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_1570087
_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
'C102 H116 B2 N12 O4 S Zn2, 1.635(C3 H7 O), 1.364(C H2 Cl2)'
_chemical_formula_sum            'C108.27 H130.17 B2 Cl2.73 N12 O5.63 S Zn2'
_chemical_formula_weight         1971.01
_chemical_name_common            'bis(semiquinone) thiophene'
_chemical_name_systematic        SQ2Th
_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             2022-07-26
_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                98.9882(12)
_cell_angle_beta                 92.331(2)
_cell_angle_gamma                98.306(2)
_cell_formula_units_Z            2
_cell_length_a                   12.3174(6)
_cell_length_b                   13.2142(6)
_cell_length_c                   33.891(2)
_cell_measurement_reflns_used    9871
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      78.82
_cell_measurement_theta_min      3.46
_cell_volume                     5380.1(5)
_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            'CPAD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device       'four-circle kappa goniometer'
_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  0.0520
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            157498
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.862
_diffrn_reflns_theta_min         2.645
_diffrn_source                   'Microfocus sealed X-ray tube'
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_type              'Incoatec I\mS 3.0'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.795
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8871
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1089 before and 0.0790 after correction.
The Ratio of minimum to maximum transmission is 0.8871.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.217
_exptl_crystal_description       block
_exptl_crystal_F_000             2083
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2 and iPrOH'
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.081
_refine_diff_density_max         1.398
_refine_diff_density_min         -0.699
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1667
_refine_ls_number_reflns         22943
_refine_ls_number_restraints     1793
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0912
_refine_ls_R_factor_gt           0.0893
_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^)+(0.0851P)^2^+13.6980P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2304
_refine_ls_wR_factor_ref         0.2313
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21998
_reflns_number_total             22943
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02341a2.cif
_cod_data_source_block           SQ2Th
_cod_depositor_comments
'Adding full bibliography for 1570087--1570089.cif.'
_cod_database_code               1570087
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.683
_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
2. Others
 Sof(C56C)=Sof(C57C)=Sof(H57G)=Sof(C58C)=Sof(H58C)=Sof(C59C)=Sof(C60C)=
 Sof(H60C)=Sof(C61C)=Sof(H61C)=Sof(C62C)=Sof(H62C)=Sof(C63C)=Sof(H63A)=
 Sof(H63B)=Sof(H63C)=Sof(C64C)=Sof(H64A)=Sof(H64B)=Sof(H64C)=1-FVAR(1)
 Sof(C47C)=Sof(C48C)=Sof(H48C)=Sof(C49C)=Sof(H49C)=Sof(C50C)=Sof(C51C)=
 Sof(H51C)=Sof(C52C)=Sof(H52C)=Sof(C53C)=Sof(H53E)=Sof(C54C)=Sof(H54G)=
 Sof(H54H)=Sof(H54I)=Sof(C55C)=Sof(H55G)=Sof(H55H)=Sof(H55I)=FVAR(1)
 Sof(H53G)=Sof(C54E)=Sof(H54M)=Sof(H54N)=Sof(H54O)=Sof(C55E)=Sof(H55M)=
 Sof(H55N)=Sof(H55O)=1-FVAR(2)
 Sof(H53H)=Sof(C56E)=Sof(H56G)=Sof(H56H)=Sof(H56I)=Sof(C57E)=Sof(H57H)=
 Sof(H57I)=Sof(H57J)=FVAR(2)
 Sof(H53B)=Sof(C56A)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C57A)=Sof(H57A)=
 Sof(H57B)=Sof(H57C)=1-FVAR(3)
 Sof(H53A)=Sof(C54A)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55A)=Sof(H55A)=
 Sof(H55B)=Sof(H55C)=FVAR(3)
 Sof(H53D)=Sof(C56B)=Sof(H56D)=Sof(H56E)=Sof(H56F)=Sof(C57B)=Sof(H57D)=
 Sof(H57E)=Sof(H57F)=1-FVAR(4)
 Sof(H53C)=Sof(C54B)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C55B)=Sof(H55D)=
 Sof(H55E)=Sof(H55F)=FVAR(4)
 Sof(O71A)=Sof(C72A)=Sof(H72A)=Sof(C73A)=Sof(H73A)=Sof(H73B)=Sof(H73C)=
 Sof(C74A)=Sof(H74A)=Sof(H74B)=Sof(H74C)=1-FVAR(5)
 Sof(O71C)=Sof(C72C)=Sof(H72C)=Sof(C73C)=Sof(H73G)=Sof(H73H)=Sof(H73I)=
 Sof(C74C)=Sof(H74G)=Sof(H74H)=Sof(H74I)=FVAR(5)
 Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(Cl91)=Sof(Cl92)=FVAR(6)
 Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(Cl88)=Sof(Cl89)=FVAR(7)
 Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(Cl94)=Sof(Cl95)=FVAR(8)
 Sof(O71D)=Sof(C72D)=Sof(H72D)=Sof(C73D)=Sof(H73J)=Sof(H73K)=Sof(H73L)=
 Sof(C74D)=Sof(H74J)=Sof(H74K)=Sof(H74L)=FVAR(9)
 Sof(O71B)=Sof(C72B)=Sof(H72B)=Sof(C73B)=Sof(H73D)=Sof(H73E)=Sof(H73F)=
 Sof(C74B)=Sof(H74D)=Sof(H74E)=Sof(H74F)=FVAR(10)
 Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(Cl85)=Sof(Cl86)=FVAR(11)
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(Cl82)=Sof(Cl83)=FVAR(12)
 Sof(Cl97)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(Cl98)=FVAR(13)
 Fixed Sof: C47F(0.5) C48F(0.5) H48F(0.5) C49F(0.5) H49F(0.5) C50F(0.5)
 C51F(0.5) H51F(0.5) C52F(0.5) H52F(0.5) C53F(0.5) H53I(0.5) C54F(0.5)
 H54P(0.5) H54Q(0.5) H54R(0.5) C55F(0.5) H55P(0.5) H55Q(0.5) H55R(0.5)
 C56F(0.5) C57F(0.5) H57K(0.5) C58F(0.5) H58F(0.5) C59F(0.5) C60F(0.5)
 H60F(0.5) C61F(0.5) H61F(0.5) C62F(0.5) H62F(0.5) C63F(0.5) H63D(0.5)
 H63E(0.5) H63F(0.5) C64F(0.5) H64D(0.5) H64E(0.5) H64F(0.5)
3.a Ternary CH refined with riding coordinates:
 C53A(H53A), C53A(H53B), C53B(H53C), C53B(H53D), C53C(H53E), C62C(H62C),
 C53D(H53F), C53E(H53G), C53E(H53H), C53F(H53I), C62F(H62F), C72A(H72A),
 C72B(H72B), C72C(H72C), C72D(H72D)
3.b Secondary CH2 refined with riding coordinates:
 C81(H81A,H81B), C84(H84A,H84B), C87(H87A,H87B), C90(H90A,H90B), C93(H93A,
 H93B), C96(H96A,H96B)
3.c Me refined with riding coordinates:
 C54C(H54G,H54H,H54I), C55C(H55G,H55H,H55I), C63C(H63A,H63B,H63C), C64C(H64A,
 H64B,H64C), C54E(H54M,H54N,H54O), C55E(H55M,H55N,H55O), C56E(H56G,H56H,H56I),
 C57E(H57H,H57I,H57J), C73A(H73A,H73B,H73C), C74A(H74A,H74B,H74C), C73B(H73D,
 H73E,H73F), C74B(H74D,H74E,H74F), C73D(H73J,H73K,H73L), C74D(H74J,H74K,H74L)
3.d Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C20(H20), C22(H22), C32(H32), C34(H34), C46A(H46A),
 C48A(H48A), C49A(H49A), C51A(H51A), C52A(H52A), C46B(H46B), C48B(H48B),
 C49B(H49B), C51B(H51B), C52B(H52B), C46C(H46C), C48C(H48C), C49C(H49C),
 C51C(H51C), C52C(H52C), C57C(H57G), C58C(H58C), C60C(H60C), C61C(H61C),
 C46D(H46D), C48D(H48D), C49D(H49D), C51D(H51D), C52D(H52D), C46E(H46E),
 C48E(H48E), C49E(H49E), C51E(H51E), C52E(H52E), C46F(H46F), C48F(H48F),
 C49F(H49F), C51F(H51F), C52F(H52F), C57F(H57K), C58F(H58F), C60F(H60F),
 C61F(H61F)
3.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41A(H41A,H41B,H41C),
 C54A(H54A,H54B,H54C), C55A(H55A,H55B,H55C), C56A(H56A,H56B,H56C), C57A(H57A,
 H57B,H57C), C41B(H41D,H41E,H41F), C54B(H54D,H54E,H54F), C55B(H55D,H55E,H55F),
 C56B(H56D,H56E,H56F), C57B(H57D,H57E,H57F), C41C(H41G,H41H,H41I), C41D(H41J,
 H41K,H41L), C54D(H54J,H54K,H54L), C55D(H55J,H55K,H55L), C41E(H41M,H41N,H41O),
 C41F(H41P,H41Q,H41R), C54F(H54P,H54Q,H54R), C55F(H55P,H55Q,H55R), C63F(H63D,
 H63E,H63F), C64F(H64D,H64E,H64F), C73C(H73G,H73H,H73I), C74C(H74G,H74H,H74I)
;
_shelx_res_checksum              28852
_olex2_submission_special_instructions 'No special instructions were received'