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_7720114
_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         'C22 H56 Al P S Si4'
_chemical_formula_sum            'C22 H56 Al P S Si4'
_chemical_formula_weight         523.03
_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             2023-08-22
_audit_creation_method
;
Olex2 1.5-dev
(compiled 2023.08.08 svn.r17d2718d for OlexSys, GUI svn.r6815)
;
_audit_update_record
;
2025-11-17 deposited with the CCDC.	2026-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                106.425(2)
_cell_angle_beta                 97.765(2)
_cell_angle_gamma                91.828(2)
_cell_formula_units_Z            2
_cell_length_a                   9.3597(2)
_cell_length_b                   13.3329(3)
_cell_length_c                   13.8931(2)
_cell_measurement_reflns_used    23733
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3590
_cell_measurement_theta_min      3.3080
_cell_volume                     1643.26(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.98a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.98a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.98a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.987
_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    -87.00  -6.00   1.00    1.00    --  -38.50 125.00 150.00   81
  2  \w    -87.00 -34.00   1.00    1.00    --  -38.50 125.00 -60.00   53
  3  \w    -51.00  31.00   1.00    1.00    --  -38.50  38.00  60.00   82
  4  \w    -56.00  22.00   1.00    1.00    --  -38.50  38.00 150.00   78
  5  \w     17.00  45.00   1.00    1.00    --   42.32  57.00  30.00   28
  6  \w     23.00  63.00   1.00    1.00    --   42.32  38.00-150.00   40
  7  \w     79.00 106.00   1.00    1.00    --   42.32  57.00 -60.00   27
  8  \w     17.00  50.00   1.00    1.00    --   42.32  57.00  90.00   33
  9  \w     12.00  40.00   1.00    1.00    --   42.32  78.00 121.63   28
 10  \w     15.00  40.00   1.00    1.00    --   42.32  79.00-113.09   25
 11  \w     23.00  58.00   1.00    1.00    --   42.32  38.00   0.00   35
 12  \w     63.00 104.00   1.00    1.00    --   42.32  38.00   0.00   41
 13  \w     17.00 101.00   1.00    1.00    --   42.32  57.00-120.00   84
 14  \w     24.00  54.00   1.00    1.00    --   42.32  38.00-180.00   30
 15  \w     21.00  48.00   1.00    1.00    --   42.32  57.00 -30.00   27
 16  \w     23.00  48.00   1.00    1.00    --   42.32  57.00 -60.00   25
 17  \w     76.00 104.00   1.00    1.00    --   42.32  38.00-180.00   28
 18  \w     59.00 111.00   1.00    1.00    --   42.32  57.00  30.00   52
 19  \w     34.00  87.00   1.00    1.00    --   42.32  38.00 120.00   53
 20  \w     13.00  41.00   1.00    1.00    --   42.32  80.00  40.73   28
 21  \w    -29.00  62.00   1.00    1.00    --   42.32 -38.00-120.00   91
 22  \w     11.00  39.00   1.00    1.00    --   42.32  81.00 -37.64   28
 23  \w     11.00  38.00   1.00    1.00    --   42.32  82.00 173.44   27
 24  \w    124.00 166.00   1.00    1.00    --  111.00  63.00 -59.71   42
 25  \w    134.00 176.00   1.00    1.00    --  111.00  64.00 -34.16   42
 26  \w     84.00 111.00   1.00    1.00    --  111.00  63.00 -59.71   27
 27  \w     84.00 111.00   1.00    1.00    --  111.00  64.00   1.86   27
 28  \w    120.00 171.00   1.00    1.00    --  111.00 125.00-120.00   51
 29  \w     85.00 122.00   1.00    1.00    --  111.00  61.00-180.00   37
 30  \w     85.00 113.00   1.00    1.00    --  111.00  61.00 120.00   28
 31  \w     84.00 121.00   1.00    1.00    --  111.00  64.00 -34.16   37
 32  \w     84.00 109.00   1.00    1.00    --  111.00-108.00-162.42   25
 33  \w    126.00 174.00   1.00    1.00    --  111.00  60.00 168.52   48
 34  \w     40.00  67.00   1.00    1.00    --  111.00-108.00-162.42   27
 35  \w    134.00 177.00   1.00    1.00    --  111.00  63.00  17.14   43
 36  \w     85.00 112.00   1.00    1.00    --  111.00  60.00 168.52   27
 37  \w    133.00 174.00   1.00    1.00    --  111.00  55.00-132.15   41
 38  \w     87.00 123.00   1.00    1.00    --  111.00  51.00  51.21   36
 39  \w     84.00 120.00   1.00    1.00    --  111.00  63.00  17.14   36
 40  \w     85.00 115.00   1.00    1.00    --  111.00  61.00-150.00   30
 41  \w     83.00 111.00   1.00    1.00    --  111.00  70.00 177.12   28
 42  \w     87.00 124.00   1.00    1.00    --  111.00  58.00  54.44   37
 43  \w     85.00 111.00   1.00    1.00    --  111.00  61.00 150.00   26
 44  \w     85.00 113.00   1.00    1.00    --  111.00  61.00-120.00   28
 45  \w    135.00 170.00   1.00    1.00    --  111.00  61.00-120.00   35
 46  \w     85.00 121.00   1.00    1.00    --  111.00  61.00 -90.00   36
 47  \w     68.00  95.00   1.00    1.00    --  111.00 -15.00 -90.00   27
 48  \w     53.00 105.00   1.00    1.00    --  111.00-125.00-180.00   52
 49  \w     90.00 117.00   1.00    1.00    --  111.00  45.00   0.00   27
 50  \w    123.00 148.00   1.00    1.00    --  111.00  45.00   0.00   25
 51  \w    150.00 177.00   1.00    1.00    --  111.00  67.00 100.39   27
 52  \w     50.00 106.00   1.00    1.00    --  111.00 -94.00 -60.00   56
 53  \w     85.00 177.00   1.00    1.00    --  111.00  61.00  90.00   92
 54  \w     90.00 130.00   1.00    1.00    --  111.00  45.00 -90.00   40
 55  \w     91.00 116.00   1.00    1.00    --  111.00  45.00 -30.00   25
 56  \w    135.00 162.00   1.00    1.00    --  111.00  45.00 -30.00   27
 57  \w     85.00 126.00   1.00    1.00    --  111.00  61.00  30.00   41
 58  \w    131.00 163.00   1.00    1.00    --  111.00  61.00  30.00   32
 59  \w     45.00  71.00   1.00    1.00    --  111.00 -61.00-150.00   26
 60  \w     83.00 130.00   1.00    1.00    --  111.00  67.00 100.39   47
 61  \w    119.00 178.00   1.00    1.00    --  111.00  65.00 123.60   59
 62  \w     33.00 102.00   1.00    1.00    --  111.00 -94.00  90.00   69
 63  \w     86.00 117.00   1.00    1.00    --  111.00  55.00-132.15   31
 64  \w     70.00 106.00   1.00    1.00    --  111.00 -94.00-120.00   36
 65  \w    125.00 178.00   1.00    1.00    --  111.00  77.00-180.00   53
 66  \w    135.00 163.00   1.00    1.00    --  111.00  50.00   8.85   28
 67  \w     99.00 171.00   1.00    1.00    --  111.00 125.00 -30.00   72
 68  \w     93.00 132.00   1.00    1.00    --  111.00 -61.00 150.00   39
 69  \w     52.00  77.00   1.00    1.00    --  111.00 -61.00 150.00   25
 70  \w     43.00 106.00   1.00    1.00    --  111.00 -77.00 -60.00   63
 71  \w     87.00 114.00   1.00    1.00    --  111.00  50.00   8.85   27
 72  \w     85.00 113.00   1.00    1.00    --  111.00  65.00 123.60   28
 73  \w     43.00 136.00   1.00    1.00    --  111.00 -61.00 -60.00   93
 74  \w     89.00 119.00   1.00    1.00    --  111.00  45.00-180.00   30
 75  \w     88.00 113.00   1.00    1.00    --  111.00-125.00  60.00   25
 76  \w     92.00 117.00   1.00    1.00    --  111.00  30.00 -90.00   25
 77  \w    139.00 166.00   1.00    1.00    --  111.00  30.00 -90.00   27
 78  \w     40.00  86.00   1.00    1.00    --  111.00 -30.00-150.00   46
 79  \w     48.00  73.00   1.00    1.00    --  111.00-125.00  60.00   25
 80  \w     74.00  99.00   1.00    1.00    --  111.00 -61.00-150.00   25
 81  \w     67.00 106.00   1.00    1.00    --  111.00 -94.00-180.00   39
 82  \w     71.00  99.00   1.00    1.00    --  111.00 -94.00  60.00   28
 83  \w     86.00 112.00   1.00    1.00    --  111.00  62.00  79.41   26
 84  \w    124.00 151.00   1.00    1.00    --  111.00 -15.00 -90.00   27
 85  \w     86.00 124.00   1.00    1.00    --  111.00  61.00  60.00   38
 86  \w    131.00 158.00   1.00    1.00    --  111.00  61.00  60.00   27
 87  \w    132.00 166.00   1.00    1.00    --  111.00  45.00 150.00   34
 88  \w     91.00 119.00   1.00    1.00    --  111.00  45.00 150.00   28
 89  \w     92.00 147.00   1.00    1.00    --  111.00  45.00-150.00   55
 90  \w     84.00 176.00   1.00    1.00    --  111.00  65.00 -75.19   92
 91  \w    152.00 177.00   1.00    1.00    --  111.00  64.00   1.86   25
 92  \w    139.00 166.00   1.00    1.00    --  111.00  51.00  51.21   27
 93  \w    147.00 178.00   1.00    1.00    --  111.00  55.00  76.61   31
 94  \w     86.00 121.00   1.00    1.00    --  111.00  55.00  76.61   35
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0336686000
_diffrn_orient_matrix_UB_12      -0.1193370000
_diffrn_orient_matrix_UB_13      -0.0260870000
_diffrn_orient_matrix_UB_21      0.1321159000
_diffrn_orient_matrix_UB_22      -0.0186697000
_diffrn_orient_matrix_UB_23      -0.0562834000
_diffrn_orient_matrix_UB_31      0.0956990000
_diffrn_orient_matrix_UB_32      -0.0007035000
_diffrn_orient_matrix_UB_33      0.0991217000
_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  0.0313
_diffrn_reflns_av_unetI/netI     0.0185
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            36904
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.577
_diffrn_reflns_theta_min         3.355
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.038
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.260
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.98a (Rigaku Oxford Diffraction, 2023)
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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.057
_exptl_crystal_description       irregular
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.960
_refine_diff_density_min         -0.561
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.137
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     339
_refine_ls_number_reflns         6836
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.137
_refine_ls_R_factor_all          0.0504
_refine_ls_R_factor_gt           0.0480
_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^)+(0.0530P)^2^+2.1466P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1266
_refine_ls_wR_factor_ref         0.1282
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6400
_reflns_number_total             6836
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           AlSP
_cod_database_code               7720114
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C22 H56 Al P Si4 S'
_shelx_estimated_absorpt_t_max   0.659
_shelx_estimated_absorpt_t_min   0.312
_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
C18A \\sim C17A \\sim C16A \\sim C15B: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 within 2A
C15A \\sim C16B \\sim C17B \\sim C18B: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 within 2A
3. Rigid body (RIGU) restrains
 C18A, C17A, C16A, C15B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C15A, C16B, C17B, C18B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(C20B)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C22B)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=Sof(C21B)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C20A)=Sof(H20D)=Sof(H20E)=
 Sof(H20F)=Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=FVAR(1)
 Sof(C16B)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17B)=Sof(H17A)=Sof(H17B)=
 Sof(H17C)=Sof(C18B)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C15B)=1-FVAR(2)
 Sof(C15A)=Sof(C18A)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C17A)=Sof(H17D)=
 Sof(H17E)=Sof(H17F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C8(H8)
5.b Me refined with riding coordinates:
 C16B(H16A,H16B,H16C), C17B(H17A,H17B,H17C), C18A(H18A,H18B,H18C), C20B(H20A,
 H20B,H20C), C21A(H21A,H21B,H21C), C22B(H22A,H22B,H22C), C20A(H20D,H20E,H20F),
 C22A(H22D,H22E,H22F), C21B(H21D,H21E,H21F), C17A(H17D,H17E,H17F), C16A(H16D,
 H16E,H16F), C18B(H18D,H18E,H18F)
5.c 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)
;
_shelx_res_checksum              54887
_olex2_date_sample_data_collection 2023-08-11
_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 1.270
_oxdiff_exptl_absorpt_empirical_full_min 0.797