Redox non-innocent bis-silylene aluminium complexes with a carborane backbone
Saddington, Artemis; Yao, Shenglai; Lorent, Christian; Driess, Matthias; Chemical Science 16 (2025) 6383–6391; doi:10.1039/D5SC01104C

data_1574078
_publ_section_title
;
 Redox non-innocent bis-silylene aluminium complexes with a carborane
 backbone
;
_journal_issue                   15
_journal_name_full               'Chemical Science'
_journal_page_first              6383
_journal_page_last               6391
_journal_paper_doi               10.1039/D5SC01104C
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C58 H100 Al B10 K N4 O2 Si2, 2[C4H10O]'
_chemical_formula_sum            'C58 H100 Al B10 K N4 O2 Si2'
_chemical_formula_weight         1115.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-17
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.11.29 svn.rc9064207 for OlexSys, GUI svn.r7097)
;
_audit_update_record
;
2025-01-20 deposited with the CCDC.	2025-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.723(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.7751(10)
_cell_length_b                   15.1015(3)
_cell_length_c                   24.8744(9)
_cell_measurement_reflns_used    11161
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.4750
_cell_measurement_theta_min      3.4340
_cell_volume                     7699.8(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 10.5435
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     20.00 108.00   1.00   15.00    --   41.37  38.00 -30.00   88
  2  \w    -33.00   1.00   1.00   15.00    --   41.37 -38.00 150.00   34
  3  \w     10.00  93.00   1.00   15.00    --   41.37-125.00 -90.00   83
  4  \w     18.00 116.00   1.00   15.00    --   41.37  38.00  60.00   98
  5  \w      7.00  80.00   1.00   15.00    --   41.37-125.00 120.00   73
  6  \w    104.00 147.00   1.00   17.50    --  103.94  77.00 120.00   43
  7  \w     52.00 128.00   1.00   17.50    --  103.94 -61.00 150.00   76
  8  \w     29.00  80.00   1.00   17.50    --  103.94 -77.00 -60.00   51
  9  \w     45.00 125.00   1.00   17.50    --  103.94 -45.00 -60.00   80
 10  \w     73.00 109.00   1.00   17.50    --  103.94-111.00-150.00   36
 11  \w     32.00  57.00   1.00   17.50    --  103.94-111.00 -90.00   25
 12  \w     82.00 144.00   1.00   17.50    --  103.94  77.00 -90.00   62
 13  \w     64.00 109.00   1.00   17.50    --  103.94-111.00  30.00   45
 14  \w    126.00 153.00   1.00   17.50    --  103.94 111.00 -30.00   27
 15  \w     37.00 123.00   1.00   17.50    --  103.94 -45.00  60.00   86
 16  \w     30.00 109.00   1.00   17.50    --  103.94-111.00 120.00   79
 17  \w     32.00  59.00   1.00   17.50    --  103.94-111.00   0.00   27
 18  \w     67.00 109.00   1.00   17.50    --  103.94-111.00 -60.00   42
 19  \w    104.00 129.00   1.00   17.50    --  103.94 -77.00 -60.00   25
 20  \w     59.00  84.00   1.00   17.50    --  103.94-111.00-180.00   25
 21  \w     16.00 136.00   1.00   17.50    --  103.94   0.00 -60.00  120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0847
_diffrn_reflns_av_unetI/netI     0.0698
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            54462
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         67.500
_diffrn_reflns_theta_min         3.483
_exptl_absorpt_coefficient_mu    1.276
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38121
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.137a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    0.963
_exptl_crystal_description       plate
_exptl_crystal_F_000             2408
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.894
_refine_diff_density_min         -0.457
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     812
_refine_ls_number_reflns         13867
_refine_ls_number_restraints     132
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.1177
_refine_ls_R_factor_gt           0.0845
_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^)+(0.1265P)^2^+9.6593P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2126
_refine_ls_wR_factor_ref         0.2445
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9291
_reflns_number_total             13867
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01104c2.cif
_cod_data_source_block           5b
_cod_depositor_comments
'Adding full bibliography for 1574073--1574078.cif.'
_cod_database_code               1574078
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C70 H90 B10 Si2 N4 Al K O2'
_chemical_oxdiff_usercomment     'Artemis Saddington AS496 (same as CU-5406) '
_cell_oxdiff_angle_alpha         89.974(4)
_cell_oxdiff_angle_beta          109.766(4)
_cell_oxdiff_angle_gamma         90.046(3)
_cell_oxdiff_length_a            21.7752(10)
_cell_oxdiff_length_b            15.1129(6)
_cell_oxdiff_length_c            24.8621(12)
_cell_oxdiff_measurement_reflns_used 11161
_cell_oxdiff_volume              7699.8(6)
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.822
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All B(H,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
 C69-C29 \\sim C30-C29 \\sim C32-C29 \\sim C68-C29 \\sim C31-C29 \\sim C67-C29
 with sigma of 0.02
 C69-C68 \\sim C32-C30 \\sim C32-C31 \\sim C68-C67 \\sim C69-C67 \\sim C31-C30
 with sigma of 0.02
 C22-C21 \\sim C60-C59 \\sim C61-C59 \\sim C21-C20 \\sim C61-C60 \\sim C22-C20
 with sigma of 0.02
 C61-C19 \\sim C20-C19 \\sim C21-C19 \\sim C59-C19 \\sim C22-C19 \\sim C60-C19
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C67 \\sim C68 \\sim C69: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C30 \\sim C32 \\sim C31: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
K1 \\sim O1 \\sim O2: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08 within 2A
C22 \\sim C20 \\sim C21: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C31, C32, C30, C29
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C68, C69, C29, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C22, C20, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C59, C60, C61, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=
 Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=1-FVAR(1)
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
 Sof(H6B)=Sof(H3B)=Sof(B2B)=Sof(H2B)=Sof(C1B)=1-FVAR(2)
 Sof(C1)=Sof(H6A)=Sof(H3A)=Sof(B2)=Sof(H2)=FVAR(2)
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=1-FVAR(3)
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C6(H6), C9(H9)
6.b Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C51(H51A,H51B), C55(H55A,H55B), C57(H57A,H57B)
6.c Aromatic/amide H refined with riding coordinates:
 C42(H42), C28(H28), C43(H43), C27(H27), C45(H45), C14(H14), C46(H46),
 C11(H11), C24(H24), C7(H7), C12(H12), C25(H25), C13(H13), C8(H8)
6.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C16(H16A,H16B,H16C), C35(H35A,H35B,H35C), C39(H39A,H39B,
 H39C), C38(H38A,H38B,H38C), C17(H17A,H17B,H17C), C40(H40A,H40B,H40C), C36(H36A,
 H36B,H36C), C34(H34A,H34B,H34C), C52(H52A,H52B,H52C), C50(H50A,H50B,H50C),
 C54(H54A,H54B,H54C), C49(H49A,H49B,H49C), C48(H48A,H48B,H48C), C58(H58A,H58B,
 H58C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C21(H21A,H21B,H21C), C56(H56A,
 H56B,H56C), C32(H32A,H32B,H32C), C31(H31A,H31B,H31C), C30(H30A,H30B,H30C),
 C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C67(H67A,H67B,H67C), C60(H60A,H60B,
 H60C), C61(H61A,H61B,H61C), C59(H59A,H59B,H59C)
6.e Boron cage BH refined with riding coordinates:
 B5(H5), B6(H6B), B6(H6A), B4(H4), B9(H9A), B3(H3A), B3(H3B), B2(H2), B2B(H2B)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 348 electrons were 
found in a volume of 1476\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C4H10O] per Asymmetric Unit 
which account for 336 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              4682
_shelx_fab_checksum              17632
_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 2.217
_oxdiff_exptl_absorpt_empirical_full_min 0.640