Enhancing the nucleophilicity of aluminyl anions: targeting selective C–H activation
Kallmeier, Fabian; Nelmes, Gareth R.; McMullin, Claire L.; Edwards, Alison J.; Hicks, Jamie; Chemical Science 16 (2025) 10750–10758; doi:10.1039/D5SC02682B

data_1574619
_publ_section_title
;
 Enhancing the nucleophilicity of aluminyl anions: targeting selective
 C--H activation
;
_journal_issue                   24
_journal_name_full               'Chemical Science'
_journal_page_first              10750
_journal_page_last               10758
_journal_paper_doi               10.1039/D5SC02682B
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C88 H146 Al2 K2 N4 O2 Si4, C6 H6'
_chemical_formula_sum            'C94 H152 Al2 K2 N4 O2 Si4'
_chemical_formula_weight         1614.71
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2025-03-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.06 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-03-20 deposited with the CCDC.	2025-05-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.2990(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.4566(3)
_cell_length_b                   18.6939(2)
_cell_length_c                   23.7291(2)
_cell_measurement_reflns_used    12285
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      77.7780
_cell_measurement_theta_min      3.3480
_cell_volume                     9510.91(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.960
_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    -78.00  -6.00   0.50    6.00    --  -46.57 108.00  12.00  144
  2  \w     27.00  65.00   0.50    6.00    --   46.57-108.00 -83.00   76
  3  \w    105.00 131.00   0.50   16.00    --  107.75 108.00  12.00   52
  4  \w     46.00  94.00   0.50   16.00    --  107.75-108.00 -83.00   96
  5  \w     -8.00  19.00   0.50    6.00    --  -46.57  19.00   0.00   54
  6  \w     -7.00  29.00   0.50    6.00    --  -46.57  19.00 -90.00   72
  7  \w     -1.00  26.00   0.50    6.00    --  -46.57  19.00 -30.00   54
  8  \w    -22.00  26.00   0.50    6.00    --  -46.57  38.00 120.00   96
  9  \w     77.00 118.00   0.50    6.00    --   46.57  57.00  90.00   82
 10  \w     32.00  57.00   0.50   16.00    --  107.75 -30.00  90.00   50
 11  \w     38.00  73.00   0.50   16.00    --  107.75 -95.00 -30.00   70
 12  \w     34.00  92.00   0.50   16.00    --  107.75 -61.00 120.00  116
 13  \w     41.00  72.00   0.50   16.00    --  107.75 -45.00 150.00   62
 14  \w     45.00  71.00   0.50   16.00    --  107.75 -45.00-120.00   52
 15  \w     37.00  92.00   0.50   16.00    --  107.75 -61.00 -30.00  110
 16  \w     77.00 105.00   0.50   16.00    --  107.75 -95.00 -30.00   56
 17  \w     32.00  59.00   0.50   16.00    --  107.75 -30.00 -30.00   54
 18  \w     37.00  71.00   0.50   16.00    --  107.75 -45.00  60.00   68
 19  \w     35.00  60.00   0.50   16.00    --  107.75 -45.00   0.00   50
 20  \w     34.00  59.00   0.50   16.00    --  107.75 -30.00 120.00   50
 21  \w     34.00  59.00   0.50   16.00    --  107.75 -30.00 -60.00   50
 22  \w     32.00  57.00   0.50   16.00    --  107.75 -30.00   0.00   50
 23  \w     38.00 110.00   0.50   16.00    --  107.75-125.00   0.00  144
 24  \w     35.00  73.00   0.50   16.00    --  107.75 -45.00-180.00   76
 25  \w     32.00  57.00   0.50   16.00    --  107.75 -30.00  30.00   50
 26  \w     34.00  59.00   0.50   16.00    --  107.75 -30.00  60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0741
_diffrn_reflns_av_unetI/netI     0.0672
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            30620
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.242
_diffrn_reflns_theta_min         3.136
_exptl_absorpt_coefficient_mu    1.891
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57040
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.128
_exptl_crystal_description       block
_exptl_crystal_F_000             3520
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.525
_refine_diff_density_min         -0.646
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     519
_refine_ls_number_reflns         9803
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0694
_refine_ls_R_factor_gt           0.0554
_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^)+(0.0650P)^2^+16.2044P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1372
_refine_ls_wR_factor_ref         0.1444
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8025
_reflns_number_total             9803
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02682b2.cif
_cod_data_source_block           compound-3
_cod_depositor_comments
'Adding full bibliography for 1574617--1574626.cif.'
_cod_database_code               1574619
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.879
_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. Uiso/Uaniso restraints and constraints
Uanis(C7) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
3.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C30(H30), C33(H33), C36(H36), C39(H39)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C11(H11), C45(H45), C47(H47), C48(H48)
3.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), 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), C28(H28A,H28B,H28C),
 C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C)
;
_shelx_res_checksum              26413
_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
;