Shape-Selective Synthesis of Pentacene Macrocycles and the Effect of Geometry on Singlet Fission.
Bergman, Harrison M.; Kiel, Gavin R.; Witzke, Ryan J.; Nenon, David P.; Schwartzberg, Adam M.; Liu, Yi; Tilley, T. Don; Journal of the American Chemical Society 142 (2020) 19850–19855; doi:10.1021/jacs.0c09941

data_4135339
_publ_section_title
;
 Shape-Selective Synthesis of Pentacene Macrocycles and the Effect of
 Geometry on Singlet Fission.
;
_journal_issue                   47
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              19850
_journal_page_last               19855
_journal_paper_doi               10.1021/jacs.0c09941
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C108 H112 Si4, 2(C4 H8 O)'
_chemical_formula_sum            'C108 H112 O Si4'
_chemical_formula_weight         1538.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-06-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.212(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   21.5851(11)
_cell_length_b                   14.7231(8)
_cell_length_c                   15.1871(8)
_cell_measurement_reflns_used    9773
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.48
_cell_measurement_theta_min      2.40
_cell_volume                     4813.4(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.39
_diffrn_detector_type            'Bruker-Nonius APEXII CCD area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'Bruker D8 with PHOTON 100 detector'
_diffrn_measurement_device_type  'Bruker D8 diffractometer'
_diffrn_measurement_method       '\f and \w shutterless scans'
_diffrn_radiation_monochromator  'Silicon 111'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.7288
_diffrn_reflns_av_R_equivalents  0.0765
_diffrn_reflns_av_unetI/netI     0.0489
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            52169
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        24.535
_diffrn_reflns_theta_max         24.535
_diffrn_reflns_theta_min         1.718
_diffrn_source                   'Bend magnet, Station 12.2.1, ALS, LBNL'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.113
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.6416
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1729 before and 0.0829 after correction. The Ratio of minimum to maximum transmission is 0.8611. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.061
_exptl_crystal_description       needle
_exptl_crystal_F_000             1648
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.852
_refine_diff_density_min         -0.742
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     582
_refine_ls_number_reflns         7402
_refine_ls_number_restraints     97
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.1050
_refine_ls_R_factor_gt           0.0899
_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^)+(0.1325P)^2^+10.5103P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2502
_refine_ls_wR_factor_ref         0.2642
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5991
_reflns_number_total             7402
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09941_si_004.cif
_cod_data_source_block           hb1f
_cod_depositor_comments
'Adding full bibliography for 4135339--4135341.cif.'
_cod_database_code               4135339
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.997
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C51, C53, C55, C52, C57, C54, C56
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
C51 \\sim C53 \\sim C55 \\sim C52 \\sim C57 \\sim C54 \\sim C56: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C44, C45, C46, C47
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: H51A(0.5) H51B(0.5) H51C(0.5) H51D(0.5) C53(0.5) H53A(0.5)
 H53B(0.5) C55(0.5) H55A(0.5) H55B(0.5) C52(0.5) H52A(0.5) H52B(0.5) C57(0.5)
 H57A(0.5) H57B(0.5) H57C(0.5) C54(0.5) H54A(0.5) H54B(0.5) H54C(0.5) C56(0.5)
 H56A(0.5) H56B(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C60(H60A,H60B), C61(H61A,H61B), C58(H58A,H58B), C59(H59A,H59B), C44(H44A,
 H44B), C45(H45A,H45B), C46(H46A,H46B), C51(H51A,H51B), C51(H51C,H51D),
 C53(H53A,H53B), C55(H55A,H55B), C52(H52A,H52B), C56(H56A,H56B)
6.b Me refined with riding coordinates:
 C57(H57A,H57B,H57C), C54(H54A,H54B,H54C)
6.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C13(H13), C20(H20), C3(H3), C10(H10), C26(H26), C37(H37), C12(H12),
 C34(H34), C40(H40), C25(H25), C33(H33), C39(H39), C31(H31), C30(H30), C36(H36),
  C6(H6), C23(H23), C11(H11), C22(H22), C17(H17), C16(H16), C5(H5), C48(H48),
 C4(H4), C41(H41)
6.d Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C), C43(H43A,H43B,H43C), C50(H50A,H50B,H50C), C47(H47A,H47B,
 H47C), C42(H42A,H42B,H42C)
;
_olex2_submission_special_instructions 'No special instructions were received'