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_4128449
_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         'C94 H78 F4 N4 O2 S4, C94 H82 F4 N4 O2 S4'
_chemical_formula_sum            'C188 H160 F8 N8 O4 S8'
_chemical_formula_weight         3003.71
_chemical_name_systematic        ITIC-4F
_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             2017-12-21
_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                73.995(4)
_cell_angle_beta                 68.809(4)
_cell_angle_gamma                81.206(4)
_cell_formula_units_Z            1
_cell_length_a                   15.4222(8)
_cell_length_b                   17.6025(11)
_cell_length_c                   21.1852(12)
_cell_measurement_reflns_used    9923
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      63.374
_cell_measurement_theta_min      2.304
_cell_volume                     5145.3(5)
_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      99.98
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.901
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Quazar optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1180
_diffrn_reflns_av_unetI/netI     0.0891
_diffrn_reflns_Laue_measured_fraction_full 0.901
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            91137
_diffrn_reflns_point_group_measured_fraction_full 0.901
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         64.197
_diffrn_reflns_theta_min         2.304
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.231
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.5473
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1273 before and 0.0905 after correction. The Ratio of minimum to maximum transmission is 0.7274. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    0.969
_exptl_crystal_description       Needle
_exptl_crystal_F_000             1576
_exptl_crystal_recrystallization_method
'The material was obtained by vapor diffusion of n-heptane into a CH2Br2 solution.'
_exptl_crystal_size_max          0.475
_exptl_crystal_size_mid          0.065
_exptl_crystal_size_min          0.055
_refine_diff_density_max         1.837
_refine_diff_density_min         -0.778
_refine_diff_density_rms         0.153
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.610
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1136
_refine_ls_number_reflns         16789
_refine_ls_number_restraints     1886
_refine_ls_restrained_S_all      1.633
_refine_ls_R_factor_all          0.1853
_refine_ls_R_factor_gt           0.1504
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4104
_refine_ls_wR_factor_ref         0.4355
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10704
_reflns_number_total             16789
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b13653_si_003.cif
_cod_data_source_block           ITIC-4F
_cod_database_code               4128449
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.935
_shelx_estimated_absorpt_t_min   0.592
_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. Restrained distances
 C34-C35 \\sim C33-C34 \\sim C33-C32 \\sim C32-C31 \\sim C31-C30 \\sim C30-C27
\\sim C90-C89 \\sim C91-C90
 \\sim C92-C91 \\sim C92-C93 \\sim C94-C93 \\sim C95-C93 \\sim C89-C86 \\sim
C42-C39 \\sim C43-C42 \\sim C44-
 C43 \\sim C45-C44 \\sim C46-C45 \\sim C46-C47 \\sim C4-C3 \\sim C2-C3 \\sim
C2-C1
 with sigma of 0.01
 C79-C80 \\sim C79-C78 \\sim C77-C74 \\sim C77-C78 \\sim C42-C39 \\sim C43-C42
\\sim C44-C43 \\sim C45-C44
 \\sim C46-C45 \\sim C46-C47
 with sigma of 0.01
 C80-C81 \\sim C77-C74 \\sim C42-C39 \\sim C43-C42 \\sim C44-C43 \\sim C45-C44
\\sim C46-C45 \\sim C46-C47
 with sigma of 0.01
 C82-C81 \\sim C80-C81 \\sim C79-C80 \\sim C79-C78 \\sim C77-C78 \\sim C77-C74
 with sigma of 0.01
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(C11) \\sim Ueq, Uanis(C11A) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
5. Others
 Sof(F1A)=Sof(F2A)=Sof(O1A)=Sof(N1A)=Sof(N2A)=Sof(H10A)=Sof(C11A)=Sof(C12A)=
 Sof(C13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(C16A)=Sof(C17A)=Sof(H17A)=
 Sof(C18A)=Sof(C19A)=Sof(C20A)=Sof(C21A)=Sof(C22A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(O1)=Sof(N1)=Sof(N2)=Sof(H10)=Sof(C11)=Sof(C12)=Sof(C13)=
 Sof(C14)=Sof(H14)=Sof(C15)=Sof(C16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(C19)=
 Sof(C20)=Sof(C21)=Sof(C22)=FVAR(1)
 Fixed Sof: C94(0.5) H94A(0.5) H94B(0.5) H94C(0.5) C95(0.5) H95A(0.5)
 H95B(0.5) H95C(0.5)
6.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), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B),
  C81(H81A,H81B), C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B), C92(H92A,
 H92B), C93(H93A,H93B), C93(H93C,H93D)
6.b Me refined with riding coordinates:
 C35(H35A,H35B,H35C), C47(H47A,H47B,H47C), C82(H82A,H82B,H82C), C94(H94A,H94B,
 H94C), C95(H95A,H95B,H95C)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C10(H10), C10(H10A), C14(H14), C14A(H14A), C17(H17),
 C17A(H17A), C25(H25), C26(H26), C28(H28), C29(H29), C37(H37), C38(H38),
 C40(H40), C41(H41), C48(H48), C53(H53), C58(H58), C62(H62), C65(H65), C72(H72),
  C73(H73), C75(H75), C76(H76), C84(H84), C85(H85), C87(H87), C88(H88)
;
_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 = 1763.9 Ang^3^ [34.6%]
Total electron count / cell = 417.6
;
_shelx_res_checksum              60561
_shelx_hkl_checksum              14348
_shelx_fab_checksum              94693
_olex2_date_sample_data_collection 2017-12-20
_olex2_date_sample_submission    2017-12-17
_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 cx1151
_olex2_submission_special_instructions 'No special instructions were received'