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_1576127
_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         'C17 H40 Fe O2 P4'
_chemical_formula_sum            'C17 H40 Fe O2 P4'
_chemical_formula_weight         456.246
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_Int_Tables_number      61
_atom_sites_solution_primary     direct
_audit_creation_date             2024-09-13
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-09-22 deposited with the CCDC.	2025-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.86988(18)
_cell_length_b                   15.39782(16)
_cell_length_c                   17.24096(19)
_cell_measurement_reflns_used    20738
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      75.2900
_cell_measurement_theta_min      5.2080
_cell_volume                     4478.50(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_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  'olex2.refine 1.5-beta (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2792
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9995
_diffrn_measured_fraction_theta_max 0.9942
_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   -117.00 -20.00   1.00    7.50    --  -42.75 -32.00 -58.00   97
  2  \w    -66.00  31.00   1.00    7.50    --  -42.75  32.00 101.00   97
  3  \w     20.00 117.00   1.00    7.50    --   42.75  32.00 101.00   97
  4  \w    -31.00  66.00   1.00    7.50    --   42.75 -32.00 -58.00   97
  5  \w     88.00 178.00   1.00   15.00    --  111.00  32.00 101.00   90
  6  \w     37.00 134.00   1.00   15.00    --  111.00 -32.00 -58.00   97
  7  \w     11.00  42.00   1.00    7.50    --   42.75  80.00  96.81   31
  8  \w     11.00  42.00   1.00    7.50    --   42.75  79.00 -36.24   31
  9  \w     27.00  96.00   1.00    7.50    --   42.75-125.00-180.00   69
 10  \w     87.00 178.00   1.00   15.00    --  111.00  30.00 150.00   91
 11  \w     30.00 107.00   1.00   15.00    --  111.00 -94.00 -60.00   77
 12  \w     87.00 178.00   1.00   15.00    --  111.00  30.00   0.00   91
 13  \w    103.00 178.00   1.00   15.00    --  111.00  77.00  30.00   75
 14  \w     97.00 178.00   1.00   15.00    --  111.00 125.00  30.00   81
 15  \w     87.00 178.00   1.00   15.00    --  111.00  30.00-150.00   91
 16  \w     87.00 178.00   1.00   15.00    --  111.00  30.00-150.00   91
 17  \w     37.00 142.00   1.00   15.00    --  111.00 -77.00-120.00  105
 18  \w    103.00 178.00   1.00   15.00    --  111.00  77.00-150.00   75
 19  \w     37.00 142.00   1.00   15.00    --  111.00 -77.00  90.00  105
 20  \w     40.00 135.00   1.00   15.00    --  111.00 -45.00-180.00   95
 21  \w     40.00 135.00   1.00   15.00    --  111.00 -45.00 -60.00   95
 22  \w     91.00 121.00   1.00   15.00    --  111.00 -45.00-180.00   30
 23  \w     38.00  82.00   1.00   15.00    --  111.00 -77.00-150.00   44
 24  \w     67.00 128.00   1.00   15.00    --  111.00  15.00   0.00   61
 25  \w    139.00 177.00   1.00   15.00    --  111.00  15.00   0.00   38
 26  \w     75.00 104.00   1.00   15.00    --  111.00 -61.00 120.00   29
 27  \w    114.00 139.00   1.00   15.00    --  111.00 -61.00 120.00   25
 28  \w     66.00  93.00   1.00   15.00    --  111.00 -94.00-180.00   27
 29  \w     98.00 139.00   1.00   15.00    --  111.00 125.00  30.00   41
 30  \w     61.00 106.00   1.00   15.00    --  111.00 -94.00 150.00   45
 31  \w    150.00 177.00   1.00   15.00    --  111.00 125.00 -30.00   27
 32  \w     38.00  64.00   1.00   15.00    --  111.00 -77.00  90.00   26
 33  \w     69.00 105.00   1.00   15.00    --  111.00-125.00-120.00   36
 34  \w     73.00 100.00   1.00   15.00    --  111.00 -94.00 -90.00   27
 35  \w    116.00 163.00   1.00   15.00    --  111.00  77.00-120.00   47
 36  \w    144.00 171.00   1.00   15.00    --  111.00  77.00 -30.00   27
 37  \w     54.00  79.00   1.00   15.00    --  111.00 -94.00 -30.00   25
 38  \w     65.00  97.00   1.00   15.00    --  111.00 -94.00  30.00   32
 39  \w     93.00 120.00   1.00   15.00    --  111.00  61.00 150.00   27
 40  \w     71.00  98.00   1.00   15.00    --  111.00 -45.00-120.00   27
 41  \w     37.00  64.00   1.00   15.00    --  111.00 -94.00 -90.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0244659000
_diffrn_orient_matrix_UB_12      0.0886781000
_diffrn_orient_matrix_UB_13      0.0336667000
_diffrn_orient_matrix_UB_21      0.0878592000
_diffrn_orient_matrix_UB_22      0.0226850000
_diffrn_orient_matrix_UB_23      0.0134127000
_diffrn_orient_matrix_UB_31      0.0043828000
_diffrn_orient_matrix_UB_32      0.0402970000
_diffrn_orient_matrix_UB_33      -0.0817281000
_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  0.0638
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 0.9995
_diffrn_reflns_Laue_measured_fraction_max 0.9942
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            67317
_diffrn_reflns_point_group_measured_fraction_full 0.9995
_diffrn_reflns_point_group_measured_fraction_max 0.9942
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         76.12
_diffrn_reflns_theta_min         4.66
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.8
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    8.160
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67399
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.116a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent pale orange'
_exptl_crystal_density_diffrn    1.353
_exptl_crystal_description       block
_exptl_crystal_F_000             1957.787
_exptl_crystal_recrystallization_method
'The material was recrystallised from pentane by slow evaporation'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.8780
_refine_diff_density_min         -0.2885
_refine_diff_density_rms         0.0692
_refine_ls_d_res_high            0.7941
_refine_ls_d_res_low             9.4934
_refine_ls_goodness_of_fit_ref   1.0802
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     577
_refine_ls_number_reflns         4655
_refine_ls_number_restraints     202
_refine_ls_restrained_S_all      1.0544
_refine_ls_R_factor_all          0.0331
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0486P)^2^+0.5358P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0713
_refine_ls_wR_factor_ref         0.0749
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              21
_reflns_limit_h_min              0
_reflns_limit_k_max              19
_reflns_limit_k_min              0
_reflns_limit_l_max              21
_reflns_limit_l_min              0
_reflns_number_gt                4156
_reflns_number_total             4655
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5sc07490h2.cif
_cod_data_source_block           22
_cod_depositor_comments
'Adding full bibliography for 1576122--1576127.cif.'
_cod_database_code               1576127
_chemical_oxdiff_formula         'C17 H40 Fe1 O2 P4'
_chemical_oxdiff_usercomment     '@ 120 K '
_olex2_refinement_description
;
1. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
;
_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:           2024-09-13_16-22-09
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil.'
_olex2_submission_original_sample_id 'JHPC_174 crystallization'
_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 1.644
_oxdiff_exptl_absorpt_empirical_full_min 0.749