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_1571577
_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         'C52 H50 O2'
_chemical_formula_sum            'C52 H50 O2'
_chemical_formula_weight         706.92
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_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-alpha
(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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.8916(6)
_cell_length_b                   16.8787(6)
_cell_length_c                   13.6585(5)
_cell_measurement_reflns_used    35033
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.9580
_cell_measurement_theta_min      3.2170
_cell_volume                     4124.7(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-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -46.00 -19.00   0.50    4.00    --    0.00 -61.00 118.00   54
  2  \w     29.00  65.00   0.50    4.00    --    0.00  61.00-102.00   72
  3  \w     72.00 148.00   0.50   16.00    --   98.30  61.00-102.00  152
  4  \w     10.00 125.00   0.50   16.00    --   98.30 -61.00 118.00  230
  5  \w    -30.00  31.00   0.50    4.00    --    0.00 -82.00 -90.00  122
  6  \w    -88.00  22.00   0.50    4.00    --    0.00 -38.00-150.00  220
  7  \w      7.00  33.00   0.50    4.00    --    0.00 -82.00 150.00   52
  8  \w    -88.00 -39.00   0.50    4.00    --    0.00 -38.00 -60.00   98
  9  \w    -66.00 -39.00   0.50    4.00    --    0.00 -38.00 -30.00   54
 10  \w     18.00  45.00   0.50    4.00    --    0.00  19.00-180.00   54
 11  \w    -29.00  13.00   0.50    4.00    --    0.00  19.00-180.00   84
 12  \w    -23.00   4.00   0.50    4.00    --    0.00 -82.00 150.00   54
 13  \w    -32.00  31.00   0.50    4.00    --    0.00 -82.00  30.00  126
 14  \w    -61.00  23.00   0.50    4.00    --    0.00 -38.00  90.00  168
 15  \w    -31.00  22.00   0.50    4.00    --    0.00 -38.00 -60.00  106
 16  \w    -13.00  22.00   0.50    4.00    --    0.00 -38.00 -30.00   70
 17  \w    -26.00  33.00   0.50    4.00    --    0.00 -82.00 -60.00  118
 18  \w    -35.00  31.00   0.50    4.00    --    0.00 -77.00  60.00  132
 19  \w     72.00 134.00   0.50   16.00    --   98.30  59.00 112.21  124
 20  \w    153.00 187.00   0.50   16.00    --   98.30  67.00   4.92   68
 21  \w     72.00  98.00   0.50   16.00    --   98.30  60.00-124.60   52
 22  \w     70.00 149.00   0.50   16.00    --   98.30  67.00   4.92  158
 23  \w     72.00 165.00   0.50   16.00    --   98.30  61.00 -90.00  186
 24  \w     72.00 102.00   0.50   16.00    --   98.30  61.00 -30.00   60
 25  \w     45.00 131.00   0.50   16.00    --   98.30 -82.00 120.00  172
 26  \w    101.00 131.00   0.50   16.00    --   98.30  67.00  83.47   60
 27  \w     40.00 101.00   0.50   16.00    --   98.30 -82.00  90.00  122
 28  \w     72.00 188.00   0.50   16.00    --   98.30  61.00  30.00  232
 29  \w     70.00  96.00   0.50   16.00    --   98.30  67.00  83.47   52
 30  \w     76.00 108.00   0.50   16.00    --   98.30  45.00-120.00   64
 31  \w     72.00  98.00   0.50   16.00    --   98.30  61.00-113.63   52
 32  \w     73.00  98.00   0.50   16.00    --   98.30  61.00 120.00   50
 33  \w     69.00  95.00   0.50   16.00    --   98.30  70.00 157.93   52
 34  \w     10.00  36.00   0.50   16.00    --   98.30 -82.00-150.00   52
 35  \w    112.00 139.00   0.50   16.00    --   98.30  67.00  69.59   54
 36  \w    134.00 160.00   0.50   16.00    --   98.30  68.00 -56.61   52
 37  \w     72.00  98.00   0.50   16.00    --   98.30  60.00 103.66   52
 38  \w     70.00  96.00   0.50   16.00    --   98.30  68.00 -56.61   52
 39  \w     70.00  96.00   0.50   16.00    --   98.30  67.00  69.59   52
 40  \w    163.00 188.00   0.50   16.00    --   98.30  60.00  23.91   50
 41  \w     72.00  98.00   0.50   16.00    --   98.30  60.00  23.91   52
 42  \w     50.00 123.00   0.50   16.00    --   98.30 -82.00   0.00  146
 43  \w     69.00  95.00   0.50   16.00    --   98.30  72.00 -36.36   52
 44  \w    157.00 183.00   0.50   16.00    --   98.30  60.00 103.66   52
 45  \w     70.00  96.00   0.50   16.00    --   98.30  68.00-179.12   52
 46  \w    162.00 188.00   0.50   16.00    --   98.30  68.00-179.12   52
 47  \w     70.00 108.00   0.50   16.00    --   98.30  68.00 -49.90   76
 48  \w     69.00  95.00   0.50   16.00    --   98.30  70.00 -69.33   52
 49  \w     35.00 131.00   0.50   16.00    --   98.30 -82.00 -90.00  192
 50  \w     68.00  94.00   0.50   16.00    --   98.30  74.00-121.67   52
 51  \w    149.00 182.00   0.50   16.00    --   98.30  60.00 137.97   66
 52  \w     70.00  96.00   0.50   16.00    --   98.30  67.00  59.61   52
 53  \w     72.00  99.00   0.50   16.00    --   98.30  61.00-150.00   54
 54  \w     71.00 181.00   0.50   16.00    --   98.30  64.00 155.91  220
 55  \w     71.00  97.00   0.50   16.00    --   98.30  64.00 -76.99   52
 56  \w     71.00 187.00   0.50   16.00    --   98.30  64.00 -71.54  232
 57  \w     39.00 131.00   0.50   16.00    --   98.30 -82.00-150.00  184
 58  \w     74.00 180.00   0.50   16.00    --   98.30  53.00  -4.16  212
 59  \w     72.00  98.00   0.50   16.00    --   98.30  60.00  -0.88   52
 60  \w     72.00  99.00   0.50   16.00    --   98.30  59.00-156.56   54
 61  \w     69.00  94.00   0.50   16.00    --   98.30  74.00  27.98   50
 62  \w     73.00  99.00   0.50   16.00    --   98.30  57.00  46.52   52
 63  \w     72.00 117.00   0.50   16.00    --   98.30  61.00 150.00   90
 64  \w    122.00 148.00   0.50   16.00    --   98.30  61.00 150.00   52
 65  \w     72.00  98.00   0.50   16.00    --   98.30  62.00 141.52   52
 66  \w     73.00  99.00   0.50   16.00    --   98.30  56.00  64.84   52
 67  \w    138.00 188.00   0.50   16.00    --   98.30  59.00 112.21  100
 68  \w     72.00  98.00   0.50   16.00    --   98.30  60.00 137.97   52
 69  \w     72.00 187.00   0.50   16.00    --   98.30  61.00-180.00  230
 70  \w     75.00 188.00   0.50   16.00    --   98.30  36.00  86.97  226
 71  \w     13.00  39.00   0.50   16.00    --   98.30 -82.00 120.00   52
 72  \w     69.00  95.00   0.50   16.00    --   98.30  72.00-160.05   52
 73  \w    116.00 180.00   0.50   16.00    --   98.30  72.00-160.05  128
 74  \w     10.00 132.00   0.50   16.00    --   98.30 -82.00 -60.00  244
;
_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      0.0625351000
_diffrn_orient_matrix_UB_12      0.0065039000
_diffrn_orient_matrix_UB_13      -0.0776969000
_diffrn_orient_matrix_UB_21      0.0077450000
_diffrn_orient_matrix_UB_22      0.0895667000
_diffrn_orient_matrix_UB_23      0.0221568000
_diffrn_orient_matrix_UB_31      0.0592458000
_diffrn_orient_matrix_UB_32      -0.0186070000
_diffrn_orient_matrix_UB_33      0.0792064000
_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  0.0613
_diffrn_reflns_av_unetI/netI     0.0411
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            38007
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.066
_diffrn_reflns_theta_max         67.066
_diffrn_reflns_theta_min         3.600
_diffrn_source                   'rotating anode'
_diffrn_source_type              'MicroMax 007 HF'
_exptl_absorpt_coefficient_mu    0.515
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.842
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.138
_exptl_crystal_description       plate
_exptl_crystal_F_000             1512
_exptl_crystal_size_max          0.126
_exptl_crystal_size_mid          0.109
_exptl_crystal_size_min          0.052
_refine_diff_density_max         0.223
_refine_diff_density_min         -0.171
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 2661 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     498
_refine_ls_number_reflns         7223
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0487
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1285
_refine_ls_wR_factor_ref         0.1348
_reflns_Friedel_coverage         0.879
_reflns_Friedel_fraction_full    0.963
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                6353
_reflns_number_total             7223
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           2Mes_nosolv2
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_database_code               1571577
_nottingham_internal_coll_name   FENCLN
_nottingham_internal_coll_number 19411
_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   01/04/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'XtalLAB PRO, A00000876'
_nottingham_internal_process_date 06/04/2023
_nottingham_internal_process_user pczntc
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C52 H50 O2'
_chemical_oxdiff_usercomment
'FENCLN #19411 MM-899 NTC/DLK fomblin oil on micromount'
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Me refined with riding coordinates:
 C51(H51A,H51B,H51C)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C13(H13), C15(H15), C22(H22), C24(H24), C31(H31),
 C32(H32), C33(H33), C37(H37), C39(H39), C46(H46), C48(H48)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C)
;
_shelx_res_checksum              64392
_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 2.007
_oxdiff_exptl_absorpt_empirical_full_min 0.624