Molecular-level insight into the multiple mechanistic pathways in iron-catalysed alkene dimerisation.
Cockcroft, Joseph H. P.; Flook, Annabel; Boaler, Patrick J.; Nichol, Gary S.; Holt, Jarle; Smit, Joost; Garden, Jennifer A.; Thomas, Stephen P.; Chemical science 16 (2025) 22394–22406; doi:10.1039/d5sc07490h

data_1576126
_publ_section_title
;
 Molecular-level insight into the multiple mechanistic pathways in
 iron-catalysed alkene dimerisation.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              22394
_journal_page_last               22406
_journal_paper_doi               10.1039/d5sc07490h
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C21 H46 Fe O4 P4'
_chemical_formula_sum            'C21 H46 Fe O4 P4'
_chemical_formula_weight         542.31
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-21
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-05-21 deposited with the CCDC.	2025-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.907(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.18470(10)
_cell_length_b                   20.6020(3)
_cell_length_c                   14.6513(3)
_cell_measurement_reflns_used    20590
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      30.2970
_cell_measurement_theta_min      2.4070
_cell_volume                     2768.80(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.911
_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     19.00  70.00   0.50   60.00    --   -0.60  19.00 -90.00  102
  2  \w     -2.00  59.00   0.50   60.00    --   -0.60  57.00 120.00  122
  3  \w     -2.00  59.00   0.50   60.00    --   -0.60  57.00 -60.00  122
  4  \w      4.00  71.00   0.50   60.00    --   -0.60  38.00-150.00  134
  5  \w     -2.00  59.00   0.50   60.00    --   -0.60  57.00  30.00  122
  6  \w     19.00  70.00   0.50   60.00    --   -0.60  19.00 -30.00  102
  7  \w     19.00  70.00   0.50   60.00    --   -0.60  19.00   0.00  102
  8  \w     19.00  70.00   0.50   60.00    --   -0.60  19.00 150.00  102
  9  \w     19.00  48.00   0.50   60.00    --   -0.60  19.00  60.00   58
 10  \w     19.00  70.00   0.50   60.00    --   -0.60  19.00  90.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0597385000
_diffrn_orient_matrix_UB_12      0.0211371000
_diffrn_orient_matrix_UB_13      -0.0058964000
_diffrn_orient_matrix_UB_21      -0.0443544000
_diffrn_orient_matrix_UB_22      0.0269887000
_diffrn_orient_matrix_UB_23      0.0100846000
_diffrn_orient_matrix_UB_31      0.0210421000
_diffrn_orient_matrix_UB_32      -0.0031410000
_diffrn_orient_matrix_UB_33      0.0470549000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0509
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.911
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            64221
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.911
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.648
_diffrn_reflns_theta_min         1.977
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.799
_exptl_absorpt_correction_T_max  0.94689
_exptl_absorpt_correction_T_min  0.94689
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
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 yellow'
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_description       block
_exptl_crystal_F_000             1160
_exptl_crystal_size_max          0.177
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.021
_exptl_crystal_size_rad          0.035
_refine_diff_density_max         0.529
_refine_diff_density_min         -0.474
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.141
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         7806
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.142
_refine_ls_R_factor_all          0.0664
_refine_ls_R_factor_gt           0.0467
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0331P)^2^+2.8337P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0975
_refine_ls_wR_factor_ref         0.1032
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6225
_reflns_number_total             7806
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07490h2.cif
_cod_data_source_block           17
_cod_depositor_comments
'Adding full bibliography for 1576122--1576127.cif.'
_cod_database_code               1576126
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C21 H45 O4 P4 Fe1 '
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.872
_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. Shared sites
{C15, C15A}
3. Uiso/Uaniso restraints and constraints
Uanis(C16) = Uanis(C20A)
Uanis(C15) = Uanis(C15A)
Uanis(C20) = Uanis(C16A)
4. Same fragment restrains
{O3, O4, C15, C16, C17, C20, C21} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O3A, O4A, C15A, C16A, C17A, C20A, C21A}
5. Others
 Sof(O3A)=Sof(O4A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16C)=Sof(H16D)=Sof(C17A)=
 Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=Sof(H21D)=Sof(H21E)=
 Sof(H21F)=1-FVAR(1)
 Sof(O3)=Sof(O4)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=
 FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C15(H15), C15A(H15A)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C7(H7A,H7B), C8(H8A,H8B), C16(H16A,H16B), C16A(H16C,
 H16D)
6.c Me refined with riding coordinates:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C20A(H20D,H20E,H20F), C21A(H21D,
 H21E,H21F)
6.d Aromatic/amide H refined with riding coordinates:
 C18(H18)
6.e Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              30369
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 1000'
_olex2_submission_original_sample_id 17
_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 1.303
_oxdiff_exptl_absorpt_empirical_full_min 0.787