Tuning reactivity through implementation of the HSAB concept in oxygen- and sulphur-bridged Al/P and Ga/P FLPs.
Buth, Julian; Vishnevskiy, Yury V.; Lamm, Jan-Hendrik; Neumann, Beate; Stammler, Hans-Georg; Mitzel, Norbert W.; Dalton transactions (Cambridge, England : 2003) 55 (2026) 2691–2701; doi:10.1039/d6dt00151c

data_7720121
_publ_section_title
;
 Tuning reactivity through implementation of the HSAB concept in oxygen-
 and sulphur-bridged Al/P and Ga/P FLPs.
;
_journal_issue                   6
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2691
_journal_page_last               2701
_journal_paper_doi               10.1039/d6dt00151c
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C23 H56 Ga P S3 Si4'
_chemical_formula_sum            'C23 H56 Ga P S3 Si4'
_chemical_formula_weight         641.90
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-03
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-11-17 deposited with the CCDC.	2026-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.6200(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.7104(2)
_cell_length_b                   11.88290(10)
_cell_length_c                   28.2287(3)
_cell_measurement_reflns_used    120122
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      37.9860
_cell_measurement_theta_min      3.4960
_cell_volume                     6946.67(12)
_computing_cell_refinement       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.127a 64-bit (release 16-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.127a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_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    -56.00  42.00   1.00    8.00    --  -31.41  41.00 -98.00   98
  2  \w   -105.00  -6.00   1.00    8.00    --  -31.41 -41.00 107.00   99
  3  \w    -42.00  57.00   1.00    8.00    --   31.72 -41.00 107.00   99
  4  \w      7.00 105.00   1.00    8.00    --   31.72  41.00 -98.00   98
  5  \w    -56.00  43.00   1.00    8.00    --  -31.41  38.00  30.00   99
  6  \w   -106.00  -7.00   1.00    8.00    --  -31.41 -38.00  30.00   99
  7  \w   -105.00   0.00   1.00    8.00    --  -31.41 -71.00   9.07  105
  8  \w   -106.00  -7.00   1.00    8.00    --  -31.41 -38.00-120.00   99
  9  \w   -100.00 -16.00   1.00    8.00    --  -31.41 145.00 106.07   84
 10  \w   -106.00  -7.00   1.00    8.00    --  -31.41 -38.00  30.00   99
 11  \w      9.00  90.00   1.00    8.00    --   31.72-130.00 128.58   81
 12  \w     -7.00  19.00   1.00    8.00    --   31.72  96.00 171.48   26
 13  \w     -6.00  23.00   1.00    8.00    --   31.72  92.00 -56.24   29
 14  \w     37.00 119.00   1.00    8.00    --   31.72-178.00  30.00   82
 15  \w   -109.00 -24.00   1.00    8.00    --  -31.41 158.00-149.13   85
 16  \w   -119.00 -37.00   1.00    8.00    --  -31.41 178.00 -90.00   82
 17  \w   -120.00  57.00   1.00    8.00    --  -31.41   0.00-180.00  177
 18  \w     -7.00  19.00   1.00    8.00    --   31.72  96.00 -85.00   26
 19  \w     39.00 120.00   1.00    8.00    --   31.72 178.00 -30.00   81
 20  \w     -7.00  19.00   1.00    8.00    --   31.72  96.00-127.86   26
 21  \w     -7.00  19.00   1.00    8.00    --   31.72  96.00 144.09   26
 22  \w      0.00  36.00   1.00    8.00    --   31.72  73.00  -4.30   36
 23  \w      7.00 106.00   1.00    8.00    --   31.72  38.00 -60.00   99
 24  \w     -7.00  21.00   1.00    8.00    --   31.72  94.00  -0.17   28
 25  \w     -7.00  19.00   1.00    8.00    --   31.72  96.00-140.62   26
 26  \w   -120.00  57.00   1.00    8.00    --  -31.41   0.00-120.00  177
 27  \w   -120.00  57.00   1.00    8.00    --  -31.41   0.00 -90.00  177
 28  \w   -120.00  57.00   1.00    8.00    --  -31.41   0.00 -60.00  177
 29  \w   -120.00  57.00   1.00    8.00    --  -31.41   0.00 -30.00  177
 30  \w   -120.00  57.00   1.00    8.00    --  -31.41   0.00   0.00  177
 31  \w   -120.00  57.00   1.00    8.00    --  -31.41   0.00  30.00  177
 32  \w   -120.00  57.00   1.00    8.00    --  -31.41   0.00  60.00  177
 33  \w   -120.00  25.00   1.00    8.00    --  -31.41   0.00  90.00  145
 34  \w   -120.00  57.00   1.00    8.00    --  -31.41   0.00-150.00  177
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0219203000
_diffrn_orient_matrix_UB_12      -0.0346667000
_diffrn_orient_matrix_UB_13      0.0128251000
_diffrn_orient_matrix_UB_21      0.0225055000
_diffrn_orient_matrix_UB_22      0.0449594000
_diffrn_orient_matrix_UB_23      0.0010407000
_diffrn_orient_matrix_UB_31      -0.0136557000
_diffrn_orient_matrix_UB_32      0.0184669000
_diffrn_orient_matrix_UB_33      0.0215739000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0420
_diffrn_reflns_av_unetI/netI     0.0105
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            323588
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.033
_diffrn_reflns_theta_min         3.413
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.168
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.489
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.127a (Rigaku Oxford Diffraction, 2024)
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            'clear violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.228
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2752
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.21
_refine_diff_density_max         1.271
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.132
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     307
_refine_ls_number_reflns         10152
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.0270
_refine_ls_R_factor_gt           0.0254
_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^)+(0.0220P)^2^+10.7750P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0612
_refine_ls_wR_factor_ref         0.0620
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9668
_reflns_number_total             10152
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           GaSPxCS2
_cod_database_code               7720121
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C23 H56 Ga P S3 Si4'
_shelx_estimated_absorpt_t_max   0.791
_shelx_estimated_absorpt_t_min   0.659
_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.a Ternary CH refined with riding coordinates:
 C1(H1), C8(H8)
2.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), 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), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,
 H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C),
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              96669
_olex2_date_sample_data_collection 2024-07-02
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.449
_oxdiff_exptl_absorpt_empirical_full_min 0.730