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_1571579
_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 H108 Fe2 O12, 4(C6 H12), 0.247(O)'
_chemical_formula_sum            'C124 H156 Fe2 O12.25'
_chemical_formula_weight         1954.18
_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   mixed
_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                81.108(2)
_cell_angle_beta                 70.509(2)
_cell_angle_gamma                70.199(2)
_cell_formula_units_Z            1
_cell_length_a                   12.9566(2)
_cell_length_b                   13.7268(3)
_cell_length_c                   17.6044(4)
_cell_measurement_reflns_used    16851
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.8290
_cell_measurement_theta_min      3.3960
_cell_volume                     2774.00(11)
_computing_cell_refinement       'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 42.91a 64-bit (release 17-04-2023))'
_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(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 0.997
_diffrn_measured_fraction_theta_max 0.979
_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     24.00  60.00   0.50   15.00    --    0.00  42.00   9.00   72
  2  \w    -21.00  19.00   0.50   15.00    --    0.00  42.00   9.00   80
  3  \w     44.00  86.00   0.50   50.00    --   98.30 -42.00-142.00   84
  4  \w     75.00 144.00   0.50   50.00    --   98.30  42.00   9.00  138
  5  \w    -23.00  41.00   0.50   15.00    --    0.00  38.00 120.00  128
  6  \w    -89.00 -25.00   0.50   15.00    --    0.00 -57.00  90.00  128
  7  \w    -23.00  51.00   0.50   15.00    --    0.00  38.00 -60.00  148
  8  \w    -80.00 -54.00   0.50   15.00    --    0.00 -42.00-142.00   52
  9  \w    -27.00  26.00   0.50   15.00    --    0.00 -82.00  90.00  106
 10  \w     49.00  87.00   0.50   15.00    --    0.00  38.00 120.00   76
 11  \w    -23.00  79.00   0.50   15.00    --    0.00  38.00-150.00  204
 12  \w    -32.00  26.00   0.50   15.00    --    0.00 -82.00   0.00  116
 13  \w     64.00  89.00   0.50   15.00    --    0.00  42.00   9.00   50
 14  \w    -18.00  31.00   0.50   15.00    --    0.00 -82.00-150.00   98
 15  \w     -5.00  25.00   0.50   15.00    --    0.00 -57.00  90.00   60
 16  \w    -25.00  10.00   0.50   15.00    --    0.00 -42.00-142.00   70
 17  \w     72.00  98.00   0.50   50.00    --   98.30  59.00 -32.95   52
 18  \w     77.00 188.00   0.50   50.00    --   98.30  45.00 -90.00  222
 19  \w    124.00 187.00   0.50   50.00    --   98.30  68.00 130.11  126
 20  \w    107.00 143.00   0.50   50.00    --   98.30  61.00  90.00   72
 21  \w     68.00 107.00   0.50   50.00    --   98.30  73.00  -3.60   78
 22  \w     72.00  98.00   0.50   50.00    --   98.30  61.00  90.00   52
 23  \w     70.00  96.00   0.50   50.00    --   98.30  68.00 130.11   52
 24  \w    161.00 188.00   0.50   50.00    --   98.30  61.00 -90.00   54
 25  \w     72.00  97.00   0.50   50.00    --   98.30  61.00 -90.00   50
 26  \w      9.00 131.00   0.50   50.00    --   98.30 -82.00-120.00  244
 27  \w    144.00 188.00   0.50   50.00    --   98.30  45.00-180.00   88
 28  \w    136.00 176.00   0.50   50.00    --   98.30  73.00  -3.60   80
 29  \w     74.00 104.00   0.50   50.00    --   98.30  30.00-120.00   60
 30  \w     72.00  97.00   0.50   50.00    --   98.30  61.00-150.00   50
 31  \w    142.00 168.00   0.50   50.00    --   98.30  61.00-150.00   52
 32  \w     72.00  97.00   0.50   50.00    --   98.30  61.00 150.00   50
 33  \w    123.00 188.00   0.50   50.00    --   98.30  61.00 150.00  130
 34  \w     58.00 120.00   0.50   50.00    --   98.30 -82.00 -30.00  124
 35  \w      9.00  35.00   0.50   50.00    --   98.30 -82.00 -30.00   52
 36  \w    161.00 187.00   0.50   50.00    --   98.30  61.00 -60.00   52
 37  \w    156.00 184.00   0.50   50.00    --   98.30  70.00-143.71   56
 38  \w     72.00  97.00   0.50   50.00    --   98.30  61.00   0.00   50
 39  \w     72.00  97.00   0.50   50.00    --   98.30  61.00 120.00   50
 40  \w    139.00 183.00   0.50   50.00    --   98.30  45.00 -60.00   88
 41  \w     76.00 102.00   0.50   50.00    --   98.30  45.00 -60.00   52
 42  \w     75.00 125.00   0.50   50.00    --   98.30  45.00  60.00  100
 43  \w     76.00 185.00   0.50   50.00    --   98.30  45.00  90.00  218
 44  \w     70.00  95.00   0.50   50.00    --   98.30  68.00 178.88   50
 45  \w     72.00 102.00   0.50   50.00    --   98.30  61.00 -30.00   60
 46  \w     72.00 121.00   0.50   50.00    --   98.30  61.00-120.00   98
 47  \w    124.00 187.00   0.50   50.00    --   98.30  61.00-120.00  126
 48  \w     77.00 114.00   0.50   50.00    --   98.30  45.00 -30.00   74
 49  \w    144.00 188.00   0.50   50.00    --   98.30  45.00 -30.00   88
 50  \w     76.00 108.00   0.50   50.00    --   98.30  45.00-180.00   64
 51  \w    102.00 127.00   0.50   50.00    --   98.30  61.00  60.00   50
 52  \w     72.00  98.00   0.50   50.00    --   98.30  61.00 -60.00   52
 53  \w     70.00  95.00   0.50   50.00    --   98.30  66.00  21.06   50
 54  \w     43.00 132.00   0.50   50.00    --   98.30 -82.00 150.00  178
 55  \w     71.00  97.00   0.50   50.00    --   98.30  68.00-122.18   52
 56  \w     74.00 153.00   0.50   50.00    --   98.30  49.00 123.22  158
 57  \w     38.00 124.00   0.50   50.00    --   98.30 -82.00  90.00  172
 58  \w     72.00  98.00   0.50   50.00    --   98.30  61.00  60.00   52
 59  \w    161.00 187.00   0.50   50.00    --   98.30  61.00-180.00   52
 60  \w     72.00  98.00   0.50   50.00    --   98.30  61.00-180.00   52
 61  \w    159.00 184.00   0.50   50.00    --   98.30  59.00 -32.95   50
 62  \w     42.00 125.00   0.50   50.00    --   98.30 -82.00  60.00  166
 63  \w     12.00 112.00   0.50   50.00    --   98.30 -61.00-120.00  200
 64  \w     69.00 116.00   0.50   50.00    --   98.30  70.00-143.71   94
;
_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      0.0137135000
_diffrn_orient_matrix_UB_12      0.1090999000
_diffrn_orient_matrix_UB_13      -0.0197515000
_diffrn_orient_matrix_UB_21      -0.1284079000
_diffrn_orient_matrix_UB_22      0.0480537000
_diffrn_orient_matrix_UB_23      0.0453461000
_diffrn_orient_matrix_UB_31      0.0300585000
_diffrn_orient_matrix_UB_32      -0.0069124000
_diffrn_orient_matrix_UB_33      0.0786760000
_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  0.0440
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            62731
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.776
_diffrn_reflns_theta_min         2.665
_diffrn_source                   'rotating anode'
_diffrn_source_type              'MicroMax 007 HF'
_exptl_absorpt_coefficient_mu    2.559
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.811
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.170
_exptl_crystal_description       plate
_exptl_crystal_F_000             1050
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.538
_refine_diff_density_min         -0.588
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     756
_refine_ls_number_reflns         11311
_refine_ls_number_restraints     920
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0726P)^2^+1.1155P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1318
_refine_ls_wR_factor_ref         0.1356
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10043
_reflns_number_total             11311
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           3Mes_H2O_4
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_original_cell_volume        2774.01(11)
_cod_database_code               1571579
_nottingham_internal_coll_name   FENCLT
_nottingham_internal_coll_number 19496
_nottingham_internal_coll_client NTC/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '15.00, 50.00'
_nottingham_internal_coll_frame_width 0.50
_nottingham_internal_coll_user   pczntc
_nottingham_internal_coll_date   25/07/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'XtalLAB PRO, A00000876'
_nottingham_internal_process_date 01/08/2023
_nottingham_internal_process_user pczntc
_nottingham_internal_solution_date 02/08/2023
_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 H108 O12 Fe2'
_chemical_oxdiff_usercomment
'FENCLT #19496 MM-936 NTC/DLK fomblin oil on micromount'
_shelx_estimated_absorpt_t_max   0.883
_shelx_estimated_absorpt_t_min   0.784
_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, All O(H,H) groups
2. Restrained distances
 C61-C60 \\sim C61A-C60A
 with sigma of 0.02
 C54-C55 \\sim C54A-C55A
 with sigma of 0.02
 C55-C56 \\sim C55A-C56A
 with sigma of 0.02
 C61-C62 \\sim C61A-C62A
 with sigma of 0.02
 C57-C58 \\sim C57A-C58A
 with sigma of 0.02
 C51-C55 \\sim C51A-C55A
 with sigma of 0.04
 C53-C55 \\sim C53A-C55A
 with sigma of 0.04
 C57-C62 \\sim C57A-C62A
 with sigma of 0.02
 C58-C59 \\sim C58A-C59A
 with sigma of 0.02
 C60-C59 \\sim C60A-C59A
 with sigma of 0.02
 C61-C57 \\sim C61A-C57A
 with sigma of 0.04
 C61-C59 \\sim C61A-C59A
 with sigma of 0.04
 C57-C59 \\sim C57A-C59A
 with sigma of 0.04
 C58-C60 \\sim C58A-C60A
 with sigma of 0.04
 C58-C62 \\sim C58A-C62A
 with sigma of 0.04
 C60-C62 \\sim C60A-C62A
 with sigma of 0.04
 C51-C52 \\sim C51A-C52A
 with sigma of 0.02
 C51-C56 \\sim C51A-C56A
 with sigma of 0.02
 C54-C53 \\sim C54A-C53A
 with sigma of 0.02
 C53-C52 \\sim C53A-C52A
 with sigma of 0.02
 C51-C53 \\sim C51A-C53A
 with sigma of 0.04
 C54-C52 \\sim C54A-C52A
 with sigma of 0.04
 C54-C56 \\sim C54A-C56A
 with sigma of 0.04
 C52-C56 \\sim C52A-C56A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C57A \\sim C61 \\sim H61A \\sim H61B \\sim C60 \\sim C62 \\sim H60A \\sim H60B
\\sim C59 \\sim C57 \\sim H62A \\sim H62B \\sim H58C \\sim H60D \\sim H59A
\\sim C59A \\sim C58A \\sim C60A \\sim H59C \\sim C58 \\sim H59B \\sim H57A
\\sim H57B \\sim C62A \\sim C61A \\sim H61D \\sim H57C \\sim H62D \\sim H57D
\\sim H59D \\sim H58D \\sim H60C \\sim H58A \\sim H58B \\sim H62C \\sim H61C:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C55 \\sim C51 \\sim H51A \\sim H51B \\sim C52 \\sim C56 \\sim C53 \\sim H52A
\\sim H52B \\sim H56A \\sim H56B \\sim C54 \\sim H53A \\sim H53B \\sim H55A
\\sim H55B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
4. Rigid body (RIGU) restrains
 C55, C51, C52, C56, C53, C51A, C52A, C56A, C53A, C54, C55A, C54A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C59A, C62A, C61A, C57A, C60A, C58A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C59, C61, C60, C62, C57, C58
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C62A)=Sof(H62C)=Sof(H62D)=Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C60A)=
 Sof(H60C)=Sof(H60D)=Sof(C59A)=Sof(H59C)=Sof(H59D)=Sof(C58A)=Sof(H58C)=
 Sof(H58D)=Sof(C57A)=Sof(H57C)=Sof(H57D)=1-FVAR(1)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=
 Sof(H58B)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C62)=
 Sof(H62A)=Sof(H62B)=FVAR(1)
 Sof(C54A)=Sof(H54C)=Sof(H54D)=Sof(C51A)=Sof(H51C)=Sof(H51D)=Sof(C52A)=
 Sof(H52C)=Sof(H52D)=Sof(C56A)=Sof(H56C)=Sof(H56D)=Sof(C53A)=Sof(H53C)=
 Sof(H53D)=Sof(C55A)=Sof(H55C)=Sof(H55D)=1-FVAR(2)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C53)=Sof(H53A)=
 Sof(H53B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=
 Sof(H56A)=Sof(H56B)=FVAR(2)
6.a Rotating group:
 O5(H5A,H5B), O6(H6A,H6B)
6.b Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C51(H51A,H51B), C57(H57A,H57B), C54(H54A,H54B), C58(H58A,
 H58B), C60(H60A,H60B), C53(H53A,H53B), C59(H59A,H59B), C62(H62A,H62B),
 C52(H52A,H52B), C55(H55A,H55B), C56(H56A,H56B), C62A(H62C,H62D), C61A(H61C,
 H61D), C60A(H60C,H60D), C59A(H59C,H59D), C58A(H58C,H58D), C57A(H57C,H57D),
 C54A(H54C,H54D), C51A(H51C,H51D), C52A(H52C,H52D), C56A(H56C,H56D), C53A(H53C,
 H53D), C55A(H55C,H55D)
6.c Aromatic/amide H refined with riding coordinates:
 C31(H31), C21(H21), C19(H19), C4(H4), C29(H29), C30(H30), C5(H5), C35(H35),
 C6(H6), C37(H37), C12(H12), C10(H10), C46(H46), C44(H44)
6.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C23(H23A,H23B,H23C), C16(H16A,H16B,H16C), C25(H25A,H25B,
 H25C), C41(H41A,H41B,H41C), C14(H14A,H14B,H14C), C50(H50A,H50B,H50C), C40(H40A,
 H40B,H40C), C24(H24A,H24B,H24C), C48(H48A,H48B,H48C), C15(H15A,H15B,H15C),
 C49(H49A,H49B,H49C)
;
_shelx_res_checksum              92316
_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 1.261
_oxdiff_exptl_absorpt_empirical_full_min 0.817