Multi-phosphine-chelated iron-carbide clusters <i>via</i> redox-promoted ligand exchange on an inert hexa-iron-carbide carbonyl cluster, [Fe<sub>6</sub>(μ<sub>6</sub>-C)(μ<sub>2</sub>-CO)<sub>4</sub>(CO)<sub>12</sub>]<sup>2</sup>.
Cobb, Caitlyn R.; Ngo, Ren K.; Dick, Emily J.; Lynch, Vincent M.; Rose, Michael J.; Chemical science 15 (2024) 11455–11471; doi:10.1039/d4sc01370k

data_1571969
_publ_section_title
;
 Multi-phosphine-chelated iron-carbide clusters <i>via</i> redox-promoted
 ligand exchange on an inert hexa-iron-carbide carbonyl cluster,
 [Fe<sub>6</sub>(&#x3bc;<sub>6</sub>-C)(&#x3bc;<sub>2</sub>-CO)<sub>4</sub>(CO)<sub>12</sub>]<sup>2</sup>.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              11455
_journal_page_last               11471
_journal_paper_doi               10.1039/d4sc01370k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C54.422 H40.265 Fe4 N0.422 O12.578 P3, C7 H8'
_chemical_formula_sum            'C61.42 H48.26 Fe4 N0.42 O12.58 P3'
_chemical_formula_weight         1309.78
_chemical_name_systematic        9
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-06-02 deposited with the CCDC.	2024-06-03 downloaded from the CCDC.
;
_cell_angle_alpha                107.235(2)
_cell_angle_beta                 91.498(2)
_cell_angle_gamma                117.671(2)
_cell_formula_units_Z            2
_cell_length_a                   12.9515(3)
_cell_length_b                   13.3229(3)
_cell_length_c                   19.7999(3)
_cell_measurement_reflns_used    23521
_cell_measurement_temperature    100.02(12)
_cell_measurement_theta_max      76.8370
_cell_measurement_theta_min      3.8200
_cell_volume                     2835.23(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.25a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.42.25a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.42.25a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.02(12)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.960
_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   -120.00 -63.00   0.50    1.29    --  -48.45-141.00 145.00  114
  2  \w    -98.00 -21.00   0.50    1.29    --  -48.45 141.00-157.00  154
  3  \w    -89.00 -15.00   0.50    1.29    --  -48.45 129.00  30.00  148
  4  \w   -120.00 -71.00   0.50    1.29    --  -48.45-129.00 -42.00   98
  5  \w     43.00 105.00   0.50    1.29    --   48.45-141.00 145.00  124
  6  \w     37.00  98.00   0.50    1.29    --   48.45-129.00 -42.00  122
  7  \w     93.00 178.00   0.50    5.16    --  107.75 129.00  30.00  170
  8  \w     43.00 124.00   0.50    5.16    --  107.75-141.00 145.00  162
  9  \w     37.00 115.00   0.50    5.16    --  107.75-129.00 -42.00  156
 10  \w     84.00 173.00   0.50    5.16    --  107.75 141.00-157.00  178
 11  \w   -120.00 -73.00   0.50    1.29    --  -48.45-125.00   0.00   94
 12  \w   -120.00 -26.00   0.50    1.29    --  -48.45 -77.00 -30.00  188
 13  \w    -61.00  25.00   0.50    1.29    --  -48.45  38.00 -90.00  172
 14  \w     32.00 121.00   0.50    5.16    --  107.75 -19.00   0.00  178
 15  \w     35.00 106.00   0.50    5.16    --  107.75 -99.00  30.00  142
 16  \w     93.00 178.00   0.50    5.16    --  107.75  57.00   0.00  170
 17  \w     35.00 120.00   0.50    5.16    --  107.75 -38.00-150.00  170
 18  \w     95.00 178.00   0.50    5.16    --  107.75 125.00 -90.00  166
 19  \w     95.00 178.00   0.50    5.16    --  107.75  38.00  30.00  166
 20  \w     35.00 123.00   0.50    5.16    --  107.75 -57.00 -90.00  176
 21  \w     35.00 106.00   0.50    5.16    --  107.75 -99.00-120.00  142
 22  \w     35.00 106.00   0.50    5.16    --  107.75 -99.00-180.00  142
 23  \w     95.00 178.00   0.50    5.16    --  107.75  38.00 -30.00  166
 24  \w   -120.00 -33.00   0.50    1.29    --  -48.45 -57.00  90.00  174
 25  \w   -120.00 -26.00   0.50    1.29    --  -48.45 -77.00  60.00  188
 26  \w   -120.00 -26.00   0.50    1.29    --  -48.45 -77.00-150.00  188
 27  \w   -120.00 -33.00   0.50    1.29    --  -48.45 -57.00 150.00  174
 28  \w   -120.00 -26.00   0.50    1.29    --  -48.45 -77.00   0.00  188
 29  \w   -120.00 -33.00   0.50    1.29    --  -48.45 -57.00-120.00  174
 30  \w     95.00 178.00   0.50    5.16    --  107.75  38.00-180.00  166
 31  \w     95.00 178.00   0.50    5.16    --  107.75  19.00 -60.00  166
 32  \w     95.00 178.00   0.50    5.16    --  107.75  19.00-120.00  166
 33  \w     95.00 178.00   0.50    5.16    --  107.75  38.00  60.00  166
 34  \w     95.00 178.00   0.50    5.16    --  107.75  19.00 120.00  166
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0284203000
_diffrn_orient_matrix_UB_12      -0.0637575000
_diffrn_orient_matrix_UB_13      -0.0823550000
_diffrn_orient_matrix_UB_21      0.0342298000
_diffrn_orient_matrix_UB_22      -0.0918125000
_diffrn_orient_matrix_UB_23      0.0099433000
_diffrn_orient_matrix_UB_31      -0.1294672000
_diffrn_orient_matrix_UB_32      -0.0831114000
_diffrn_orient_matrix_UB_33      0.0037112000
_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  0.0552
_diffrn_reflns_av_unetI/netI     0.0398
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            52147
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.020
_diffrn_reflns_theta_min         3.875
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.388
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32954
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.25a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.534
_exptl_crystal_description       needle
_exptl_crystal_F_000             1339
_exptl_crystal_preparation
'Made from the reaction of 2 with Triphos in MeCN.'
_exptl_crystal_recrystallization_method
'Cyrstal grown from vapor diffusion of pentane into toluene at RT under N2.'
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.117
_exptl_crystal_size_min          0.096
_refine_diff_density_max         0.533
_refine_diff_density_min         -0.459
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     808
_refine_ls_number_reflns         11522
_refine_ls_number_restraints     247
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0432
_refine_ls_R_factor_gt           0.0382
_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^)+(0.0455P)^2^+1.6688P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0912
_refine_ls_wR_factor_ref         0.0935
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10410
_reflns_number_total             11522
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01370k3.cif
_cod_data_source_block           compound9
_cod_depositor_comments
'Adding full bibliography for 1571968--1571976.cif.'
_cod_original_cell_volume        2835.23(11)
_cod_database_code               1571969
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Fe P C O H'
_olex2_refinement_description
;
1. Restrained distances
 C54-O13 = N1-C55
 1.14 with sigma of 0.01
 C55-C56
 1.45 with sigma of 0.01
 N1-C56
 2.6 with sigma of 0.01
 C023-C026 \\sim C60-C59
 with sigma of 0.02
 C023-C027 \\sim C60-C61
 with sigma of 0.02
 C026-C027 \\sim C59-C61
 with sigma of 0.04
 C024-C025 \\sim C62-C57
 with sigma of 0.02
 C024-C027 \\sim C62-C61
 with sigma of 0.02
 C024-C029 \\sim C62-C0
 with sigma of 0.04
 C025-C026 \\sim C57-C59
 with sigma of 0.04
 C025-C028 \\sim C57-C58
 with sigma of 0.02
 C026-C028 \\sim C59-C58
 with sigma of 0.02
 C024-C028 \\sim C62-C58
 with sigma of 0.04
 C027-C029 \\sim C61-C0
 with sigma of 0.02
 C025-C027 \\sim C57-C61
 with sigma of 0.04
 C023-C024 \\sim C60-C62
 with sigma of 0.04
 C023-C028 \\sim C60-C58
 with sigma of 0.04
 C023-C029 \\sim C60-C0
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
C0 \\sim C028 \\sim C026 \\sim C61 \\sim C60 \\sim C025 \\sim C59 \\sim C024
\\sim C58 \\sim C027 \\sim C57 \\sim C62 \\sim C023 \\sim C029: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C023) = Uanis(C62)
Uanis(C54) = Uanis(N1)
Uanis(O13) = Uanis(C55)
3. Others
 Sof(C0)=Sof(H0A)=Sof(H0B)=Sof(H0C)=Sof(C61)=Sof(C62)=Sof(H62)=Sof(C57)=
 Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=1-FVAR(1)
 Sof(C023)=Sof(H023)=Sof(C024)=Sof(H024)=Sof(C025)=Sof(H025)=Sof(C026)=
 Sof(H026)=Sof(C027)=Sof(C028)=Sof(H028)=Sof(C029)=Sof(H02A)=Sof(H02B)=
 Sof(H02C)=FVAR(1)
 Sof(N1)=Sof(C55)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=1-FVAR(2)
 Sof(C54)=Sof(O13)=FVAR(2)
4.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C15(H15A,H15B), C16(H16A,H16B)
4.b Aromatic/amide H refined with riding coordinates:
 C31(H31), C28(H28), C29(H29), C43(H43), C27(H27), C35(H35), C49(H49),
 C25(H25), C41(H41), C19(H19), C40(H40), C37(H37), C47(H47), C34(H34), C32(H32),
  C33(H33), C26(H26), C39(H39), C46(H46), C50(H50), C44(H44), C53(H53),
 C38(H38), C45(H45), C20(H20), C23(H23), C51(H51), C52(H52), C22(H22), C21(H21),
  C023(H023), C024(H024), C025(H025), C026(H026), C028(H028), C62(H62),
 C57(H57), C58(H58), C59(H59), C60(H60)
4.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C029(H02A,H02B,H02C), C0(H0A,H0B,H0C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              25997
_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 2.523
_oxdiff_exptl_absorpt_empirical_full_min 0.615