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_7720126
_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 O2 P S2 Si4'
_chemical_formula_sum            'C22 H56 Ga O2 P S2 Si4'
_chemical_formula_weight         629.859
_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'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-26
_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                 97.744(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.9878(5)
_cell_length_b                   11.5830(3)
_cell_length_c                   17.3586(4)
_cell_measurement_reflns_used    27052
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      34.5130
_cell_measurement_theta_min      3.6530
_cell_volume                     3384.50(15)
_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  'olex2.refine 1.5-alpha (Bourhis et al., 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 0.9972
_diffrn_measured_fraction_theta_max 0.9983
_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    -53.00  48.00   1.00    7.50    --  -23.64  62.00 -68.00  101
  2  \w    -91.00 -10.00   1.00    7.50    --  -23.64 -62.00 153.00   81
  3  \w    -43.00  53.00   1.00    7.50    --   23.80 -62.00 153.00   96
  4  \w      1.00  96.00   1.00    7.50    --   23.80  62.00 -68.00   95
  5  \w    -42.00   3.00   1.00    7.50    --  -23.64 -77.00  60.00   45
  6  \w    -99.00 -29.00   1.00    7.50    --  -23.64 153.00  14.51   70
  7  \w    -98.00   1.00   1.00    7.50    --  -23.64 -38.00   0.00   99
  8  \w     30.00  99.00   1.00    7.50    --   23.80-153.00  95.92   69
  9  \w    -13.00  86.00   1.00    7.50    --   23.80  19.00 -60.00   99
 10  \w     -5.00  42.00   1.00    7.50    --   23.80  77.00  30.00   47
;
_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      -0.0328411000
_diffrn_orient_matrix_UB_12      0.0275403000
_diffrn_orient_matrix_UB_13      -0.0221198000
_diffrn_orient_matrix_UB_21      0.0263810000
_diffrn_orient_matrix_UB_22      0.0321573000
_diffrn_orient_matrix_UB_23      -0.0200987000
_diffrn_orient_matrix_UB_31      -0.0012995000
_diffrn_orient_matrix_UB_32      -0.0442573000
_diffrn_orient_matrix_UB_33      -0.0283872000
_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  0.0567
_diffrn_reflns_av_unetI/netI     0.0427
_diffrn_reflns_Laue_measured_fraction_full 0.9972
_diffrn_reflns_Laue_measured_fraction_max 0.9983
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            96998
_diffrn_reflns_point_group_measured_fraction_full 0.9972
_diffrn_reflns_point_group_measured_fraction_max 0.9983
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         30.03
_diffrn_reflns_theta_min         3.31
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.143
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.691
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.236
_exptl_crystal_description       block
_exptl_crystal_F_000             1356.309
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.5482
_refine_diff_density_min         -0.3399
_refine_diff_density_rms         0.0829
_refine_ls_d_res_high            0.7100
_refine_ls_d_res_low             6.1587
_refine_ls_goodness_of_fit_ref   1.0452
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    56
_refine_ls_number_parameters     457
_refine_ls_number_reflns         9897
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0452
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0232
_refine_ls_shift/su_max          -0.0004
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0134P)^2^+0.5616P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0428
_refine_ls_wR_factor_ref         0.0462
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              15
_reflns_limit_h_min              -23
_reflns_limit_k_max              16
_reflns_limit_k_min              0
_reflns_limit_l_max              24
_reflns_limit_l_min              -15
_reflns_number_gt                8435
_reflns_number_total             9897
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           GaSPxSO2
_cod_database_code               7720126
_chemical_oxdiff_formula         'C22 H56 Ga O2 P S2 Si4'
_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
;
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         R2SCAN
   BASIS SET:      def2-TZVPP
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2024-06-26_11-49-18
;
_olex2_date_sample_data_collection 2024-06-25
_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 1.267
_oxdiff_exptl_absorpt_empirical_full_min 0.795