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_1571575
_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         'C100 H100 Fe2 O8, C6 H12'
_chemical_formula_sum            'C106 H112 Fe2 O8'
_chemical_formula_weight         1625.65
_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             2023-08-04
_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                67.027(2)
_cell_angle_beta                 83.240(2)
_cell_angle_gamma                84.686(2)
_cell_formula_units_Z            1
_cell_length_a                   12.6674(3)
_cell_length_b                   13.2102(3)
_cell_length_c                   14.2164(3)
_cell_measurement_reflns_used    20780
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.5620
_cell_measurement_theta_min      4.6580
_cell_volume                     2172.22(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 41.123a (release 20-01-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_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      120.15
_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 0.983
_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    -89.00  -8.00   1.00    1.50    --  -42.12 125.00-150.00   81
  2  \w     -5.00  27.00   1.00    1.50    --  -42.12  19.00  90.00   32
  3  \w    -15.00  29.00   1.00    1.50    --  -42.12  38.00 120.00   44
  4  \w     28.00  55.00   1.00    1.50    --   42.12  38.00  30.00   27
  5  \w     11.00  36.00   1.00    1.50    --   42.12  76.00-127.00   25
  6  \w     11.00  42.00   1.00    1.50    --   42.12  81.00 112.53   31
  7  \w     18.00  46.00   1.00    1.50    --   42.12  57.00 -90.00   28
  8  \w      9.00  42.00   1.00    1.50    --   42.12  82.00 160.87   33
  9  \w     22.00  57.00   1.00    1.50    --   42.12  38.00-150.00   35
 10  \w     12.00  41.00   1.00    1.50    --   42.12  81.00 -75.84   29
 11  \w     53.00 111.00   1.00    1.50    --   42.12  69.00  87.68   58
 12  \w     13.00 106.00   1.00    1.50    --   42.12  68.00 -26.77   93
 13  \w     19.00  60.00   1.00    1.50    --   42.12  57.00  60.00   41
 14  \w     11.00  79.00   1.00    1.50    --   42.12 -99.00 120.00   68
 15  \w    -34.00  48.00   1.00    1.50    --   42.12 -19.00 -60.00   82
 16  \w     12.00  39.00   1.00    1.50    --   42.12  80.00  13.17   27
 17  \w     78.00 113.00   1.00    1.50    --   42.12  38.00  30.00   35
 18  \w     64.00  93.00   1.00    1.50    --   42.12  57.00 -90.00   29
 19  \w     13.00  39.00   1.00    1.50    --   42.12  69.00  87.68   26
 20  \w     74.00 164.00   1.00    6.00    --  101.44  63.00 -84.81   90
 21  \w     28.00 109.00   1.00    6.00    --  101.44-110.00 -65.78   81
 22  \w     76.00 102.00   1.00    6.00    --  101.44  57.00  84.67   26
 23  \w     74.00 102.00   1.00    6.00    --  101.44  63.00-140.58   28
 24  \w    130.00 156.00   1.00    6.00    --  101.44  54.00 144.60   26
 25  \w     83.00 113.00   1.00    6.00    --  101.44-125.00-150.00   30
 26  \w    107.00 171.00   1.00    6.00    --  101.44  63.00-140.58   64
 27  \w     75.00 118.00   1.00    6.00    --  101.44  60.00 104.94   43
 28  \w     29.00  90.00   1.00    6.00    --  101.44-125.00 -90.00   61
 29  \w     74.00 168.00   1.00    6.00    --  101.44  68.00 179.26   94
 30  \w     27.00 102.00   1.00    6.00    --  101.44 -77.00   0.00   75
 31  \w     77.00 105.00   1.00    6.00    --  101.44  54.00 144.60   28
 32  \w     73.00 172.00   1.00    6.00    --  101.44  68.00 -21.26   99
 33  \w    113.00 172.00   1.00    6.00    --  101.44  64.00  64.73   59
 34  \w     73.00 127.00   1.00    6.00    --  101.44  66.00-101.39   54
 35  \w     74.00 100.00   1.00    6.00    --  101.44  64.00  64.73   26
 36  \w     75.00 102.00   1.00    6.00    --  101.44  61.00-120.00   27
 37  \w     75.00 100.00   1.00    6.00    --  101.44  64.00 -77.90   25
 38  \w     78.00 114.00   1.00    6.00    --  101.44  45.00-177.33   36
 39  \w     21.00 107.00   1.00    6.00    --  101.44 -94.00 -30.00   86
 40  \w     75.00 101.00   1.00    6.00    --  101.44  61.00 -30.00   26
 41  \w     75.00 101.00   1.00    6.00    --  101.44  61.00 -60.00   26
 42  \w     76.00 101.00   1.00    6.00    --  101.44  61.00 150.00   25
 43  \w     76.00 133.00   1.00    6.00    --  101.44  61.00  30.00   57
 44  \w    148.00 173.00   1.00    6.00    --  101.44  70.00-170.79   25
 45  \w     30.00 111.00   1.00    6.00    --  101.44-125.00 150.00   81
 46  \w     72.00  98.00   1.00    6.00    --  101.44  70.00-170.79   26
 47  \w     74.00 100.00   1.00    6.00    --  101.44  62.00  17.02   26
 48  \w     32.00  91.00   1.00    6.00    --  101.44 -61.00 120.00   59
 49  \w     74.00 100.00   1.00    6.00    --  101.44  64.00   1.44   26
 50  \w     75.00 101.00   1.00    6.00    --  101.44  61.00-180.00   26
 51  \w     75.00 171.00   1.00    6.00    --  101.44  61.00 120.00   96
 52  \w     74.00 141.00   1.00    6.00    --  101.44  62.00  47.86   67
 53  \w     75.00 101.00   1.00    6.00    --  101.44  61.00  90.00   26
 54  \w     76.00 101.00   1.00    6.00    --  101.44  61.00-150.00   25
 55  \w     73.00 166.00   1.00    6.00    --  101.44  68.00 -49.41   93
;
_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      -0.0231696000
_diffrn_orient_matrix_UB_12      0.1247502000
_diffrn_orient_matrix_UB_13      -0.0303446000
_diffrn_orient_matrix_UB_21      -0.0727616000
_diffrn_orient_matrix_UB_22      -0.0223460000
_diffrn_orient_matrix_UB_23      0.1000373000
_diffrn_orient_matrix_UB_31      0.0959502000
_diffrn_orient_matrix_UB_32      0.0049054000
_diffrn_orient_matrix_UB_33      0.0550961000
_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  0.0254
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            36898
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.592
_diffrn_reflns_theta_min         3.390
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    3.132
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.227
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.63a (Rigaku Oxford Diffraction, 2023)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.243
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.52
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.293
_refine_diff_density_min         -0.351
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     534
_refine_ls_number_reflns         8472
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0327
_refine_ls_R_factor_gt           0.0317
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0505P)^2^+0.5809P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0891
_refine_ls_wR_factor_ref         0.0899
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8225
_reflns_number_total             8472
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           3Mes_CyH
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_database_code               1571575
_nottingham_internal_coll_name   FENCLS
_nottingham_internal_coll_number 19492
_nottingham_internal_coll_client NTC/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '6.00, 1.50'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczntc
_nottingham_internal_coll_date   18/07/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 19/07/2023
_nottingham_internal_process_user pczntc
_nottingham_internal_solution_date 04/08/2023
_nottingham_internal_solution_user pczntc
_nottingham_internal_refinement_date 04/08/2023
_nottingham_internal_refinement_user pczntc
_nottingham_internal_self_archive_date 04/08/2023
_nottingham_internal_self_validation_date 04/08/2023
_nottingham_internal_self_validation_user pczntc
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C100 H100 Fe2 O8'
_chemical_oxdiff_usercomment
'FENCLS #19492 GVA-2076 NTC/DLK fomblin oil on micromount'
_shelx_estimated_absorpt_t_max   0.766
_shelx_estimated_absorpt_t_min   0.293
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B)
2.b Me refined with riding coordinates:
 C40(H40A,H40B,H40C)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C10(H10), C12(H12), C19(H19), C21(H21), C29(H29),
 C30(H30), C31(H31), C35(H35), C37(H37), C44(H44), C46(H46)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C39(H39A,H39B,H39C), C41(H41A,
 H41B,H41C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C)
;
_shelx_res_checksum              37265
_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 1.405
_oxdiff_exptl_absorpt_empirical_full_min 0.837