cell_length_b                   26.34880(17)
_cell_length_c                   20.88177(13)
_cell_measurement_reflns_used    39208
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.4440
_cell_measurement_theta_min      1.6640
_cell_volume                     6687.14(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(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 0.983
_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     50.00  75.00   0.50    2.28    --   56.90-171.00  -2.00   50
  2  \w     12.00  42.00   0.50    2.28    --   56.90-115.00 139.00   60
  3  \w     51.00  76.00   0.50    2.28    --   56.90 171.00  11.00   50
  4  \w     80.00 106.00   0.50    2.28    --   69.66-171.00  -2.00   52
  5  \w     57.00  82.00   0.50    2.28    --   69.66 171.00  11.00   50
  6  \w     26.00  92.00   0.50    2.28    --   69.66-115.00 139.00  132
  7  \w     64.00  89.00   0.50    2.28    --   84.11-171.00  -2.00   50
  8  \w     84.00 109.00   0.50    2.28    --   84.11-115.00 139.00   50
  9  \w     54.00  98.00   0.50    2.28    --   84.11 171.00  11.00   88
 10  \w      7.00  33.00   0.50    2.28    --   56.90 -30.00 -90.00   52
 11  \w      7.00  37.00   0.50    2.28    --   56.90 -30.00 -60.00   60
 12  \w     64.00 108.00   0.50    2.28    --   56.90  45.00  60.00   88
 13  \w      8.00  34.00   0.50    2.28    --   56.90 -30.00  30.00   52
 14  \w      6.00  37.00   0.50    2.28    --   56.90 -30.00-120.00   62
 15  \w     34.00  85.00   0.50    2.28    --   69.66 -95.00 -30.00  102
 16  \w     25.00  53.00   0.50    2.28    --   69.66 -45.00  30.00   56
 17  \w     20.00  46.00   0.50    2.28    --   69.66 -45.00 -30.00   52
 18  \w     44.00  84.00   0.50    2.28    --   69.66 -95.00-150.00   80
 19  \w     71.00 108.00   0.50    2.28    --   69.66  77.00 150.00   74
 20  \w     28.00  53.00   0.50    2.28    --   69.66 -45.00-180.00   50
 21  \w     28.00  53.00   0.50    2.28    --   69.66 -45.00 120.00   50
 22  \w     47.00  80.00   0.50    2.28    --   84.11 -77.00 -30.00   66
 23  \w     45.00  78.00   0.50    2.28    --   84.11 -77.00-150.00   66
 24  \w     37.00  71.00   0.50    2.28    --   84.11 -61.00  90.00   68
 25  \w     94.00 119.00   0.50    2.28    --   84.11  45.00-120.00   50
 26  \w     80.00 108.00   0.50    2.28    --   84.11-111.00-180.00   56
 27  \w     38.00  63.00   0.50    2.28    --   84.11-111.00 150.00   50
 28  \w     47.00  73.00   0.50    2.28    --   84.11 -77.00  30.00   52
 29  \w     71.00  96.00   0.50    2.28    --   84.11 -95.00 -30.00   50
 30  \w     71.00 103.00   0.50    2.28    --   84.11-111.00 150.00   64
 31  \w     71.00  97.00   0.50    2.28    --   84.11 -95.00  60.00   52
 32  \w     40.00  65.00   0.50    2.28    --   84.11 -61.00 150.00   50
 33  \w     56.00  82.00   0.50    2.28    --   84.11 -95.00  90.00   52
 34  \w     94.00 135.00   0.50    2.28    --   84.11  45.00-150.00   82
 35  \w     55.00  81.00   0.50    2.28    --   84.11 -95.00-180.00   52
 36  \w     79.00 104.00   0.50    2.28    --   86.75-114.00 -76.63   50
 37  \w     44.00  70.00   0.50    2.28    --   86.75-114.00 -76.63   52
 38  \w     62.00 133.00   0.50    2.28    --   86.75   3.00 -65.00  142
 39  \w     91.00 132.00   0.50    2.28    --   86.75  49.00 167.42   82
 40  \w    103.00 135.00   0.50    2.28    --   86.75  23.00  14.36   64
 41  \w     77.00 102.00   0.50    2.28    --   86.75 -96.00-150.80   50
 42  \w     58.00  84.00   0.50    2.28    --   86.75  23.00  14.36   52
 43  \w    111.00 137.00   0.50    2.28    --   86.75  16.00-148.82   52
 44  \w     82.00 112.00   0.50    2.28    --   86.75   3.00  42.09   60
 45  \w     49.00  96.00   0.50    2.28    --   86.75  16.00-148.82   94
 46  \w     84.00 119.00   0.50    2.28    --   86.75  14.00 123.65   70
 47  \w     53.00  80.00   0.50    2.28    --   86.75 -97.00-114.00   54
 48  \w     74.00 109.00   0.50    2.28    --   86.75-116.00-133.08   70
 49  \w     83.00 108.00   0.50    2.28    --   86.75-110.00  21.90   50
 50  \w     38.00  63.00   0.50    2.28    --   86.75 -56.00-100.75   50
 51  \w     72.00  98.00   0.50    2.28    --   69.66-115.00 139.00   52
 52  \w      0.00  33.00   0.50    2.28    --   -6.75  61.00  90.00   66
 53  \w      4.00  45.00   0.50    2.28    --   -6.75  45.00 -60.00   82
 54  \w     -2.00  31.00   0.50    2.28    --   -6.75  61.00  30.00   66
 55  \w     -9.00  16.00   0.50    2.28    --   10.00 101.00 145.35   50
 56  \w     -7.00  18.00   0.50    2.28    --   10.00  99.00-138.36   50
 57  \w     -3.00  22.00   0.50    2.28    --   14.00  98.00  13.64   50
 58  \w     17.00  42.00   0.50    2.28    --   22.00  80.00 113.34   50
 59  \w     16.00  41.00   0.50    2.28    --   26.00  87.00-156.21   50
 60  \w     13.00  38.00   0.50    2.28    --   26.00  92.00  86.26   50
 61  \w     15.00  40.00   0.50    2.28    --   26.00  89.00 151.78   50
 62  \w     14.00  39.00   0.50    2.28    --   26.00  90.00 -48.19   50
 63  \w     14.00  39.00   0.50    2.28    --   26.00  90.00  36.57   50
 64  \w     14.00  22.50   0.50    2.28    --   26.00  90.00-107.37   17
;
_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      0.0137459000
_diffrn_orient_matrix_UB_12      0.0574826000
_diffrn_orient_matrix_UB_13      0.0126119000
_diffrn_orient_matrix_UB_21      0.0611818000
_diffrn_orient_matrix_UB_22      0.0045570000
_diffrn_orient_matrix_UB_23      -0.0570998000
_diffrn_orient_matrix_UB_31      -0.1101693000
_diffrn_orient_matrix_UB_32      0.0097389000
_diffrn_orient_matrix_UB_33      -0.0473813000
_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  0.0460
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            100468
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.938
_diffrn_reflns_theta_min         2.734
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.402
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86221
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.135
_exptl_crystal_description       block
_exptl_crystal_F_000             2480
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.535
_refine_diff_density_min         -0.884
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     780
_refine_ls_number_reflns         13731
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0543
_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^)+(0.0858P)^2^+4.6469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1504
_refine_ls_wR_factor_ref         0.1585
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11349
_reflns_number_total             13731
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00723f3.cif
_cod_data_source_block           Compound_3
_cod_depositor_comments
'Adding full bibliography for 1576673--1576682.cif.'
_cod_database_code               1576678
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C79 H101 P1 Cl2'
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.884
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
P1A \\sim P1B \\sim Cl1A \\sim Cl2A \\sim Cl1B \\sim Cl2B: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
2. Rigid body (RIGU) restrains
 P1A, P1B, Cl1A, Cl2A, Cl1B, Cl2B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(P1B)=Sof(Cl1B)=Sof(Cl2B)=1-FVAR(1)
 Sof(Cl1A)=Sof(Cl2A)=Sof(P1A)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C10(H10A,H10B), C21(H21A,H21B), C22(H22A,H22B), C31(H31A,H31B),
 C32(H32A,H32B), C49(H49A,H49B), C50(H50A,H50B), C59(H59A,H59B), C60(H60A,H60B),
  C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B)
4.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C18(H18), C25(H25), C28(H28), C35(H35), C46(H46), C53(H53), C56(H56),
 C63(H63)
4.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C),
 C44(H44A,H44B,H44C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,
 H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C71(H71A,
 H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C78(H78A,H78B,H78C)
;
_shelx_res_checksum              17747
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.312
_oxdiff_exptl_absorpt_empirical_full_min 0.797