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_7720128
_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 P S3 Si4'
_chemical_formula_sum            'C23 H56 Al P S3 Si4'
_chemical_formula_weight         599.196
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_Int_Tables_number      15
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-14
_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                 90.657(1)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.7333(1)
_cell_length_b                   11.8416(1)
_cell_length_c                   28.2218(1)
_cell_measurement_reflns_used    87875
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      75.8430
_cell_measurement_theta_min      3.0690
_cell_volume                     6928.43(7)
_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  '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 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9998
_diffrn_measured_fraction_theta_max 0.9954
_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 -30.00   95
  2  \w    -87.00  -6.00   1.00    1.00    --  -41.83 125.00  90.00   81
  3  \w    -87.00  -6.00   1.00    1.00    --  -41.83 125.00 -90.00   81
  4  \w   -114.00 -19.00   1.00    1.00    --  -41.83 -38.00-120.00   95
  5  \w   -112.00 -15.00   1.00    1.00    --  -41.83 -57.00  90.00   97
  6  \w   -112.00 -15.00   1.00    1.00    --  -41.83 -57.00-180.00   97
  7  \w     10.00  42.00   1.00    1.00    --   41.83  80.00 124.24   32
  8  \w     10.00  42.00   1.00    1.00    --   41.83  79.00  72.33   32
  9  \w    -28.00  68.00   1.00    1.00    --   41.83 -57.00-150.00   96
 10  \w     10.00  42.00   1.00    1.00    --   41.83  78.00-107.93   32
 11  \w     15.00 112.00   1.00    1.00    --   41.83  57.00  60.00   97
 12  \w      9.00  42.00   1.00    1.00    --   41.83  82.00-177.74   33
 13  \w     10.00  42.00   1.00    1.00    --   41.83  79.00  -0.88   32
 14  \w     19.00 114.00   1.00    1.00    --   41.83  38.00-180.00   95
 15  \w    -28.00  68.00   1.00    1.00    --   41.83 -57.00  30.00   96
 16  \w      9.00  42.00   1.00    1.00    --   41.83  82.00 -50.28   33
 17  \w     15.00 112.00   1.00    1.00    --   41.83  57.00  60.00   97
 18  \w     83.00 178.00   1.00    4.00    --  111.00  61.00 -30.00   95
 19  \w     83.00 178.00   1.00    4.00    --  111.00  61.00-180.00   95
 20  \w     83.00 178.00   1.00    4.00    --  111.00  61.00-120.00   95
 21  \w     39.00 109.00   1.00    4.00    --  111.00-111.00  90.00   70
 22  \w     83.00 178.00   1.00    4.00    --  111.00  61.00 -90.00   95
 23  \w     87.00 178.00   1.00    4.00    --  111.00  45.00 120.00   91
 24  \w     87.00 178.00   1.00    4.00    --  111.00  45.00  60.00   91
 25  \w     83.00 178.00   1.00    4.00    --  111.00  61.00 -90.00   95
 26  \w     83.00 178.00   1.00    4.00    --  111.00  61.00-180.00   95
 27  \w     39.00 109.00   1.00    4.00    --  111.00-111.00 150.00   70
 28  \w     83.00 178.00   1.00    4.00    --  111.00  61.00 120.00   95
 29  \w     83.00 178.00   1.00    4.00    --  111.00  61.00 120.00   95
 30  \w     83.00 178.00   1.00    4.00    --  111.00  61.00  30.00   95
 31  \w     83.00 178.00   1.00    4.00    --  111.00  61.00 -60.00   95
 32  \w     83.00 178.00   1.00    4.00    --  111.00  61.00-120.00   95
 33  \w     83.00 178.00   1.00    4.00    --  111.00  61.00 -60.00   95
 34  \w     83.00 178.00   1.00    4.00    --  111.00  61.00  60.00   95
 35  \w     83.00 178.00   1.00    4.00    --  111.00  61.00  90.00   95
 36  \w     83.00 178.00   1.00    4.00    --  111.00  61.00  60.00   95
 37  \w     87.00 178.00   1.00    4.00    --  111.00  45.00  30.00   91
 38  \w     87.00 178.00   1.00    4.00    --  111.00  45.00  90.00   91
 39  \w     83.00 178.00   1.00    4.00    --  111.00  61.00-150.00   95
 40  \w     83.00 178.00   1.00    4.00    --  111.00  61.00  90.00   95
 41  \w     87.00 178.00   1.00    4.00    --  111.00  45.00 -30.00   91
 42  \w     87.00 178.00   1.00    4.00    --  111.00  45.00-120.00   91
 43  \w     87.00 178.00   1.00    4.00    --  111.00  45.00-180.00   91
 44  \w     87.00 178.00   1.00    4.00    --  111.00  45.00 -90.00   91
 45  \w     87.00 178.00   1.00    4.00    --  111.00  45.00-150.00   91
 46  \w     87.00 178.00   1.00    4.00    --  111.00  45.00  60.00   91
 47  \w     87.00 178.00   1.00    4.00    --  111.00  45.00   0.00   91
 48  \w     87.00 178.00   1.00    4.00    --  111.00  45.00   0.00   91
 49  \w     87.00 178.00   1.00    4.00    --  111.00  45.00 150.00   91
 50  \w     87.00 178.00   1.00    4.00    --  111.00  45.00 -60.00   91
 51  \w     40.00 135.00   1.00    4.00    --  111.00 -45.00 -90.00   95
 52  \w     40.00 135.00   1.00    4.00    --  111.00 -45.00 -90.00   95
 53  \w     83.00 178.00   1.00    4.00    --  111.00  61.00 150.00   95
 54  \w     39.00 109.00   1.00    4.00    --  111.00-111.00-180.00   70
 55  \w     39.00 109.00   1.00    4.00    --  111.00-111.00  30.00   70
 56  \w     40.00 135.00   1.00    4.00    --  111.00 -45.00-180.00   95
 57  \w     39.00 109.00   1.00    4.00    --  111.00-111.00 -90.00   70
 58  \w     39.00 109.00   1.00    4.00    --  111.00-111.00  60.00   70
 59  \w     39.00 109.00   1.00    4.00    --  111.00-111.00  60.00   70
 60  \w     30.00 107.00   1.00    4.00    --  111.00 -94.00 -90.00   77
 61  \w     39.00 109.00   1.00    4.00    --  111.00-111.00   0.00   70
 62  \w     40.00 135.00   1.00    4.00    --  111.00 -45.00  30.00   95
 63  \w     83.00 178.00   1.00    4.00    --  111.00  61.00 150.00   95
 64  \w     39.00 109.00   1.00    4.00    --  111.00-111.00 120.00   70
 65  \w     50.00 106.00   1.00    4.00    --  111.00 -94.00-180.00   56
 66  \w     83.00 109.00   1.00    4.00    --  111.00-111.00 -30.00   26
 67  \w    127.00 160.00   1.00    4.00    --  111.00 111.00 -60.00   33
 68  \w     39.00  66.00   1.00    4.00    --  111.00-111.00 -30.00   27
 69  \w     79.00 135.00   1.00    4.00    --  111.00 -45.00  30.00   56
 70  \w     46.00 100.00   1.00    4.00    --  111.00 -94.00-150.00   54
 71  \w    124.00 177.00   1.00    4.00    --  111.00  61.00  30.00   53
 72  \w    147.00 178.00   1.00    4.00    --  111.00  61.00 -30.00   31
 73  \w     92.00 119.00   1.00    4.00    --  111.00 -45.00-180.00   27
 74  \w     83.00 133.00   1.00    4.00    --  111.00  61.00   0.00   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      -0.0420981000
_diffrn_orient_matrix_UB_12      0.0396987000
_diffrn_orient_matrix_UB_13      -0.0421477000
_diffrn_orient_matrix_UB_21      -0.0512169000
_diffrn_orient_matrix_UB_22      -0.0890050000
_diffrn_orient_matrix_UB_23      0.0125401000
_diffrn_orient_matrix_UB_31      -0.0335494000
_diffrn_orient_matrix_UB_32      0.0861749000
_diffrn_orient_matrix_UB_33      0.0323605000
_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  0.0776
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.9998
_diffrn_reflns_Laue_measured_fraction_max 0.9954
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            124642
_diffrn_reflns_point_group_measured_fraction_full 0.9998
_diffrn_reflns_point_group_measured_fraction_max 0.9954
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         76.08
_diffrn_reflns_theta_min         3.13
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.041
_exptl_absorpt_correction_T_max  0.551
_exptl_absorpt_correction_T_min  0.151
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.93a (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 violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.149
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2632.289
_exptl_crystal_size_max          0.58
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.7552
_refine_diff_density_min         -0.2493
_refine_diff_density_rms         0.0704
_refine_ls_d_res_high            0.7942
_refine_ls_d_res_low             14.1100
_refine_ls_goodness_of_fit_ref   1.0468
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    56
_refine_ls_number_parameters     457
_refine_ls_number_reflns         7188
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0468
_refine_ls_R_factor_all          0.0307
_refine_ls_R_factor_gt           0.0305
_refine_ls_shift/su_max          0.0009
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0597P)^2^+1.9277P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0798
_refine_ls_wR_factor_ref         0.0801
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              26
_reflns_limit_h_min              -26
_reflns_limit_k_max              14
_reflns_limit_k_min              0
_reflns_limit_l_max              35
_reflns_limit_l_min              0
_reflns_number_gt                7113
_reflns_number_total             7188
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           AlSPxCS2
_cod_database_code               7720128
_chemical_oxdiff_formula         'C23 H56 Al P S3 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-TZVP
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2023-11-14_11-03-26
;
_olex2_date_sample_data_collection 2023-11-13
_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 4.857
_oxdiff_exptl_absorpt_empirical_full_min 0.526