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_7720127
_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 O2 P S2 Si4'
_chemical_formula_sum            'C22 H56 Al O2 P S2 Si4'
_chemical_formula_weight         587.118
_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             2025-02-07
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.12.18 svn.re4d4a415 for OlexSys, GUI svn.r7107)
;
_audit_update_record
;
2025-11-17 deposited with the CCDC.	2026-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.8697(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.00365(7)
_cell_length_b                   11.56562(3)
_cell_length_c                   17.31949(6)
_cell_measurement_reflns_used    99216
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.8810
_cell_measurement_theta_min      2.5550
_cell_volume                     3373.93(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9989
_diffrn_measured_fraction_theta_max 0.9956
_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   -114.00 -19.00   1.00    1.00    --  -41.83 -38.00 120.00   95
  2  \w    -64.00  31.00   1.00    1.00    --  -41.83  38.00  60.00   95
  3  \w    -64.00  31.00   1.00    1.00    --  -41.83  38.00-120.00   95
  4  \w   -120.00  -5.00   1.00    1.00    --  -41.83 -19.00-120.00  115
  5  \w   -112.00 -15.00   1.00    1.00    --  -41.83 -57.00  30.00   97
  6  \w    -64.00  31.00   1.00    1.00    --  -41.83  38.00 -60.00   95
  7  \w   -112.00 -15.00   1.00    1.00    --  -41.83 -57.00 -30.00   97
  8  \w   -112.00 -15.00   1.00    1.00    --  -41.83 -57.00-150.00   97
  9  \w      9.00  42.00   1.00    1.00    --   41.83  81.00-115.62   33
 10  \w     10.00  42.00   1.00    1.00    --   41.83  80.00   3.28   32
 11  \w      8.00  83.00   1.00    1.00    --   41.83-103.00 121.00   75
 12  \w     10.00  42.00   1.00    1.00    --   41.83  80.00  84.04   32
 13  \w     10.00  42.00   1.00    1.00    --   41.83  79.00 179.38   32
 14  \w     27.00  95.00   1.00    1.00    --   41.83-125.00 -30.00   68
 15  \w      9.00  42.00   1.00    1.00    --   41.83  81.00 -53.75   33
 16  \w     10.00  42.00   1.00    1.00    --   41.83  79.00 153.85   32
 17  \w     83.00 178.00   1.00    4.50    --  111.00  61.00   0.00   95
 18  \w     87.00 178.00   1.00    4.50    --  111.00  45.00-150.00   91
 19  \w     87.00 178.00   1.00    4.50    --  111.00  45.00 150.00   91
 20  \w     83.00 178.00   1.00    4.50    --  111.00  61.00  30.00   95
 21  \w     87.00 178.00   1.00    4.50    --  111.00  45.00  90.00   91
 22  \w     83.00 178.00   1.00    4.50    --  111.00  61.00 -60.00   95
 23  \w     83.00 178.00   1.00    4.50    --  111.00  61.00 -90.00   95
 24  \w     83.00 178.00   1.00    4.50    --  111.00  61.00 -60.00   95
 25  \w     87.00 178.00   1.00    4.50    --  111.00  45.00 120.00   91
 26  \w     41.00 112.00   1.00    4.50    --  111.00-125.00   0.00   71
 27  \w     40.00 135.00   1.00    4.50    --  111.00 -45.00   0.00   95
 28  \w     83.00 178.00   1.00    4.50    --  111.00  61.00-180.00   95
 29  \w     83.00 178.00   1.00    4.50    --  111.00  61.00-180.00   95
 30  \w     41.00 112.00   1.00    4.50    --  111.00-125.00  30.00   71
 31  \w     38.00 134.00   1.00    4.50    --  111.00 -38.00-167.98   96
 32  \w     83.00 178.00   1.00    4.50    --  111.00  61.00-120.00   95
 33  \w     83.00 178.00   1.00    4.50    --  111.00  61.00-120.00   95
 34  \w     83.00 178.00   1.00    4.50    --  111.00  61.00 -90.00   95
 35  \w     83.00 178.00   1.00    4.50    --  111.00  61.00-150.00   95
 36  \w     37.00 142.00   1.00    4.50    --  111.00 -77.00  90.00  105
 37  \w     83.00 178.00   1.00    4.50    --  111.00  61.00 -30.00   95
 38  \w     39.00 141.00   1.00    4.50    --  111.00 -70.00  14.32  102
 39  \w     83.00 178.00   1.00    4.50    --  111.00  61.00  90.00   95
 40  \w     83.00 178.00   1.00    4.50    --  111.00  61.00  90.00   95
 41  \w     37.00 142.00   1.00    4.50    --  111.00 -77.00  90.00  105
 42  \w     87.00 178.00   1.00    4.50    --  111.00  45.00 -60.00   91
 43  \w     87.00 178.00   1.00    4.50    --  111.00  45.00 -30.00   91
 44  \w     87.00 178.00   1.00    4.50    --  111.00  45.00  60.00   91
 45  \w     87.00 178.00   1.00    4.50    --  111.00  45.00-120.00   91
 46  \w     87.00 178.00   1.00    4.50    --  111.00  45.00 -90.00   91
 47  \w     83.00 178.00   1.00    4.50    --  111.00  61.00 -30.00   95
 48  \w     87.00 178.00   1.00    4.50    --  111.00  45.00  90.00   91
 49  \w     87.00 178.00   1.00    4.50    --  111.00  45.00   0.00   91
 50  \w     87.00 178.00   1.00    4.50    --  111.00  45.00  30.00   91
 51  \w     83.00 178.00   1.00    4.50    --  111.00  61.00 150.00   95
 52  \w     87.00 178.00   1.00    4.50    --  111.00  45.00-180.00   91
 53  \w     87.00 178.00   1.00    4.50    --  111.00  45.00-180.00   91
 54  \w     87.00 178.00   1.00    4.50    --  111.00  45.00-150.00   91
 55  \w     40.00 135.00   1.00    4.50    --  111.00 -45.00  90.00   95
 56  \w     83.00 178.00   1.00    4.50    --  111.00  61.00 150.00   95
 57  \w     40.00 135.00   1.00    4.50    --  111.00 -45.00   0.00   95
 58  \w     41.00 112.00   1.00    4.50    --  111.00-125.00 120.00   71
 59  \w     37.00 142.00   1.00    4.50    --  111.00 -77.00-180.00  105
 60  \w     96.00 142.00   1.00    4.50    --  111.00 -77.00-180.00   46
 61  \w     67.00 112.00   1.00    4.50    --  111.00-125.00 -90.00   45
 62  \w     42.00 106.00   1.00    4.50    --  111.00 -94.00  30.00   64
 63  \w    128.00 156.00   1.00    4.50    --  111.00  61.00  60.00   28
 64  \w     86.00 112.00   1.00    4.50    --  111.00-125.00 -30.00   26
 65  \w     42.00  83.00   1.00    4.50    --  111.00-125.00 -30.00   41
 66  \w     82.00 107.00   1.00    4.50    --  111.00 -94.00 120.00   25
 67  \w    106.00 171.00   1.00    4.50    --  111.00 125.00  90.00   65
 68  \w     39.00  66.00   1.00    4.50    --  111.00 -94.00 120.00   27
 69  \w     83.00 134.00   1.00    4.50    --  111.00  61.00 120.00   51
 70  \w     50.00  79.00   1.00    4.50    --  111.00 -45.00  90.00   29
 71  \w     83.00 109.00   1.00    4.50    --  111.00  61.00  60.00   26
 72  \w     42.00 111.00   1.00    4.50    --  111.00-125.00 -60.00   69
 73  \w     34.00  71.00   1.00    4.50    --  111.00 -94.00-180.00   37
 74  \w     79.00 106.00   1.00    4.50    --  111.00 -94.00-180.00   27
 75  \w     67.00 107.00   1.00    4.50    --  111.00 -94.00 150.00   40
 76  \w     49.00  88.00   1.00    4.50    --  111.00 -70.00  14.32   39
 77  \w     39.00  66.00   1.00    4.50    --  111.00 -38.00-167.98   27
;
_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      -0.0388537000
_diffrn_orient_matrix_UB_12      0.0096440000
_diffrn_orient_matrix_UB_13      -0.0855002000
_diffrn_orient_matrix_UB_21      -0.0136827000
_diffrn_orient_matrix_UB_22      0.1302091000
_diffrn_orient_matrix_UB_23      0.0114195000
_diffrn_orient_matrix_UB_31      0.0816412000
_diffrn_orient_matrix_UB_32      0.0264013000
_diffrn_orient_matrix_UB_33      -0.0250008000
_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  0.0257
_diffrn_reflns_av_unetI/netI     0.0088
_diffrn_reflns_Laue_measured_fraction_full 0.9989
_diffrn_reflns_Laue_measured_fraction_max 0.9956
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            124076
_diffrn_reflns_point_group_measured_fraction_full 0.9989
_diffrn_reflns_point_group_measured_fraction_max 0.9956
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         76.08
_diffrn_reflns_theta_min         3.92
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.622
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.256
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (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    1.156
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1291.109
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.1957
_refine_diff_density_min         -0.1497
_refine_diff_density_rms         0.0346
_refine_ls_d_res_high            0.7942
_refine_ls_d_res_low             11.2724
_refine_ls_goodness_of_fit_ref   1.0071
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     513
_refine_ls_number_reflns         7025
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0071
_refine_ls_R_factor_all          0.0162
_refine_ls_R_factor_gt           0.0161
_refine_ls_shift/su_max          0.0006
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+1.5931P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0360
_refine_ls_wR_factor_ref         0.0361
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              14
_reflns_limit_h_min              -21
_reflns_limit_k_max              14
_reflns_limit_k_min              0
_reflns_limit_l_max              21
_reflns_limit_l_min              -13
_reflns_number_gt                7001
_reflns_number_total             7025
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           AlSPxSO2
_cod_original_cell_volume        3373.94(2)
_cod_database_code               7720127
_chemical_oxdiff_formula         'C22 H56 Al O2 P S2 Si4'
_diffrn_oxdiff_digest_hkl
;
4362e66f0409659916be749129d698132f9219
;
_olex2_refinement_description
;
;
_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:           2025-02-07_09-41-00
;
_olex2_date_sample_data_collection 2025-02-06
_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 1.313
_oxdiff_exptl_absorpt_empirical_full_min 0.753