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_7720124
_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         'C25 H62 Al P S2 Si4'
_chemical_formula_sum            'C25 H62 Al P S2 Si4'
_chemical_formula_weight         597.200
_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             2025-09-28
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7317)
;
_audit_update_record
;
2025-11-17 deposited with the CCDC.	2026-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                83.294(2)
_cell_angle_beta                 86.526(2)
_cell_angle_gamma                76.911(2)
_cell_formula_units_Z            4
_cell_length_a                   12.1972(3)
_cell_length_b                   17.2090(4)
_cell_length_c                   18.0410(3)
_cell_measurement_reflns_used    25117
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      32.9280
_cell_measurement_theta_min      2.0700
_cell_volume                     3660.93(14)
_computing_cell_refinement       'CrysAlisPro 1.171.44.120a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.120a 64-bit (release 22-08-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.120a (Rigaku OD, 2025)'
_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 8.0951
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9995
_diffrn_measured_fraction_theta_max 0.9997
_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     10.00 101.00   1.00    4.00    --   31.72  57.00-150.00   91
  2  \w    -10.00  20.00   1.00    4.00    --   31.72  95.00 -89.34   30
  3  \w    -15.00  68.00   1.00    4.00    --   31.72 -99.00-180.00   83
  4  \w    -10.00  19.00   1.00    4.00    --   31.72  96.00  48.46   29
  5  \w      4.00 104.00   1.00    4.00    --   31.72  38.00 -30.00  100
  6  \w    -37.00  50.00   1.00    4.00    --   31.72 -57.00  60.00   87
  7  \w     -2.00  42.00   1.00    4.00    --   31.72  80.00  89.89   44
  8  \w      4.00  72.00   1.00    4.00    --   31.72 -99.00 -90.00   68
  9  \w      4.00  57.00   1.00    4.00    --   31.72  38.00-180.00   53
 10  \w     68.00 104.00   1.00    4.00    --   31.72  38.00-180.00   36
 11  \w     10.00  85.00   1.00    4.00    --   31.72  57.00   0.00   75
 12  \w    -15.00  74.00   1.00    4.00    --   31.72 -99.00  30.00   89
 13  \w    -25.00  32.00   1.00    4.00    --  -31.88  57.00 -30.00   57
 14  \w    -93.00  24.00   1.00    4.00    --  -31.88   0.00 -30.00  117
;
_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      -0.0488022000
_diffrn_orient_matrix_UB_12      0.0281149000
_diffrn_orient_matrix_UB_13      0.0106975000
_diffrn_orient_matrix_UB_21      0.0317063000
_diffrn_orient_matrix_UB_22      0.0300929000
_diffrn_orient_matrix_UB_23      -0.0023681000
_diffrn_orient_matrix_UB_31      -0.0134919000
_diffrn_orient_matrix_UB_32      0.0107230000
_diffrn_orient_matrix_UB_33      -0.0380660000
_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  0.0547
_diffrn_reflns_av_unetI/netI     0.0637
_diffrn_reflns_Laue_measured_fraction_full 0.9995
_diffrn_reflns_Laue_measured_fraction_max 0.9997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            95073
_diffrn_reflns_point_group_measured_fraction_full 0.9995
_diffrn_reflns_point_group_measured_fraction_max 0.9997
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         29.57
_diffrn_reflns_theta_min         1.87
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.357
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.277
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.120a (Rigaku Oxford Diffraction, 2025)
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    1.084
_exptl_crystal_description       block
_exptl_crystal_F_000             1315.328
_exptl_crystal_size_max          0.67
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.7897
_refine_diff_density_min         -0.8927
_refine_diff_density_rms         0.0883
_refine_ls_d_res_high            0.7200
_refine_ls_d_res_low             10.8741
_refine_ls_goodness_of_fit_ref   1.0429
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    198
_refine_ls_number_parameters     708
_refine_ls_number_reflns         20502
_refine_ls_number_restraints     402
_refine_ls_restrained_S_all      1.0325
_refine_ls_R_factor_all          0.0571
_refine_ls_R_factor_gt           0.0377
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0187P)^2^+1.1277P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0682
_refine_ls_wR_factor_ref         0.0764
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              16
_reflns_limit_h_min              -16
_reflns_limit_k_max              23
_reflns_limit_k_min              -23
_reflns_limit_l_max              25
_reflns_limit_l_min              0
_reflns_number_gt                15725
_reflns_number_total             20502
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           AlSPxSC3H6
_cod_database_code               7720124
_chemical_oxdiff_formula         'C25 H62 Al P S2 Si4'
_diffrn_oxdiff_digest_hkl
;
431737852a309e83a7484933c3f97bb3cc0df1
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name butH64.par
_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. Uiso/Uaniso restraints and constraints
Si7A \\sim Si7B \\sim Si8 \\sim C33A \\sim C33B \\sim C34A \\sim C34B \\sim
C35A \\sim C35B \\sim C36A \\sim C36B \\sim C37 \\sim C38 \\sim C39: within 2A
with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C15 \\sim C16A \\sim C16B \\sim C17A \\sim C17B \\sim C18B: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C15 \\sim C16A \\sim C16B \\sim C17A \\sim C17B \\sim C18A \\sim C18B: within
2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
3. Rigid body (RIGU) restrains
 Si7A, Si7B, Si8, C33A, C33B, C34A, C34B, C35A, C35B, C36A, C36B, C37, C38, C39
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C15, C16A, C16B, C17A, C17B, C18B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C15, C16A, C16B, C17A, C17B, C18A, C18B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(Si7B)=Sof(C33B)=Sof(H33B)=Sof(C34B)=Sof(H34d)=Sof(H34e)=Sof(H34f)=
 Sof(C35B)=Sof(H35d)=Sof(H35e)=Sof(H35f)=Sof(C36B)=Sof(H36d)=Sof(H36e)=
 Sof(H36f)=1-FVAR(1)
 Sof(Si7A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34a)=Sof(H34b)=Sof(H34c)=
 Sof(C35A)=Sof(H35a)=Sof(H35b)=Sof(H35c)=Sof(C36A)=Sof(H36a)=Sof(H36b)=
 Sof(H36c)=FVAR(1)
 Sof(C16B)=Sof(H16d)=Sof(H16e)=Sof(H16f)=Sof(C17B)=Sof(H17d)=Sof(H17e)=
 Sof(H17f)=Sof(C18B)=Sof(H18d)=Sof(H18e)=Sof(H18f)=1-FVAR(2)
 Sof(C16A)=Sof(H16a)=Sof(H16b)=Sof(H16c)=Sof(C17A)=Sof(H17a)=Sof(H17b)=
 Sof(H17c)=Sof(C18A)=Sof(H18a)=Sof(H18b)=Sof(H18c)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C8(H8), C24(H24), C26(H26), C33A(H33A), C33B(H33B), C49(H49)
5.b Secondary CH2 refined with riding coordinates:
 C23(H23a,H23b), C48(H48a,H48b)
5.c Me refined with riding coordinates:
 C16A(H16a,H16b,H16c), C17A(H17a,H17b,H17c), C17B(H17d,H17e,H17f), C18A(H18a,
 H18b,H18c), C18B(H18d,H18e,H18f)
5.d Idealised Me refined as rotating group:
 C2(H2a,H2b,H2c), C3(H3a,H3b,H3c), C4(H4a,H4b,H4c), 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),
 C16B(H16d,H16e,H16f), C20(H20a,H20b,H20c), C21(H21a,H21b,H21c), C22(H22a,H22b,
 H22c), C25(H25a,H25b,H25c), C27(H27a,H27b,H27c), C28(H28a,H28b,H28c), C29(H29a,
 H29b,H29c), C30(H30a,H30b,H30c), C31(H31a,H31b,H31c), C32(H32a,H32b,H32c),
 C34A(H34a,H34b,H34c), C34B(H34d,H34e,H34f), C35A(H35a,H35b,H35c), C35B(H35d,
 H35e,H35f), C36A(H36a,H36b,H36c), C36B(H36d,H36e,H36f), C37(H37a,H37b,H37c),
 C38(H38a,H38b,H38c), C39(H39a,H39b,H39c), C41(H41a,H41b,H41c), C42(H42a,H42b,
 H42c), C43(H43a,H43b,H43c), C45(H45a,H45b,H45c), C46(H46a,H46b,H46c), C47(H47a,
 H47b,H47c), C50(H50a,H50b,H50c)
;
_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:           2025-09-26_20-30-43
;
_olex2_date_sample_data_collection 2025-09-25
_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 1.414
_oxdiff_exptl_absorpt_empirical_full_min 0.635