Raising the HOMO level of the [closo-B10H10]2− anion: apical alkyl derivatives for modern materials
Jakubowski, Rafał; Ogunmola, Kehinde; Hietsoi, Oleksandr; Friedli, Andrienne C.; Shaughnessy, Kevin H.; Kaszyński, Piotr; Chemical Science  (2025) –; doi:10.1039/D5SC08516K

data_1576303
_publ_section_title
;
 Raising the HOMO level of the [closo-B10H10]2&#x2212; anion: apical alkyl
 derivatives for modern materials
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC08516K
_journal_year                    2025
_chemical_formula_moiety         '2(C24 H20 P), C8 H26 B10'
_chemical_formula_sum            'C56 H66 B10 P2'
_chemical_formula_weight         909.12
_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
_audit_creation_date             2024-05-17
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2024-06-14 deposited with the CCDC.	2025-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                92.6460(10)
_cell_angle_beta                 92.8540(10)
_cell_angle_gamma                101.7570(10)
_cell_formula_units_Z            2
_cell_length_a                   10.61970(10)
_cell_length_b                   11.52740(10)
_cell_length_c                   21.5302(3)
_cell_measurement_reflns_used    19998
_cell_measurement_temperature    99.9(8)
_cell_measurement_theta_max      76.4700
_cell_measurement_theta_min      3.9060
_cell_volume                     2572.90(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(8)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.963
_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    -95.00 -70.00   0.50    1.00    --  -38.50 -57.00 -30.00   50
  2  \w    -53.00 -28.00   0.50    1.00    --  -38.50 -57.00 -60.00   50
  3  \w    -90.00 -65.00   0.50    1.00    --  -38.50 -57.00 -60.00   50
  4  \w    -69.00 -33.00   0.50    1.00    --  -38.50 -57.00 -30.00   72
  5  \w    -48.00  20.00   0.50    1.00    --  -38.50  57.00-180.00  136
  6  \w    -49.00  23.00   0.50    1.00    --  -38.50  57.00 120.00  144
  7  \w    -37.00  26.00   0.50    1.00    --  -38.50  38.00 -90.00  126
  8  \w   -105.00 -50.00   0.50    1.00    --  -38.50 -19.00   0.00  110
  9  \w     53.00 111.00   0.50    1.00    --   50.96-150.00  54.00  116
 10  \w     76.00 102.00   0.50    1.00    --   50.96  38.00  90.00   52
 11  \w     44.00 112.00   0.50    5.00    --  103.48 -61.00 -60.00  136
 12  \w     47.00 105.00   0.50    5.00    --  103.48 -94.00-150.00  116
 13  \w    140.00 168.00   0.50    5.00    --  103.48  30.00   0.00   56
 14  \w    105.00 155.00   0.50    5.00    --  103.48  30.00 -30.00  100
 15  \w     42.00 101.00   0.50    5.00    --  103.48 -15.00   0.00  118
 16  \w     75.00 106.00   0.50    5.00    --  103.48 -94.00  90.00   62
 17  \w    110.00 136.00   0.50    5.00    --  103.48  45.00   0.00   52
 18  \w     43.00  77.00   0.50    5.00    --  103.48 -45.00-180.00   68
 19  \w    106.00 169.00   0.50    5.00    --  103.48  30.00  30.00  126
 20  \w     43.00  69.00   0.50    5.00    --  103.48 -94.00  90.00   52
 21  \w     55.00 123.00   0.50    5.00    --  103.48 -77.00  90.00  136
 22  \w     39.00  66.00   0.50    5.00    --  103.48 -94.00 -30.00   54
 23  \w     75.00 106.00   0.50    5.00    --  103.48 -94.00 -30.00   62
 24  \w     43.00  96.00   0.50    5.00    --  103.48 -45.00  30.00  106
 25  \w     80.00 105.00   0.50    5.00    --  103.48 -94.00 -60.00   50
 26  \w    109.00 136.00   0.50    5.00    --  103.48  30.00   0.00   54
 27  \w     43.00  82.00   0.50    5.00    --  103.48 -45.00  90.00   78
 28  \w     43.00  97.00   0.50    5.00    --  103.48 -45.00 120.00  108
 29  \w     54.00  99.00   0.50    5.00    --  103.48 -45.00-150.00   90
 30  \w     66.00 102.00   0.50    5.00    --  103.48 -94.00  30.00   72
 31  \w     51.00  99.00   0.50    5.00    --  103.48 -45.00 -30.00   96
 32  \w    107.00 166.00   0.50    5.00    --  103.48  77.00  30.00  118
 33  \w    106.00 168.00   0.50    5.00    --  103.48  15.00 -60.00  124
 34  \w     58.00 117.00   0.50    5.00    --  103.48 -77.00-150.00  118
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0128346000
_diffrn_orient_matrix_UB_12      -0.1304073000
_diffrn_orient_matrix_UB_13      0.0163999000
_diffrn_orient_matrix_UB_21      0.0273431000
_diffrn_orient_matrix_UB_22      0.0399239000
_diffrn_orient_matrix_UB_23      0.0694914000
_diffrn_orient_matrix_UB_31      -0.1453418000
_diffrn_orient_matrix_UB_32      -0.0098175000
_diffrn_orient_matrix_UB_33      0.0071887000
_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  0.0208
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            27494
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.723
_diffrn_reflns_theta_min         3.923
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.030
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.685
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.173
_exptl_crystal_description       plate
_exptl_crystal_F_000             964
_exptl_crystal_preparation       'isolated from MeOH'
_exptl_crystal_recrystallization_method 'isolated from MeOH'
_exptl_crystal_size_max          0.208
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.062
_refine_diff_density_max         0.863
_refine_diff_density_min         -0.372
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     643
_refine_ls_number_reflns         10475
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0686P)^2^+1.0684P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1177
_refine_ls_wR_factor_ref         0.1198
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9753
_reflns_number_total             10475
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08516k2.cif
_cod_data_source_block           rj_007_auto
_cod_database_code               1576303
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C56H66B10P2
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.814
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C51-C52 \\sim C51-C52A
 with sigma of 0.02
 C52-C53 \\sim C52A-C53A
 with sigma of 0.02
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 C53-C55 \\sim C53A-C55
 with sigma of 0.04
 C54-C55 \\sim C54A-C55
 with sigma of 0.02
 C51-C53 \\sim C51-C53A
 with sigma of 0.04
 C52-C54 \\sim C52A-C54A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C52 \\sim C53 \\sim C54 \\sim C52A \\sim C53A \\sim C54A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C52, C53, C54, C52A, C53A, C54A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H55A)=Sof(C52A)=Sof(H52A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=1-FVAR(1)
 Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53)=Sof(C54)=Sof(H54)=Sof(H55)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B)
6.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26),
  C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C34(H34), C35(H35),
 C36(H36), C37(H37), C38(H38), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44),
  C46(H46), C47(H47), C48(H48), C49(H49), C50(H50), C52(H52), C53(H53),
 C54(H54), C55(H55), C55(H55A), C56(H56), C52A(H52A), C53A(H53A), C54A(H54A)
6.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C8(H8A,H8B,H8C)
6.d Boron cage BH refined with riding coordinates:
 B2(H2), B3(H3), B4(H4), B5(H5), B6(H6), B7(H7), B8(H8), B9(H9)
;
_shelx_res_checksum              5419
_olex2_submission_original_sample_id RMJ-33
_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 1.125
_oxdiff_exptl_absorpt_empirical_full_min 0.884