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_4038935
_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_formula_moiety         'C46 H28 N2 O6 S3, 1.5(C H2 Cl2)'
_chemical_formula_sum            'C47.5 H31 Cl3 N2 O6 S3'
_chemical_formula_weight         928.27
_chemical_melting_point          601
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-11-25
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                93.0414(17)
_cell_angle_beta                 92.2764(15)
_cell_angle_gamma                105.0333(16)
_cell_formula_units_Z            2
_cell_length_a                   7.3272(2)
_cell_length_b                   13.9943(5)
_cell_length_c                   21.5754(8)
_cell_measurement_reflns_used    9896
_cell_measurement_temperature    120
_cell_measurement_theta_max      75.47
_cell_measurement_theta_min      3.75
_cell_volume                     2130.31(13)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'APEX3 v.2016.1-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2016/6 multi-CPU (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS 2013/1 (Sheldrick, 2008)'
_diffrn_ambient_temperature      120
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.941
_diffrn_measured_fraction_theta_max 0.879
_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           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0411
_diffrn_reflns_av_unetI/netI     0.0409
_diffrn_reflns_Laue_measured_fraction_full 0.941
_diffrn_reflns_Laue_measured_fraction_max 0.879
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            23375
_diffrn_reflns_point_group_measured_fraction_full 0.941
_diffrn_reflns_point_group_measured_fraction_max 0.879
_diffrn_reflns_theta_full        66.000
_diffrn_reflns_theta_max         75.589
_diffrn_reflns_theta_min         3.277
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\mS microsource'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.764
_exptl_absorpt_correction_T_max  0.9298
_exptl_absorpt_correction_T_min  0.6121
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
; SADABS-2014/5 (Krause et al., 2015) was used for absorption correction. wR2(int) was 
 0.0669 before and 0.0535 after correction. The Ratio of minimum to maximum 
 transmission is 0.6583. The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.447
_exptl_crystal_description       plate
_exptl_crystal_F_000             954
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.024
_refine_diff_density_max         1.087
_refine_diff_density_min         -0.630
_refine_diff_density_rms         0.068
_refine_ls_extinction_coef       0.00050(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     672
_refine_ls_number_reflns         7777
_refine_ls_number_restraints     529
_refine_ls_restrained_S_all      0.994
_refine_ls_R_factor_all          0.0796
_refine_ls_R_factor_gt           0.0566
_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^)+(0.0610P)^2^+3.8840P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1365
_refine_ls_wR_factor_ref         0.1536
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5978
_reflns_number_total             7777
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            2a.cif
_cod_data_source_block           2a_16s448
_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_original_formula_sum        'C47.50 H31 Cl3 N2 O6 S3'
_cod_database_code               4038935
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.886
_shelx_estimated_absorpt_t_min   0.831
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 O5B-C45B \\sim O5-C45
 with sigma of 0.02
 O6-C45 \\sim O6B-C45B
 with sigma of 0.02
 O5-C46 \\sim O5B-C46B
 with sigma of 0.02
 C28-C27 \\sim C28B-C27B
 with sigma of 0.02
 C29B-C28B \\sim C29-C28
 with sigma of 0.02
 C30-C29 \\sim C30B-C29B
 with sigma of 0.02
 S3B-C26B \\sim S3-C26
 with sigma of 0.02
 C27-C26 \\sim C27B-C26B
 with sigma of 0.02
 O3-C37 \\sim O3B-C37
 with sigma of 0.02
 C35B-C34B \\sim C35-C34
 with sigma of 0.02
 C36-C35 \\sim C36-C35B
 with sigma of 0.02
 C34-C33 \\sim C34B-C33B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O6) = Uanis(O6B)
Uanis(C42B) = Uanis(C42)
Uanis(S3) = Uanis(S3B)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C45, O6, O5, C41
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(S3B)=Sof(O3B)=Sof(O4B)=Sof(O5B)=Sof(O6B)=Sof(H36A)=Sof(H37C)=Sof(H37D)=
 Sof(C25B)=Sof(C26B)=Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(H28B)=Sof(C29B)=
 Sof(C30B)=Sof(H30B)=Sof(C32B)=Sof(C33B)=Sof(H33B)=Sof(C34B)=Sof(H34B)=
 Sof(C35B)=Sof(H35B)=Sof(C38B)=Sof(C41B)=Sof(C40B)=Sof(H40B)=Sof(C39B)=
 Sof(C44B)=Sof(H44B)=Sof(C43B)=Sof(H43B)=Sof(C42B)=Sof(H42B)=Sof(C45B)=
 Sof(C46B)=Sof(H46C)=Sof(H46D)=1-FVAR(1)
 Sof(S3)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(O6)=Sof(H36)=Sof(H37A)=Sof(H37B)=Sof(C25)=
 Sof(C26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(C30)=Sof(H30)=
 Sof(C32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=Sof(C38)=
 Sof(C41)=Sof(C40)=Sof(H40)=Sof(C39)=Sof(C44)=Sof(H44)=Sof(C43)=Sof(H43)=
 Sof(C42)=Sof(H42)=Sof(C45)=Sof(C46)=Sof(H46A)=Sof(H46B)=FVAR(1)
 Fixed Sof: Cl1(0.8) Cl2(0.67) Cl5(0.45) Cl6(0.45) Cl4(0.23) Cl3(0.15)
 Cl7(0.07) Cl8(0.1) C4S(0.45) H4SA(0.45) H4SB(0.45) C1S(0.67) H1SA(0.67)
 H1SB(0.67) C3S(0.08) H3SA(0.08) H3SB(0.08) C2S(0.15) H2SA(0.15) H2SB(0.15)
 Cl9(0.08)
6.a Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C37(H37C,H37D), C46(H46A,H46B), C46B(H46C,H46D), C4S(H4SA,
 H4SB), C1S(H1SA,H1SB), C2S(H2SA,H2SB)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C8(H8), C10(H10), C11(H11), C15(H15), C16(H16),
 C18(H18), C21(H21), C22(H22), C23(H23), C24(H24), C36(H36), C36(H36A),
 C27(H27), C28(H28), C30(H30), C33(H33), C34(H34), C35(H35), C40(H40), C44(H44),
  C43(H43), C42(H42), C27B(H27B), C28B(H28B), C30B(H30B), C33B(H33B),
 C34B(H34B), C35B(H35B), C40B(H40B), C44B(H44B), C43B(H43B), C42B(H42B)
6.c Fitted hexagon refined as free rotating group:
 C41(C40,C39,C44,C43,C42), C41B(C40B,C39B,C44B,C43B,C42B)
;
_shelx_res_checksum              77170
_shelx_hkl_checksum              4187