Mechanistic investigations of the Fe(ii) mediated synthesis of squaraines.
Liu, Yu; Coles, Nathan T.; Cajiao, Nathalia; Taylor, Laurence J.; Davies, E. Stephen; Barbour, Alistair; Morgan, Patrick J.; Butler, Kevin; Pointer-Gleadhill, Ben; Argent, Stephen P.; McMaster, Jonathan; Neidig, Michael L.; Robinson, David; Kays, Deborah L.; Chemical science 15 (2024) 9599–9611; doi:10.1039/d4sc01286k

data_1571572
_publ_section_title
;
 Mechanistic investigations of the Fe(ii) mediated synthesis of
 squaraines.
;
_journal_issue                   25
_journal_name_full               'Chemical science'
_journal_page_first              9599
_journal_page_last               9611
_journal_paper_doi               10.1039/d4sc01286k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C53 H50 Fe O5'
_chemical_formula_sum            'C53 H50 Fe O5'
_chemical_formula_weight         822.78
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-03-30
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-02-21 deposited with the CCDC.	2024-05-07 downloaded from the CCDC.
;
_cell_angle_alpha                86.062(3)
_cell_angle_beta                 76.881(3)
_cell_angle_gamma                79.062(3)
_cell_formula_units_Z            2
_cell_length_a                   12.3798(4)
_cell_length_b                   12.6107(4)
_cell_length_c                   14.6241(5)
_cell_measurement_reflns_used    14427
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.6240
_cell_measurement_theta_min      3.7050
_cell_volume                     2182.32(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N2
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_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   -105.00 -20.00   1.00    1.50    --  -43.06 -44.00 128.81   85
  2  \w      0.00  32.00   1.00    1.50    --  -43.06  19.00 -30.00   32
  3  \w    -20.00  28.00   1.00    1.50    --  -43.06  38.00-180.00   48
  4  \w    -16.00  28.00   1.00    1.50    --  -43.06  38.00  60.00   44
  5  \w   -113.00 -23.00   1.00    1.50    --  -43.06 -38.00-120.00   90
  6  \w     83.00 113.00   1.00    1.50    --   43.06  70.00-162.11   30
  7  \w     17.00  44.00   1.00    1.50    --   43.06  65.00 -83.73   27
  8  \w     15.00  65.00   1.00    1.50    --   43.06  70.00-162.11   50
  9  \w     13.00  41.00   1.00    1.50    --   43.06  76.00  78.17   28
 10  \w     28.00  96.00   1.00    1.50    --   43.06-125.00  90.00   68
 11  \w     17.00  45.00   1.00    1.50    --   43.06  70.00 -49.96   28
 12  \w     19.00  46.00   1.00    1.50    --   43.06  60.00  65.91   27
 13  \w     17.00 112.00   1.00    1.50    --   43.06  71.00 -10.15   95
 14  \w    -26.00  59.00   1.00    1.50    --   43.06 -57.00-150.00   85
 15  \w     17.00  59.00   1.00    1.50    --   43.06  67.00 136.22   42
 16  \w     55.00  82.00   1.00    1.50    --   43.06  60.00  65.91   27
 17  \w     73.00 168.00   1.00    4.00    --  100.81  69.00-120.18   95
 18  \w    144.00 170.00   1.00    4.00    --  100.81  65.00 -70.68   26
 19  \w     78.00 103.00   1.00    4.00    --  100.81  57.00 -33.29   25
 20  \w    110.00 169.00   1.00    4.00    --  100.81  66.00  42.12   59
 21  \w     30.00 112.00   1.00    4.00    --  100.81-125.00 -30.00   82
 22  \w     78.00 105.00   1.00    4.00    --  100.81  45.00-150.00   27
 23  \w     76.00 167.00   1.00    4.00    --  100.81  58.00 172.07   91
 24  \w     73.00 100.00   1.00    4.00    --  100.81  69.00 -97.53   27
 25  \w     25.00 108.00   1.00    4.00    --  100.81-106.00  28.98   83
 26  \w     74.00 101.00   1.00    4.00    --  100.81  65.00 -70.68   27
 27  \w     74.00 100.00   1.00    4.00    --  100.81  66.00  42.12   26
 28  \w     77.00 104.00   1.00    4.00    --  100.81  54.00  82.02   27
 29  \w     74.00 127.00   1.00    4.00    --  100.81 -77.00 150.00   53
 30  \w     73.00 100.00   1.00    4.00    --  100.81  69.00 -34.54   27
 31  \w     73.00  99.00   1.00    4.00    --  100.81  69.00 168.24   26
 32  \w     76.00 160.00   1.00    4.00    --  100.81  60.00-129.58   84
 33  \w     30.00 113.00   1.00    4.00    --  100.81-125.00-150.00   83
 34  \w     76.00 105.00   1.00    4.00    --  100.81  61.00  60.00   29
 35  \w     74.00 151.00   1.00    4.00    --  100.81  66.00   3.13   77
 36  \w     76.00 102.00   1.00    4.00    --  100.81  61.00   0.00   26
 37  \w     74.00 114.00   1.00    4.00    --  100.81  66.00  88.19   40
 38  \w     76.00 169.00   1.00    4.00    --  100.81  61.00 120.00   93
 39  \w     80.00 106.00   1.00    4.00    --  100.81 -94.00  60.00   26
 40  \w     76.00 103.00   1.00    4.00    --  100.81  59.00 143.50   27
 41  \w     76.00 102.00   1.00    4.00    --  100.81  61.00  30.00   26
 42  \w     24.00  75.00   1.00    4.00    --  100.81 -94.00  60.00   51
 43  \w     76.00 113.00   1.00    4.00    --  100.81  61.00-150.00   37
 44  \w    136.00 161.00   1.00    4.00    --  100.81  61.00-150.00   25
 45  \w     73.00 154.00   1.00    4.00    --  100.81  69.00  95.22   81
 46  \w     79.00 106.00   1.00    4.00    --  100.81  60.00 -17.91   27
 47  \w     51.00  89.00   1.00    4.00    --  100.81 -61.00 -90.00   38
 48  \w     31.00  93.00   1.00    4.00    --  100.81 -61.00  60.00   62
 49  \w     77.00 104.00   1.00    4.00    --  100.81  61.00 150.00   27
 50  \w     29.00  56.00   1.00    4.00    --  100.81 -30.00 150.00   27
 51  \w     78.00 167.00   1.00    4.00    --  100.81  45.00 -30.00   89
 52  \w     33.00  67.00   1.00    4.00    --  100.81-125.00 -90.00   34
 53  \w     88.00 113.00   1.00    4.00    --  100.81-125.00 -90.00   25
 54  \w     76.00 157.00   1.00    4.00    --  100.81  61.00 -79.37   81
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Titan S2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1113213000
_diffrn_orient_matrix_UB_12      -0.0267608000
_diffrn_orient_matrix_UB_13      0.0602130000
_diffrn_orient_matrix_UB_21      0.0041675000
_diffrn_orient_matrix_UB_22      0.0783967000
_diffrn_orient_matrix_UB_23      0.0748928000
_diffrn_orient_matrix_UB_31      -0.0667758000
_diffrn_orient_matrix_UB_32      0.0928986000
_diffrn_orient_matrix_UB_33      -0.0497391000
_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  0.0362
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            38409
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.578
_diffrn_reflns_theta_min         3.571
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    3.145
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.470
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.54a (Rigaku Oxford Diffraction, 2022)
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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.252
_exptl_crystal_description       block
_exptl_crystal_F_000             868
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.377
_refine_diff_density_min         -0.389
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     544
_refine_ls_number_reflns         8546
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0379
_refine_ls_R_factor_gt           0.0345
_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^)+(0.0428P)^2^+0.6357P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0870
_refine_ls_wR_factor_ref         0.0892
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7950
_reflns_number_total             8546
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_database_code               1571572
_nottingham_internal_coll_name   FENCLM
_nottingham_internal_coll_number 19407
_nottingham_internal_coll_client NTC/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '1.50, 4.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczntc
_nottingham_internal_coll_date   29/03/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 30/03/2023
_nottingham_internal_process_user pczntc
_nottingham_internal_solution_date 30/03/2023
_nottingham_internal_solution_user pczntc
_nottingham_internal_refinement_date 30/03/2023
_nottingham_internal_refinement_user pczntc
_nottingham_internal_self_archive_date 30/03/2023
_nottingham_internal_self_validation_date 30/03/2023
_nottingham_internal_self_validation_user pczntc
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C52 H50 Fe O5'
_chemical_oxdiff_usercomment
'FENCLM #19407 GVA-2048 NTC/DLK fomblin oil on micromount'
_shelx_estimated_absorpt_t_max   0.667
_shelx_estimated_absorpt_t_min   0.462
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C44(H44), C11(H11), C5(H5), C29(H29), C6(H6), C13(H13), C31(H31), C46(H46),
 C7(H7), C30(H30), C37(H37), C20(H20), C22(H22), C35(H35)
2.b Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C), C17(H17A,H17B,H17C), C26(H26A,H26B,H26C), C48(H48A,H48B,
 H48C), C15(H15A,H15B,H15C), C24(H24A,H24B,H24C), C39(H39A,H39B,H39C), C16(H16A,
 H16B,H16C), C50(H50A,H50B,H50C), C41(H41A,H41B,H41C), C25(H25A,H25B,H25C),
 C40(H40A,H40B,H40C)
;
_shelx_res_checksum              88910
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_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 1.178
_oxdiff_exptl_absorpt_empirical_full_min 0.875