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_1571580
_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         'C77 H76 Fe O4, 1[C6H14]'
_chemical_formula_sum            'C83 H90 Fe O4'
_chemical_formula_weight         1207.39
_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             2023-12-14
_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                102.728(2)
_cell_angle_beta                 99.634(2)
_cell_angle_gamma                107.973(2)
_cell_formula_units_Z            2
_cell_length_a                   12.1282(3)
_cell_length_b                   14.9679(3)
_cell_length_c                   20.5823(5)
_cell_measurement_reflns_used    15319
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.4430
_cell_measurement_theta_min      3.9680
_cell_volume                     3353.35(15)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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 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                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.2349
_diffrn_detector_type            'Agilent Diffraction Atlas S2 detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.968
_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    -83.00 -46.00   1.00    3.00    --  -42.83 125.00-180.00   37
  2  \w    -46.00   7.00   1.00    3.00    --  -42.83  38.00-180.00   53
  3  \w    -49.00  30.00   1.00    3.00    --  -42.83  38.00   0.00   79
  4  \w   -120.00  -6.00   1.00    3.00    --  -42.83 -19.00-180.00  114
  5  \w      7.00  78.00   1.00    3.00    --   42.83 -99.00  90.00   71
  6  \w     32.00  80.00   1.00   12.00    --  106.43 -30.00-120.00   48
  7  \w     82.00 168.00   1.00   12.00    --  106.43  45.00  60.00   86
  8  \w     32.00  77.00   1.00   12.00    --  106.43 -30.00 -60.00   45
  9  \w    124.00 170.00   1.00   12.00    --  106.43 125.00 -90.00   46
 10  \w     35.00  82.00   1.00   12.00    --  106.43 -30.00-180.00   47
 11  \w     85.00 113.00   1.00   12.00    --  106.43-112.00  86.00   28
 12  \w     38.00  79.00   1.00   12.00    --  106.43-125.00  30.00   41
 13  \w     41.00  67.00   1.00   12.00    --  106.43-125.00-120.00   26
 14  \w     89.00 115.00   1.00   12.00    --  106.43-125.00-120.00   26
 15  \w     52.00 131.00   1.00   12.00    --  106.43 -77.00   0.00   79
 16  \w     27.00 124.00   1.00   12.00    --  106.43 -15.00  90.00   97
 17  \w     90.00 117.00   1.00   12.00    --  106.43  30.00 120.00   27
 18  \w    124.00 177.00   1.00   12.00    --  106.43  30.00 120.00   53
 19  \w     64.00 113.00   1.00   12.00    --  106.43-125.00   0.00   49
 20  \w     34.00 132.00   1.00   12.00    --  106.43 -77.00-180.00   98
 21  \w     33.00  90.00   1.00   12.00    --  106.43 -30.00  30.00   57
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Atlas 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      -0.0736575000
_diffrn_orient_matrix_UB_12      0.0161103000
_diffrn_orient_matrix_UB_13      0.0526704000
_diffrn_orient_matrix_UB_21      -0.1167323000
_diffrn_orient_matrix_UB_22      -0.0559551000
_diffrn_orient_matrix_UB_23      -0.0573805000
_diffrn_orient_matrix_UB_31      -0.0027016000
_diffrn_orient_matrix_UB_32      -0.0969166000
_diffrn_orient_matrix_UB_33      0.0150455000
_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  0.0228
_diffrn_reflns_av_unetI/netI     0.0288
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            26597
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.625
_diffrn_reflns_theta_min         3.243
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    2.191
_exptl_absorpt_correction_T_max  0.799
_exptl_absorpt_correction_T_min  0.497
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.196
_exptl_crystal_description       block
_exptl_crystal_F_000             1292
_exptl_crystal_size_max          0.475
_exptl_crystal_size_mid          0.294
_exptl_crystal_size_min          0.139
_refine_diff_density_max         0.282
_refine_diff_density_min         -0.432
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     803
_refine_ls_number_reflns         13303
_refine_ls_number_restraints     276
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0408
_refine_ls_R_factor_gt           0.0395
_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^)+(0.0614P)^2^+0.8740P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1082
_refine_ls_wR_factor_ref         0.1095
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12829
_reflns_number_total             13303
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           13
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_original_cell_volume        3353.35(14)
_cod_database_code               1571580
_nottingham_internal_coll_name   FEYLLO
_nottingham_internal_coll_number 17907
_nottingham_internal_coll_client YL/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '12.00, 3.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pcxyl12
_nottingham_internal_coll_date   07/09/2018
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVB, PL13110001'
_nottingham_internal_process_date 07/09/2018
_nottingham_internal_process_user pcxyl12
_nottingham_internal_solution_date 14/12/2023
_nottingham_internal_solution_user pczntc
_nottingham_internal_refinement_date 14/12/2023
_nottingham_internal_refinement_user pczntc/pczspa
_nottingham_internal_self_archive_date 14/12/2023
_nottingham_internal_self_validation_date 14/12/2023
_nottingham_internal_self_validation_user pczntc
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C83 H64 O4 Fe'
_chemical_oxdiff_usercomment
'FEYLLO  GVB-1590 IN FOMBLIN FILM ON MICROMOUNT FOR HMH/NRC'
_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. Shared sites
{O1A, O1B}
3. Restrained distances
 C4A-C3A = C4B-C3B
 1.56 with sigma of 0.02
 C3A-C2A = C3B-C2B
 1.53 with sigma of 0.02
 C6A-C11 \\sim C6B-C41
 with sigma of 0.02
 C41-C3A \\sim C3B-C11
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O1A \\sim C2A \\sim C3A \\sim C4A \\sim O5A \\sim C6A \\sim O1B \\sim C2B \\sim
C3B \\sim C4B \\sim O5B \\sim C6B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(O1A) = Uanis(O1B)
5. Rigid body (RIGU) restrains
 O1A, C2A, C3A, C4A, O5A, C6A, O1B, C2B, C3B, C4B, O5B, C6B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{O1A, C2A, C3A, C4A, O5A, C6A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1B, C2B, C3B, C4B, O5B, C6B}
7. Others
 Sof(O1B)=Sof(C2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(O5B)=Sof(C6B)=1-FVAR(1)
 Sof(O1A)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(O5A)=Sof(C6A)=FVAR(1)
8.a Ternary CH refined with riding coordinates:
 C3A(H3A), C3B(H3B)
8.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C23(H23), C25(H25), C33(H33), C35(H35),
 C43(H43), C44(H44), C45(H45), C53(H53), C55(H55), C63(H63), C65(H65), C73(H73),
  C74(H74), C75(H75), C83(H83), C85(H85), C93(H93), C95(H95)
8.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C57(H57A,H57B,H57C), C58(H58A,
 H58B,H58C), C59(H59A,H59B,H59C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C),
 C69(H69A,H69B,H69C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C89(H89A,H89B,
 H89C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 101 electrons were 
found in a volume of 472\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[C6H14] per Asymmetric Unit 
which account for 100 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              3843
_shelx_fab_checksum              56108
_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 1.494
_oxdiff_exptl_absorpt_empirical_full_min 0.586