Variation from closed-shell to open shell electronic structures in oligothiophene bis(dioxolene) complexes.
Miller, Paul D.; Shultz, David A.; Mengell, Joshua; Kirk, Martin L.; Wojtas, Lukasz; Chemical science 14 (2023) 12264–12276; doi:10.1039/d3sc02341a

data_1570088
_publ_section_title
;
 Variation from closed-shell to open shell electronic structures in
 oligothiophene bis(dioxolene) complexes.
;
_journal_issue                   43
_journal_name_full               'Chemical science'
_journal_page_first              12264
_journal_page_last               12276
_journal_paper_doi               10.1039/d3sc02341a
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety
'C106 H118 B2 N12 O4 S2 Zn2, 3.571(C H2 Cl2), 3.726(C2 H6 O), 1.466 O'
_chemical_formula_sum            'C117.02 H147.5 B2 Cl7.14 N12 O9.19 S2 Zn2'
_chemical_formula_weight         2338.83
_chemical_name_common            'bis(semiquinone) bithiophene'
_chemical_name_systematic        SQ2Th2
_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   mixed
_audit_creation_date             2022-07-27
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-05-05 deposited with the CCDC.	2023-10-09 downloaded from the CCDC.
;
_cell_angle_alpha                86.9480(10)
_cell_angle_beta                 83.9220(10)
_cell_angle_gamma                73.1760(10)
_cell_formula_units_Z            1
_cell_length_a                   11.4225(3)
_cell_length_b                   14.9204(4)
_cell_length_c                   19.1678(5)
_cell_measurement_reflns_used    9305
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      79.80
_cell_measurement_theta_min      3.82
_cell_volume                     3108.46(14)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Bruker PHOTON II CMOS area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture Photon-II CPAD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0462
_diffrn_reflns_av_unetI/netI     0.0205
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            136799
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         80.199
_diffrn_reflns_theta_min         2.319
_diffrn_source                   'Microfocus sealed X-ray tube'
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_type              'Incoatec 3.0 Imus'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.659
_exptl_absorpt_correction_T_max  0.7543
_exptl_absorpt_correction_T_min  0.5008
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1274 before and 0.0647 after correction.
The Ratio of minimum to maximum transmission is 0.6639.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       rod
_exptl_crystal_F_000             1231
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2 and EtOH'
_exptl_crystal_size_max          0.506
_exptl_crystal_size_mid          0.252
_exptl_crystal_size_min          0.098
_refine_diff_density_max         0.706
_refine_diff_density_min         -0.665
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     793
_refine_ls_number_reflns         13426
_refine_ls_number_restraints     255
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0461
_refine_ls_R_factor_gt           0.0418
_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^)+(0.0618P)^2^+2.7066P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1154
_refine_ls_wR_factor_ref         0.1194
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12177
_reflns_number_total             13426
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02341a2.cif
_cod_data_source_block           SQ2Th2
_cod_depositor_comments
'Adding full bibliography for 1570087--1570089.cif.'
_cod_original_formula_sum        'C117.02 H147.50 B2 Cl7.14 N12 O9.19 S2 Zn2'
_cod_database_code               1570088
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.781
_shelx_estimated_absorpt_t_min   0.346
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Others
 Sof(O121)=Sof(H121)=Sof(C122)=Sof(H12D)=Sof(H12E)=Sof(C123)=Sof(H12F)=
 Sof(H12G)=Sof(H12H)=FVAR(1)
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(Cl82)=Sof(Cl83)=FVAR(2)
 Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(Cl92)=Sof(Cl93)=FVAR(3)
 Sof(H111)=Sof(C112)=Sof(H11A)=Sof(H11B)=Sof(C113)=Sof(H11C)=Sof(H11D)=
 Sof(H11E)=1-FVAR(4)
 Sof(O101)=Sof(H101)=Sof(C102)=Sof(H10A)=Sof(H10B)=Sof(C103)=Sof(H10C)=
 Sof(H10D)=Sof(H10E)=FVAR(4)
 Sof(C132)=Sof(H13D)=Sof(H13E)=Sof(O131)=Sof(H131)=Sof(C133)=Sof(H13F)=
 Sof(H13G)=Sof(H13H)=FVAR(5)
3.a Ternary CH refined with riding coordinates:
 C32(H32), C47(H47), C62(H62)
3.b Secondary CH2 refined with riding coordinates:
 C71(H71A,H71B), C81(H81A,H81B), C91(H91A,H91B), C102(H10A,H10B), C112(H11A,
 H11B), C122(H12D,H12E), C132(H13D,H13E)
3.c Me refined with riding coordinates:
 C133(H13F,H13G,H13H)
3.d Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C18(H18), C19(H19), C24(H24), C27(H27), C28(H28), C30(H30),
 C31(H31), C39(H39), C42(H42), C43(H43), C45(H45), C46(H46), C54(H54), C57(H57),
  C58(H58), C60(H60), C61(H61)
3.e Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C23(H23A,H23B,
 H23C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C38(H38A,H38B,H38C), C48(H48A,
 H48B,H48C), C49(H49A,H49B,H49C), C53(H53A,H53B,H53C), C63(H63A,H63B,H63C),
 C64(H64A,H64B,H64C), C103(H10C,H10D,H10E), C113(H11C,H11D,H11E), C123(H12F,
 H12G,H12H)
3.f Idealised tetrahedral OH refined as rotating group:
 O101(H101), O111(H111), O121(H121), O131(H131)
;
_shelx_res_checksum              40544
_olex2_submission_special_instructions 'No special instructions were received'