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_7720119
_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 O3 P S Si4'
_chemical_formula_sum            'C22 H56 Ga O3 P S Si4'
_chemical_formula_weight         613.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-25
_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                 101.560(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.9783(5)
_cell_length_b                   11.9478(5)
_cell_length_c                   19.4795(7)
_cell_measurement_reflns_used    18060
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      33.0470
_cell_measurement_theta_min      3.5690
_cell_volume                     3415.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.90 64-bit (release 15-09-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (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 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 0.997
_diffrn_measured_fraction_theta_max 0.919
_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    -62.00 -19.00   1.00   15.00    --  -18.49 105.00 158.00   43
  2  \w      1.00  26.00   1.00   15.00    --   18.80-105.00  57.00   25
  3  \w   -107.00 -53.00   1.00   15.00    --  -18.49-178.00  30.00   54
  4  \w    -14.00  55.00   1.00   15.00    --  -18.49  38.00-180.00   69
  5  \w    -69.00 -38.00   1.00   15.00    --  -18.49 178.00  60.00   31
  6  \w    -12.00  42.00   1.00   15.00    --   18.80 -38.00  60.00   54
  7  \w    -14.00  58.00   1.00   15.00    --   18.80 -99.00 -30.00   72
  8  \w    -12.00  36.00   1.00   15.00    --   18.80  77.00 150.00   48
;
_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      0.0031615000
_diffrn_orient_matrix_UB_12      -0.0567473000
_diffrn_orient_matrix_UB_13      0.0109455000
_diffrn_orient_matrix_UB_21      0.0041643000
_diffrn_orient_matrix_UB_22      -0.0167266000
_diffrn_orient_matrix_UB_23      -0.0341388000
_diffrn_orient_matrix_UB_31      0.0480656000
_diffrn_orient_matrix_UB_32      0.0051270000
_diffrn_orient_matrix_UB_33      0.0097077000
_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  0.0328
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.919
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            43689
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.919
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.246
_diffrn_reflns_theta_min         3.251
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.074
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.386
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (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    1.194
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1320
_exptl_crystal_size_max          0.67
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.750
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     369
_refine_ls_number_reflns         12070
_refine_ls_number_restraints     207
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0447
_refine_ls_R_factor_gt           0.0322
_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^)+(0.0364P)^2^+1.2085P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0756
_refine_ls_wR_factor_ref         0.0816
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9976
_reflns_number_total             12070
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           GaOPxSO2
_cod_database_code               7720119
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H56 Ga O3 P S Si4'
_shelx_estimated_absorpt_t_max   0.839
_shelx_estimated_absorpt_t_min   0.533
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Ga1-O2A \\sim Ga1-O2B
 with sigma of 0.02
 S1A-O2A \\sim S1A-O2B
 with sigma of 0.02
 S1B-O3B \\sim S1A-O3A
 with sigma of 0.02
 S1B-O2B \\sim S1A-O2A
 with sigma of 0.02
 Ga1-O2B \\sim Ga1-O2A
 with sigma of 0.02
 Si1A-C1 \\sim Si1B-C1
 with sigma of 0.02
 Si1A-C4A \\sim Si1B-C4B \\sim Si1A-C3A \\sim Si1B-C3B \\sim Si1A-C2A \\sim
Si1B-C2B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si1A \\sim Si1B \\sim C2A \\sim C2B \\sim C3A \\sim C3B \\sim C4A \\sim C4B:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
S1A \\sim S1B \\sim O2A \\sim O2B \\sim O3A \\sim O3B: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 Si1A, Si1B, C2A, C2B, C3A, C3B, C4A, C4B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S1A, S1B, O2A, O2B, O3A, O3B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(S1B)=Sof(O2B)=Sof(O3B)=1-FVAR(1)
 Sof(S1A)=Sof(O2A)=Sof(O3A)=FVAR(1)
 Sof(Si1B)=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)=1-FVAR(2)
 Sof(Si1A)=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)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C8(H8)
6.b Me refined with riding coordinates:
 C2A(H2AA,H2AB,H2AC), C2B(H2BA,H2BB,H2BC), C3A(H3AA,H3AB,H3AC), C3B(H3BA,H3BB,
 H3BC), C4A(H4AA,H4AB,H4AC), C4B(H4BA,H4BB,H4BC)
6.c Idealised Me refined as rotating group:
 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)
;
_olex2_date_sample_data_collection 2024-11-19
_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 1.348
_oxdiff_exptl_absorpt_empirical_full_min 0.762