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_1576302
_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), C4 H18 B10, C H4 O'
_chemical_formula_sum            'C53 H62 B10 O P2'
_chemical_formula_weight         885.06
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-12
_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                90
_cell_angle_beta                 98.3290(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5108(2)
_cell_length_b                   13.8768(2)
_cell_length_c                   31.3332(4)
_cell_measurement_reflns_used    16531
_cell_measurement_temperature    99.8(8)
_cell_measurement_theta_max      76.5060
_cell_measurement_theta_min      2.8230
_cell_volume                     4952.16(13)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.8(8)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.969
_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   -103.00 -40.00   0.50    0.50    --  -38.50 -19.00 150.00  126
  2  \w    -32.00  23.00   0.50    0.50    --  -38.50  19.00 150.00  110
  3  \w   -104.00 -48.00   0.50    0.50    --  -38.50 -19.00-150.00  112
  4  \w     41.00  78.00   0.50    0.50    --   50.71  57.00  60.00   74
  5  \w     89.00 115.00   0.50    0.50    --   50.71  38.00-150.00   52
  6  \w     86.00 115.00   0.50    0.50    --   50.71  38.00 -30.00   58
  7  \w     40.00 102.00   0.50    1.00    --  103.48 -30.00   0.00  124
  8  \w    103.00 145.00   0.50    1.00    --  103.48  30.00 -60.00   84
  9  \w     41.00  97.00   0.50    1.00    --  103.48 -45.00   0.00  112
 10  \w     70.00  98.00   0.50    1.00    --  103.48 -45.00  30.00   56
 11  \w     41.00  81.00   0.50    1.00    --  103.48 -45.00 -60.00   80
 12  \w     46.00  96.00   0.50    1.00    --  103.48 -30.00  60.00  100
 13  \w     48.00  94.00   0.50    1.00    --  103.48 -45.00-180.00   92
 14  \w     49.00 102.00   0.50    1.00    --  103.48 -30.00 -60.00  106
 15  \w     64.00  99.00   0.50    1.00    --  103.48 -15.00  60.00   70
 16  \w     38.00  98.00   0.50    1.00    --  103.48 -15.00 150.00  120
 17  \w     41.00  88.00   0.50    1.00    --  103.48 -45.00 150.00   94
 18  \w    102.00 147.00   0.50    1.00    --  103.48  45.00-180.00   90
 19  \w    128.00 171.00   0.50    1.00    --  103.48  15.00 -90.00   86
;
_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      0.1302734000
_diffrn_orient_matrix_UB_12      0.0215848000
_diffrn_orient_matrix_UB_13      0.0159328000
_diffrn_orient_matrix_UB_21      -0.0359709000
_diffrn_orient_matrix_UB_22      0.0857459000
_diffrn_orient_matrix_UB_23      0.0263922000
_diffrn_orient_matrix_UB_31      -0.0040900000
_diffrn_orient_matrix_UB_32      -0.0671606000
_diffrn_orient_matrix_UB_33      0.0389769000
_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  0.0254
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            29114
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.701
_diffrn_reflns_theta_min         2.851
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.073
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.416
_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    1.187
_exptl_crystal_description       plate
_exptl_crystal_F_000             1872
_exptl_crystal_preparation       'islated from MeOH'
_exptl_crystal_recrystallization_method 'isolated from MeOH'
_exptl_crystal_size_max          0.402
_exptl_crystal_size_mid          0.356
_exptl_crystal_size_min          0.143
_refine_diff_density_max         0.508
_refine_diff_density_min         -0.525
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     663
_refine_ls_number_reflns         10117
_refine_ls_number_restraints     318
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0638
_refine_ls_R_factor_gt           0.0583
_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^)+(0.0880P)^2^+4.1733P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1639
_refine_ls_wR_factor_ref         0.1682
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9020
_reflns_number_total             10117
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08516k2.cif
_cod_data_source_block           rj_013_d_auto
_cod_database_code               1576302
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C53H62B10OP2
_chemical_oxdiff_usercomment     'New sample'
_shelx_estimated_absorpt_t_max   0.862
_shelx_estimated_absorpt_t_min   0.672
_reflns_odcompleteness_completeness 99.86
_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, All C(H,H,H,H,H,H) groups, All O(H) groups
2. Restrained distances
 C23-C28 \\sim C23-C28A
 with sigma of 0.02
 C23-C24 \\sim C23-C24A
 with sigma of 0.02
 C26-C25 \\sim C26A-C25A
 with sigma of 0.02
 C26-C27 \\sim C26A-C27A
 with sigma of 0.02
 C25-C27 \\sim C25A-C27A
 with sigma of 0.04
 C24-C25 \\sim C24A-C25A
 with sigma of 0.02
 C27-C28 \\sim C27A-C28A
 with sigma of 0.02
 C23-C25 \\sim C23-C25A
 with sigma of 0.04
 C23-C27 \\sim C23-C27A
 with sigma of 0.04
 C26-C24 \\sim C26A-C24A
 with sigma of 0.04
 C26-C28 \\sim C26A-C28A
 with sigma of 0.04
 O1-C53 \\sim O1A-C53
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C12 \\sim C13 \\sim C14 \\sim C12A \\sim C13A \\sim C14A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C24A \\sim C25A
\\sim C26A \\sim C27A \\sim C28A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(C28) = Uanis(C28A)
Uanis(C25) = Uanis(C25A)
Uanis(C13) = Uanis(C13A)
Uanis(O1) = Uanis(O1A)
4. Rigid body (RIGU) restrains
 C12, C13, C14, C12A, C13A, C14A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23, C24, C25, C26, C27, C28, C24A, C25A, C26A, C27A, C28A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H15A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=1-FVAR(1)
 Sof(H15)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=FVAR(1)
 Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=
 Sof(H27A)=Sof(C28A)=Sof(H28A)=1-FVAR(2)
 Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=
 Sof(C28)=Sof(H28)=FVAR(2)
 Sof(H53D)=Sof(H53E)=Sof(H53F)=Sof(O1A)=Sof(H1AA)=1-FVAR(3)
 Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(O1)=Sof(H1)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C15(H15), C15(H15A), C16(H16),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C12(H12), C13(H13), C14(H14),
  C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C12A(H12A), C13A(H13A),
 C14A(H14A), C24A(H24A), C25A(H25A), C26A(H26A), C27A(H27A), C28A(H28A),
 C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C37(H37), C38(H38),
  C39(H39), C40(H40), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46),
 C48(H48), C49(H49), C50(H50), C51(H51), C52(H52)
6.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C53(H53A,H53B,H53C), C53(H53D,H53E,H53F)
6.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O1A(H1AA)
6.e Boron cage BH refined with riding coordinates:
 B2(H2), B3(H3), B4(H4), B5(H5), B6(H6A), B7(H7A), B8(H8A), B9(H9A)
;
_shelx_res_checksum              98896
_olex2_submission_original_sample_id RMJ-47
_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 1.167
_oxdiff_exptl_absorpt_empirical_full_min 0.905