A crystalline phosphorus-substituted borinium ion: double dihydrogen activation by an ambiphilic inorganic allene
Ordyszewska-Lach, Anna; Cieplińska, Kinga; Anusiewicz, Iwona; Chojnacki, Jarosław; Kaniewska-Laskowska, Kinga; Grubba, Rafał; Chemical Science  (2025) –; doi:10.1039/D5SC07702H

data_1576271
_publ_section_title
;
 A crystalline phosphorus-substituted borinium ion: double dihydrogen
 activation by an ambiphilic inorganic allene
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC07702H
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 Al F36 O4 -, C27 H56 B N2 P2 +'
_chemical_formula_sum            'C43 H56 Al B F36 N2 O4 P2'
_chemical_formula_weight         1448.62
_space_group_crystal_system      trigonal
_space_group_IT_number           144
_space_group_name_Hall           'P 31'
_space_group_name_H-M_alt        'P 31'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-04-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-06-16 deposited with the CCDC.	2025-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   15.9121(13)
_cell_length_b                   15.9121(13)
_cell_length_c                   20.735(2)
_cell_measurement_reflns_used    9551
_cell_measurement_temperature    120
_cell_measurement_theta_max      61.76
_cell_measurement_theta_min      3.97
_cell_volume                     4546.6(7)
_computing_cell_refinement       'X-Area Recipe 1.34.0.0 (STOE, 2019)'
_computing_data_collection       'X-Area WinXpose 2.0.22.0 (STOE, 2016)'
_computing_data_reduction
'X-Area Integrate 1.77.0.0 (STOE, 2019) X-Area X-Red32 1.65.0.0 (STOE, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      120.0
_diffrn_detector_area_resol_mean 6.67
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0650
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            27531
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        65.997
_diffrn_reflns_theta_max         65.997
_diffrn_reflns_theta_min         3.207
_diffrn_source                   'GeniX Cu, 0.05 x 0.05 mm2 microfocus'
_exptl_absorpt_coefficient_mu    2.205
_exptl_absorpt_correction_T_max  0.9456
_exptl_absorpt_correction_T_min  0.7461
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
'STOE X-Red32, absorption correction by Gaussian integration, analogous to P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal Structure Analysis", published in F. R. Ahmed (Editor), "Crystallographic Computing", Munksgaard, Copenhagen (1970), 255 - 270'
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.587
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2196
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.886
_refine_diff_density_min         -0.385
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details
;
 Flack x determined using 2669 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     934
_refine_ls_number_reflns         10309
_refine_ls_number_restraints     235
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.1280
_refine_ls_R_factor_gt           0.0834
_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^)+(0.0550P)^2^+24.4093P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1751
_refine_ls_wR_factor_ref         0.2078
_reflns_Friedel_coverage         0.970
_reflns_Friedel_fraction_full    0.964
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                7666
_reflns_number_total             10309
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07702h2.cif
_cod_data_source_block           4_WCA
_cod_original_cell_volume        4546.7(9)
_cod_database_code               1576271
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.719
_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. Restrained distances
 Al1-O3 \\sim Al1-O3A
 with sigma of 0.02
 F19-C37 \\sim F19A-C37A \\sim F20-C37 \\sim F20A-C37A \\sim F21-C37 \\sim
F21A-C37A
 with sigma of 0.02
 F22-C38 \\sim F22A-C38A \\sim F23-C38 \\sim F23A-C38A \\sim F24-C38 \\sim
F24A-C38A
 with sigma of 0.02
 F25-C39 \\sim F25A-C39A \\sim F26-C39 \\sim F26A-C39A \\sim F27-C39 \\sim
F27A-C39A
 with sigma of 0.02
 O3-C36 \\sim O3A-C36A
 with sigma of 0.02
 C36-C37 \\sim C36A-C37A \\sim C36-C38 \\sim C36A-C38A \\sim C36-C39 \\sim
C36A-C39A
 with sigma of 0.02
 Al1-C36 \\sim Al1-C36A
 with sigma of 0.04
 F19-F20 \\sim F19A-F20A \\sim F19-F21 \\sim F19A-F21A
 with sigma of 0.04
 F19-C36 \\sim F19A-C36A
 with sigma of 0.04
 F20-F21 \\sim F20A-F21A
 with sigma of 0.04
 F20-C36 \\sim F20A-C36A \\sim F21-C36 \\sim F21A-C36A
 with sigma of 0.04
 F22-F23 \\sim F22A-F23A \\sim F22-F24 \\sim F22A-F24A
 with sigma of 0.04
 F22-C36 \\sim F22A-C36A
 with sigma of 0.04
 F23-F24 \\sim F23A-F24A
 with sigma of 0.04
 F23-C36 \\sim F23A-C36A \\sim F24-C36 \\sim F24A-C36A
 with sigma of 0.04
 F25-F26 \\sim F25A-F26A \\sim F25-F27 \\sim F25A-F27A
 with sigma of 0.04
 F25-C36 \\sim F25A-C36A
 with sigma of 0.04
 F26-F27 \\sim F26A-F27A
 with sigma of 0.04
 F26-C36 \\sim F26A-C36A \\sim F27-C36 \\sim F27A-C36A
 with sigma of 0.04
 O3-C37 \\sim O3A-C37A \\sim O3-C38 \\sim O3A-C38A \\sim O3-C39 \\sim O3A-C39A
 with sigma of 0.04
 C37-C38 \\sim C37A-C38A \\sim C37-C39 \\sim C37A-C39A \\sim C38-C39 \\sim
C38A-C39A
 with sigma of 0.04
 Al1-O4 \\sim Al1-O4A
 with sigma of 0.02
 F28-C41 \\sim F28A-C41A \\sim F29-C41 \\sim F29A-C41A \\sim F30-C41 \\sim
F30A-C41A
 with sigma of 0.02
 F31-C42 \\sim F31A-C42A \\sim F32-C42 \\sim F32A-C42A \\sim F33-C42 \\sim
F33A-C42A
 with sigma of 0.02
 F34-C43 \\sim F34A-C43A \\sim F35-C43 \\sim F35A-C43A \\sim F36-C43 \\sim
F36A-C43A
 with sigma of 0.02
 O4-C40 \\sim O4A-C40A
 with sigma of 0.02
 C40-C41 \\sim C40A-C41A \\sim C40-C42 \\sim C40A-C42A \\sim C40-C43 \\sim
C40A-C43A
 with sigma of 0.02
 Al1-C40 \\sim Al1-C40A
 with sigma of 0.04
 F28-F29 \\sim F28A-F29A
 with sigma of 0.04
 F28-F30 \\sim F28A-F30A
 with sigma of 0.04
 F28-C40 \\sim F28A-C40A
 with sigma of 0.04
 F29-F30 \\sim F29A-F30A
 with sigma of 0.04
 F29-C40 \\sim F29A-C40A
 with sigma of 0.04
 F30-C40 \\sim F30A-C40A
 with sigma of 0.04
 F31-F32 \\sim F31A-F32A
 with sigma of 0.04
 F31-F33 \\sim F31A-F33A
 with sigma of 0.04
 F31-C40 \\sim F31A-C40A
 with sigma of 0.04
 F32-F33 \\sim F32A-F33A
 with sigma of 0.04
 F32-C40 \\sim F32A-C40A
 with sigma of 0.04
 F33-C40 \\sim F33A-C40A
 with sigma of 0.04
 F34-F35 \\sim F34A-F35A
 with sigma of 0.04
 F34-F36 \\sim F34A-F36A
 with sigma of 0.04
 F34-C40 \\sim F34A-C40A
 with sigma of 0.04
 F35-F36 \\sim F35A-F36A
 with sigma of 0.04
 F35-C40 \\sim F35A-C40A
 with sigma of 0.04
 F36-C40 \\sim F36A-C40A
 with sigma of 0.04
 O4-C41 \\sim O4A-C41A
 with sigma of 0.04
 O4-C42 \\sim O4A-C42A
 with sigma of 0.04
 O4-C43 \\sim O4A-C43A
 with sigma of 0.04
 C41-C42 \\sim C41A-C42A
 with sigma of 0.04
 C41-C43 \\sim C41A-C43A
 with sigma of 0.04
 C42-C43 \\sim C42A-C43A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O3 \\sim O3A: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
C36 \\sim C37: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(O3A)=Sof(C36A)=Sof(C37A)=Sof(F20A)=Sof(F21A)=Sof(F19A)=Sof(C38A)=
 Sof(F24A)=Sof(F22A)=Sof(F23A)=Sof(C39A)=Sof(F27A)=Sof(F25A)=Sof(F26A)=1-FVAR(1)
 Sof(F19)=Sof(F20)=Sof(F21)=Sof(F22)=Sof(F23)=Sof(F24)=Sof(F25)=Sof(F26)=
 Sof(F27)=Sof(O3)=Sof(C36)=Sof(C37)=Sof(C38)=Sof(C39)=FVAR(1)
 Sof(O4A)=Sof(C40A)=Sof(C41A)=Sof(F28A)=Sof(F30A)=Sof(F29A)=Sof(C42A)=
 Sof(F31A)=Sof(F32A)=Sof(F33A)=Sof(C43A)=Sof(F36A)=Sof(F34A)=Sof(F35A)=1-FVAR(2)
 Sof(F28)=Sof(F29)=Sof(F30)=Sof(F31)=Sof(F32)=Sof(F33)=Sof(F34)=Sof(F35)=
 Sof(F36)=Sof(O4)=Sof(C40)=Sof(C41)=Sof(C42)=Sof(C43)=FVAR(2)
 Fixed Uiso: C38A(0.08072) C39A(0.08) C41A(0.08) C42A(0.08) C43A(0.08)
5.a Ternary CH refined with riding coordinates:
 C4(H4), C9(H9)
5.b Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,
 H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              54968
_olex2_submission_special_instructions 'No special instructions were received'