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_1571574
_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         'C52 H50 Fe O2'
_chemical_formula_sum            'C52 H50 Fe O2'
_chemical_formula_weight         762.77
_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             2023-05-01
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-02-21 deposited with the CCDC.	2024-05-07 downloaded from the CCDC.
;
_cell_angle_alpha                86.655(3)
_cell_angle_beta                 89.550(3)
_cell_angle_gamma                76.007(3)
_cell_formula_units_Z            2
_cell_length_a                   10.4522(4)
_cell_length_b                   11.8004(4)
_cell_length_c                   16.7576(7)
_cell_measurement_reflns_used    9498
_cell_measurement_temperature    119.99(10)
_cell_measurement_theta_max      73.7490
_cell_measurement_theta_min      6.4850
_cell_volume                     2002.09(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      119.99(10)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.970
_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      6.00  31.00   0.50   13.00    --    0.00 -77.00-180.00   50
  2  \w    -36.00  -9.00   0.50   13.00    --    0.00 -77.00-180.00   54
  3  \w    -33.00  28.00   0.50   13.00    --    0.00 -82.00 120.00  122
  4  \w    -21.00  77.00   0.50   13.00    --    0.00  38.00 -30.00  196
  5  \w     -8.00  19.00   0.50   13.00    --    0.00 -38.00  30.00   54
  6  \w      0.00  29.00   0.50   13.00    --    0.00 -77.00-120.00   58
  7  \w     63.00  89.00   0.50   13.00    --    0.00  38.00-120.00   52
  8  \w    -21.00  31.00   0.50   13.00    --    0.00 -77.00 -90.00  104
  9  \w    -45.00  -7.00   0.50   13.00    --    0.00 -77.00-120.00   76
 10  \w    -21.00  56.00   0.50   13.00    --    0.00  38.00  60.00  154
 11  \w    -23.00  30.00   0.50   13.00    --    0.00  38.00-120.00  106
 12  \w    -79.00 -11.00   0.50   13.00    --    0.00 -38.00  30.00  136
 13  \w     75.00 103.00   0.50   52.00    --   97.40  48.00-117.67   56
 14  \w     71.00  97.00   0.50   52.00    --   97.40  61.00  81.00   52
 15  \w     67.00  93.00   0.50   52.00    --   97.40  73.00  72.78   52
 16  \w     67.00  98.00   0.50   52.00    --   97.40  73.00 118.71   62
 17  \w     70.00 187.00   0.50   52.00    --   97.40  65.00 -48.81  234
 18  \w     72.00 185.00   0.50   52.00    --   97.40  56.00  81.74  226
 19  \w     72.00  98.00   0.50   52.00    --   97.40  55.00 153.03   52
 20  \w    162.00 187.00   0.50   52.00    --   97.40  61.00-150.00   50
 21  \w     71.00  97.00   0.50   52.00    --   97.40  61.00-150.00   52
 22  \w    107.00 185.00   0.50   52.00    --   97.40  62.00 168.05  156
 23  \w     71.00 187.00   0.50   52.00    --   97.40  61.00   0.00  232
 24  \w     42.00 131.00   0.50   52.00    --   97.40 -82.00 -30.00  178
 25  \w    138.00 164.00   0.50   52.00    --   97.40  61.00-120.00   52
 26  \w     41.00 129.00   0.50   52.00    --   97.40 -82.00  90.00  176
 27  \w     65.00 130.00   0.50   52.00    --   97.40 -82.00 150.00  130
 28  \w     71.00  97.00   0.50   52.00    --   97.40  61.00-180.00   52
 29  \w    123.00 187.00   0.50   52.00    --   97.40  61.00-180.00  128
 30  \w     71.00  98.00   0.50   52.00    --   97.40  61.00  60.00   54
 31  \w     71.00  99.00   0.50   52.00    --   97.40  61.00 120.00   56
 32  \w     48.00 130.00   0.50   52.00    --   97.40 -82.00-180.00  164
 33  \w     71.00  97.00   0.50   52.00    --   97.40  62.00 168.05   52
 34  \w     70.00 101.00   0.50   52.00    --   97.40  67.00-115.45   62
 35  \w     71.00 184.00   0.50   52.00    --   97.40  61.00 -60.00  226
 36  \w     85.00 122.00   0.50   52.00    --   97.40 -82.00   0.00   74
 37  \w     68.00  95.00   0.50   52.00    --   97.40  70.00 141.51   54
 38  \w     11.00  72.00   0.50   52.00    --   97.40 -82.00   0.00  122
 39  \w     72.00 187.00   0.50   52.00    --   97.40  61.00 -90.00  230
 40  \w     70.00  95.00   0.50   52.00    --   97.40  69.00 -89.97   50
 41  \w    116.00 180.00   0.50   52.00    --   97.40  62.00  19.18  128
 42  \w    132.00 184.00   0.50   52.00    --   97.40  45.00-150.00  104
 43  \w     75.00 114.00   0.50   52.00    --   97.40  45.00-150.00   78
 44  \w    107.00 184.00   0.50   52.00    --   97.40  68.00  98.56  154
 45  \w     74.00 108.00   0.50   52.00    --   97.40  45.00-180.00   68
 46  \w     74.00 103.00   0.50   52.00    --   97.40  45.00 120.00   58
 47  \w    134.00 159.00   0.50   52.00    --   97.40  45.00 120.00   50
 48  \w     74.00 111.00   0.50   52.00    --   97.40  45.00   0.00   74
 49  \w     69.00  95.00   0.50   52.00    --   97.40  68.00  98.56   52
 50  \w     71.00  97.00   0.50   52.00    --   97.40  61.00-120.00   52
 51  \w     71.00 115.00   0.50   52.00    --   97.40  62.00  19.18   88
 52  \w     71.00 116.00   0.50   52.00    --   97.40  61.00  30.00   90
 53  \w     71.00 174.00   0.50   52.00    --   97.40  65.00 -77.84  206
 54  \w     74.00 101.00   0.50   52.00    --   97.40  45.00  69.18   54
 55  \w     23.00 121.00   0.50   52.00    --   97.40 -82.00 -90.00  196
 56  \w     72.00  98.00   0.50   52.00    --   97.40  55.00 -24.41   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_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      -0.0453059000
_diffrn_orient_matrix_UB_12      -0.0437555000
_diffrn_orient_matrix_UB_13      -0.0772682000
_diffrn_orient_matrix_UB_21      -0.1008736000
_diffrn_orient_matrix_UB_22      -0.0516149000
_diffrn_orient_matrix_UB_23      0.0481417000
_diffrn_orient_matrix_UB_31      -0.1041434000
_diffrn_orient_matrix_UB_32      0.1165540000
_diffrn_orient_matrix_UB_33      -0.0138834000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            10797
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.768
_diffrn_reflns_theta_min         2.641
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.328
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85995
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.265
_exptl_crystal_description       plank
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.087
_exptl_crystal_size_mid          0.039
_exptl_crystal_size_min          0.036
_refine_diff_density_max         1.008
_refine_diff_density_min         -0.844
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     510
_refine_ls_number_reflns         10797
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.1204
_refine_ls_R_factor_gt           0.0941
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1292P)^2^+5.1264P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2529
_refine_ls_wR_factor_ref         0.2726
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8046
_reflns_number_total             10797
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.8205\% 
 around [0.00 0.01 1.00] (reciprocal) or [0.01 -0.06 1.00] (direct)
Component 3 rotated by 5.6559\% 
 around [-0.40 -0.57 0.72] (reciprocal) or [-0.50 -0.70 0.51] (direct)
;
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           10
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_database_code               1571574
_nottingham_internal_coll_name   FENCLL
_nottingham_internal_coll_number 19363
_nottingham_internal_coll_client NTC/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '13.00, 52.00'
_nottingham_internal_coll_frame_width 0.50
_nottingham_internal_coll_user   pczntc
_nottingham_internal_coll_date   13/02/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'XtalLAB PRO, A00000876'
_nottingham_internal_process_date 20/02/2023
_nottingham_internal_process_user pczntc
_nottingham_internal_solution_date 01/05/2023
_nottingham_internal_solution_user pczntc
_nottingham_internal_refinement_date 01/05/2023
_nottingham_internal_refinement_user pczntc
_nottingham_internal_self_archive_date 01/05/2023
_nottingham_internal_self_validation_date 01/05/2023
_nottingham_internal_self_validation_user pczntc
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C52H50FeO2
_chemical_oxdiff_usercomment
'FENCLL #19363 MM-885 NTC/DLK fomblin oil on micromount'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.503(6)
 0.427(3) 0.070(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C48(H48), C22(H22), C13(H13), C39(H39), C31(H31), C33(H33), C5(H5), C32(H32),
 C37(H37), C11(H11), C7(H7), C6(H6), C20(H20), C46(H46)
3.b Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C26(H26A,H26B,H26C), C16(H16A,H16B,H16C), C43(H43A,H43B,
 H43C), C50(H50A,H50B,H50C), C17(H17A,H17B,H17C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C24(H24A,H24B,H24C), C15(H15A,H15B,H15C), C51(H51A,H51B,H51C),
 C25(H25A,H25B,H25C)
;
_shelx_res_checksum              88178
_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 2.013
_oxdiff_exptl_absorpt_empirical_full_min 0.633
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               3