Fluorination Effects on Indacenodithienothiophene Acceptor Packing and Electronic Structure, End-Group Redistribution, and Solar Cell Photovoltaic Response.
Aldrich, Thomas J.; Matta, Micaela; Zhu, Weigang; Swick, Steven M.; Stern, Charlotte L.; Schatz, George C.; Facchetti, Antonio; Melkonyan, Ferdinand S.; Marks, Tobin J.; Journal of the American Chemical Society 141 (2019) 3274–3287; doi:10.1021/jacs.8b13653

data_4128450
_publ_section_title
;
 Fluorination Effects on Indacenodithienothiophene Acceptor Packing and
 Electronic Structure, End-Group Redistribution, and Solar Cell
 Photovoltaic Response.
;
_journal_issue                   7
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3274
_journal_page_last               3287
_journal_paper_doi               10.1021/jacs.8b13653
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C188 H160 F4 N8 O4 S8, C H2 Br2'
_chemical_formula_sum            'C189 H162 Br2 F4 N8 O4 S8'
_chemical_formula_weight         3101.56
_chemical_name_systematic        'ITIC-0F:ITIC-4F cocrystal'
_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     dual
_audit_creation_date             2018-01-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-12-18 deposited with the CCDC.
2018-12-18 downloaded from the CCDC.
;
_cell_angle_alpha                82.827(3)
_cell_angle_beta                 68.565(2)
_cell_angle_gamma                80.934(2)
_cell_formula_units_Z            1
_cell_length_a                   15.4670(5)
_cell_length_b                   17.5307(7)
_cell_length_c                   20.7381(8)
_cell_measurement_reflns_used    9940
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      65.058
_cell_measurement_theta_min      3.092
_cell_volume                     5154.9(3)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.795
_diffrn_measured_fraction_theta_max 0.905
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0478
_diffrn_reflns_av_unetI/netI     0.0695
_diffrn_reflns_Laue_measured_fraction_full 0.795
_diffrn_reflns_Laue_measured_fraction_max 0.905
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            29823
_diffrn_reflns_point_group_measured_fraction_full 0.795
_diffrn_reflns_point_group_measured_fraction_max 0.905
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         62.379
_diffrn_reflns_theta_min         2.295
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.650
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.4868
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1052 before and 0.0577 after correction. The Ratio of minimum to maximum transmission is 0.6468. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    0.999
_exptl_crystal_description       needle
_exptl_crystal_F_000             1618
_exptl_crystal_recrystallization_method
'The material was obtained by vapor diffusion of n-heptane into a CH2Br2 solution.'
_exptl_crystal_size_max          0.568
_exptl_crystal_size_mid          0.072
_exptl_crystal_size_min          0.064
_refine_diff_density_max         1.453
_refine_diff_density_min         -0.741
_refine_diff_density_rms         0.124
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.773
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1002
_refine_ls_number_reflns         14834
_refine_ls_number_restraints     781
_refine_ls_restrained_S_all      1.739
_refine_ls_R_factor_all          0.1754
_refine_ls_R_factor_gt           0.1532
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4224
_refine_ls_wR_factor_ref         0.4418
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11101
_reflns_number_total             14834
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b13653_si_006.cif
_cod_data_source_block           ITIC-0F:ITIC-4F
_cod_database_code               4128450
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.902
_shelx_estimated_absorpt_t_min   0.454
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C46-C47 = C46-C45 = C44-C45 = C44-C43 = C42-C43 = C42-C39
 1.5 with sigma of 0.02
 C47A-C46A \\sim C46A-C45A \\sim C45A-C44A \\sim C44A-C43A \\sim C43A-C42A
\\sim C42A-C39A
 with sigma of 0.01
 C47A-C45A \\sim C46A-C44A \\sim C43A-C39A
 with sigma of 0.01
 C42-C39 \\sim C42-C43 \\sim C44-C43
 with sigma of 0.01
 C44-C43 \\sim C44-C45 \\sim C46-C45
 with sigma of 0.01
 C46-C44 \\sim C45-C43 \\sim C42-C38
 with sigma of 0.01
 C47-C45 \\sim C46-C44 \\sim C43-C39
 with sigma of 0.01
 C46-C47 \\sim C46-C45 \\sim C44-C45 \\sim C44-C43 \\sim C42-C43 \\sim C42-C39
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
4. Others
 Fixed Sof: F1(0.5) F2(0.5) H16(0.5) H17(0.5) F1A(0.5) F2A(0.5) H16A(0.5)
 H17A(0.5) Br1(0.5) Br2(0.5) C48(0.5) H48A(0.5) H48B(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,
 H34B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B),
 C46(H46A,H46B), C30A(H30C,H30D), C31A(H31C,H31D), C32A(H32C,H32D), C33A(H33C,
 H33D), C34A(H34C,H34D), C42A(H42C,H42D), C43A(H43C,H43D), C44A(H44C,H44D),
 C45A(H45C,H45D), C46A(H46C,H46D), C48(H48A,H48B)
5.b Me refined with riding coordinates:
 C47(H47A,H47B,H47C), C35A(H35D,H35E,H35F)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C7(H7), C11(H11), C15(H15), C16(H16), C17(H17), C18(H18), C25(H25),
 C26(H26), C28(H28), C29(H29), C37(H37), C38(H38), C40(H40), C41(H41), C1A(H1A),
  C7A(H7A), C11A(H11A), C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A),
 C25A(H25A), C26A(H26A), C28A(H28A), C29A(H29A), C37A(H37A), C38A(H38A),
 C40A(H40A), C41A(H41A)
5.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C47A(H47D,H47E,H47F)
;
_smtbx_masks_special_details
;
The solvent masking procedure as implemented in Olex2 was used to remove the
electronic contribution of solvent molecules from the refinement.  As the exact
solvent content is not known, only the atoms used in the refinement model are
reported in the formula here.

Total solvent accessible volume / cell = 1695.1 Ang^3^ [32.9%]
Total electron count / cell = 680.9
;
_shelx_res_checksum              72529
_shelx_hkl_checksum              30676
_shelx_fab_checksum              2598
_olex2_date_sample_data_collection 2018-01-26
_olex2_date_sample_submission    2018-01-22
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id cx1189
_olex2_submission_special_instructions 'No special instructions were received'