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_1576680
_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         'C75.5 H94 K P, 2(C7 H8)'
_chemical_formula_sum            'C89.5 H110 K P'
_chemical_formula_weight         1255.84
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-29
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-12-04 deposited with the CCDC.	2026-02-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.66718(11)
_cell_length_b                   25.26153(15)
_cell_length_c                   25.92072(16)
_cell_measurement_reflns_used    21135
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      76.1500
_cell_measurement_theta_min      3.8540
_cell_volume                     14842.40(15)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a (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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_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     -5.00  21.00   1.00    8.42    --  -42.53  19.00 -30.00   26
  2  \w   -110.00 -37.00   1.00    8.42    --  -42.53 -38.00-150.00   73
  3  \w    -19.00  23.00   1.00    8.42    --  -42.53  57.00 -30.00   42
  4  \w     95.00 126.00   1.00    8.42    --   42.53 178.00 -60.00   31
  5  \w     78.00 104.00   1.00   33.69    --  111.00-125.00 -90.00   26
  6  \w    110.00 176.00   1.00   33.69    --  111.00  77.00 150.00   66
  7  \w     98.00 150.00   1.00   33.69    --  111.00  45.00   0.00   52
  8  \w     84.00 149.00   1.00   33.69    --  111.00  61.00 120.00   65
  9  \w     97.00 173.00   1.00   33.69    --  111.00 125.00  30.00   76
 10  \w     52.00  88.00   1.00   33.69    --  111.00 -61.00  60.00   36
 11  \w     57.00 112.00   1.00   33.69    --  111.00-125.00 -30.00   55
 12  \w     41.00  73.00   1.00   33.69    --  111.00 -61.00-150.00   32
 13  \w     41.00  42.00   1.00   33.69    --  111.00-129.00 166.00    1
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0036941000
_diffrn_orient_matrix_UB_12      0.0242447000
_diffrn_orient_matrix_UB_13      0.0544590000
_diffrn_orient_matrix_UB_21      -0.0160532000
_diffrn_orient_matrix_UB_22      -0.0540134000
_diffrn_orient_matrix_UB_23      0.0236957000
_diffrn_orient_matrix_UB_31      0.0659294000
_diffrn_orient_matrix_UB_32      -0.0145873000
_diffrn_orient_matrix_UB_33      0.0026482000
_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  0.0305
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            52114
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.179
_diffrn_reflns_theta_min         3.125
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.153
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91656
_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    1.124
_exptl_crystal_description       block
_exptl_crystal_F_000             5448
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.587
_refine_diff_density_min         -1.567
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1018
_refine_ls_number_reflns         15356
_refine_ls_number_restraints     740
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0704
_refine_ls_R_factor_gt           0.0616
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1064P)^2^+9.1882P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1804
_refine_ls_wR_factor_ref         0.1887
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13178
_reflns_number_total             15356
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00723f3.cif
_cod_data_source_block           Compound_5
_cod_depositor_comments
'Adding full bibliography for 1576673--1576682.cif.'
_cod_original_formula_sum        'C89.50 H110 K P'
_cod_database_code               1576680
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C79 H101 P K'
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.777
_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
 C90A-C84A \\sim C90B-C84B
 with sigma of 0.02
 C84A-C85A \\sim C84B-C85B
 with sigma of 0.02
 C85A-C86A \\sim C85B-C86B
 with sigma of 0.02
 C86A-C87A \\sim C86B-C87B
 with sigma of 0.02
 C87A-C88A \\sim C87B-C88B
 with sigma of 0.02
 C88A-C89A \\sim C88B-C89B
 with sigma of 0.02
 C89A-C84A \\sim C89B-C84B
 with sigma of 0.02
 C84A-C86A \\sim C84B-C86B
 with sigma of 0.02
 C84A-C88A \\sim C84B-C88B
 with sigma of 0.02
 C85A-C87A \\sim C85B-C87B
 with sigma of 0.02
 C86A-C88A \\sim C86B-C88B
 with sigma of 0.02
 C87A-C89A \\sim C87B-C89B
 with sigma of 0.02
 C90A-C85A \\sim C90B-C85B
 with sigma of 0.02
 C90A-C89A \\sim C90B-C89B
 with sigma of 0.02
 C84A-C85A \\sim C84A-C89A
 with sigma of 0.02
 C85A-C86A \\sim C89A-C88A
 with sigma of 0.02
 C86A-C87A \\sim C88A-C87A
 with sigma of 0.02
 C84A-C86A \\sim C84A-C88A
 with sigma of 0.02
 C89A-C87A \\sim C85A-C87A
 with sigma of 0.02
 K1-P1 \\sim K1-P1A
 with sigma of 0.02
 P1-C1 \\sim P1A-C1
 with sigma of 0.02
 P1-H1 \\sim P1A-H1A
 with sigma of 0.02
 K1-H1 \\sim K1-H1A
 with sigma of 0.04
 C1-H1 \\sim C1-H1A
 with sigma of 0.04
 C9-C15 \\sim C9-C15A
 with sigma of 0.02
 C9-C16 \\sim C9-C16A
 with sigma of 0.02
 C59-C60 \\sim C59-C60A
 with sigma of 0.02
 C60-C61 \\sim C60A-C61
 with sigma of 0.02
 C61-C69 \\sim C61-C69A
 with sigma of 0.02
 C61-C70 \\sim C61-C70A
 with sigma of 0.02
 C58-C59 \\sim C58-C59A
 with sigma of 0.02
 C58-C71 \\sim C58-C71A
 with sigma of 0.02
 C58-C72 \\sim C58-C72A
 with sigma of 0.02
 C59-C60 \\sim C59A-C60
 with sigma of 0.02
 C59-C60A \\sim C59A-C60A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84A
\\sim C85A \\sim C86A \\sim C87A \\sim C88A \\sim C89A \\sim C90A \\sim C84B
\\sim C85B \\sim C86B \\sim C87B \\sim C88B \\sim C89B \\sim C90B: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C4 \\sim C5 \\sim C9 \\sim C10 \\sim C13 \\sim C14 \\sim C15 \\sim C16: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C58 \\sim C59 \\sim C59A \\sim C60 \\sim C60A \\sim C61 \\sim C69 \\sim C69A
\\sim C70 \\sim C70A \\sim C71 \\sim C71A \\sim C72 \\sim C72A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C77, C78, C79, C80, C81, C82, C83, C84A, C85A, C86A, C87A, C88A, C89A, C90A,
 C84B, C85B, C86B, C87B, C88B, C89B, C90B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C4, C5, C9, C10, C13, C14, C15, C16
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C58, C59, C59A, C60, C60A, C61, C69, C69A, C70, C70A, C71, C71A, C72, C72A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C84B)=Sof(C85B)=Sof(H85B)=Sof(C86B)=Sof(H86B)=Sof(C87B)=Sof(H87B)=
 Sof(C88B)=Sof(H88B)=Sof(C89B)=Sof(H89B)=Sof(C90B)=Sof(H90D)=Sof(H90E)=
 Sof(H90F)=1-FVAR(1)
 Sof(C84A)=Sof(C85A)=Sof(H85A)=Sof(C86A)=Sof(H86A)=Sof(C87A)=Sof(H87A)=
 Sof(C88A)=Sof(H88A)=Sof(C89A)=Sof(H89A)=Sof(C90A)=Sof(H90A)=Sof(H90B)=
 Sof(H90C)=FVAR(1)
 Sof(P1A)=Sof(H1A)=1-FVAR(2)
 Sof(P1)=Sof(H1)=FVAR(2)
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=1-FVAR(3)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 FVAR(3)
 Sof(C59A)=Sof(H59C)=Sof(H59D)=Sof(C60A)=Sof(H60C)=Sof(H60D)=Sof(C69A)=
 Sof(H69D)=Sof(H69E)=Sof(H69F)=Sof(C70A)=Sof(H70D)=Sof(H70E)=Sof(H70F)=
 Sof(C71A)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C72A)=Sof(H72D)=Sof(H72E)=
 Sof(H72F)=1-FVAR(4)
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C69)=Sof(H69A)=
 Sof(H69B)=Sof(H69C)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C71)=Sof(H71A)=
 Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=FVAR(4)
 Fixed Sof: H73(0.5) C76(0.5) H76A(0.5) H76B(0.5) H76C(0.5)
6.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), C59A(H59C,
 H59D), C60(H60A,H60B), C60A(H60C,H60D)
6.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), C73(H73), C74(H74), C75(H75), C78(H78), C79(H79), C80(H80), C81(H81),
  C82(H82), C85A(H85A), C86A(H86A), C87A(H87A), C88A(H88A), C89A(H89A),
 C85B(H85B), C86B(H86B), C87B(H87B), C88B(H88B), C89B(H89B)
6.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C15A(H15D,H15E,
 H15F), C16(H16A,H16B,H16C), C16A(H16D,H16E,H16F), 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), C69A(H69D,H69E,H69F), C70(H70A,H70B,H70C), C70A(H70D,H70E,
 H70F), C71(H71A,H71B,H71C), C71A(H71D,H71E,H71F), C72(H72A,H72B,H72C),
 C72A(H72D,H72E,H72F), C76(H76A,H76B,H76C), C83(H83A,H83B,H83C), C90A(H90A,H90B,
 H90C), C90B(H90D,H90E,H90F)
;
_shelx_res_checksum              91256
_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 1.238
_oxdiff_exptl_absorpt_empirical_full_min 0.846