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_7720122
_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 H57 Al Br P S Si4, 0.5[C6H6]'
_chemical_formula_sum            'C25 H60 Al Br P S Si4'
_chemical_formula_weight         643.022
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-04
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.01.22 svn.rc7346086 for OlexSys, GUI svn.r7128)
;
_audit_update_record
;
2025-11-17 deposited with the CCDC.	2026-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                97.116(2)
_cell_angle_beta                 92.578(2)
_cell_angle_gamma                115.830(3)
_cell_formula_units_Z            2
_cell_length_a                   11.4899(3)
_cell_length_b                   12.8148(4)
_cell_length_c                   13.9414(4)
_cell_measurement_reflns_used    14826
_cell_measurement_temperature    100.00(16)
_cell_measurement_theta_max      34.0220
_cell_measurement_theta_min      1.9830
_cell_volume                     1822.14(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.131a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.131a 64-bit (release 19-07-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.131a (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      100.00(16)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0951
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9994
_diffrn_measured_fraction_theta_max 0.9996
_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    -37.00  48.00   1.00    7.50    --   32.10 -57.00-120.00   85
  2  \w    -10.00  62.00   1.00    7.50    --   32.10 -99.00-180.00   72
  3  \w     12.00 101.00   1.00    7.50    --   32.10  57.00  30.00   89
  4  \w     -4.00  21.00   1.00    7.50    --   32.10  94.00 147.34   25
  5  \w      7.00 104.00   1.00    7.50    --   32.10  38.00 150.00   97
  6  \w     -9.00  70.00   1.00    7.50    --   32.10 -99.00   0.00   79
  7  \w     -7.00  19.00   1.00    7.50    --   32.10  96.00-161.65   26
  8  \w     -7.00  19.00   1.00    7.50    --   32.10  96.00 -23.24   26
  9  \w      2.00  42.00   1.00    7.50    --   32.10  77.00 -80.64   40
 10  \w    -35.00  62.00   1.00    7.50    --   32.10 -77.00  60.00   97
 11  \w    -13.00  31.00   1.00    7.50    --   32.10 -99.00-150.00   44
 12  \w     46.00  73.00   1.00    7.50    --   32.10 -99.00-150.00   27
 13  \w     -8.00  19.00   1.00    7.50    --   32.10  95.00  94.32   27
 14  \w   -101.00  -7.00   1.00    7.50    --  -32.25 -38.00 150.00   94
 15  \w   -105.00  10.00   1.00    7.50    --  -32.25 -19.00-120.00  115
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0102390000
_diffrn_orient_matrix_UB_12      -0.0500802000
_diffrn_orient_matrix_UB_13      0.0217336000
_diffrn_orient_matrix_UB_21      -0.0682387000
_diffrn_orient_matrix_UB_22      -0.0200640000
_diffrn_orient_matrix_UB_23      -0.0083542000
_diffrn_orient_matrix_UB_31      -0.0010191000
_diffrn_orient_matrix_UB_32      -0.0311408000
_diffrn_orient_matrix_UB_33      -0.0460365000
_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  0.0467
_diffrn_reflns_av_unetI/netI     0.0495
_diffrn_reflns_Laue_measured_fraction_full 0.9994
_diffrn_reflns_Laue_measured_fraction_max 0.9996
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            47733
_diffrn_reflns_point_group_measured_fraction_full 0.9994
_diffrn_reflns_point_group_measured_fraction_max 0.9996
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         28.70
_diffrn_reflns_theta_min         1.98
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.401
_exptl_absorpt_correction_T_max  0.08675
_exptl_absorpt_correction_T_min  0.05158
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.131a (Rigaku Oxford Diffraction, 2024)
Spherical absorption correction
using equivalent radius and absorption coefficient.
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    1.172
_exptl_crystal_description       irregular
_exptl_crystal_F_000             691.036
_exptl_crystal_size_max          0.68
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.18
_exptl_crystal_size_rad          0.157
_refine_diff_density_max         0.5538
_refine_diff_density_min         -0.4488
_refine_diff_density_rms         0.0775
_refine_ls_d_res_high            0.7400
_refine_ls_d_res_low             10.2783
_refine_ls_goodness_of_fit_ref   1.0304
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    89
_refine_ls_number_parameters     348
_refine_ls_number_reflns         9414
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.0257
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0279
_refine_ls_shift/su_max          0.0007
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0247P)^2^+0.1816P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0602
_refine_ls_wR_factor_ref         0.0635
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              15
_reflns_limit_h_min              -15
_reflns_limit_k_max              17
_reflns_limit_k_min              -17
_reflns_limit_l_max              18
_reflns_limit_l_min              0
_reflns_number_gt                8080
_reflns_number_total             9414
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           AlSPxHBr
_cod_database_code               7720122
_chemical_oxdiff_formula         'C25 H60 Al Br P S Si4'
_diffrn_oxdiff_digest_hkl
;
43432106a5a03352bc6fe69fd1bb54573dec73
;
_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
2. Uiso/Uaniso restraints and constraints
C23A \\sim C23B \\sim C24A \\sim C24B \\sim C25A \\sim C25B: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
3. Rigid body (RIGU) restrains
 C23A, C23B, C24A, C24B, C25A, C25B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(C25B)=Sof(H25B)=Sof(C23B)=Sof(H23B)=Sof(C24B)=Sof(H24B)=1-FVAR(1)
 Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1A), C8(H8)
5.b Aromatic/amide H refined with riding coordinates:
 C23A(H23A), C25B(H25B), C24A(H24A), C23B(H23B), C24B(H24B), C25A(H25A)
5.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C7(H7A,H7B,H7C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C),
 C12(H12A,H12B,H12C), C4(H4A,H4B,H4C), C3(H3A,H3B,H3C), C14(H14A,H14B,H14C),
 C2(H2A,H2B,H2C), C22(H22A,H22B,H22C), C20(H20A,H20B,H20C), C16(H16A,H16B,H16C),
  C10(H10A,H10B,H10C), C21(H21A,H21B,H21C), C9(H9A,H9B,H9C), C13(H13A,H13B,
 H13C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_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:           2025-02-04_13-13-06
;
_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 2.326
_oxdiff_exptl_absorpt_empirical_full_min 0.453