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_7720123
_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 Ga O P S Si4'
_chemical_formula_sum            'C22 H56 Ga O P S Si4'
_chemical_formula_weight         581.77
_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_Hall           'P 4abw 2nw'
_space_group_name_H-M_alt        'P 41 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-22
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_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
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.79070(10)
_cell_length_b                   11.79070(10)
_cell_length_c                   47.9511(9)
_cell_measurement_reflns_used    56889
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      30.2540
_cell_measurement_theta_min      3.6540
_cell_volume                     6666.19(15)
_computing_cell_refinement       'CrysAlisPro 1.171.44.116a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 43.90 64-bit (release 15-09-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.44.116a (Rigaku OD, 2025)'
_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      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_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    -88.00 -63.00   1.00   40.00    --  -19.01 163.00 -79.00   25
  2  \w    -58.00 -33.00   1.00   40.00    --  -19.01 117.00 131.00   25
  3  \w    -98.00 -73.00   1.00   40.00    --  -19.01-163.00-105.00   25
  4  \w     60.00 100.00   1.00   40.00    --   19.32-163.00-105.00   40
  5  \w     52.00  77.00   1.00   40.00    --   19.32 163.00 -79.00   25
  6  \w      7.00  69.00   1.00   40.00    --   19.32-117.00  43.00   62
  7  \w    -88.00  11.00   1.00   40.00    --  -19.01 -57.00  90.00   99
  8  \w    -95.00   7.00   1.00   40.00    --  -19.01 -38.00-150.00  102
  9  \w     -8.00  57.00   1.00   40.00    --  -19.01  38.00-120.00   65
 10  \w    -37.00  13.00   1.00   40.00    --  -19.01 -77.00 -90.00   50
 11  \w    -84.00   3.00   1.00   40.00    --  -19.01 -38.00 120.00   87
 12  \w    -35.00  57.00   1.00   40.00    --  -19.01  38.00-180.00   92
 13  \w    -97.00 -27.00   1.00   40.00    --  -19.01 155.00  -0.17   70
;
_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      -0.0128381000
_diffrn_orient_matrix_UB_12      0.0587004000
_diffrn_orient_matrix_UB_13      0.0006698000
_diffrn_orient_matrix_UB_21      0.0091428000
_diffrn_orient_matrix_UB_22      -0.0007432000
_diffrn_orient_matrix_UB_23      0.0146208000
_diffrn_orient_matrix_UB_31      0.0580541000
_diffrn_orient_matrix_UB_32      0.0131093000
_diffrn_orient_matrix_UB_33      -0.0021586000
_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  0.0989
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       63
_diffrn_reflns_limit_l_min       -63
_diffrn_reflns_number            129842
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.277
_diffrn_reflns_theta_min         3.440
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.092
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.588
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.116a (Rigaku Oxford Diffraction, 2025)
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    1.159
_exptl_crystal_description       plate
_exptl_crystal_F_000             2512
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.692
_refine_diff_density_min         -1.071
_refine_diff_density_rms         0.105
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.26(3)
_refine_ls_extinction_coef       0.0013(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.283
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     410
_refine_ls_number_reflns         8263
_refine_ls_number_restraints     534
_refine_ls_restrained_S_all      1.272
_refine_ls_R_factor_all          0.0857
_refine_ls_R_factor_gt           0.0831
_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^)+29.1350P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1603
_refine_ls_wR_factor_ref         0.1615
_reflns_Friedel_coverage         0.715
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                7933
_reflns_number_total             8263
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           GaOPxS
_cod_original_cell_volume        6666.19(17)
_cod_database_code               7720123
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H56 Ga O P Si4 S'
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.675
_diffrn_oxdiff_digest_hkl
;
439bb6c3d2d054f667ff5e26d9838f30456474
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name buth53.par
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.74(3)
 0.26(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 Ga1-C1A \\sim Ga1-C1B
 with sigma of 0.02
 Si2A-C1A \\sim Si1B-C1B
 with sigma of 0.02
 Si2A-C7A \\sim Si1B-C2B
 with sigma of 0.02
 Si2A-C5A \\sim Si1B-C4B
 with sigma of 0.02
 Si2A-C6A \\sim Si1B-C3B
 with sigma of 0.02
 Si1A-C1A \\sim Si2B-C1B
 with sigma of 0.02
 Si1A-C2A \\sim Si2B-C7B
 with sigma of 0.02
 Si1A-C3A \\sim Si2B-C6B
 with sigma of 0.02
 Si1A-C4A \\sim Si2B-C5B
 with sigma of 0.02
 Ga1-Si2A \\sim Ga1-Si1B
 with sigma of 0.04
 Ga1-Si1A \\sim Ga1-Si2B
 with sigma of 0.04
 Si2A-Si1A \\sim Si1B-Si2B
 with sigma of 0.04
 C1A-C2A \\sim C1B-C7B
 with sigma of 0.04
 C1A-C7A \\sim C1B-C2B
 with sigma of 0.04
 C1A-C5A \\sim C1B-C4B
 with sigma of 0.04
 C1A-C3A \\sim C1B-C6B
 with sigma of 0.04
 C1A-C4A \\sim C1B-C5B
 with sigma of 0.04
 C1A-C6A \\sim C1B-C3B
 with sigma of 0.04
 C2A-C3A \\sim C7B-C6B
 with sigma of 0.04
 C2A-C4A \\sim C7B-C5B
 with sigma of 0.04
 C7A-C5A \\sim C2B-C4B
 with sigma of 0.04
 C7A-C6A \\sim C2B-C3B
 with sigma of 0.04
 C5A-C6A \\sim C4B-C3B
 with sigma of 0.04
 C3A-C4A \\sim C6B-C5B
 with sigma of 0.04
 Ga1-C1B \\sim Ga1-C1A
 with sigma of 0.02
 Si4-C14B \\sim Si4-C14A
 with sigma of 0.02
 Si4-C13B \\sim Si4-C13A
 with sigma of 0.02
 Si4-C12B \\sim Si4-C12A
 with sigma of 0.02
 C8-C14B \\sim C8-C14A
 with sigma of 0.04
 C8-C13B \\sim C8-C13A
 with sigma of 0.04
 C8-C12B \\sim C8-C12A
 with sigma of 0.04
 C14B-C13B \\sim C14A-C13A
 with sigma of 0.04
 C14B-C12B \\sim C14A-C12A
 with sigma of 0.04
 C13B-C12B \\sim C13A-C12A
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Si1A \\sim Si1B \\sim Si2A \\sim Si2B \\sim Si3 \\sim Si4 \\sim C1A \\sim C1B
\\sim C2A \\sim C2B \\sim C3A \\sim C4A \\sim C4B \\sim C5A \\sim C5B \\sim C6A
\\sim C6B \\sim C7A \\sim C7B \\sim C8 \\sim C10 \\sim C11 \\sim C12A \\sim
C12B \\sim C13A \\sim C13B \\sim C14A \\sim C14B \\sim C3B \\sim C9: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
5. Rigid body (RIGU) restrains
 Si1A, Si1B, Si2A, Si2B, Si3, Si4, C1A, C1B, C2A, C2B, C3A, C4A, C4B, C5A, C5B,
  C6A, C6B, C7A, C7B, C8, C10, C11, C12A, C12B, C13A, C13B, C14A, C14B, C3B, C9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Others
 Sof(Si1B)=Sof(Si2B)=Sof(C1B)=Sof(H1B)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=
 Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=
 Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(H5BC)=Sof(C6B)=Sof(H6BA)=Sof(H6BB)=Sof(H6BC)=
 Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(H7BC)=1-FVAR(1)
 Sof(Si1A)=Sof(Si2A)=Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=
 Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=FVAR(1)
 Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13A)=Sof(H13A)=Sof(H13B)=
 Sof(H13C)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=1-FVAR(2)
 Sof(C12B)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13B)=Sof(H13D)=Sof(H13E)=
 Sof(H13F)=Sof(C14B)=Sof(H14D)=Sof(H14E)=Sof(H14F)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C1A(H1A), C1B(H1B), C8(H8)
7.b Idealised Me refined as rotating group:
 C2A(H2AA,H2AB,H2AC), C2B(H2BA,H2BB,H2BC), C3A(H3AA,H3AB,H3AC), C3B(H3BA,H3BB,
 H3BC), C4A(H4AA,H4AB,H4AC), C4B(H4BA,H4BB,H4BC), C5A(H5AA,H5AB,H5AC), C5B(H5BA,
 H5BB,H5BC), C6A(H6AA,H6AB,H6AC), C6B(H6BA,H6BB,H6BC), C7A(H7AA,H7AB,H7AC),
 C7B(H7BA,H7BB,H7BC), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C),
  C12A(H12A,H12B,H12C), C12B(H12D,H12E,H12F), C13A(H13A,H13B,H13C), C13B(H13D,
 H13E,H13F), C14A(H14A,H14B,H14C), C14B(H14D,H14E,H14F), C16(H16A,H16B,H16C),
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C)
;
_olex2_date_sample_data_collection 2024-11-26
_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 1.394
_oxdiff_exptl_absorpt_empirical_full_min 0.788