A Heterometallic σ-Silane Adduct from Cooperative Reactivity of an Iron–Aluminium Complex
Crimmin, Mark Richard; Stadler, Benedek; Chemical Communications  (2025) –; doi:10.1039/D5CC06456B

data_7135255
_publ_section_title
;
 A Heterometallic \s-Silane Adduct from Cooperative Reactivity of an
 Iron--Aluminium Complex
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D5CC06456B
_journal_year                    2025
_chemical_formula_moiety         'C39 H67 Al Fe N2 O P2 Si, 0.5(C5 H12)'
_chemical_formula_sum            'C41.5 H73 Al Fe N2 O P2 Si'
_chemical_formula_weight         788.915
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2p9zrr
_audit_creation_date             2025-02-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-08-22 deposited with the CCDC.	2025-11-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.962(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.6664(2)
_cell_length_b                   11.4726(1)
_cell_length_c                   22.7577(2)
_cell_measurement_reflns_used    22471
_cell_measurement_temperature    173(3)
_cell_measurement_theta_max      73.0510
_cell_measurement_theta_min      3.9000
_cell_volume                     4587.57(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4115
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9996
_diffrn_measured_fraction_theta_max 0.9941
_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      9.00  63.00   1.00   14.34    --   41.86  77.00   0.00   54
  2  \w     17.00 114.00   1.00   14.34    --   41.86  38.00   0.00   97
  3  \w     59.00 108.00   1.00   14.34    --   41.86  57.00  90.00   49
  4  \w      9.00 115.00   1.00   14.34    --   41.86  77.00-180.00  106
  5  \w     14.00  52.00   1.00   14.34    --   41.86  57.00  90.00   38
  6  \w     88.00 114.00   1.00   14.34    --   41.86  77.00   0.00   26
  7  \w    -30.00  69.00   1.00   14.34    --   41.86 -57.00 -60.00   99
  8  \w      9.00  70.00   1.00   14.34    --   41.86  77.00 120.00   61
  9  \w      4.00  95.00   1.00   14.34    --   41.86-125.00 -90.00   91
 10  \w    -29.00  70.00   1.00   14.34    --   41.86 -57.00  60.00   99
 11  \w      9.00  77.00   1.00   14.34    --   41.86  77.00 -90.00   68
 12  \w    143.00 169.00   1.00   50.66    --  105.13  61.00-180.00   26
 13  \w     25.00  56.00   1.00   50.66    --  105.13 -95.00 150.00   31
 14  \w     73.00  99.00   1.00   50.66    --  105.13  77.00 -90.00   26
 15  \w     76.00 138.00   1.00   50.66    --  105.13  61.00-180.00   62
 16  \w    130.00 156.00   1.00   50.66    --  105.13  61.00   0.00   26
 17  \w    110.00 178.00   1.00   50.66    --  105.13  77.00  60.00   68
 18  \w     73.00 177.00   1.00   50.66    --  105.13  77.00-120.00  104
 19  \w     76.00 102.00   1.00   50.66    --  105.13  61.00 150.00   26
 20  \w     73.00  99.00   1.00   50.66    --  105.13  77.00  60.00   26
 21  \w     76.00 102.00   1.00   50.66    --  105.13  61.00  60.00   26
 22  \w     76.00 111.00   1.00   50.66    --  105.13  61.00   0.00   35
 23  \w     29.00 138.00   1.00   50.66    --  105.13 -77.00  60.00  109
 24  \w     73.00  99.00   1.00   50.66    --  105.13  77.00-180.00   26
 25  \w     76.00 102.00   1.00   50.66    --  105.13  61.00 -90.00   26
 26  \w     76.00 172.00   1.00   50.66    --  105.13  61.00 -60.00   96
 27  \w     73.00  99.00   1.00   50.66    --  105.13  73.00 -47.00   26
 28  \w     73.00  99.00   1.00   50.66    --  105.13  77.00   0.00   26
 29  \w     73.00 176.00   1.00   50.66    --  105.13  77.00  30.00  103
 30  \w     73.00  99.00   1.00   50.66    --  105.13  77.00 150.00   26
 31  \w     26.00 109.00   1.00   50.66    --  105.13 -95.00-120.00   83
 32  \w    109.00 178.00   1.00   50.66    --  105.13  77.00 -30.00   69
 33  \w     77.00 102.00   1.00   50.66    --  105.13  61.00-120.00   25
 34  \w     73.00  99.00   1.00   50.66    --  105.13  77.00  90.00   26
 35  \w     76.00 151.00   1.00   50.66    --  105.13  61.00 120.00   75
 36  \w     76.00 171.00   1.00   50.66    --  105.13  61.00-150.00   95
 37  \w     42.00  84.00   1.00   50.66    --  105.13 -77.00 -60.00   42
 38  \w    128.00 159.00   1.00   50.66    --  105.13  61.00  90.00   31
 39  \w     76.00 105.00   1.00   50.66    --  105.13  61.00  90.00   29
 40  \w     76.00 116.00   1.00   50.66    --  105.13  61.00  30.00   40
 41  \w     73.00 177.00   1.00   50.66    --  105.13  77.00 120.00  104
 42  \w     73.00  99.00   1.00   50.66    --  105.13  77.00-150.00   26
 43  \w    116.00 141.00   1.00   50.66    --  105.13  77.00 -90.00   25
 44  \w     81.00 108.00   1.00   50.66    --  105.13 -95.00 150.00   27
 45  \w     73.00  99.00   1.00   50.66    --  105.13  77.00 -30.00   26
 46  \w     32.00 121.00   1.00   50.66    --  105.13-125.00  60.00   89
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0431796000
_diffrn_orient_matrix_UB_12      0.1068130000
_diffrn_orient_matrix_UB_13      0.0204828000
_diffrn_orient_matrix_UB_21      -0.0258911000
_diffrn_orient_matrix_UB_22      -0.0718048000
_diffrn_orient_matrix_UB_23      0.0514954000
_diffrn_orient_matrix_UB_31      0.0717822000
_diffrn_orient_matrix_UB_32      0.0383043000
_diffrn_orient_matrix_UB_33      0.0395039000
_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  0.0467
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 0.9996
_diffrn_reflns_Laue_measured_fraction_max 0.9941
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            70378
_diffrn_reflns_point_group_measured_fraction_full 0.9996
_diffrn_reflns_point_group_measured_fraction_max 0.9941
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         73.67
_diffrn_reflns_theta_min         3.91
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.956
_exptl_absorpt_correction_T_max  0.706
_exptl_absorpt_correction_T_min  0.565
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.142
_exptl_crystal_description       'blocky needle'
_exptl_crystal_F_000             1712.009
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.155
_exptl_crystal_size_min          0.117
_refine_diff_density_max         0.3199
_refine_diff_density_min         -0.4290
_refine_diff_density_rms         0.0682
_refine_ls_d_res_high            0.8033
_refine_ls_d_res_low             11.3173
_refine_ls_goodness_of_fit_ref   1.0958
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    15
_refine_ls_number_parameters     1196
_refine_ls_number_reflns         9215
_refine_ls_number_restraints     2619
_refine_ls_restrained_S_all      0.9456
_refine_ls_R_factor_all          0.0378
_refine_ls_R_factor_gt           0.0282
_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^)+(0.0258P)^2^+0.9405P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0652
_refine_ls_wR_factor_ref         0.0694
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              21
_reflns_limit_h_min              -21
_reflns_limit_k_max              14
_reflns_limit_k_min              0
_reflns_limit_l_max              28
_reflns_limit_l_min              0
_reflns_number_gt                8014
_reflns_number_total             9215
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5cc06456b3.cif
_cod_data_source_block           4a-HAR
_cod_database_code               7135255
_chemical_oxdiff_formula         'C41.5 H73 Al1 Fe1 N2 O1 P2 Si1'
_chemical_oxdiff_usercomment     BS216-B
_olex2_refinement_description
;
1. Restrained distances
 Si1-C1 \\sim Si1-C1A
 with sigma of 0.02
 C44-C43 \\sim C43-C42 \\sim C42-C41 \\sim C41-C40
 with sigma of 0.02
 C1-C2 \\sim C1A-C6A
 with sigma of 0.02
 C44-C42 \\sim C42-C40 \\sim C43-C41
 with sigma of 0.04
 C1-C6 \\sim C1A-C2A
 with sigma of 0.02
 C2-C3 \\sim C6A-C5A
 with sigma of 0.02
 C6-C5 \\sim C2A-C3A
 with sigma of 0.02
 C5-C4 \\sim C3A-C4A
 with sigma of 0.02
 C3-C4 \\sim C5A-C4A
 with sigma of 0.02
 Si1-C2 \\sim Si1-C6A
 with sigma of 0.04
 Si1-C6 \\sim Si1-C2A
 with sigma of 0.04
 C1-C5 \\sim C1A-C3A
 with sigma of 0.04
 C1-C3 \\sim C1A-C5A
 with sigma of 0.04
 C2-C6 \\sim C6A-C2A
 with sigma of 0.04
 C2-C4 \\sim C6A-C4A
 with sigma of 0.04
 C6-C4 \\sim C2A-C4A
 with sigma of 0.04
 C5-C3 \\sim C3A-C5A
 with sigma of 0.04
 C7-C8 \\sim C7-C8A
 with sigma of 0.02
 C7-C10 \\sim C7-C10A
 with sigma of 0.02
 C7-C9 \\sim C7-C9A
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.1 and sigma
for terminal atoms of 0.2 within 2A
C8 \\sim C8A \\sim C10 \\sim C10A \\sim C9 \\sim C9A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C1 \\sim C1A \\sim C6 \\sim C2A \\sim C5 \\sim C3A \\sim C4 \\sim C4A \\sim C5A
\\sim C3 \\sim C6A \\sim C2: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Others
 Sof(C1A)=Sof(C2A)=Sof(H7)=Sof(C3A)=Sof(H8)=Sof(C4A)=Sof(H10)=Sof(C5A)=Sof(H9)=
 Sof(C6A)=Sof(H0)=1-FVAR(1)
 Sof(C1)=Sof(C2)=Sof(H013)=Sof(C3)=Sof(H019)=Sof(C4)=Sof(H01P)=Sof(C5)=
 Sof(H018)=Sof(C6)=Sof(H017)=FVAR(1)
 Sof(C8A)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C9A)=Sof(H01W)=Sof(H01X)=Sof(H01Y)=
 Sof(C10A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=1-FVAR(2)
 Sof(C8)=Sof(H01M)=Sof(H01N)=Sof(H01O)=Sof(C9)=Sof(H01T)=Sof(H01U)=Sof(H01V)=
 Sof(C10)=Sof(H01Q)=Sof(H01R)=Sof(H01S)=FVAR(2)
 Fixed Sof: C40(0.5) H6A(0.5) H6B(0.5) H6C(0.5) C41(0.5) H5A(0.5) H5B(0.5)
 C42(0.5) H4A(0.5) H4B(0.5) C43(0.5) H3A(0.5) H3B(0.5) C44(0.5) H2A(0.5)
 H2B(0.5) H2C(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C41(H5A,H5B), C42(H4A,H4B), C43(H3A,H3B)
5.b Me refined with riding coordinates:
 C8A(H11A,H11B,H11C), C9A(H01W,H01X,H01Y), C10A(H12A,H12B,H12C), C40(H6A,H6B,
 H6C), C44(H2A,H2B,H2C)
5.c Aromatic/amide H refined with riding coordinates:
 C2A(H7), C3A(H8), C4A(H10), C5A(H9), C6A(H0)
;
_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:         B3LYP
   BASIS SET:      def2-TZVP
   CHARGE:         0
   MULTIPLICITY:   1
   SOLVATION:      Hexane
   DATE:           2025-02-10_23-48-34
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.275
_oxdiff_exptl_absorpt_empirical_full_min 0.747