Cyclophane Molecules Exhibiting Thermally Activated Delayed Fluorescence: Linking Donor Units to Influence Molecular Conformation
Hempe, Matthias; Harrison, Alastair K.; Ward, Jonathan S.; Batsanov, Andrei S.; Fox, Mark A.; Dias, Fernando B.; Bryce, Martin R.; The Journal of Organic Chemistry  (2020) –; doi:10.1021/acs.joc.0c02174

data_4038931
_publ_section_title
;
 Cyclophane Molecules Exhibiting Thermally Activated Delayed Fluorescence:
 Linking Donor Units to Influence Molecular Conformation
;
_journal_name_full               'The Journal of Organic Chemistry'
_journal_paper_doi               10.1021/acs.joc.0c02174
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C46 H32 N2 O4 S3, C3 H6 O'
_chemical_formula_sum            'C49 H38 N2 O5 S3'
_chemical_formula_weight         830.99
_chemical_melting_point          593
_space_group_crystal_system      orthorhombic
_space_group_IT_number           26
_space_group_name_Hall           'P 2c -2'
_space_group_name_H-M_alt        'P m c 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-11-11
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.10.31 svn.r3677 for OlexSys, GUI svn.r5972)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.974(2)
_cell_length_b                   7.3487(7)
_cell_length_c                   22.763(2)
_cell_measurement_reflns_used    9953
_cell_measurement_temperature    120
_cell_measurement_theta_max      26.40
_cell_measurement_theta_min      2.90
_cell_volume                     4010.3(6)
_computing_cell_refinement       'SAINT v8.38A (Bruker, 2017)'
_computing_data_collection       'APEX3 v.2016.1-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.38A (Bruker, 2017)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 multi-CPU (Sheldrick, 2015a)'
_computing_structure_solution    'ShelXT 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_temperature      120
_diffrn_detector                 'Bruker PHOTON 100 CMOS'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS sensor'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       '3-circle area detector diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'focusing mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0834
_diffrn_reflns_av_unetI/netI     0.0632
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            50650
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.468
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\mS microsource'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.238
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8488
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.
wR2(int) was 0.1454 before and 0.0742 after correction.
The Ratio of minimum to maximum transmission is 0.8488.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description       plate
_exptl_crystal_F_000             1736
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.296
_exptl_crystal_size_min          0.106
_refine_diff_density_max         1.528
_refine_diff_density_min         -0.891
_refine_diff_density_rms         0.140
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.5(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     508
_refine_ls_number_reflns         7267
_refine_ls_number_restraints     365
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.1254
_refine_ls_R_factor_gt           0.1015
_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^)+(0.1588P)^2^+13.8084P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2622
_refine_ls_wR_factor_ref         0.2804
_reflns_Friedel_coverage         0.944
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                5761
_reflns_number_total             7267
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            2b.cif
_cod_data_source_block           2b_18s476
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               4038931
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.915
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5(2)
 0.5(2)
2. 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
3. Restrained distances
 O6A-C45 = O6A-C46A = O6B-C46B
 1.4 with sigma of 0.02
 O6B_$1-C46B_$1 \\sim O6A-C46A \\sim O6B_$1-C45 \\sim O6A-C45
 with sigma of 0.02
 O3A-C19A \\sim O3B-C19B \\sim O3B-C20B \\sim O3A-C20A
 with sigma of 0.02
 C16B-C15B \\sim C16A-C15A
 with sigma of 0.02
 C18A-C17A \\sim C18B-C17B
 with sigma of 0.02
 C19B-C16B \\sim C19A-C16A
 with sigma of 0.02
 C17B-C16B \\sim C17A-C16A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uiso(C17A) = Uiso(C17B)
Uanis(O3B) = Uanis(O3A)
Uiso(C15B) = Uiso(C15A)
Uiso(C16B) = Uiso(C16A)
Uiso(C18B) = Uiso(C18A)
Uiso(O6B) = Uiso(O6A)
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. Others
 Fixed Sof: O3A(0.5) O3B(0.5) C15A(0.5) H15A(0.5) C15B(0.5) H15B(0.5)
 C16A(0.5) C16B(0.5) C17A(0.5) H17A(0.5) C17B(0.5) H17B(0.5) C18A(0.5)
 H18A(0.5) C18B(0.5) H18B(0.5) C19A(0.5) H19A(0.5) H19B(0.5) C19B(0.5)
 H19C(0.5) H19D(0.5) C20A(0.5) H20A(0.5) H20B(0.5) C20B(0.5) H20C(0.5)
 H20D(0.5) C21(0.5) C22(0.5) H22(0.5) C23(0.5) C24(0.5) H24(0.5) C25(0.5)
 H25(0.5) C26(0.5) H26(0.5) O6A(0.5) O6B(0.5) C46A(0.5) H46A(0.5) H46B(0.5)
 C46B(0.5) H46C(0.5) H46D(0.5) C47(0.5) C48(0.5) H48(0.5) C49(0.5) C50(0.5)
 H50(0.5) C51(0.5) H51(0.5) C52(0.5) H52(0.5)
7.a Riding coordinates:
 C2(H2), C3(H3), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12), C15A(H15A),
 C15B(H15B), C17A(H17A), C17B(H17B), C18A(H18A), C18B(H18B), C19A(H19A,H19B),
 C19B(H19C,H19D), C20A(H20A,H20B), C20B(H20C,H20D), C22(H22), C24(H24),
 C25(H25), C26(H26), C28(H28), C29(H29), C31(H31), C35(H35), C36(H36), C37(H37),
  C38(H38), C45(H45A,H45B), C46A(H46A,H46B), C46B(H46C,H46D), C48(H48),
 C50(H50), C51(H51), C52(H52), C54(H54A,H54B,H54C), C56(H56A,H56B,H56C)
7.b Aromatic/amide H refined with riding coordinates:
 C41(H41), C43(H43), C44(H44)
7.c Fitted hexagon refined as free rotating group:
 C21(C22,C23,C24,C25,C26), C47(C48,C49,C50,C51,C52)
;
_shelx_res_checksum              50700
_shelx_hkl_checksum              33624