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_1571569
_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 O4'
_chemical_formula_sum            'C52 H50 Fe O4'
_chemical_formula_weight         794.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-07-28
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-02-21 deposited with the CCDC.	2024-05-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.955(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1688(3)
_cell_length_b                   16.2148(5)
_cell_length_c                   21.5184(5)
_cell_measurement_reflns_used    19571
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      74.9490
_cell_measurement_theta_min      3.4100
_cell_volume                     4243.42(19)
_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 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1806
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.980
_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    -50.00  34.00   1.00    5.00    --  -38.50  38.00-180.00   84
  2  \w    -65.00  32.00   1.00    5.00    --  -38.50  57.00  60.00   97
  3  \w    -93.00  -2.00   1.00    5.00    --  -38.50 125.00   0.00   91
  4  \w   -112.00  -7.00   1.00    5.00    --  -38.50 -77.00 -90.00  105
  5  \w    -27.00  70.00   1.00    5.00    --   43.13 -57.00 150.00   97
  6  \w     62.00 178.00   1.00   20.00    --  107.38  15.00   0.00  116
  7  \w     37.00 135.00   1.00   20.00    --  107.38 -61.00 150.00   98
  8  \w     33.00  91.00   1.00   20.00    --  107.38 -30.00  60.00   58
  9  \w     27.00 109.00   1.00   20.00    --  107.38 -95.00   0.00   82
 10  \w     36.00 117.00   1.00   20.00    --  107.38-125.00  90.00   81
 11  \w     27.00 109.00   1.00   20.00    --  107.38 -95.00-180.00   82
 12  \w     33.00  91.00   1.00   20.00    --  107.38 -30.00  30.00   58
 13  \w     36.00  98.00   1.00   20.00    --  107.38 -45.00 -30.00   62
 14  \w     33.00  91.00   1.00   20.00    --  107.38 -30.00-180.00   58
 15  \w     36.00  98.00   1.00   20.00    --  107.38 -45.00  60.00   62
 16  \w     33.00  91.00   1.00   20.00    --  107.38 -30.00-150.00   58
 17  \w     36.00 117.00   1.00   20.00    --  107.38-125.00 -90.00   81
 18  \w     27.00 109.00   1.00   20.00    --  107.38 -95.00  90.00   82
 19  \w     27.00 109.00   1.00   20.00    --  107.38 -95.00 -60.00   82
 20  \w     33.00  91.00   1.00   20.00    --  107.38 -30.00-120.00   58
 21  \w     83.00 178.00   1.00   20.00    --  107.38  45.00-150.00   95
 22  \w     16.00 113.00   1.00    5.00    --   43.13  57.00 120.00   97
 23  \w    -27.00  70.00   1.00    5.00    --   43.13 -57.00-120.00   97
 24  \w     16.00 113.00   1.00    5.00    --   43.13  57.00  30.00   97
 25  \w     12.00 117.00   1.00    5.00    --   43.13  77.00 -90.00  105
 26  \w     12.00 117.00   1.00    5.00    --   43.13  77.00  60.00  105
 27  \w     12.00 117.00   1.00    5.00    --   43.13  77.00-180.00  105
 28  \w     62.00 178.00   1.00   20.00    --  107.38  15.00 150.00  116
 29  \w     76.00 140.00   1.00   20.00    --  107.38  77.00  30.00   64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0080385000
_diffrn_orient_matrix_UB_12      -0.0945690000
_diffrn_orient_matrix_UB_13      -0.0055801000
_diffrn_orient_matrix_UB_21      0.1257877000
_diffrn_orient_matrix_UB_22      -0.0052380000
_diffrn_orient_matrix_UB_23      -0.0048103000
_diffrn_orient_matrix_UB_31      0.0123387000
_diffrn_orient_matrix_UB_32      -0.0076788000
_diffrn_orient_matrix_UB_33      0.0712267000
_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  0.0703
_diffrn_reflns_av_unetI/netI     0.0498
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            46376
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.280
_diffrn_reflns_theta_min         4.111
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.198
_exptl_absorpt_correction_T_max  0.872
_exptl_absorpt_correction_T_min  0.648
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             1680
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.675
_refine_diff_density_min         -0.805
_refine_diff_density_rms         0.127
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     526
_refine_ls_number_reflns         8611
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.124
_refine_ls_R_factor_all          0.0910
_refine_ls_R_factor_gt           0.0789
_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^)+(0.1297P)^2^+2.7217P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2116
_refine_ls_wR_factor_ref         0.2232
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7243
_reflns_number_total             8611
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_database_code               1571569
_nottingham_internal_coll_name   FEYLLN
_nottingham_internal_coll_number 17903
_nottingham_internal_coll_client YL/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '20.00, 5.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pcxyl12
_nottingham_internal_coll_date   06/09/2018
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'SN, XDA 017-09'
_nottingham_internal_process_date 08/02/2021
_nottingham_internal_process_user pczntc
_nottingham_internal_solution_date 22/07/2022
_nottingham_internal_solution_user pczntc
_nottingham_internal_refinement_date 22/07/2022
_nottingham_internal_refinement_user pczntc
_nottingham_internal_self_archive_date 22/07/2022
_nottingham_internal_self_validation_date 28/07/2022
_nottingham_internal_self_validation_user pczntc
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C52 H50 O4 Fe'
_chemical_oxdiff_usercomment
'FEYLLN1 #17903 IN A FOMBLIN FILM ON A MICROMOUNT FOR YL/DLK'
_shelx_estimated_absorpt_t_max   0.681
_shelx_estimated_absorpt_t_min   0.468
_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:
 C3(H3), C4(H4), C5(H5), C9(H9), C11(H11), C18(H18), C20(H20), C27(H27),
 C28(H28), C29(H29), C33(H33), C35(H35), C42(H42), C44(H44)
2.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C39(H39A,H39B,H39C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C),
 C48(H48A,H48B,H48C)
;
_shelx_res_checksum              6446
_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 1.510
_oxdiff_exptl_absorpt_empirical_full_min 0.739