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_1571581
_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, 1[C6H14]'
_chemical_formula_sum            'C106 H114 Fe2 O8'
_chemical_formula_weight         1627.67
_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                65.894(2)
_cell_angle_beta                 83.350(2)
_cell_angle_gamma                84.359(2)
_cell_formula_units_Z            1
_cell_length_a                   12.4176(2)
_cell_length_b                   13.2980(2)
_cell_length_c                   14.4695(2)
_cell_measurement_reflns_used    21295
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.7890
_cell_measurement_theta_min      3.5480
_cell_volume                     2162.86(7)
_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 1.5 (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(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'PILATUS3 R 200K Hybrid Pixel Array Detector'
_diffrn_measured_fraction_theta_full 0.995
_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     92.00 118.00   0.50   16.00    --   98.30 -76.00-136.00   52
  2  \w    131.00 161.00   0.50   16.00    --   98.30  76.00  -9.00   60
  3  \w     53.00  83.00   0.50   16.00    --   98.30 -76.00-136.00   60
  4  \w    -37.00  30.00   0.50    4.00    --    0.00 -76.00-136.00  134
  5  \w    -18.00  55.00   0.50    4.00    --   32.00 -44.00-120.42  146
  6  \w     11.00  49.00   0.50    4.00    --   40.00  71.00  31.21   76
  7  \w    108.00 133.00   0.50    4.00    --   44.00  72.00 121.22   50
  8  \w     68.00  94.00   0.50    4.00    --   44.00  72.00 121.22   52
  9  \w     15.00  41.00   0.50    4.00    --   44.00  72.00 121.22   52
 10  \w     19.00  44.00   0.50    4.00    --   48.00  72.00-158.21   50
 11  \w     22.00  49.00   0.50    4.00    --   48.00  72.00 138.10   54
 12  \w    109.00 135.00   0.50    4.00    --   48.00  72.00-158.21   52
 13  \w     32.00  62.00   0.50   16.00    --   56.00  75.00-159.80   60
 14  \w     28.00  55.00   0.50   16.00    --   56.00  73.00-120.81   54
 15  \w     93.00 147.00   0.50   16.00    --   64.00  74.00 158.17  108
 16  \w     33.00  79.00   0.50   16.00    --   64.00  75.00 -55.16   92
 17  \w     33.00  91.00   0.50   16.00    --   64.00  75.00  14.32  116
 18  \w     34.00  82.00   0.50   16.00    --   64.00  74.00 -22.55   96
 19  \w    128.00 153.00   0.50   16.00    --   64.00  75.00 -86.53   50
 20  \w     34.00  61.00   0.50   16.00    --   64.00  74.00 158.17   54
 21  \w    128.00 153.00   0.50   16.00    --   64.00  75.00 -55.16   50
 22  \w     33.00  66.00   0.50   16.00    --   64.00  75.00 -86.53   66
 23  \w    111.00 153.00   0.50   16.00    --   64.00  75.00-119.32   84
 24  \w     34.00  65.00   0.50   16.00    --   64.00  75.00-119.32   62
 25  \w     37.00  71.00   0.50   16.00    --   68.00  75.00  49.75   68
 26  \w     41.00  69.00   0.50   16.00    --   72.00  75.00  83.27   56
 27  \w     45.00  78.00   0.50   16.00    --   76.00  75.00-177.76   66
 28  \w     50.00  95.00   0.50   16.00    --   80.00  74.00 104.60   90
 29  \w    131.00 157.00   0.50   16.00    --   80.00  66.00  17.52   52
 30  \w     52.00  86.00   0.50   16.00    --   80.00  66.00  17.52   68
 31  \w    135.00 166.00   0.50   16.00    --   80.00  74.00-152.29   62
 32  \w    112.00 168.00   0.50   16.00    --   80.00  73.00 -71.99  112
 33  \w    141.00 167.00   0.50   16.00    --   80.00  74.00 104.60   52
 34  \w     50.00  81.00   0.50   16.00    --   80.00  73.00 -71.99   62
 35  \w     50.00 104.00   0.50   16.00    --   80.00  74.00-152.29  108
 36  \w    117.00 167.00   0.50   16.00    --   84.00  62.00-164.27  100
 37  \w     58.00 107.00   0.50   16.00    --   84.00  62.00-164.27   98
 38  \w     54.00 172.00   0.50   16.00    --   84.00  74.00 -36.42  236
 39  \w     97.00 170.00   0.50   16.00    --   84.00  66.00 167.77  146
 40  \w     57.00  87.00   0.50   16.00    --   84.00  66.00 167.77   60
 41  \w     61.00 176.00   0.50   16.00    --   88.00  63.00 -99.11  230
 42  \w     84.00 137.00   0.50   16.00    --   92.00  61.00-107.49  106
 43  \w    142.00 180.00   0.50   16.00    --   92.00  61.00-107.49   76
 44  \w     68.00 186.00   0.50   16.00    --   98.30  73.00  69.24  236
 45  \w     71.00 188.00   0.50   16.00    --   98.30  65.00   8.46  234
 46  \w     73.00 166.00   0.50   16.00    --   98.30  60.00 145.01  186
 47  \w     86.00 132.00   0.50   16.00    --   98.30 -82.00   0.00   92
 48  \w     15.00 129.00   0.50   16.00    --   98.30 -82.00 -30.00  228
 49  \w     75.00 165.00   0.50   16.00    --   98.30  61.00  30.00  180
 50  \w     43.00  81.00   0.50   16.00    --   98.30 -82.00   0.00   76
 51  \w     13.00 121.00   0.50   16.00    --   98.30 -82.00  60.00  216
 52  \w     75.00 166.00   0.50   16.00    --   98.30  61.00  60.00  182
 53  \w    139.00 188.00   0.50   16.00    --   98.30  61.00-150.00   98
 54  \w     72.00 131.00   0.50   16.00    --   98.30  61.00-150.00  118
 55  \w     81.00 152.00   0.50   16.00    --   98.30  77.00 -60.00  142
 56  \w     74.00 119.00   0.50   16.00    --   98.30  61.00 -60.00   90
 57  \w     70.00 170.00   0.50   16.00    --   98.30  70.00 117.79  200
 58  \w     28.00 125.00   0.50   16.00    --   98.30 -82.00-180.00  194
 59  \w     41.00 130.00   0.50   16.00    --   98.30 -82.00 150.00  178
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'XtalLAB PRO MM007, PILATUS3 R 200K'
_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      0.0417095000
_diffrn_orient_matrix_UB_12      -0.0969681000
_diffrn_orient_matrix_UB_13      -0.0292287000
_diffrn_orient_matrix_UB_21      0.0692521000
_diffrn_orient_matrix_UB_22      -0.0472433000
_diffrn_orient_matrix_UB_23      0.0917428000
_diffrn_orient_matrix_UB_31      -0.0954714000
_diffrn_orient_matrix_UB_32      -0.0672634000
_diffrn_orient_matrix_UB_33      0.0665517000
_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  0.0412
_diffrn_reflns_av_unetI/netI     0.0279
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.970
_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       -18
_diffrn_reflns_number            54294
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.543
_diffrn_reflns_theta_min         3.358
_diffrn_source                   'rotating anode'
_diffrn_source_type              'MicroMax 007 HF'
_exptl_absorpt_coefficient_mu    3.146
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.879
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_description       block
_exptl_crystal_F_000             866
_exptl_crystal_size_max          0.079
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.523
_refine_diff_density_min         -0.473
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     508
_refine_ls_number_reflns         8700
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0449
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0768P)^2^+0.5932P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1281
_refine_ls_wR_factor_ref         0.1335
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7598
_reflns_number_total             8700
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           3Mes_iHex
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_database_code               1571581
_nottingham_internal_coll_name   FENCLO
_nottingham_internal_coll_number 19418
_nottingham_internal_coll_client NTC/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '16.00, 4.00'
_nottingham_internal_coll_frame_width 0.50
_nottingham_internal_coll_user   pczntc
_nottingham_internal_coll_date   03/04/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'XtalLAB PRO, A00000876'
_nottingham_internal_process_date 06/04/2023
_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         'C104 H100 Fe'
_chemical_oxdiff_usercomment
'FENCLO #19418 MM-900 NTC/DLK fomblin oil on micromount'
_shelx_estimated_absorpt_t_max   0.884
_shelx_estimated_absorpt_t_min   0.789
_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:
 C21(H21), C4(H4), C31(H31), C19(H19), C29(H29), C6(H6), C44(H44), C46(H46),
 C30(H30), C35(H35), C5(H5), C10(H10), C37(H37), C12(H12)
2.b Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C25(H25A,H25B,H25C), C23(H23A,H23B,H23C), C39(H39A,H39B,
 H39C), C50(H50A,H50B,H50C), C24(H24A,H24B,H24C), C14(H14A,H14B,H14C), C41(H41A,
 H41B,H41C), C49(H49A,H49B,H49C), C40(H40A,H40B,H40C), C15(H15A,H15B,H15C),
 C16(H16A,H16B,H16C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 48 electrons were 
found in a volume of 201\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[C6H14] per unit cell
which account for 50 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              58053
_shelx_fab_checksum              89635
_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 1.300
_oxdiff_exptl_absorpt_empirical_full_min 0.811