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_1571578
_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         'C101 H100 Fe2 O7, C51 H50 Fe O3, 0.75[C6H14]'
_chemical_formula_sum            'C156.5 H160.5 Fe3 O10'
_chemical_formula_weight         2368.89
_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                79.731(2)
_cell_angle_beta                 83.226(2)
_cell_angle_gamma                72.453(3)
_cell_formula_units_Z            2
_cell_length_a                   13.2353(3)
_cell_length_b                   13.8441(5)
_cell_length_c                   36.1863(7)
_cell_measurement_reflns_used    24699
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.5490
_cell_measurement_theta_min      3.4100
_cell_volume                     6206.1(3)
_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 0.985
_diffrn_measured_fraction_theta_max 0.985
_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    108.00 134.00   0.50   42.00    --  102.00  48.00 -53.00   52
  2  \w    146.00 175.00   0.50   42.00    --  102.00  48.00 -53.00   58
  3  \w     44.00  88.00   0.50   42.00    --  102.00 -48.00 157.00   88
  4  \w     63.00  93.00   0.50   42.00    --  102.00  48.00 -53.00   60
  5  \w      7.00  99.00   0.50    9.00    --   45.50  72.00 -42.38  184
  6  \w     15.00  63.00   0.50    9.00    --   45.50  71.00-115.07   96
  7  \w    -31.00  82.00   0.50    9.00    --   45.50 -82.00   0.00  226
  8  \w    -35.00  77.00   0.50    9.00    --   45.50 -48.00 157.00  224
  9  \w    -43.00  81.00   0.50    9.00    --   45.50 -57.00  30.00  248
 10  \w     13.00  92.00   0.50    9.00    --   45.50  72.00-160.50  158
 11  \w     95.00 129.00   0.50    9.00    --   45.50  72.00 105.39   68
 12  \w     10.00  82.00   0.50    9.00    --   45.50  72.00 105.39  144
 13  \w      6.00  59.00   0.50    9.00    --   45.50  48.00 -53.00  106
 14  \w      8.00 134.00   0.50    9.00    --   45.50  71.00  53.27  252
 15  \w      7.00 107.00   0.50    9.00    --   45.50  71.00 170.20  200
 16  \w      7.00 134.00   0.50    9.00    --   45.50  72.00 -12.11  254
 17  \w     66.00  92.00   0.50   42.00    --  102.00  62.00  45.57   52
 18  \w    111.00 190.00   0.50   42.00    --  102.00  71.00  90.67  158
 19  \w    104.00 157.00   0.50   42.00    --  102.00  74.00 178.96  106
 20  \w     63.00 106.00   0.50   42.00    --  102.00  71.00  90.67   86
 21  \w     65.00 185.00   0.50   42.00    --  102.00  61.00   0.00  240
 22  \w     62.00  87.00   0.50   42.00    --  102.00  74.00 178.96   50
 23  \w     65.00  96.00   0.50   42.00    --  102.00  61.00-120.00   62
 24  \w     64.00 160.00   0.50   42.00    --  102.00  68.00 -30.44  192
 25  \w     66.00 133.00   0.50   42.00    --  102.00  62.00  69.83  134
 26  \w     98.00 190.00   0.50   42.00    --  102.00  69.00  75.51  184
 27  \w     64.00 160.00   0.50   42.00    --  102.00  66.00 -92.41  192
 28  \w    163.00 191.00   0.50   42.00    --  102.00  66.00 -92.41   56
 29  \w     65.00 168.00   0.50   42.00    --  102.00  61.00 150.00  206
 30  \w     64.00  91.00   0.50   42.00    --  102.00  68.00 106.62   54
 31  \w     98.00 190.00   0.50   42.00    --  102.00  68.00 106.62  184
 32  \w     63.00  89.00   0.50   42.00    --  102.00  72.00   0.31   52
 33  \w    118.00 144.00   0.50   42.00    --  102.00  72.00   0.31   52
 34  \w     63.00 191.00   0.50   42.00    --  102.00  73.00 153.11  256
 35  \w    117.00 191.00   0.50   42.00    --  102.00  61.00 -60.00  148
 36  \w     64.00  90.00   0.50   42.00    --  102.00  69.00  75.51   52
 37  \w     62.00  88.00   0.50   42.00    --  102.00  74.00 115.23   52
 38  \w    151.00 177.00   0.50   42.00    --  102.00  66.00-146.97   52
 39  \w     65.00  91.00   0.50   42.00    --  102.00  61.00 -60.00   52
 40  \w    103.00 128.00   0.50   42.00    --  102.00  66.00-146.97   50
 41  \w     64.00  91.00   0.50   42.00    --  102.00  66.00-146.97   54
 42  \w     65.00  91.00   0.50   42.00    --  102.00  61.00  30.00   52
 43  \w     64.00 191.00   0.50   42.00    --  102.00  67.00-113.07  254
 44  \w     21.00  48.00   0.50   42.00    --  102.00 -82.00-150.00   54
 45  \w     52.00 138.00   0.50   42.00    --  102.00 -82.00-150.00  172
 46  \w    163.00 191.00   0.50   42.00    --  102.00  61.00 -30.00   56
 47  \w    102.00 129.00   0.50   42.00    --  102.00  61.00  60.00   54
 48  \w    137.00 180.00   0.50   42.00    --  102.00  62.00  69.83   86
 49  \w     66.00  93.00   0.50   42.00    --  102.00  61.00  60.00   54
 50  \w     65.00 130.00   0.50   42.00    --  102.00  61.00 -30.00  130
 51  \w     16.00  43.00   0.50   42.00    --  102.00 -82.00  60.00   54
 52  \w     52.00 138.00   0.50   42.00    --  102.00 -82.00  60.00  172
 53  \w    111.00 161.00   0.50   42.00    --  102.00  61.00-150.00  100
 54  \w     15.00  41.00   0.50   42.00    --  102.00 -82.00 -90.00   52
 55  \w     68.00 143.00   0.50   42.00    --  102.00 -82.00 -90.00  150
 56  \w     66.00  94.00   0.50   42.00    --  102.00  61.00-150.00   56
 57  \w     98.00 190.00   0.50   42.00    --  102.00  62.00  45.57  184
 58  \w    166.00 191.00   0.50   42.00    --  102.00  74.00 178.96   50
 59  \w     43.00 124.00   0.50   42.00    --  102.00 -82.00   0.00  162
 60  \w     14.00 119.00   0.50   42.00    --  102.00 -82.00  90.00  210
 61  \w     18.00  47.00   0.50   42.00    --  102.00 -82.00 150.00   58
 62  \w     67.00 134.00   0.50   42.00    --  102.00 -82.00 150.00  134
;
_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      -0.1103407000
_diffrn_orient_matrix_UB_12      -0.0101202000
_diffrn_orient_matrix_UB_13      0.0156606000
_diffrn_orient_matrix_UB_21      0.0521603000
_diffrn_orient_matrix_UB_22      -0.1085521000
_diffrn_orient_matrix_UB_23      0.0202556000
_diffrn_orient_matrix_UB_31      0.0088062000
_diffrn_orient_matrix_UB_32      0.0452983000
_diffrn_orient_matrix_UB_33      0.0350032000
_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  0.0880
_diffrn_reflns_av_unetI/netI     0.0576
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_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       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            116054
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         3.387
_diffrn_source                   'rotating anode'
_diffrn_source_type              'MicroMax 007 HF'
_exptl_absorpt_coefficient_mu    3.262
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.542
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       block
_exptl_crystal_F_000             2515
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.145
_exptl_crystal_size_min          0.122
_refine_diff_density_max         1.526
_refine_diff_density_min         -0.813
_refine_diff_density_rms         0.085
_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     1520
_refine_ls_number_reflns         21827
_refine_ls_number_restraints     2467
_refine_ls_restrained_S_all      0.991
_refine_ls_R_factor_all          0.1464
_refine_ls_R_factor_gt           0.1085
_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^)+(0.1521P)^2^+18.6050P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2951
_refine_ls_wR_factor_ref         0.3229
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14470
_reflns_number_total             21827
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           11_12
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_original_formula_sum        'C156.50 H160.50 Fe3 O10'
_cod_database_code               1571578
_nottingham_internal_coll_name   FENCLP
_nottingham_internal_coll_number 19435
_nottingham_internal_coll_client NTC/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '42.00, 9.00'
_nottingham_internal_coll_frame_width 0.50
_nottingham_internal_coll_user   pczntc
_nottingham_internal_coll_date   24/04/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'XtalLAB PRO, A00000876'
_nottingham_internal_process_date 27/04/2023
_nottingham_internal_process_user pczntc
_nottingham_internal_solution_date 27/04/2023
_nottingham_internal_solution_user pczntc
_nottingham_internal_refinement_date 03/08/2023
_nottingham_internal_refinement_user pczntc/pczspa
_nottingham_internal_validation_date 03/08/2023
_nottingham_internal_validation_user pczspa
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C52 H50 Fe O4'
_chemical_oxdiff_usercomment
'FENCLP #19435 MM-903 NTC/DLK fomblin oil on micromount'
_shelx_estimated_absorpt_t_max   0.692
_shelx_estimated_absorpt_t_min   0.617
_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. Restrained distances
 C129-C128
 1.5 with sigma of 0.01
 O3-O2 \\sim O4-O5 \\sim O7-O6 \\sim O10_$1-O9_$1
 with sigma of 0.02
3. Restrained planarity
 O9, C128, O10, C129
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(O9) \\sim Ueq, Uanis(O10) \\sim Ueq, Uanis(C128) \\sim Ueq, Uanis(C129)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Me refined with riding coordinates:
 C51(H51a,H51b,H51c), C100(H10d,H10e,H10f)
6.b Aromatic/amide H refined with riding coordinates:
 C45(H45), C47(H47), C13(H13), C86(H86), C5(H5), C70(H70), C11(H11), C88(H88),
 C55(H55), C32(H32), C72(H72), C80(H80), C57(H57), C56(H56), C7(H7), C6(H6),
 C82(H82), C38(H38), C95(H95), C61(H61), C31(H31), C30(H30), C97(H97), C63(H63),
  C81(H81), C20(H20), C36(H36), C22(H22), C114(H114), C112(H112), C137(H137),
 C139(H139), C106(H106), C108(H108), C146(H146), C107(H107), C148(H148),
 C133(H133), C131(H131), C123(H123), C121(H121), C132(H132)
6.c Idealised Me refined as rotating group:
 C90(H90a,H90b,H90c), C17(H17a,H17b,H17c), C50(H50a,H50b,H50c), C76(H76a,H76b,
 H76c), C16(H16a,H16b,H16c), C15(H15a,H15b,H15c), C49(H49a,H49b,H49c), C67(H67a,
 H67b,H67c), C91(H91a,H91b,H91c), C92(H92a,H92b,H92c), C74(H74a,H74b,H74c),
 C42(H42a,H42b,H42c), C75(H75a,H75b,H75c), C101(H10a,H10b,H10c), C40(H40a,H40b,
 H40c), C65(H65a,H65b,H65c), C24(H24a,H24b,H24c), C26(H26a,H26b,H26c), C99(H99a,
 H99b,H99c), C41(H41a,H41b,H41c), C117(H11a,H11b,H11c), C66(H66a,H66b,H66c),
 C142(H14a,H14b,H14c), C116(H11d,H11e,H11f), C118(H11g,H11h,H11i), C25(H25a,
 H25b,H25c), C143(H14d,H14e,H14f), C151(H15d,H15e,H15f), C152(H15g,H15h,H15i),
 C141(H14g,H14h,H14i), C126(H12a,H12b,H12c), C127(H12d,H12e,H12f), C150(H15j,
 H15k,H15l), C125(H12g,H12h,H12i)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              1198
_shelx_fab_checksum              60851
_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 2.133
_oxdiff_exptl_absorpt_empirical_full_min 0.434