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_4128451
_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         '2(C47 H41 N2 O S2), 2(C H2 Br2)'
_chemical_formula_sum            'C96 H86 Br4 N4 O2 S4'
_chemical_formula_weight         1775.56
_chemical_name_systematic        ITIC-0F
_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             2017-12-15
_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                101.780(10)
_cell_angle_beta                 95.319(10)
_cell_angle_gamma                91.105(14)
_cell_formula_units_Z            2
_cell_length_a                   8.420(6)
_cell_length_b                   23.019(17)
_cell_length_c                   23.126(17)
_cell_measurement_reflns_used    9857
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.421
_cell_measurement_theta_min      2.183
_cell_volume                     4366(6)
_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      100.02
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'QuazarTM optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0563
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            50025
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.440
_diffrn_reflns_theta_min         0.904
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.990
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6611
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0568 before and 0.0392 after correction. The Ratio of minimum to maximum transmission is 0.8869. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.351
_exptl_crystal_description       plate
_exptl_crystal_F_000             1820
_exptl_crystal_recrystallization_method
'The material was obtained by vapor diffusion of n-heptane into a CH2Br2 solution.'
_exptl_crystal_size_max          0.088
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.021
_refine_diff_density_max         2.243
_refine_diff_density_min         -3.642
_refine_diff_density_rms         0.167
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1103
_refine_ls_number_reflns         17919
_refine_ls_number_restraints     1645
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.1266
_refine_ls_R_factor_gt           0.0960
_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^)+(0.1834P)^2^+21.4707P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2792
_refine_ls_wR_factor_ref         0.3063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12760
_reflns_number_total             17919
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b13653_si_002.cif
_cod_data_source_block           ITIC-0F
_cod_original_cell_volume        4366(5)
_cod_database_code               4128451
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.844
_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
 C78-C77 \\sim C77-C78A \\sim C79-C78 \\sim C80-C79 \\sim C77-C74 \\sim
C79A-C78A \\sim C80A-C79A ~
 C81-C80 \\sim C82-C81 \\sim C81A-C80A \\sim C82A-C81A \\sim C89-C86 \\sim
C89-C90A \\sim C90A-C91A ~
 C91A-C92A \\sim C90-C89 \\sim C91-C90 \\sim C92-C91 \\sim C93-C92 \\sim
C94-C93 \\sim C42_$1-C39_$1 ~
 C43_$1-C42_$1 \\sim C44_$1-C43_$1 \\sim C45_$1-C44_$1 \\sim C46_$1-C45_$1
\\sim C47_$1-C46_$1
 \\sim C46_$1-C47A_$1 \\sim C30_$1-C27_$1 \\sim C31_$1-C30_$1 \\sim
C32_$1-C31_$1 \\sim C33_$1-
 C32_$1 \\sim C34_$1-C33_$1 \\sim C35_$1-C34_$1 \\sim C91A-C92A \\sim C93A-C92A
\\sim C94A-C93A ~
 C90A-C91A
 with sigma of 0.01
 C35-C33 \\sim C34-C32 \\sim C27-C31 \\sim C47A-C45 \\sim C46-C44 \\sim C43-C39
\\sim C94_$1-C92_$1 ~
 C93_$1-C91_$1 \\sim C90_$1-C86_$1 \\sim C89_$1-C91A_$1 \\sim C82_$1-C80_$1
\\sim C81_$1-C79_$1
 \\sim C78_$1-C74_$1 \\sim C77_$1-C79A_$1 \\sim C80A_$1-C82A_$1 \\sim
C92A_$1-C90A_$1 \\sim C91A_$1-
 C89_$1 \\sim C94A_$1-C92A_$1 \\sim C93A_$1-C91A_$1
 with sigma of 0.01
 C77-C77 \\sim C74-C77 \\sim C86-C89 \\sim C89-C90A \\sim C90A-C91A \\sim
C91A-C92A \\sim C89-C90 ~
 C90-C91 \\sim C91-C92 \\sim C92-C93 \\sim C93-C94 \\sim C42_$1-C39_$1 \\sim
C42_$1-C43_$1 \\sim C43_$1-
 C44_$1 \\sim C44_$1-C45_$1 \\sim C45_$1-C46_$1 \\sim C46_$1-C47 \\sim
C46_$1-C47A \\sim C30_$1-
 C27_$1 \\sim C30_$1-C31_$1 \\sim C31_$1-C32_$1 \\sim C32_$1-C33_$1 \\sim
C33_$1-C34_$1 ~
 C34_$1-C35_$1 \\sim C92A-C93A \\sim C93A-C94A
 with sigma of 0.01
 C33-C35 \\sim C32-C34 \\sim C27-C31 \\sim C45-C44 \\sim C46-C39 \\sim
C43-C94_$1 \\sim C92_$1-C93_$1
 \\sim C91_$1-C90_$1 \\sim C86_$1-C89_$1 \\sim C91A_$1-C82 \\sim C80-C81 \\sim
C79-C78 \\sim C74_$1-
 C77_$1 \\sim C79A-C80A \\sim C82A-C92A_$1 \\sim C90A_$1-C92A_$1 \\sim
C94A_$1-C91A_$1 ~
 C93A_$1-?
 with sigma of 0.01
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(H77A)=Sof(H77B)=Sof(C78A)=Sof(H78C)=Sof(H78D)=Sof(C79A)=Sof(H79C)=
 Sof(H79D)=Sof(C80A)=Sof(H80C)=Sof(H80D)=Sof(C81A)=Sof(H81C)=Sof(H81D)=
 Sof(C82A)=Sof(H82D)=Sof(H82E)=Sof(H82F)=1-FVAR(1)
 Sof(H77C)=Sof(H77D)=Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(C79)=Sof(H79A)=Sof(H79B)=
 Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(C82)=Sof(H82A)=
 Sof(H82B)=Sof(H82C)=FVAR(1)
 Sof(Br1A)=Sof(H96C)=Sof(H96D)=1-FVAR(2)
 Sof(Br4)=Sof(H96A)=Sof(H96B)=FVAR(2)
 Sof(H46C)=Sof(H46D)=Sof(C47A)=Sof(H47D)=Sof(H47E)=Sof(H47F)=1-FVAR(3)
 Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(3)
 Fixed Sof: H89A(0.5) H89B(0.5) H89C(0.5) H89D(0.5) C90(0.5) H90A(0.5)
 H90B(0.5) C90A(0.5) H90C(0.5) H90D(0.5) C91(0.5) H91A(0.5) H91B(0.5) C91A(0.5)
 H91C(0.5) H91D(0.5) C92(0.5) H92A(0.5) H92B(0.5) C92A(0.5) H92C(0.5) H92D(0.5)
 C93(0.5) H93A(0.5) H93B(0.5) C93A(0.5) H93C(0.5) H93D(0.5) C94(0.5) H94A(0.5)
 H94B(0.5) H94C(0.5) C94A(0.5) H94D(0.5) H94E(0.5) H94F(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), C46(H46C,H46D), C77(H77C,H77D), C77(H77A,H77B), C78(H78A,H78B),
  C78A(H78C,H78D), C79(H79A,H79B), C79A(H79C,H79D), C80(H80A,H80B), C80A(H80C,
 H80D), C81(H81A,H81B), C81A(H81C,H81D), C89(H89A,H89B), C89(H89C,H89D),
 C90(H90A,H90B), C90A(H90C,H90D), C91(H91A,H91B), C91A(H91C,H91D), C92(H92A,
 H92B), C92A(H92C,H92D), C93(H93A,H93B), C93A(H93C,H93D), C95(H95A,H95B),
 C96(H96C,H96D), C96(H96A,H96B)
5.b Me refined with riding coordinates:
 C35(H35A,H35B,H35C), C47(H47A,H47B,H47C), C47A(H47D,H47E,H47F), C82(H82A,H82B,
 H82C), C82A(H82D,H82E,H82F), C94A(H94D,H94E,H94F)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C13(H13), C15(H15), C21(H21), C25(H25),
 C26(H26), C28(H28), C29(H29), C37(H37), C38(H38), C40(H40), C41(H41), C51(H51),
  C52(H52), C53(H53), C54(H54), C60(H60), C62(H62), C68(H68), C72(H72),
 C73(H73), C75(H75), C76(H76), C84(H84), C85(H85), C87(H87), C88(H88)
5.d Idealised Me refined as rotating group:
 C94(H94A,H94B,H94C)
;
_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 = 434.4 Ang^3^ [10.0%]
Total electron count / cell = 113.3
;
_shelx_res_checksum              17324
_shelx_hkl_checksum              45994
_shelx_fab_checksum              83931
_olex2_date_sample_data_collection 2017-12-12
_olex2_date_sample_submission    2017-12-11
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id cx1140
_olex2_submission_special_instructions 'No special instructions were received'