Spiroconjugated Donor-σ-Acceptor Charge-Transfer Dyes: Effect of the π-Subsystems on the Optoelectronic Properties.
Wössner, Jan S; Esser, Birgit; The Journal of organic chemistry 85 (2020) 5048–5057; doi:10.1021/acs.joc.0c00567

data_4038119
_publ_section_title
;
 Spiroconjugated Donor-\s-Acceptor Charge-Transfer Dyes: Effect of the
 \p-Subsystems on the Optoelectronic Properties.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5048
_journal_page_last               5057
_journal_paper_doi               10.1021/acs.joc.0c00567
_journal_volume                  85
_journal_year                    2020
_chemical_formula_moiety         'C15 H8 O3 S'
_chemical_formula_sum            'C15 H8 O3 S'
_chemical_formula_weight         268.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.586(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.457(3)
_cell_length_b                   9.423(4)
_cell_length_c                   13.368(5)
_cell_measurement_reflns_used    3436
_cell_measurement_temperature    109(2)
_cell_measurement_theta_max      27.18
_cell_measurement_theta_min      2.626
_cell_volume                     1191.2(8)
_computing_cell_refinement       'SAINT V8.38A (Madison, 2016)'
_computing_data_collection       'Bruker APEX2 software'
_computing_data_reduction        'SAINT V8.38A (Madison, 2016)'
_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      109.4
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'fixed-chi two circle goniometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_av_unetI/netI     0.0430
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            9330
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.551
_diffrn_reflns_theta_min         2.626
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           50
_diffrn_source_type              'Incoatec Mo I\ms'
_diffrn_source_voltage           0.6
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.271
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6884
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1259 before and 0.0500 after correction. The Ratio of minimum to maximum transmission is 0.9233. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.496
_exptl_crystal_description       plate
_exptl_crystal_F_000             552
_exptl_crystal_recrystallization_method
'The material was recrystallised from Isopropanole by slow evaporation'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.519
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         2752
_refine_ls_number_restraints     424
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0716
_refine_ls_R_factor_gt           0.0562
_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^)+(0.0293P)^2^+1.2565P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1179
_refine_ls_wR_factor_ref         0.1227
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2257
_reflns_number_total             2752
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00567_si_002.cif
_cod_data_source_block           esser_jw269_0m_a
_cod_depositor_comments
'Adding full bibliography for 4038114--4038124.cif.'
_cod_original_cell_volume        1191.1(8)
_cod_database_code               4038119
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.923
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C10_2-C11_2 \\sim C11_2-C12_2 \\sim C12_2-C13_2 \\sim C13_2-C14_2 \\sim
C14_2-C15_2 \\sim C15_2-
 C10_2
 C10_1-C11_1 \\sim C11_1-C12_1 \\sim C12_1-C13_1 \\sim C13_1-C14_1 \\sim
C14_1-C15_1 \\sim C15_1-
 C10_1
 with sigma of 0.02
 C15_2-O1_2
 C15_1-O1_1
 with sigma of 0.02
 C10_2-S1_2
 C10_1-S1_1
 with sigma of 0.02
 C10_2-O1_2
 C10_1-O1_1
 with sigma of 0.04
 C15_2-S1_2
 C15_1-S1_1
 with sigma of 0.04
 C10_2-C12_2 \\sim C12_2-C14_2 \\sim C14_2-C10_2 \\sim C15_2-C11_2 \\sim
C11_2-C13_2 \\sim C13_2-
 C15_2
 C10_1-C12_1 \\sim C12_1-C14_1 \\sim C14_1-C10_1 \\sim C15_1-C11_1 \\sim
C11_1-C13_1 \\sim C13_1-
 C15_1
 with sigma of 0.04
 C1-S1_1 \\sim C1-S1_2
 with sigma of 0.04
 C1-O1_1 \\sim C1-O1_2
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 0.9A with sigma of 0.04 and sigma
for terminal atoms of 0.08
All non-hydrogen atoms have similar U: within 0.6A with sigma of 0.02 and sigma
for terminal atoms of 0.04
All non-hydrogen atoms have similar U: within 0.3A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(C12_2) = Uanis(C13_1)
Uanis(C12_1) = Uanis(C13_2)
Uanis(C14_2) = Uanis(C11_1)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O1_1, S1_1, C10_1, C11_1, C12_1, C13_1, C14_1, C15_1}
as
{O1_2, S1_2, C10_2, C11_2, C12_2, C13_2, C14_2, C15_2} sigma for 1-2: 0.02 1-3:
0.04
6. Others
 Sof(O1)=Sof(S1)=Sof(C10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=
 Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=1-FVAR(1)
 Sof(O1)=Sof(S1)=Sof(C10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=
 Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=FVAR(1)
7.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13), C14(H14),
 C11(H11), C12(H12), C13(H13), C14(H14)
;
_shelx_res_checksum              33136
_shelx_hkl_checksum              32895
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id JW269
_olex2_submission_special_instructions 'No special instructions were received'