Synthesis and Structures of Polyiodide Radical Cation Salts of Donors Combining Tetrathiafulvalene with Multiple Thiophene or Oligo-thiophene Substituents.
Short, Jonni; Blundell, Toby J.; Yang, Songjie; Sahin, Onur; Shakespeare, Yiana; Smith, Emma Louise; Martin, Lee; Wallis, John D.; CrystEngComm  (2020) –; doi:10.1039/D0CE00954G

data_7241259
_publ_section_title
;
 Synthesis and Structures of Polyiodide Radical Cation Salts of Donors
 Combining Tetrathiafulvalene with Multiple Thiophene or Oligo-thiophene
 Substituents.
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D0CE00954G
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         '1.333(I3), C16 H10 S10'
_chemical_formula_sum            'C16 H10 I4 S10'
_chemical_formula_weight         1030.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-06-23 deposited with the CCDC.	2020-09-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.212(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.0576(10)
_cell_length_b                   28.632(2)
_cell_length_c                   10.5799(10)
_cell_measurement_reflns_used    3217
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      28.6360
_cell_measurement_theta_min      3.5000
_cell_volume                     2700.3(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector_area_resol_mean 15.9832
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.854
_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    -20.00  23.00   1.00  130.00    --  -16.16 -99.00-120.00   43
  2  \w     53.00  88.00   1.00  130.00    --   16.24 178.00-150.00   35
  3  \w      0.00  83.00   1.00  130.00    --   16.24  77.00-150.00   83
  4  \w    -30.00  45.00   1.00  130.00    --   16.24 -19.00   0.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0538
_diffrn_reflns_av_unetI/netI     0.0903
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.854
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13901
_diffrn_reflns_point_group_measured_fraction_full 0.723
_diffrn_reflns_point_group_measured_fraction_max 0.590
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.351
_diffrn_reflns_theta_min         3.261
_exptl_absorpt_coefficient_mu    5.396
_exptl_absorpt_correction_T_max  0.947
_exptl_absorpt_correction_T_min  0.440
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    2.535
_exptl_crystal_description       block
_exptl_crystal_F_000             1912
_exptl_crystal_preparation       'electrical insulator'
_exptl_crystal_recrystallization_method
'Diffusion of iodine/hexane into donor/DCM'
_exptl_crystal_size_max          0.64
_exptl_crystal_size_mid          0.055
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.821
_refine_diff_density_min         -1.472
_refine_diff_density_rms         0.257
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.46(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.107
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     698
_refine_ls_number_reflns         8784
_refine_ls_number_restraints     1416
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0858
_refine_ls_R_factor_gt           0.0718
_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^)+(0.0741P)^2^+1.7328P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1521
_refine_ls_wR_factor_ref         0.1608
_reflns_Friedel_coverage         0.357
_reflns_Friedel_fraction_full    0.437
_reflns_Friedel_fraction_max     0.316
_reflns_number_gt                7496
_reflns_number_total             8784
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ce00954g2.cif
_cod_data_source_block           19a2i5i3
_cod_original_cell_volume        2700.3(5)
_cod_database_code               7241259
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.130
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 S19-C25 \\sim S19B-C25 \\sim S9-C9 \\sim S9B-C9 \\sim S10-C13 \\sim S10B-C13B
\\sim S20-C29 \\sim S20B-C29
 with sigma of 0.01
 C26-C25 \\sim C26B-C25 \\sim C29-C30B \\sim C29-C30 \\sim C10B-C9 \\sim C9-C10
\\sim C13-C14 \\sim C13B-
 C14B
 with sigma of 0.01
 S8-C13B \\sim S8-C13 \\sim S7-C9 \\sim S17-C25 \\sim S18-C29
 with sigma of 0.01
 S9B-C12B \\sim S9-C12 \\sim S19B-C28B \\sim S19-C28 \\sim S20B-C32B \\sim
S20-C32 \\sim S10B-C16B ~
 S10-C16
 with sigma of 0.01
 C15-C14 \\sim C15B-C14B \\sim C11-C10 \\sim C11B-C10B \\sim C31-C30 \\sim
C31B-C30B \\sim C27B-C26B ~
 C27-C26
 with sigma of 0.01
 C27-C28 \\sim C27B-C28B \\sim C32B-C31B \\sim C32-C31 \\sim C16B-C15B \\sim
C16-C15 \\sim C11-C12 ~
 C11B-C12B
 with sigma of 0.01
 S19B-C27B \\sim S19-C27
 with sigma of 0.02
3. Restrained planarity
 C25, S19B, C26B, C27B, C28B
 with sigma of 0.1
 C9, S9B, C10B, C11B, C12B
 with sigma of 0.1
 S10B, C13B, C14B, C15B, C16B
 with sigma of 0.1
 C29, S20B, C30B, C31B, C32B
 with sigma of 0.1
 C9, S9, C10, C11, C12
 with sigma of 0.1
 S10, C13, C14, C15, C16
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
5. 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
6. Others
 Sof(S9B)=Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(H12B)=1-FVAR(1)
 Sof(S9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=FVAR(1)
 Sof(S20B)=Sof(C30B)=Sof(H30B)=Sof(C31B)=Sof(H31B)=Sof(C32B)=Sof(H32B)=1-FVAR(2)
 Sof(S20)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=FVAR(2)
 Sof(S10B)=Sof(C13B)=Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(H15B)=Sof(C16B)=
 Sof(H16B)=1-FVAR(3)
 Sof(S10)=Sof(C13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=FVAR(3)
 Sof(S19B)=Sof(C26B)=Sof(H26B)=Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(H28B)=1-FVAR(4)
 Sof(S19)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=FVAR(4)
7.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C21(H21A,H21B), C22(H22A,H22B)
7.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C14(H14), C15(H15), C16(H16), C10B(H10B),
 C11B(H11B), C12B(H12B), C14B(H14B), C15B(H15B), C16B(H16B), C26(H26), C27(H27),
  C28(H28), C30(H30), C31(H31), C32(H32), C26B(H26B), C27B(H27B), C28B(H28B),
 C30B(H30B), C31B(H31B), C32B(H32B)
;
_shelx_res_checksum              4411
_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
;