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_1571573
_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         'C51 H50 Fe O3, 1.5[C6H14]'
_chemical_formula_sum            'C60 H71 Fe O3'
_chemical_formula_weight         896.01
_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             2024-02-19
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-21 deposited with the CCDC.	2024-05-07 downloaded from the CCDC.
;
_cell_angle_alpha                73.812(3)
_cell_angle_beta                 89.056(4)
_cell_angle_gamma                72.173(4)
_cell_formula_units_Z            2
_cell_length_a                   11.0369(5)
_cell_length_b                   13.8006(5)
_cell_length_c                   18.0187(8)
_cell_measurement_reflns_used    9616
_cell_measurement_temperature    119.99(11)
_cell_measurement_theta_max      73.5700
_cell_measurement_theta_min      2.5240
_cell_volume                     2502.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_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      N~2~
_diffrn_ambient_temperature      119.99(11)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.2207
_diffrn_detector_type            TitanS2
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.953
_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   -112.00 -19.00   1.00   27.50    --  -43.19 -57.00-180.00   93
  2  \w    -67.00  26.00   1.00   27.50    --  -43.19  57.00 -30.00   93
  3  \w     28.00  55.00   1.00   27.50    --   43.19-125.00  90.00   27
  4  \w    -25.00  64.00   1.00   27.50    --   43.19 -70.00  56.00   89
  5  \w     54.00  91.00   1.00  110.00    --  102.38-125.00-120.00   37
  6  \w    100.00 175.00   1.00  110.00    --  102.38  30.00-150.00   75
  7  \w     30.00  70.00   1.00  110.00    --  102.38 -30.00 -60.00   40
  8  \w     31.00  70.00   1.00  110.00    --  102.38 -30.00  90.00   39
  9  \w     22.00 103.00   1.00  110.00    --  102.38 -94.00-120.00   81
 10  \w     47.00  90.00   1.00  110.00    --  102.38 -45.00-150.00   43
 11  \w     30.00  89.00   1.00  110.00    --  102.38 -30.00  30.00   59
 12  \w     36.00  98.00   1.00  110.00    --  102.38 -45.00 -30.00   62
 13  \w     91.00 117.00   1.00  110.00    --  102.38-125.00-180.00   26
 14  \w     70.00 117.00   1.00  110.00    --  102.38-125.00  60.00   47
 15  \w     55.00  80.00   1.00  110.00    --  102.38 -30.00 -90.00   25
 16  \w     34.00  88.00   1.00  110.00    --  102.38 -94.00 -30.00   54
 17  \w     34.00  59.00   1.00  110.00    --  102.38 -30.00 120.00   25
 18  \w     36.00 138.00   1.00  110.00    --  102.38 -15.00-180.00  102
 19  \w     51.00 121.00   1.00  110.00    --  102.38 -77.00  60.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'GV1000, TitanS2'
_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      -0.1218490000
_diffrn_orient_matrix_UB_12      -0.0048927000
_diffrn_orient_matrix_UB_13      -0.0372132000
_diffrn_orient_matrix_UB_21      -0.0793192000
_diffrn_orient_matrix_UB_22      0.0475951000
_diffrn_orient_matrix_UB_23      0.0598666000
_diffrn_orient_matrix_UB_31      -0.0219569000
_diffrn_orient_matrix_UB_32      0.1126963000
_diffrn_orient_matrix_UB_33      -0.0547929000
_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  0.0393
_diffrn_reflns_av_unetI/netI     0.0511
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            18052
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.551
_diffrn_reflns_theta_min         2.561
_diffrn_source                   'gradient vaccum rotating-anode X-ray tube'
_diffrn_source_type              'GV1000 (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.746
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.913
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.189
_exptl_crystal_description       plate
_exptl_crystal_F_000             962
_exptl_crystal_recrystallization_method
'crystallised from hexane at room temperature'
_exptl_crystal_size_max          0.122
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.059
_refine_diff_density_max         0.369
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     508
_refine_ls_number_reflns         9606
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0601
_refine_ls_R_factor_gt           0.0506
_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^)+(0.0675P)^2^+1.1095P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1323
_refine_ls_wR_factor_ref         0.1393
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8184
_reflns_number_total             9606
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           7
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_original_cell_volume        2502.04(19)
_cod_database_code               1571573
_nottingham_internal_coll_name   OYLALM2
_nottingham_internal_coll_number 17718
_nottingham_internal_coll_client YL/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '10.00, 40.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pcxyl12
_nottingham_internal_coll_date   14/01/2019
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 26/04/2021
_nottingham_internal_process_user pczlt
_nottingham_internal_solution_date 26/04/2021
_nottingham_internal_solution_user pczlt
_nottingham_internal_refinement_date 26/04/2021
_nottingham_internal_refinement_user pczlt
_nottingham_internal_self_archive_date 03/08/2022
_nottingham_internal_self_validation_date 03/08/2022
_nottingham_internal_self_validation_user pczntc
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C51H50FeO3
_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)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 148 electrons were 
found in a volume of 732\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1.5[C6H14] per Formula Unit 
which account for 150 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              90403
_shelx_fab_checksum              59293
_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 1.597
_oxdiff_exptl_absorpt_empirical_full_min 0.700