Highly Flexible Phosphabenzenes: A Missing Coordination Mode of 2,4,6-Triaryl-λ3-Phosphinines
Yue, Erlin; Petrov, Andrey; Frost, Daniel Sebastian; Dettling, Lea; Conrad, Lawrence; Wossidlo, Friedrich; Coles, Nathan Thomas; Weber, Manuela; Muller, Christian; Chemical Communications  (2022) –; doi:10.1039/D2CC01817A

data_7129977
_publ_section_title
;
 Highly Flexible Phosphabenzenes: A Missing Coordination Mode of
 2,4,6-Triaryl-\l3-Phosphinines
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC01817A
_journal_year                    2022
_chemical_formula_moiety         'C32 H12 B F24, C66 H58 Cr2 O6 P2 Rh'
_chemical_formula_sum            'C98 H70 B Cr2 F24 O6 P2 Rh'
_chemical_formula_weight         2079.20
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6403)
;
_audit_update_record
;
2021-10-04 deposited with the CCDC.	2022-04-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.1304(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.25337(7)
_cell_length_b                   32.9923(2)
_cell_length_c                   29.7568(2)
_cell_measurement_reflns_used    9405
_cell_measurement_temperature    102.6
_cell_measurement_theta_max      72.575
_cell_measurement_theta_min      3.074
_cell_volume                     10059.24(11)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      102.6
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker Photon CMOS Detector, D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0878
_diffrn_reflns_av_unetI/netI     0.0650
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            93226
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.442
_diffrn_reflns_theta_min         2.000
_exptl_absorpt_coefficient_mu    4.189
_exptl_absorpt_correction_T_max  0.4696
_exptl_absorpt_correction_T_min  0.2458
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1606 before and 0.1112 after correction.
The Ratio of minimum to maximum transmission is 0.5234.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.373
_exptl_crystal_description       needle
_exptl_crystal_F_000             4200
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene, DCM'
_exptl_crystal_size_max          0.61
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.532
_refine_diff_density_min         -1.970
_refine_diff_density_rms         0.130
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1280
_refine_ls_number_reflns         19639
_refine_ls_number_restraints     124
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.1049
_refine_ls_R_factor_gt           0.0951
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0301P)^2^+112.0776P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2193
_refine_ls_wR_factor_ref         0.2246
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17084
_reflns_number_total             19639
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01817a2.cif
_cod_data_source_block           ap1217_sq
_cod_original_cell_volume        10059.25(13)
_cod_database_code               7129977
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.184
_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
 C98-C95 \\sim C98-F19A \\sim C98-F20A \\sim C98-F21A
 with sigma of 0.02
 C98-F20B \\sim C98-F19B \\sim C98-F21B \\sim C98-C95
 with sigma of 0.02
 F19A-F20A \\sim F19A-F21A \\sim F20A-F21A
 with sigma of 0.04
 C98-F19A \\sim C98-F20A \\sim C98-F21A \\sim C98-C95
 with sigma of 0.02
 F20B-F19B \\sim F20B-F21B \\sim F19B-F21B
 with sigma of 0.04
 F5-F6 \\sim F5-F4 \\sim F6-F4
 with sigma of 0.04
 C74-F5 \\sim C74-F6 \\sim C74-F4 \\sim C74-C71
 with sigma of 0.02
 F5A-F6A \\sim F4A-F6A
 with sigma of 0.04
 C74-F5A \\sim C74-F4A \\sim C74-F6A \\sim C74-C71
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F19A, C98, F20A, F21A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C98
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C98, F21A, F19A, F20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C98, F21B, F19B, F20B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F4, F6, C74, F5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 H86, C74, F6A, F5A, F4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F19B)=Sof(F21B)=Sof(F20B)=1-FVAR(1)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=FVAR(1)
 Sof(F4A)=Sof(F6A)=Sof(F5A)=1-FVAR(2)
 Sof(F5)=Sof(F4)=Sof(F6)=FVAR(2)
 Sof(C56B)=Sof(H56D)=Sof(H56E)=Sof(H56F)=1-FVAR(3)
 Sof(C56A)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C4(H4), C31(H31), C33(H33), C59(H59), C60(H60), C63(H63), C64(H64)
5.b Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C62(H62A,H62B), C65(H65A,H65B), C66(H66A,H66B)
5.c Aromatic/amide H refined with riding coordinates:
 C68(H68), C70(H70), C72(H72), C76(H76), C78(H78), C80(H80), C84(H84),
 C86(H86), C88(H88), C92(H92), C94(H94), C96(H96), C7(H7), C8(H8), C10(H10),
 C11(H11), C13(H13), C14(H14), C16(H16), C17(H17), C19(H19), C20(H20), C22(H22),
  C23(H23), C36(H36), C37(H37), C39(H39), C40(H40), C42(H42), C43(H43),
 C45(H45), C46(H46), C48(H48), C49(H49), C51(H51), C52(H52)
5.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C56A(H56A,H56B,
 H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C56B(H56D,H56E,H56F)
;
_shelx_res_checksum              74779
_shelx_fab_checksum              92804
_olex2_submission_special_instructions 'No special instructions were received'