Conjugation Length Effect on the Conducting Behavior of Single-crystalline Oligo(3,4-ethylenedioxythiophene) (nEDOT) Radical Cation Salts
Kameyama, Ryohei; Fujino, Tomoko; Dekura, Shun; Mori, Hatsumi; Physical Chemistry Chemical Physics  (2022) –; doi:10.1039/D2CP00250G

data_7244453
_publ_section_title
;
 Conjugation Length Effect on the Conducting Behavior of
 Single-crystalline Oligo(3,4-ethylenedioxythiophene) (nEDOT) Radical
 Cation Salts
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D2CP00250G
_journal_year                    2022
_chemical_formula_moiety         'C20 H18 O6 S5, F6 P'
_chemical_formula_sum            'C20 H18 F6 O6 P S5'
_chemical_formula_weight         659.61
_chemical_name_common
'5,5''-dimethylthio-2,2':5',2''-ter(3,4-ethylenedioxythiophene) radical cation hexafluoro-phosphate dichloromethane solvate'
_chemical_name_systematic        2MeS-3EDOT_PF6_CH2Cl2
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-C 2y'
_space_group_name_H-M_alt        'C 1 2/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2021-11-19 deposited with the CCDC.	2022-02-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.400(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.4985(13)
_cell_length_b                   29.366(2)
_cell_length_c                   7.0331(6)
_cell_measurement_reflns_used    3695
_cell_measurement_temperature    293
_cell_measurement_theta_max      29.5470
_cell_measurement_theta_min      2.6170
_cell_volume                     2722.9(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -110.00  70.00   0.50   50.00    --  -20.00  45.00   0.00  360
  2  \w   -110.00  70.00   0.50   50.00    --  -20.00  45.00  90.00  360
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0160979000
_diffrn_orient_matrix_UB_12      0.0230511000
_diffrn_orient_matrix_UB_13      -0.0056867000
_diffrn_orient_matrix_UB_21      0.0466386000
_diffrn_orient_matrix_UB_22      0.0064516000
_diffrn_orient_matrix_UB_23      0.0616845000
_diffrn_orient_matrix_UB_31      0.0214944000
_diffrn_orient_matrix_UB_32      0.0032329000
_diffrn_orient_matrix_UB_33      -0.0825728000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0513
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            9292
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         2.592
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.560
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91170
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic bluish black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.609
_exptl_crystal_description       needle
_exptl_crystal_F_000             1340
_exptl_crystal_preparation
'electrochemical oxidation of the corresponding donor,Magnetic properties'
_exptl_crystal_recrystallization_method 'electrochemical crystallization'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.312
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.061
_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     243
_refine_ls_number_reflns         2539
_refine_ls_number_restraints     150
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.1105
_refine_ls_R_factor_gt           0.0568
_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^)+(0.0671P)^2^+3.8037P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1354
_refine_ls_wR_factor_ref         0.1602
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1476
_reflns_number_total             2539
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cp00250g2.cif
_cod_data_source_block           200308-rk03-143_2mes3edot_pf6_ch2cl2
_cod_database_code               7244453
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 88.10
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.45
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P1-F3 \\sim P1-F5 \\sim P1-F6 \\sim P1-F2 \\sim P1-F4 \\sim P1-F1
 with sigma of 0.02
 O4-C10 \\sim O4-C9A
 with sigma of 0.02
 F3-F5 \\sim F3-F2 \\sim F3-F4 \\sim F3-F1 \\sim F6-F5 \\sim F6-F2 \\sim F6-F4
\\sim F6-F1 \\sim F2-F3 \\sim F2-F6
 \\sim F5-F6 \\sim F5-F3
 with sigma of 0.04
 O3-C10 \\sim O3-C9A
 with sigma of 0.04
 O3-C9 \\sim O3-C10A
 with sigma of 0.02
 F3-F6 \\sim F5-F2 \\sim F1-F4
 with sigma of 0.05
 C10-C9 \\sim C9A-C10A
 with sigma of 0.02
 O4-C9 \\sim O4-C10A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
P1 \\sim F3 \\sim F5 \\sim F6 \\sim F2 \\sim F4 \\sim F1: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 P1, F3, F5, F6, F2, F4, F1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C9A)=Sof(H9Aa)=Sof(H9Ab)=Sof(C10A)=Sof(H10c)=Sof(H10d)=1-FVAR(1)
 Sof(C10)=Sof(H10a)=Sof(H10b)=Sof(C9)=Sof(H9a)=Sof(H9b)=FVAR(1)
 Fixed Sof: O2(0.5) P1(0.5) F3(0.5) F5(0.5) F6(0.5) F2(0.5) F4(0.5) F1(0.5)
 C8(0.5) H8a(0.5) H8b(0.5) C7(0.5) H7a(0.5) H7b(0.5) O1(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C10(H10a,H10b), C9(H9a,H9b), C9A(H9Aa,H9Ab), C10A(H10c,H10d), C8(H8a,H8b),
 C7(H7a,H7b)
6.b Idealised Me refined as rotating group:
 C11(H11a,H11b,H11c)
;
_shelx_res_checksum              5845
_shelx_hkl_checksum              89266
_shelx_fab_checksum              52320
_olex2_exptl_crystal_mounting_method 'MiteGen microloop'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.158
_oxdiff_exptl_absorpt_empirical_full_min 0.910