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_1571571
_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, C3 H3'
_chemical_formula_sum            'C55 H53 O2'
_chemical_formula_weight         745.97
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-06-05
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.89460(10)
_cell_length_b                   20.08990(10)
_cell_length_c                   23.55470(10)
_cell_measurement_reflns_used    98077
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      75.3070
_cell_measurement_theta_min      3.2920
_cell_volume                     8467.93(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      N2
_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 1.000
_diffrn_measured_fraction_theta_max 0.996
_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     45.00  85.00   0.50    0.50    --    0.00  57.00-120.00   80
  2  \w     50.00  89.00   0.50    0.50    --    0.00  38.00 -60.00   78
  3  \w    -18.00  31.00   0.50    0.50    --    0.00 -77.00-150.00   98
  4  \w    -33.00  33.00   0.50    0.50    --    0.00 -82.00  60.00  132
  5  \w    -25.00  49.00   0.50    0.50    --    0.00  57.00-180.00  148
  6  \w    -22.00  61.00   0.50    0.50    --    0.00  38.00  90.00  166
  7  \w    -23.00  15.00   0.50    0.50    --    0.00  38.00 -60.00   76
  8  \w    -25.00  88.00   0.50    0.50    --    0.00  57.00 -30.00  226
  9  \w    -25.00  43.00   0.50    0.50    --    0.00  57.00-120.00  136
 10  \w     -1.00  31.00   0.50    0.50    --    0.00 -77.00 -60.00   64
 11  \w    -38.00 -12.00   0.50    0.50    --    0.00 -77.00 -60.00   52
 12  \w     58.00  87.00   0.50    0.50    --    0.00  57.00-180.00   58
 13  \w    114.00 186.00   0.50    2.00    --   97.40  75.00 -22.82  144
 14  \w     66.00  91.00   0.50    2.00    --   97.40  75.00 -22.82   50
 15  \w     69.00 122.00   0.50    2.00    --   97.40  67.00 124.90  106
 16  \w     68.00  94.00   0.50    2.00    --   97.40  73.00-130.66   52
 17  \w     69.00  95.00   0.50    2.00    --   97.40  66.00  26.54   52
 18  \w     68.00 180.00   0.50    2.00    --   97.40  71.00-117.43  224
 19  \w     68.00 184.00   0.50    2.00    --   97.40  72.00 126.62  232
 20  \w      9.00 130.00   0.50    2.00    --   97.40 -82.00 -30.00  242
 21  \w     69.00  95.00   0.50    2.00    --   97.40  69.00 109.98   52
 22  \w     70.00 185.00   0.50    2.00    --   97.40  64.00 -54.42  230
 23  \w     15.00  76.00   0.50    2.00    --   97.40 -82.00 -90.00  122
 24  \w     89.00 131.00   0.50    2.00    --   97.40 -82.00 -90.00   84
 25  \w     67.00  93.00   0.50    2.00    --   97.40 -82.00  90.00   52
 26  \w    103.00 130.00   0.50    2.00    --   97.40 -82.00  90.00   54
 27  \w     71.00  97.00   0.50    2.00    --   97.40  61.00 -90.00   52
 28  \w    116.00 155.00   0.50    2.00    --   97.40  69.00  -1.53   78
 29  \w     71.00  97.00   0.50    2.00    --   97.40  61.00  90.00   52
 30  \w     69.00  95.00   0.50    2.00    --   97.40  69.00  -1.53   52
 31  \w    148.00 183.00   0.50    2.00    --   97.40  72.00  98.40   70
 32  \w     68.00  93.00   0.50    2.00    --   97.40  70.00 -52.03   50
 33  \w     66.00  91.00   0.50    2.00    --   97.40  75.00-102.18   50
 34  \w    114.00 140.00   0.50    2.00    --   97.40  61.00-180.00   52
 35  \w     71.00  96.00   0.50    2.00    --   97.40  61.00-180.00   50
 36  \w     72.00 178.00   0.50    2.00    --   97.40  55.00 -66.99  212
 37  \w      9.00 129.00   0.50    2.00    --   97.40 -82.00  60.00  240
 38  \w     68.00  94.00   0.50    2.00    --   97.40  72.00  98.40   52
 39  \w      9.00 124.00   0.50    2.00    --   97.40 -82.00-120.00  230
 40  \w     71.00  96.00   0.50    2.00    --   97.40  61.00 -60.00   50
 41  \w     74.00 152.00   0.50    2.00    --   97.40  45.00  60.00  156
 42  \w     75.00 107.00   0.50    2.00    --   97.40  45.00   0.00   64
 43  \w     71.00  96.00   0.50    2.00    --   97.40  61.00-150.00   50
 44  \w     74.00 185.00   0.50    2.00    --   97.40  45.00 120.00  222
 45  \w     74.00 105.00   0.50    2.00    --   97.40  45.00  30.00   62
 46  \w     71.00 113.00   0.50    2.00    --   97.40  61.00  60.00   84
 47  \w     40.00 128.00   0.50    2.00    --   97.40 -82.00-180.00  176
 48  \w     73.00 123.00   0.50    2.00    --   97.40  30.00 120.00  100
 49  \w     71.00  96.00   0.50    2.00    --   97.40  61.00 -30.00   50
 50  \w      9.00 123.00   0.50    2.00    --   97.40 -61.00  60.00  228
 51  \w    123.00 178.00   0.50    2.00    --   97.40  73.00  55.20  110
 52  \w     67.00  92.00   0.50    2.00    --   97.40  73.00  55.20   50
 53  \w     71.00  97.00   0.50    2.00    --   97.40  61.00 150.00   52
 54  \w     68.00 167.00   0.50    2.00    --   97.40  70.00-132.48  198
 55  \w     69.00 126.00   0.50    2.00    --   97.40  67.00-147.54  114
 56  \w     71.00 186.00   0.50    2.00    --   97.40  59.00 164.00  230
 57  \w     70.00  95.00   0.50    2.00    --   97.40  64.00-171.98   50
;
_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      -0.0244777000
_diffrn_orient_matrix_UB_12      -0.0236178000
_diffrn_orient_matrix_UB_13      -0.0593828000
_diffrn_orient_matrix_UB_21      -0.0202204000
_diffrn_orient_matrix_UB_22      -0.0686937000
_diffrn_orient_matrix_UB_23      0.0247007000
_diffrn_orient_matrix_UB_31      -0.0800062000
_diffrn_orient_matrix_UB_32      0.0245840000
_diffrn_orient_matrix_UB_33      0.0119248000
_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  0.0415
_diffrn_reflns_av_unetI/netI     0.0132
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            202923
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.872
_diffrn_reflns_theta_min         3.753
_diffrn_source                   'rotating anode'
_diffrn_source_type              'MicroMax 007 HF'
_exptl_absorpt_coefficient_mu    0.528
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.547
_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    1.170
_exptl_crystal_description       tablet
_exptl_crystal_F_000             3192
_exptl_crystal_size_max          0.344
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.049
_refine_diff_density_max         0.731
_refine_diff_density_min         -0.432
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     526
_refine_ls_number_reflns         8791
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0495
_refine_ls_R_factor_gt           0.0475
_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^)+(0.0524P)^2^+3.7834P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1217
_refine_ls_wR_factor_ref         0.1232
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8297
_reflns_number_total             8791
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01286k15.cif
_cod_data_source_block           2Mes_C6H6
_cod_depositor_comments
'Adding full bibliography for 1571567--1571581.cif.'
_cod_database_code               1571571
_nottingham_internal_coll_name   FENCLR
_nottingham_internal_coll_number 19437
_nottingham_internal_coll_client NTC/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '0.50, 2.00'
_nottingham_internal_coll_frame_width 0.50
_nottingham_internal_coll_user   pczntc
_nottingham_internal_coll_date   02/06/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'XtalLAB PRO, A00000876'
_nottingham_internal_process_date 05/06/2023
_nottingham_internal_process_user pczntc
_nottingham_internal_solution_date 05/06/2023
_nottingham_internal_solution_user pczntc
_nottingham_internal_refinement_date 05/06/2023
_nottingham_internal_refinement_user pczntc
_nottingham_internal_self_archive_date 05/06/2023
_nottingham_internal_self_validation_date 05/06/2023
_nottingham_internal_self_validation_user pczntc
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H52 O2'
_chemical_oxdiff_usercomment
'FENCLR # MM-912 for NTC/DLK fomblin oil on micromount'
_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. Rigid body (RIGU) restrains
 C54, C53, H53, H54, C55, H55
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a 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), C53(H53), C54(H54),
  C55(H55)
3.b 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), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C)
;
_shelx_res_checksum              55264
_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 1.296
_oxdiff_exptl_absorpt_empirical_full_min 0.869