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_7720120
_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 Al O2 P S Si4, 1.5(C6 H6)'
_chemical_formula_sum            'C32 H65 Al O2 P S Si4'
_chemical_formula_weight         684.21
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-10
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-11-17 deposited with the CCDC.	2026-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.8720(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1936(2)
_cell_length_b                   23.2523(3)
_cell_length_c                   15.3726(2)
_cell_measurement_reflns_used    30369
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      75.7410
_cell_measurement_theta_min      3.7050
_cell_volume                     4148.26(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.93a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.93a 64-bit (release 17-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.93a (Rigaku OD, 2023)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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   -113.00 -19.00   1.00    4.50    --  -41.83 -38.00  90.00   94
  2  \w    -68.00  28.00   1.00    4.50    --  -41.83  57.00 120.00   96
  3  \w    -82.00 -19.00   1.00    4.50    --  -41.83 -38.00-120.00   63
  4  \w    -86.00  -6.00   1.00    4.50    --  -41.83 125.00 120.00   80
  5  \w    -87.00  -6.00   1.00    4.50    --  -41.83 125.00 -60.00   81
  6  \w   -109.00 -19.00   1.00    4.50    --  -41.83 -38.00 -30.00   90
  7  \w    -35.00  31.00   1.00    4.50    --  -41.83  38.00 -90.00   66
  8  \w   -113.00 -24.00   1.00    4.50    --  -41.83 -38.00-180.00   89
  9  \w     10.00  39.00   1.00    4.50    --   41.83  80.00 -33.44   29
 10  \w     10.00  42.00   1.00    4.50    --   41.83  79.00  20.44   32
 11  \w     14.00  42.00   1.00    4.50    --   41.83  79.00 149.73   28
 12  \w      9.00  42.00   1.00    4.50    --   41.83  82.00-122.76   33
 13  \w      9.00  41.00   1.00    4.50    --   41.83  82.00  77.59   32
 14  \w     15.00  55.00   1.00    4.50    --   41.83  57.00 120.00   40
 15  \w    117.00 172.00   1.00   13.50    --  111.00  61.00 -90.00   55
 16  \w     83.00 109.00   1.00   13.50    --  111.00  61.00 -90.00   26
 17  \w     83.00 109.00   1.00   13.50    --  111.00  61.00-180.00   26
 18  \w    131.00 174.00   1.00   13.50    --  111.00  61.00 120.00   43
 19  \w    131.00 174.00   1.00   13.50    --  111.00  61.00-150.00   43
 20  \w    125.00 178.00   1.00   13.50    --  111.00  61.00  30.00   53
 21  \w     42.00 109.00   1.00   13.50    --  111.00-111.00   0.00   67
 22  \w     83.00 109.00   1.00   13.50    --  111.00  61.00-150.00   26
 23  \w     87.00 119.00   1.00   13.50    --  111.00  45.00  90.00   32
 24  \w     83.00 122.00   1.00   13.50    --  111.00  61.00 120.00   39
 25  \w     43.00 109.00   1.00   13.50    --  111.00-111.00  30.00   66
 26  \w     83.00 109.00   1.00   13.50    --  111.00  61.00-120.00   26
 27  \w    126.00 175.00   1.00   13.50    --  111.00  61.00-120.00   49
 28  \w     83.00 109.00   1.00   13.50    --  111.00  61.00 150.00   26
 29  \w    126.00 178.00   1.00   13.50    --  111.00  61.00 150.00   52
 30  \w     83.00 173.00   1.00   13.50    --  111.00  61.00  90.00   90
 31  \w     83.00 116.00   1.00   13.50    --  111.00  61.00 -30.00   33
 32  \w     83.00 110.00   1.00   13.50    --  111.00  61.00  30.00   27
 33  \w     87.00 121.00   1.00   13.50    --  111.00  45.00 -90.00   34
 34  \w     87.00 128.00   1.00   13.50    --  111.00  45.00-180.00   41
 35  \w    121.00 148.00   1.00   13.50    --  111.00  45.00 -30.00   27
 36  \w    122.00 178.00   1.00   13.50    --  111.00  61.00 -60.00   56
 37  \w     87.00 120.00   1.00   13.50    --  111.00  45.00 -30.00   33
 38  \w     88.00 140.00   1.00   13.50    --  111.00  45.00-150.00   52
 39  \w     87.00 133.00   1.00   13.50    --  111.00  45.00 150.00   46
 40  \w     48.00 109.00   1.00   13.50    --  111.00-111.00 -60.00   61
 41  \w     87.00 162.00   1.00   13.50    --  111.00  45.00   0.00   75
 42  \w     87.00 114.00   1.00   13.50    --  111.00  45.00 -60.00   27
 43  \w    115.00 142.00   1.00   13.50    --  111.00  45.00 -60.00   27
 44  \w     87.00 153.00   1.00   13.50    --  111.00  45.00 120.00   66
 45  \w     87.00 113.00   1.00   13.50    --  111.00  45.00  30.00   26
 46  \w    119.00 146.00   1.00   13.50    --  111.00  45.00  30.00   27
 47  \w     83.00 176.00   1.00   13.50    --  111.00  61.00   0.00   93
 48  \w     83.00 109.00   1.00   13.50    --  111.00  61.00 -60.00   26
 49  \w     40.00 108.00   1.00   13.50    --  111.00-111.00-120.00   68
 50  \w    127.00 154.00   1.00   13.50    --  111.00  45.00  60.00   27
 51  \w     87.00 114.00   1.00   13.50    --  111.00  45.00  60.00   27
 52  \w    140.00 176.00   1.00   13.50    --  111.00  61.00  60.00   36
 53  \w     45.00  98.00   1.00   13.50    --  111.00-111.00  60.00   53
 54  \w     43.00 109.00   1.00   13.50    --  111.00-111.00 150.00   66
 55  \w     83.00 109.00   1.00   13.50    --  111.00  61.00  60.00   26
 56  \w    123.00 175.00   1.00   13.50    --  111.00  61.00-180.00   52
 57  \w     39.00 109.00   1.00   13.50    --  111.00-111.00-150.00   70
 58  \w     54.00  89.00   1.00   13.50    --  111.00 -45.00  30.00   35
 59  \w    106.00 133.00   1.00   13.50    --  111.00 -45.00  30.00   27
 60  \w     46.00 109.00   1.00   13.50    --  111.00-111.00  90.00   63
 61  \w     45.00 109.00   1.00   13.50    --  111.00-111.00 -90.00   64
 62  \w     47.00  87.00   1.00   13.50    --  111.00-111.00 -30.00   40
 63  \w     87.00 137.00   1.00   13.50    --  111.00  45.00-120.00   50
;
_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      0.0557657000
_diffrn_orient_matrix_UB_12      0.0202637000
_diffrn_orient_matrix_UB_13      -0.0720678000
_diffrn_orient_matrix_UB_21      -0.0534119000
_diffrn_orient_matrix_UB_22      -0.0517507000
_diffrn_orient_matrix_UB_23      -0.0608899000
_diffrn_orient_matrix_UB_31      -0.1079382000
_diffrn_orient_matrix_UB_32      0.0360569000
_diffrn_orient_matrix_UB_33      -0.0468083000
_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  0.0790
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            77529
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.150
_diffrn_reflns_theta_min         3.569
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.553
_exptl_absorpt_correction_T_max  0.91504
_exptl_absorpt_correction_T_min  0.91504
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.93a (Rigaku Oxford Diffraction, 2023)
Spherical absorption correction
using equivalent radius and absorption coefficient.
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    1.096
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1492
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.16
_exptl_crystal_size_rad          0.094
_refine_diff_density_max         0.598
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     461
_refine_ls_number_reflns         8612
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0530
_refine_ls_R_factor_gt           0.0468
_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^)+(0.0780P)^2^+1.5320P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1236
_refine_ls_wR_factor_ref         0.1310
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7528
_reflns_number_total             8612
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           AlSPxCO2
_cod_database_code               7720120
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C23 H56 Al O2 P S Si4'
_shelx_estimated_absorpt_t_max   0.685
_shelx_estimated_absorpt_t_min   0.568
_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
C9A \\sim C34 \\sim C10B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C9A: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within
2A
3. Rigid body (RIGU) restrains
 C9A, C10A, C11, C9B, C34, C10B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(S1B)=Sof(Si3B)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(H9BC)=Sof(C13B)=Sof(H13D)=
 Sof(H13E)=Sof(H13F)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C10B)=Sof(H10D)=
 Sof(H10E)=Sof(H10F)=Sof(C8B)=Sof(H8B)=Sof(C14B)=Sof(H14D)=Sof(H14E)=Sof(H14F)=
 1-FVAR(1)
 Sof(S1A)=Sof(Si3A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=
 Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14A)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C8A(H8A), C8B(H8B)
5.b Me refined with riding coordinates:
 C9B(H9BA,H9BB,H9BC), C13B(H13D,H13E,H13F), C34(H34A,H34B,H34C), C10B(H10D,
 H10E,H10F), C14B(H14D,H14E,H14F)
5.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30),
 C31(H31), C32(H32)
5.d 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), C9A(H9AA,H9AB,H9AC), C10A(H10A,H10B,H10C), C11(H11A,
 H11B,H11C), C12(H12A,H12B,H12C), C13A(H13A,H13B,H13C), C14A(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              83667
_olex2_date_sample_data_collection 2023-11-07
_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 6.124
_oxdiff_exptl_absorpt_empirical_full_min 0.588