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_1571568
_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
_chemical_name_systematic        FEYLLS
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-02-28
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2024-02-21 deposited with the CCDC.	2024-05-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.500(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.9292(2)
_cell_length_b                   15.7523(3)
_cell_length_c                   12.3261(3)
_cell_measurement_reflns_used    5237
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.5470
_cell_measurement_theta_min      3.5870
_cell_volume                     2112.29(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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 2014/5 (Sheldrick, 2014)'
_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 Atlas S2 detector'
_diffrn_measured_fraction_theta_full 0.996
_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     28.00  96.00   1.00   13.50    --   43.06-125.00-120.00   68
  2  \w      5.00  43.00   1.00   13.50    --   43.06 -99.00 -30.00   38
  3  \w     19.00 112.00   1.00   13.50    --   43.06  57.00-180.00   93
  4  \w     38.00  88.00   1.00   54.00    --  103.00 -30.00   0.00   50
  5  \w    111.00 162.00   1.00   54.00    --  103.00 125.00-120.00   51
  6  \w     94.00 149.00   1.00   54.00    --  103.00 125.00 -90.00   55
  7  \w     95.00 139.00   1.00   54.00    --  103.00 -15.00 150.00   44
  8  \w     32.00  66.00   1.00   54.00    --  103.00 -15.00 150.00   34
  9  \w     78.00 165.00   1.00   54.00    --  103.00  61.00 -30.00   87
 10  \w     64.00  90.00   1.00   54.00    --  103.00 -30.00-120.00   26
 11  \w     48.00 128.00   1.00   54.00    --  103.00 -61.00-180.00   80
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Atlas'
_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      0.1337218000
_diffrn_orient_matrix_UB_12      -0.0199471000
_diffrn_orient_matrix_UB_13      -0.0209738000
_diffrn_orient_matrix_UB_21      -0.0111526000
_diffrn_orient_matrix_UB_22      0.0609445000
_diffrn_orient_matrix_UB_23      -0.0981417000
_diffrn_orient_matrix_UB_31      0.0455574000
_diffrn_orient_matrix_UB_32      0.0739191000
_diffrn_orient_matrix_UB_33      0.0752037000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_wavelength_determination fundamental
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0254
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            9050
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.611
_diffrn_reflns_theta_min         3.602
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    3.212
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.746
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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            'clear orangish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_description       block
_exptl_crystal_F_000             840
_exptl_crystal_preparation
'REACTED WITH CO AND FREEZED IMMEDIATELY, THEN EXTRACTED BY HEXANE (FIRST EXTRACTION)'
_exptl_crystal_recrystallization_method 'KEPT AT -30 CELSIUS'
_exptl_crystal_size_max          0.151
_exptl_crystal_size_mid          0.059
_exptl_crystal_size_min          0.048
_refine_diff_density_max         2.474
_refine_diff_density_min         -1.061
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         4297
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0648
_refine_ls_R_factor_gt           0.0609
_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^)+(0.0960P)^2^+2.2439P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1664
_refine_ls_wR_factor_ref         0.1733
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4013
_reflns_number_total             4297
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           6
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_database_code               1571568
_nottingham_internal_coll_name   FEYLLS
_nottingham_internal_coll_number 17974
_nottingham_internal_coll_client YL/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '13.50, 54.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pcxyl12
_nottingham_internal_coll_date   05/11/2018
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 05/11/2018
_nottingham_internal_process_user pcxyl12
_nottingham_internal_solution_date 28/02/2023
_nottingham_internal_solution_user pczntc
_nottingham_internal_refinement_date 28/02/2023
_nottingham_internal_refinement_user pczntc
_nottingham_internal_self_archive_date 28/02/2023
_nottingham_internal_self_validation_date 28/02/2023
_nottingham_internal_self_validation_user pczntc
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C52 H50 Fe O4'
_chemical_oxdiff_usercomment
'GVA-1524 FEYLLS #17974 in fomblin on micromount for YL/DLK'
_shelx_estimated_absorpt_t_max   0.861
_shelx_estimated_absorpt_t_min   0.643
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Others
 Fixed Sof: H17A(0.5) H17B(0.5) H17C(0.5) H19A(0.5) H19B(0.5) H19C(0.5)
3.a Aromatic/amide H refined with riding coordinates:
 C23(H23), C6(H6), C22(H22), C5(H5), C14(H14), C4(H4), C10(H10), C28(H28),
 C26(H26)
3.b Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C18(H18A,H18B,H18C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C30(H30A,H30B,H30C), C19(H19A,H19B,H19C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              32426
_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 1.223
_oxdiff_exptl_absorpt_empirical_full_min 0.903