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_1576270
_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_formula_moiety         'C16 Al F36 O4 -, C23 H48 B N2 P2 +, C H2 Cl2'
_chemical_formula_sum            'C40 H50 Al B Cl2 F36 N2 O4 P2'
_chemical_formula_weight         1477.45
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_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                96.311(9)
_cell_angle_beta                 117.899(8)
_cell_angle_gamma                117.537(8)
_cell_formula_units_Z            4
_cell_length_a                   20.238(2)
_cell_length_b                   20.360(2)
_cell_length_c                   20.160(2)
_cell_measurement_reflns_used    9446
_cell_measurement_temperature    120
_cell_measurement_theta_max      22.60
_cell_measurement_theta_min      2.50
_cell_volume                     5918.7(16)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120.0
_diffrn_detector_area_resol_mean 6.67
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0600
_diffrn_reflns_av_unetI/netI     0.0579
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            88112
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.377
_diffrn_reflns_theta_min         2.013
_diffrn_source                   'GeniX Mo, 0.05 x 0.05 mm2 microfocus'
_exptl_absorpt_coefficient_mu    0.333
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.658
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2968
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.449
_refine_diff_density_min         -0.828
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1918
_refine_ls_number_reflns         31743
_refine_ls_number_restraints     742
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.1625
_refine_ls_R_factor_gt           0.0957
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0662P)^2^+27.3457P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2069
_refine_ls_wR_factor_ref         0.2543
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18943
_reflns_number_total             31743
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07702h2.cif
_cod_data_source_block           3_WCA
_cod_original_cell_volume        5918.8(13)
_cod_database_code               1576270
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.898
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C52-F10 = C52-F11 = C52-F12
 1.34575 with sigma of 0.02
 C53-F13 = C53-F14 = C53-F15
 1.34575 with sigma of 0.02
 C54-F16 = C54-F17 = C54-F18
 1.34575 with sigma of 0.02
 C56-F19 = C56-F20 = C56-F21
 1.34575 with sigma of 0.02
 C57-F22 = C57-F23 = C57-F24
 1.34575 with sigma of 0.02
 C58-F25 = C58-F26 = C58-F27
 1.35 with sigma of 0.02
 C60-F28 = C60-F29 = C60-F30
 1.34575 with sigma of 0.02
 C61-F31 = C61-F32 = C61-F33
 1.34575 with sigma of 0.02
 C62-F34 = C62-F35 = C62-F36
 1.34575 with sigma of 0.02
 Cl3-C80 = Cl4-C80
 1.75 with sigma of 0.02
 Cl3A-C80A = Cl4A-C80A
 1.75 with sigma of 0.02
 Cl3-Cl4 = Cl3A-Cl4A
 2.9 with sigma of 0.02
 F19A-F20A = F20A-F21A = F21A-F19A
 2.15 with sigma of 0.02
 F4A-F5A = F5A-F6A = F6A-F4A
 2.15 with sigma of 0.02
 C51-C52 \\sim C51-C53 \\sim C51-C54
 with sigma of 0.02
 C55-C56 \\sim C55-C57 \\sim C55-C58
 with sigma of 0.02
 C59-C60 \\sim C59-C61 \\sim C59-C62
 with sigma of 0.02
 F1-C48 \\sim F1A-C48A \\sim F2-C48 \\sim F2A-C48A \\sim F3-C48 \\sim F3A-C48A
 with sigma of 0.02
 C47-C48 \\sim C47-C48A
 with sigma of 0.02
 F1-F2 \\sim F1A-F2A \\sim F1-F3 \\sim F1A-F3A
 with sigma of 0.04
 F1-C47 \\sim F1A-C47
 with sigma of 0.04
 F2-F3 \\sim F2A-F3A
 with sigma of 0.04
 F2-C47 \\sim F2A-C47 \\sim F3-C47 \\sim F3A-C47
 with sigma of 0.04
 F4-C49 \\sim F4A-C49A \\sim F5-C49 \\sim F5A-C49A \\sim F6-C49 \\sim F6A-C49A
 with sigma of 0.02
 C47-C49 \\sim C47-C49A
 with sigma of 0.02
 F4-F5 \\sim F4A-F5A
 with sigma of 0.04
 F4-F6 \\sim F4A-F6A
 with sigma of 0.04
 F4-C47 \\sim F4A-C47
 with sigma of 0.04
 F5-F6 \\sim F5A-F6A
 with sigma of 0.04
 F5-C47 \\sim F5A-C47
 with sigma of 0.04
 F6-C47 \\sim F6A-C47
 with sigma of 0.04
 F7-C50 \\sim F7A-C50A \\sim F8-C50 \\sim F8A-C50A \\sim F9-C50 \\sim F9A-C50A
 with sigma of 0.02
 F7-F4A \\sim F7A-F4A
 with sigma of 0.02
 C47-C50 \\sim C47-C50A
 with sigma of 0.02
 F7-F8 \\sim F7A-F8A
 with sigma of 0.04
 F7-F9 \\sim F7A-F9A
 with sigma of 0.04
 F7-C47 \\sim F7A-C47
 with sigma of 0.04
 F8-F9 \\sim F8A-F9A
 with sigma of 0.04
 F8-C47 \\sim F8A-C47
 with sigma of 0.04
 F9-C47 \\sim F9A-C47
 with sigma of 0.04
 C50-F4A \\sim C50A-F4A
 with sigma of 0.04
 F19-C56 \\sim F19A-C56A \\sim F20-C56 \\sim F20A-C56A \\sim F21-C56 \\sim
F21A-C56A
 with sigma of 0.02
 F22-C57 \\sim F22A-C57A \\sim F23-C57 \\sim F23A-C57A \\sim F24-C57 \\sim
F24A-C57A
 with sigma of 0.02
 F25-C58 \\sim F25A-C58A \\sim F26-C58 \\sim F26A-C58A \\sim F27-C58 \\sim
F27A-C58A
 with sigma of 0.02
 O3-C55 \\sim O3-C55A
 with sigma of 0.02
 C55-C56 \\sim C55A-C56A \\sim C55-C57 \\sim C55A-C57A \\sim C55-C58 \\sim
C55A-C58A
 with sigma of 0.02
 F19-F20 \\sim F19A-F20A \\sim F19-F21 \\sim F19A-F21A \\sim F20-F21 \\sim
F20A-F21A
 with sigma of 0.04
 F19-C55 \\sim F19A-C55A \\sim F20-C55 \\sim F20A-C55A \\sim F21-C55 \\sim
F21A-C55A
 with sigma of 0.04
 F22-F23 \\sim F22A-F23A \\sim F22-F24 \\sim F22A-F24A \\sim F23-F24 \\sim
F23A-F24A
 with sigma of 0.04
 F22-C55 \\sim F22A-C55A \\sim F23-C55 \\sim F23A-C55A \\sim F24-C55 \\sim
F24A-C55A
 with sigma of 0.04
 F25-F26 \\sim F25A-F26A \\sim F25-F27 \\sim F25A-F27A \\sim F26-F27 \\sim
F26A-F27A
 with sigma of 0.04
 F25-C55 \\sim F25A-C55A \\sim F26-C55 \\sim F26A-C55A \\sim F27-C55 \\sim
F27A-C55A
 with sigma of 0.04
 O3-C56 \\sim O3-C56A \\sim O3-C57 \\sim O3-C57A \\sim O3-C58 \\sim O3-C58A
 with sigma of 0.04
 C56-C57 \\sim C56A-C57A \\sim C56-C58 \\sim C56A-C58A \\sim C57-C58 \\sim
C57A-C58A
 with sigma of 0.04
 Al1-O4 \\sim Al1-O4A
 with sigma of 0.02
 F35-C62 \\sim F35A-C62A \\sim F28-C60 \\sim F28A-C60A \\sim F29-C60 \\sim
F29A-C60A
 with sigma of 0.02
 F30-C60 \\sim F30A-C60A \\sim F31-C61 \\sim F31A-C61A \\sim F33-C61 \\sim
F33A-C61A
 with sigma of 0.02
 F32-C61 \\sim F32A-C61A \\sim F36-C62 \\sim F36A-C62A \\sim F34-C62 \\sim
F34A-C62A
 with sigma of 0.02
 O4-C59 \\sim O4A-C59A
 with sigma of 0.02
 C59-C60 \\sim C59A-C60A
 with sigma of 0.02
 C59-C61 \\sim C59A-C61A
 with sigma of 0.02
 C59-C62 \\sim C59A-C62A
 with sigma of 0.02
 Al1-C59 \\sim Al1-C59A
 with sigma of 0.04
 F35-F36 \\sim F35A-F36A \\sim F35-F34 \\sim F35A-F34A \\sim F28-F29 \\sim
F28A-F29A
 with sigma of 0.04
 F35-C59 \\sim F35A-C59A \\sim F28-C59 \\sim F28A-C59A \\sim F29-C59 \\sim
F29A-C59A \\sim F30-C59 ~
 F30A-C59A
 with sigma of 0.04
 F28-F30 \\sim F28A-F30A \\sim F29-F30 \\sim F29A-F30A \\sim F31-F33 \\sim
F31A-F33A \\sim F31-F32 ~
 F31A-F32A
 with sigma of 0.04
 F31-C59 \\sim F31A-C59A
 with sigma of 0.04
 F33-F32 \\sim F33A-F32A
 with sigma of 0.04
 F33-C59 \\sim F33A-C59A \\sim F32-C59 \\sim F32A-C59A
 with sigma of 0.04
 F36-F34 \\sim F36A-F34A
 with sigma of 0.04
 F36-C59 \\sim F36A-C59A \\sim F34-C59 \\sim F34A-C59A
 with sigma of 0.04
 O4-C60 \\sim O4A-C60A \\sim O4-C61 \\sim O4A-C61A \\sim O4-C62 \\sim O4A-C62A
 with sigma of 0.04
 C60-C61 \\sim C60A-C61A
 with sigma of 0.04
 C60-C62 \\sim C60A-C62A
 with sigma of 0.04
 C61-C62 \\sim C61A-C62A
 with sigma of 0.04
 Al1-O2 \\sim Al1-O2A
 with sigma of 0.02
 F10-C52 \\sim F10A-C52A \\sim F11-C52 \\sim F11A-C52A \\sim F12-C52 \\sim
F12A-C52A
 with sigma of 0.02
 F13-C53 \\sim F13A-C53A \\sim F14-C53 \\sim F14A-C53A \\sim F15-C53 \\sim
F15A-C53A
 with sigma of 0.02
 F16-C54 \\sim F16A-C54A \\sim F17-C54 \\sim F17A-C54A \\sim F18-C54 \\sim
F18A-C54A
 with sigma of 0.02
 O2-C51 \\sim O2A-C51
 with sigma of 0.02
 O2A-C52A \\sim O2A-C53A \\sim O2A-C54A
 with sigma of 0.02
 C52A-C53A \\sim C53A-C54A \\sim C54A-C52A
 with sigma of 0.02
 C51-C52 \\sim C51-C52A \\sim C51-C53 \\sim C51-C53A \\sim C51-C54 \\sim
C51-C54A
 with sigma of 0.02
 F10-F11 \\sim F10A-F11A \\sim F10-F12 \\sim F10A-F12A \\sim F11-F12 \\sim
F11A-F12A
 with sigma of 0.04
 F10-C51 \\sim F10A-C51 \\sim F11-C51 \\sim F11A-C51 \\sim F12-C51 \\sim
F12A-C51
 with sigma of 0.04
 F13-F14 \\sim F13A-F14A \\sim F13-F15 \\sim F13A-F15A \\sim F14-F15 \\sim
F14A-F15A
 with sigma of 0.04
 F13-C51 \\sim F13A-C51 \\sim F14-C51 \\sim F14A-C51 \\sim F15-C51 \\sim
F15A-C51
 with sigma of 0.04
 F16-F17 \\sim F16A-F17A \\sim F16-F18 \\sim F16A-F18A \\sim F17-F18 \\sim
F17A-F18A
 with sigma of 0.04
 F16-C51 \\sim F16A-C51 \\sim F17-C51 \\sim F17A-C51 \\sim F18-C51 \\sim
F18A-C51
 with sigma of 0.04
 F46-C68 \\sim F46A-C68A \\sim F47-C68 \\sim F47A-C68A \\sim F48-C68 \\sim
F48A-C68A
 with sigma of 0.02
 F49-C69 \\sim F49A-C69A \\sim F50-C69 \\sim F50A-C69A \\sim F51-C69 \\sim
F51A-C69A
 with sigma of 0.02
 F52-C70 \\sim F52A-C70A \\sim F53-C70 \\sim F53A-C70A \\sim F54-C70 \\sim
F54A-C70A
 with sigma of 0.02
 C67-C68 \\sim C67-C68A \\sim C67-C69 \\sim C67-C69A \\sim C67-C70 \\sim
C67-C70A
 with sigma of 0.02
 F46-F47 \\sim F46A-F47A \\sim F46-F48 \\sim F46A-F48A
 with sigma of 0.04
 F46-C67 \\sim F46A-C67
 with sigma of 0.04
 F47-F48 \\sim F47A-F48A
 with sigma of 0.04
 F47-C67 \\sim F47A-C67
 with sigma of 0.04
 F48-C67 \\sim F48A-C67
 with sigma of 0.04
 F49-F50 \\sim F49A-F50A
 with sigma of 0.04
 F49-F51 \\sim F49A-F51A
 with sigma of 0.04
 F49-C67 \\sim F49A-C67
 with sigma of 0.04
 F50-F51 \\sim F50A-F51A
 with sigma of 0.04
 F50-C67 \\sim F50A-C67
 with sigma of 0.04
 F51-C67 \\sim F51A-C67
 with sigma of 0.04
 F52-F53 \\sim F52A-F53A
 with sigma of 0.04
 F52-F54 \\sim F52A-F54A
 with sigma of 0.04
 F52-C67 \\sim F52A-C67
 with sigma of 0.04
 F53-F54 \\sim F53A-F54A
 with sigma of 0.04
 F53-C67 \\sim F53A-C67
 with sigma of 0.04
 F54-C67 \\sim F54A-C67
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C49 \\sim C49A \\sim C50 \\sim C50A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C48 \\sim C48A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
F19 \\sim F20 \\sim F21: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
F19A \\sim F20A \\sim F21A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C53 \\sim C53A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C54 \\sim C54A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C56 \\sim C56A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C57 \\sim C57A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C58 \\sim C58A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(C55) = Uanis(C55A)
4. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=
 Sof(F9A)=Sof(C48A)=Sof(C49A)=Sof(C50A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=
 Sof(C48)=Sof(C49)=Sof(C50)=FVAR(1)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=Sof(F22A)=Sof(F23A)=Sof(F24A)=Sof(F25A)=
 Sof(F26A)=Sof(F27A)=Sof(O3A)=Sof(C55A)=Sof(C56A)=Sof(C57A)=Sof(C58A)=1-FVAR(2)
 Sof(F19)=Sof(F20)=Sof(F21)=Sof(F22)=Sof(F23)=Sof(F24)=Sof(F25)=Sof(F26)=
 Sof(F27)=Sof(O3)=Sof(C55)=Sof(C56)=Sof(C57)=Sof(C58)=FVAR(2)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=FVAR(3)
 Sof(F28A)=Sof(F29A)=Sof(F30A)=Sof(F31A)=Sof(F32A)=Sof(F33A)=Sof(F34A)=
 Sof(F35A)=Sof(F36A)=Sof(O4A)=Sof(C59A)=Sof(C60A)=Sof(C61A)=Sof(C62A)=1-FVAR(4)
 Sof(F28)=Sof(F29)=Sof(F30)=Sof(F31)=Sof(F32)=Sof(F33)=Sof(F34)=Sof(F35)=
 Sof(F36)=Sof(O4)=Sof(C59)=Sof(C60)=Sof(C61)=Sof(C62)=FVAR(4)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=
 Sof(F17A)=Sof(F18A)=Sof(O2A)=Sof(C52A)=Sof(C53A)=Sof(C54A)=1-FVAR(5)
 Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=Sof(F17)=
 Sof(F18)=Sof(O2)=Sof(C52)=Sof(C53)=Sof(C54)=FVAR(5)
 Sof(F46A)=Sof(F47A)=Sof(F48A)=Sof(F49A)=Sof(F50A)=Sof(F51A)=Sof(F52A)=
 Sof(F53A)=Sof(F54A)=Sof(C68A)=Sof(C69A)=Sof(C70A)=1-FVAR(6)
 Sof(F46)=Sof(F47)=Sof(F48)=Sof(F49)=Sof(F50)=Sof(F51)=Sof(F52)=Sof(F53)=
 Sof(F54)=Sof(C68)=Sof(C69)=Sof(C70)=FVAR(6)
 Sof(Cl3A)=Sof(Cl4A)=Sof(C80A)=Sof(H80C)=Sof(H80D)=1-FVAR(7)
 Sof(Cl3)=Sof(Cl4)=Sof(C80)=Sof(H80A)=Sof(H80B)=FVAR(7)
 Fixed Uiso: F2A(0.08) F20A(0.08)
5.a Secondary CH2 refined with riding coordinates:
 C79(H79A,H79B), C80(H80A,H80B), C80A(H80C,H80D)
5.b Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C36(H36A,
 H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C),
 C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,
 H45C), C46(H46A,H46B,H46C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C),
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), 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)
;
_shelx_res_checksum              29543
_olex2_submission_special_instructions 'No special instructions were received'