The case of a μ<sub>2</sub>-P aromatic phosphinine as a 4-electron donor forming σ- and π-three-center-two-electron bonds.
Zhang, Jie; Hou, Yuanfeng; Liu, Shihua; Lin, Jieli; Li, Zhongshu; Dalton transactions (Cambridge, England : 2003) 53 (2024) 5608–5615; doi:10.1039/d4dt00228h

data_7715202
_publ_section_title
;
 The case of a &#x3bc;<sub>2</sub>-P aromatic phosphinine as a 4-electron
 donor forming &#x3c3;- and &#x3c0;-three-center-two-electron bonds.
;
_journal_issue                   12
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5608
_journal_page_last               5615
_journal_paper_doi               10.1039/d4dt00228h
_journal_volume                  53
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C51 H36 Cl O3 P4 Rh, C51 H37 Cl O3 P4 Rh'
_chemical_formula_sum            'C102 H73 Cl2 O6 P8 Rh2'
_chemical_formula_weight         1919.08
_space_group_crystal_system      tetragonal
_space_group_IT_number           76
_space_group_name_Hall           'P 4w'
_space_group_name_H-M_alt        'P 41'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-09-20
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-10-20 deposited with the CCDC.	2024-02-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.27277(12)
_cell_length_b                   19.27277(12)
_cell_length_c                   49.9982(6)
_cell_measurement_reflns_used    80139
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.9920
_cell_measurement_theta_min      2.4920
_cell_volume                     18571.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_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    -29.00  16.00   0.50    5.68    --    0.00 -19.00  90.00   90
  2  \w    -13.00  26.00   0.50    5.68    --    0.00  57.00  60.00   78
  3  \w    -65.00  22.00   0.50    5.68    --    0.00 -57.00 -90.00  174
  4  \w    -88.00 -33.00   0.50    5.68    --    0.00 -19.00  90.00  110
  5  \w    -58.00 -27.00   0.50    5.68    --    0.00 -38.00-180.00   62
  6  \w    -19.00  57.00   0.50    5.68    --    0.00  57.00  90.00  152
  7  \w      7.00 112.00   0.50   22.73    --   95.20 -15.00  90.00  210
  8  \w     21.00  46.00   0.50   22.73    --   95.20 -61.00-120.00   50
  9  \w     81.00 107.00   0.50   22.73    --   95.20 -82.00   0.00   52
 10  \w      9.00 127.00   0.50   22.73    --   95.20 -82.00  90.00  236
 11  \w     70.00 113.00   0.50   22.73    --   95.20 -61.00 -60.00   86
 12  \w     50.00  76.00   0.50   22.73    --   95.20 -61.00-120.00   52
 13  \w     33.00 111.00   0.50   22.73    --   95.20 -61.00  90.00  156
 14  \w     18.00 101.00   0.50   22.73    --   95.20 -45.00 -60.00  166
 15  \w    126.00 185.00   0.50   22.73    --   95.20  30.00  90.00  118
 16  \w     79.00 118.00   0.50   22.73    --   95.20  30.00  90.00   78
 17  \w     59.00 126.00   0.50   22.73    --   95.20 -82.00-180.00  134
 18  \w     25.00 114.00   0.50   22.73    --   95.20 -82.00 -30.00  178
 19  \w     93.00 167.00   0.50   22.73    --   95.20  45.00  30.00  148
 20  \w     15.00 112.00   0.50   22.73    --   95.20 -82.00-120.00  194
 21  \w     40.00 103.00   0.50   22.73    --   95.20 -30.00  90.00  126
 22  \w     77.00 102.00   0.50   22.73    --   95.20 -82.00 -90.00   50
 23  \w     76.00 155.00   0.50   22.73    --   95.20  77.00  60.00  158
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0760032000
_diffrn_orient_matrix_UB_12      0.0238644000
_diffrn_orient_matrix_UB_13      -0.0026648000
_diffrn_orient_matrix_UB_21      -0.0096646000
_diffrn_orient_matrix_UB_22      -0.0078574000
_diffrn_orient_matrix_UB_23      0.0304529000
_diffrn_orient_matrix_UB_31      0.0229482000
_diffrn_orient_matrix_UB_32      0.0758220000
_diffrn_orient_matrix_UB_33      0.0038956000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0663
_diffrn_reflns_av_unetI/netI     0.0501
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       61
_diffrn_reflns_limit_l_min       -62
_diffrn_reflns_number            193095
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.410
_diffrn_reflns_theta_min         2.457
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.133
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77466
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.373
_exptl_crystal_description       block
_exptl_crystal_F_000             7816
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.833
_refine_diff_density_min         -1.448
_refine_diff_density_rms         0.120
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.501(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.122
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1991
_refine_ls_number_reflns         37011
_refine_ls_number_restraints     5474
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.1049
_refine_ls_R_factor_gt           0.0812
_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^)+(0.0934P)^2^+75.6858P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2162
_refine_ls_wR_factor_ref         0.2287
_reflns_Friedel_coverage         0.977
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                29629
_reflns_number_total             37011
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00228h2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7715202--7715205.cif.'
_cod_database_code               7715202
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.578
_shelx_estimated_absorpt_t_min   0.494
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.499(17)
 0.501(17)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 C1HA-C25
 1.5 with sigma of 0.005
 C109-C25
 1.5 with sigma of 0.005
4. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C8HA
\\sim C9HA \\sim C6LA \\sim C9MA \\sim C0IA \\sim C8IA \\sim C9 \\sim C10 \\sim
C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C66 \\sim C65 \\sim C64 \\sim
C63 \\sim C62 \\sim C61 \\sim C67 \\sim C72 \\sim C71 \\sim C70 \\sim C69 \\sim
C68 \\sim C76 \\sim C75 \\sim C74 \\sim C73 \\sim C78 \\sim C77 \\sim C79 \\sim
C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C86 \\sim C87 \\sim C88 \\sim
C89 \\sim C90 \\sim C85 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim
C29 \\sim C30 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim
C97 \\sim C98 \\sim C99 \\sim C100 \\sim C101 \\sim C102 \\sim C104 \\sim C103
\\sim C108 \\sim C107 \\sim C106 \\sim C105 \\sim C120 \\sim C119 \\sim C118
\\sim C117 \\sim C116 \\sim C115 \\sim C121 \\sim C122 \\sim C123 \\sim C124
\\sim C125 \\sim C126 \\sim C7JA \\sim C9KA \\sim C1HA \\sim C5KA \\sim C8KA
\\sim C4AA \\sim C114 \\sim C113 \\sim C112 \\sim C111 \\sim C110 \\sim C109
\\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38
\\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim
C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132 \\sim C137 \\sim
C138 \\sim C133 \\sim C134 \\sim C135 \\sim C136 \\sim C143 \\sim C144 \\sim
C139 \\sim C140 \\sim C141 \\sim C142 \\sim C145 \\sim C146 \\sim C147 \\sim
C148 \\sim C149 \\sim C150 \\sim C151 \\sim C152 \\sim C153 \\sim C154 \\sim
C155 \\sim C156 \\sim C157 \\sim C203 \\sim C202 \\sim C201 \\sim C200 \\sim
C199 \\sim C158 \\sim C159 \\sim C160 \\sim C161 \\sim C162 \\sim C0AA \\sim
C1AA \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52
\\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60
\\sim C167 \\sim C166 \\sim C165 \\sim C164 \\sim C163 \\sim C168 \\sim C170
\\sim C169 \\sim C174 \\sim C173 \\sim C172 \\sim C171 \\sim C176 \\sim C177
\\sim C178 \\sim C179 \\sim C180 \\sim C175 \\sim C181 \\sim C182 \\sim C183
\\sim C184 \\sim C185 \\sim C186 \\sim C187 \\sim C188 \\sim C189 \\sim C190
\\sim C191 \\sim C192 \\sim C193 \\sim C196 \\sim C197 \\sim C198: within 3.8A
with sigma of 0.005 and sigma for terminal atoms of 0.01 within 3.8A
Uanis(Rh3) \\sim Ueq, Uanis(Rh4) \\sim Ueq: with sigma of 0.0005 and sigma for
terminal atoms of 0.001
Uanis(C56) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.05
Uanis(C15) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C109) \\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C113) \\sim Ueq,
Uanis(C112) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C110) \\sim Ueq,
Uanis(C106) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C167)
\\sim Ueq, Uanis(C196) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C87) \\sim Ueq,
Uanis(C172) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C7JA) \\sim Ueq, Uanis(C9KA) \\sim Ueq, Uanis(C1HA) \\sim Ueq,
Uanis(C4AA) \\sim Ueq, Uanis(C8KA) \\sim Ueq, Uanis(C5KA) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
Uanis(C112) = Uanis(C113) = Uanis(C114) = Uanis(C109) = Uanis(C110) =
Uanis(C111)
Uanis(C157) = Uanis(C158) = Uanis(C159) = Uanis(C160) = Uanis(C161) =
Uanis(C162)
Uanis(C157) = Uanis(C203) = Uanis(C200) = Uanis(C201) = Uanis(C199) =
Uanis(C202)
5. Others
 Sof(C158)=Sof(H158)=Sof(C159)=Sof(H159)=Sof(C160)=Sof(H160)=Sof(C161)=
 Sof(H161)=Sof(C162)=Sof(H162)=1-FVAR(1)
 Sof(C203)=Sof(H203)=Sof(C202)=Sof(H202)=Sof(C201)=Sof(H201)=Sof(C200)=
 Sof(H200)=Sof(C199)=Sof(H199)=FVAR(1)
 Fixed Sof: C7JA(0.75) H7JA(0.75) C9KA(0.75) H9KA(0.75) C1HA(0.75) C5KA(0.75)
 H5KA(0.75) C8KA(0.75) H8KA(0.75) C4AA(0.75) H4AA(0.75) C114(0.25) H114(0.25)
 C113(0.25) H113(0.25) C112(0.25) H112(0.25) C111(0.25) H111(0.25) C110(0.25)
 H110(0.25) C109(0.25)
 Fixed Z: Rh4(0.0536)
6.a Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C54(H54A,H54B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C7(H7), C8HA(H8HA), C9HA(H9HA), C6LA(H6LA), C0IA(H0IA),
 C8IA(H8IA), C9(H9), C12(H12), C14(H14), C66(H66), C65(H65), C64(H64), C63(H63),
  C62(H62), C72(H72), C71(H71), C70(H70), C69(H69), C68(H68), C76(H76),
 C75(H75), C74(H74), C78(H78), C77(H77), C80(H80), C81(H81), C82(H82), C83(H83),
  C84(H84), C86(H86), C87(H87), C88(H88), C89(H89), C90(H90), C17(H17),
 C19(H19), C22(H22), C24(H24), C27(H27), C29(H29), C92(H92), C93(H93), C94(H94),
  C95(H95), C96(H96), C98(H98), C99(H99), C100(H100), C101(H101), C102(H102),
 C104(H104), C108(H108), C107(H107), C106(H106), C105(H105), C120(H120),
 C119(H119), C118(H118), C117(H117), C116(H116), C122(H122), C123(H123),
 C124(H124), C125(H125), C126(H126), C7JA(H7JA), C9KA(H9KA), C5KA(H5KA),
 C8KA(H8KA), C4AA(H4AA), C114(H114), C113(H113), C112(H112), C111(H111),
 C110(H110), C32(H32), C37(H37), C39(H39), C42(H42), C44(H44), C127(H127),
 C128(H128), C129(H129), C130(H130), C131(H131), C137(H137), C138(H138),
 C134(H134), C135(H135), C136(H136), C143(H143), C144(H144), C140(H140),
 C141(H141), C142(H142), C146(H146), C147(H147), C148(H148), C149(H149),
 C150(H150), C152(H152), C153(H153), C154(H154), C155(H155), C156(H156),
 C203(H203), C202(H202), C201(H201), C200(H200), C199(H199), C158(H158),
 C159(H159), C160(H160), C161(H161), C162(H162), C0AA(H0AA), C1AA(H1AA),
 C47(H47), C49(H49), C52(H52), C57(H57), C59(H59), C167(H167), C166(H166),
 C165(H165), C164(H164), C168(H168), C170(H170), C174(H174), C173(H173),
 C172(H172), C171(H171), C176(H176), C177(H177), C178(H178), C179(H179),
 C180(H180), C181(H181), C182(H182), C183(H183), C184(H184), C185(H185),
 C188(H188), C189(H189), C190(H190), C191(H191), C192(H192), C196(H196),
 C197(H197), C198(H198)
6.c Fitted hexagon refined as free rotating group:
 C8HA(C9HA,C6LA,C9MA,C0IA,C8IA), C66(C65,C64,C63,C62,C61), C67(C72,C71,C70,C69,
 C68), C76(C75,C74,C73,C78,C77), C86(C87,C88,C89,C90,C85), C104(C103,C108,C107,
 C106,C105), C120(C119,C118,C117,C116,C115), C7JA(C9KA,C1HA,C5KA,C8KA,C4AA),
 C114(C113,C112,C111,C110,C109), C137(C138,C133,C134,C135,C136), C143(C144,C139,
 C140,C141,C142), C157(C203,C202,C201,C200,C199), C167(C166,C165,C164,C163,
 C168), C170(C169,C174,C173,C172,C171), C176(C177,C178,C179,C180,C175)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 1.247
_oxdiff_exptl_absorpt_empirical_full_min 0.524