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_1570089
_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         'C110 H120 B2 N12 O4 S3 Zn2, 6.408(C H Cl3)'
_chemical_formula_sum            'C116.41 H126.41 B2 Cl19.23 N12 O4 S3 Zn2'
_chemical_formula_weight         2687.68
_chemical_name_common            'bis(semiquinone) terthiophene'
_chemical_name_systematic        SQ2Th3
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-05-05 deposited with the CCDC.	2023-10-09 downloaded from the CCDC.
;
_cell_angle_alpha                73.7860(10)
_cell_angle_beta                 89.4140(10)
_cell_angle_gamma                76.8000(10)
_cell_formula_units_Z            2
_cell_length_a                   13.9530(4)
_cell_length_b                   19.5674(5)
_cell_length_c                   25.3044(6)
_cell_measurement_reflns_used    9037
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      79.11
_cell_measurement_theta_min      3.78
_cell_volume                     6448.0(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.970
_diffrn_measurement_device_type  'Bruker D8 Venture Photon-II CMOS'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0542
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            155286
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.626
_diffrn_reflns_theta_min         2.419
_diffrn_source                   'INCOATEC Imus micro-focus source'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.005
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6440
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1265 before and 0.0772 after correction.
The Ratio of minimum to maximum transmission is 0.6440.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.384
_exptl_crystal_description       block
_exptl_crystal_F_000             2771
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2 and MeOH'
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.795
_refine_diff_density_min         -0.687
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1996
_refine_ls_number_reflns         27216
_refine_ls_number_restraints     2339
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0639
_refine_ls_R_factor_gt           0.0562
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0763P)^2^+9.5200P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1486
_refine_ls_wR_factor_ref         0.1552
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23485
_reflns_number_total             27216
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02341a2.cif
_cod_data_source_block           pdm3_57
_cod_depositor_comments
'Adding full bibliography for 1570087--1570089.cif.'
_cod_database_code               1570089
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.634
_shelx_estimated_absorpt_t_min   0.289
_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. Restrained distances
 Cl2F-C1F = Cl3F-C1F = Cl4F-C1F
 1.75 with sigma of 0.005
 Cl3E-C1E = Cl4E-C1E = Cl2E-C1E
 1.75 with sigma of 0.005
 Cl2N-C1N = Cl3N-C1N = Cl4N-C1N
 1.75 with sigma of 0.02
 Cl3D-C1D = Cl4D-C1D = Cl2D-C1D
 1.75 with sigma of 0.02
 Cl2Q-C1Q = Cl3Q-C1Q = Cl4Q-C1Q
 1.75 with sigma of 0.005
 Cl4G-C1G = Cl2G-C1G = Cl3G-C1G
 1.75 with sigma of 0.005
 Cl2H-C1H = Cl4H-C1H = Cl3H-C1H
 1.75 with sigma of 0.005
 Cl4I-C1I = Cl2I-C1I = Cl3I-C1I
 1.75 with sigma of 0.005
 Cl4K-C1K = Cl2K-C1K = Cl3K-C1K
 1.75 with sigma of 0.005
 Cl4L-C1L = Cl2L-C1L = Cl3L-C1L
 1.75 with sigma of 0.005
 Cl2M-C1M = Cl3M-C1M = C1M-Cl4M
 1.75 with sigma of 0.02
 Cl2O-C1O = Cl3O-C1O = C1O-Cl4O
 1.75 with sigma of 0.02
 Cl2P-C1P = Cl3P-C1P = C1P-Cl4P
 1.75 with sigma of 0.02
 Cl4R-C1R = Cl2R-C1R = Cl3R-C1R
 1.75 with sigma of 0.02
 Cl4S-C1S = Cl2S-C1S = Cl3S-C1S
 1.75 with sigma of 0.02
 C83A-C80A = C103-C100 = C203-C100 = C123-C120 = C183-C180
 1.52 with sigma of 0.02
 C105-C103 = C104-C103 = C204-C203 = C205-C203
 1.53 with sigma of 0.02
 C125-C123 = C124-C123 = C184-C183 = C185-C183
 1.53 with sigma of 0.02
 C85A-C83A = C84A-C83A
 1.53 with sigma of 0.02
 C165-C163 = C164-C163 = C214-C163 = C215-C163
 1.53 with sigma of 0.02
 Cl3Q-Cl2Q = Cl4Q-Cl3Q = Cl4Q-Cl2Q
 2.88 with sigma of 0.01
 Cl4D-Cl2D = Cl3D-Cl4D = Cl2D-Cl3D
 2.88 with sigma of 0.01
 Cl3E-Cl4E = Cl2E-Cl3E = Cl4E-Cl2E
 2.88 with sigma of 0.01
 Cl3F-Cl4F = Cl2F-Cl4F = Cl2F-Cl3F
 2.88 with sigma of 0.01
 Cl4G-Cl2G = Cl3G-Cl2G = Cl4G-Cl3G
 2.88 with sigma of 0.01
 Cl2H-Cl4H = Cl3H-Cl2H = Cl4H-Cl3H
 2.88 with sigma of 0.01
 Cl2I-Cl4I = Cl3I-Cl2I = Cl4I-Cl3I
 2.88 with sigma of 0.01
 Cl2K-Cl4K = Cl3K-Cl2K = Cl4K-Cl3K
 2.88 with sigma of 0.01
 Cl2L-Cl4L = Cl3L-Cl2L = Cl4L-Cl3L
 2.88 with sigma of 0.01
 Cl2M-Cl3M = Cl4M-Cl3M = Cl2M-Cl4M
 2.88 with sigma of 0.04
 Cl2N-Cl3N = Cl2N-Cl4N = Cl3N-Cl4N
 2.88 with sigma of 0.04
 Cl2O-Cl3O = Cl2O-Cl4O = Cl3O-Cl4O
 2.88 with sigma of 0.04
 Cl2P-Cl3P = Cl2P-Cl4P = Cl3P-Cl4P
 2.88 with sigma of 0.04
 Cl2R-Cl3R = Cl4R-Cl3R = Cl2R-Cl4R
 2.88 with sigma of 0.04
 Cl2S-Cl3S = Cl4S-Cl3S = Cl2S-Cl4S
 2.88 with sigma of 0.04
 C85A-C84A = C104-C105 = C125-C124 = C185-C184 = C205-C204
 2.51 with sigma of 0.04
 C165-C164 = C215-C214
 2.51 with sigma of 0.04
 C77A-C74 \\sim C77-C74
 with sigma of 0.005
3. Restrained planarity
 C81A, C80A, C79A, C83A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C1C \\sim Cl2C \\sim Cl3C \\sim Cl4C \\sim C1D \\sim Cl2D \\sim Cl3D \\sim Cl4D
\\sim C1E \\sim Cl2E \\sim Cl3E \\sim Cl4E \\sim C1F \\sim Cl2F \\sim Cl3F
\\sim Cl4F \\sim C1G \\sim Cl2G \\sim Cl4G \\sim C1H \\sim Cl2H \\sim Cl3H
\\sim Cl4H \\sim C1I \\sim Cl2I \\sim Cl3I \\sim Cl4I \\sim C1K \\sim Cl2K
\\sim Cl3K \\sim Cl4K \\sim C1L \\sim Cl2L \\sim Cl3L \\sim Cl4L \\sim C1M
\\sim Cl2M \\sim Cl3M \\sim Cl4M \\sim C1N \\sim Cl2N \\sim Cl3N \\sim Cl4N
\\sim C1O \\sim Cl2O \\sim Cl3O \\sim Cl4O \\sim C1P \\sim Cl2P \\sim Cl3P
\\sim Cl4P \\sim C1Q \\sim Cl2Q \\sim Cl3Q \\sim Cl4Q \\sim Cl2R \\sim Cl3R
\\sim Cl4R \\sim C1R \\sim Cl4G \\sim C1G \\sim Cl2G \\sim Cl3G \\sim Cl4S
\\sim C1S \\sim Cl2S \\sim Cl3S: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C100 \\sim C103 \\sim C104 \\sim C105 \\sim C203 \\sim C204 \\sim C205: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C118 \\sim C119 \\sim C120 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim
C125 \\sim C178 \\sim C179 \\sim C180 \\sim C181 \\sim C182 \\sim C183 \\sim
C184 \\sim C185 \\sim C117 \\sim C177 \\sim C114: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim
C85 \\sim C77A \\sim C82A \\sim C81A \\sim C80A \\sim C79A \\sim C78A \\sim
C83A \\sim C84A \\sim C85A \\sim C74: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
C160 \\sim C163 \\sim C214 \\sim C215 \\sim C164 \\sim C165: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C77A) = Uanis(C77)
Uanis(C78A) = Uanis(C78)
Uanis(C79A) = Uanis(C79)
Uanis(C80) = Uanis(C80A)
Uanis(C81A) = Uanis(C81)
Uanis(C82) = Uanis(C82A)
Uanis(C103) = Uanis(C203)
Uanis(C125) = Uanis(C185)
Uanis(C177) = Uanis(C117)
Uanis(C178) = Uanis(C118)
Uanis(C179) = Uanis(C119)
5. Rigid body (RIGU) restrains
 C1C, Cl2C, Cl3C, Cl4C, C1D, Cl2D, Cl3D, Cl4D, C1E, Cl2E, Cl3E, Cl4E, C1F,
 Cl2F, Cl3F, Cl4F, C1G, Cl2G, Cl4G, C1H, Cl2H, Cl3H, Cl4H, C1I, Cl2I, Cl3I,
 Cl4I, C1K, Cl2K, Cl3K, Cl4K, C1L, Cl2L, Cl3L, Cl4L, C1M, Cl2M, Cl3M, Cl4M, C1N,
  Cl2N, Cl3N, Cl4N, C1O, Cl2O, Cl3O, Cl4O, C1P, Cl2P, Cl3P, Cl4P, C1Q, Cl2Q,
 Cl3Q, Cl4Q, Cl2R, Cl3R, Cl4R, C1R, Cl4G, C1G, Cl2G, Cl3G, Cl4S, C1S, Cl2S, Cl3S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C100, C103, C104, C105, C203, C204, C205
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C118, C119, C120, C121, C122, C123, C124, C125, C178, C179, C180, C181, C182,
 C183, C184, C185, C117, C177, C114
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C77, C78, C79, C80, C81, C82, C83, C84, C85, C77A, C82A, C81A, C80A, C79A,
 C78A, C83A, C84A, C85A, C74
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C160, C163, C214, C215, C164, C165
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 -1*[Sof(C1N)+Sof(H1N)+Sof(Cl2N)+Sof(Cl3N)]+1*[Sof(Cl4N)]=0 with esd of 0
 Sof(C203)=Sof(H203)=Sof(C204)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C205)=
 Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(C103)=Sof(H103)=Sof(C104)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C105)=
 Sof(H10D)=Sof(H10E)=Sof(H10F)=FVAR(1)
 Sof(C1D)=Sof(H1D)=Sof(Cl2D)=Sof(Cl3D)=Sof(Cl4D)=FVAR(2)
 Sof(C1H)=Sof(H1H)=Sof(Cl2H)=Sof(Cl3H)=Sof(Cl4H)=FVAR(3)
 Sof(C1I)=Sof(H1I)=Sof(Cl2I)=Sof(Cl3I)=Sof(Cl4I)=FVAR(4)
 Sof(C1C)=Sof(H1C)=Sof(Cl2C)=Sof(Cl3C)=Sof(Cl4C)=FVAR(5)
 Sof(C177)=Sof(C178)=Sof(H178)=Sof(C179)=Sof(H179)=Sof(C180)=Sof(C181)=
 Sof(H181)=Sof(C182)=Sof(H182)=Sof(C183)=Sof(H183)=Sof(C184)=Sof(H18A)=
 Sof(H18B)=Sof(H18C)=Sof(C185)=Sof(H18D)=Sof(H18E)=Sof(H18F)=1-FVAR(6)
 Sof(C117)=Sof(C118)=Sof(H118)=Sof(C119)=Sof(H119)=Sof(C120)=Sof(C121)=
 Sof(H121)=Sof(C122)=Sof(H122)=Sof(C123)=Sof(H123)=Sof(C124)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C125)=Sof(H12D)=Sof(H12E)=Sof(H12F)=FVAR(6)
 Sof(C77A)=Sof(C82A)=Sof(H82A)=Sof(C81A)=Sof(H81A)=Sof(C80A)=Sof(C79A)=
 Sof(H79A)=Sof(C78A)=Sof(H78A)=Sof(C83A)=Sof(H83A)=Sof(C84A)=Sof(H84D)=
 Sof(H84E)=Sof(H84F)=Sof(C85A)=Sof(H85D)=Sof(H85E)=Sof(H85F)=1-FVAR(7)
 Sof(C77)=Sof(C78)=Sof(H78)=Sof(C79)=Sof(H79)=Sof(C80)=Sof(C81)=Sof(H81)=
 Sof(C82)=Sof(H82)=Sof(C83)=Sof(H83)=Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(H84C)=
 Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(H85C)=FVAR(7)
 Sof(C1G)=Sof(H1G)=Sof(Cl2G)=Sof(Cl4G)=Sof(Cl3G)=FVAR(8)
 Sof(C1M)=Sof(H1M)=Sof(Cl2M)=Sof(Cl3M)=Sof(Cl4M)=FVAR(9)
 Sof(C1L)=Sof(H1L)=Sof(Cl2L)=Sof(Cl3L)=Sof(Cl4L)=FVAR(10)
 Sof(C1K)=Sof(H1K)=Sof(Cl2K)=Sof(Cl3K)=Sof(Cl4K)=FVAR(11)
 Sof(C1E)=Sof(H1E)=Sof(Cl2E)=Sof(Cl3E)=Sof(Cl4E)=FVAR(12)
 Sof(C1F)=Sof(H1F)=Sof(Cl2F)=Sof(Cl3F)=Sof(Cl4F)=FVAR(13)
 Sof(C1P)=Sof(H1P)=Sof(Cl2P)=Sof(Cl3P)=Sof(Cl4P)=FVAR(14)
 Sof(C1O)=Sof(H1O)=Sof(Cl2O)=Sof(Cl3O)=Sof(Cl4O)=FVAR(15)
 Sof(H163)=Sof(C214)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C215)=Sof(H21D)=
 Sof(H21E)=Sof(H21F)=1-FVAR(16)
 Sof(H16A)=Sof(C164)=Sof(H16B)=Sof(H16C)=Sof(H16D)=Sof(C165)=Sof(H16E)=
 Sof(H16F)=Sof(H16G)=FVAR(16)
 Sof(C1R)=Sof(H1R)=Sof(Cl2R)=Sof(Cl3R)=Sof(Cl4R)=FVAR(17)
 Sof(C1N)=Sof(H1N)=Sof(Cl2N)=Sof(Cl3N)=FVAR(18)
 Sof(Cl4S)=Sof(Cl3S)=Sof(Cl2S)=Sof(C1S)=Sof(H1S)=FVAR(20)
 Sof(C1Q)=Sof(H1Q)=Sof(Cl2Q)=Sof(Cl3Q)=Sof(Cl4Q)=FVAR(21)
7.a Ternary CH refined with riding coordinates:
 C63(H63), C83(H83), C83A(H83A), C103(H103), C203(H203), C123(H123),
 C183(H183), C143(H143), C163(H16A), C163(H163), C1A(H1A), C1B(H1B), C1C(H1C),
 C1D(H1D), C1E(H1E), C1F(H1F), C1G(H1G), C1H(H1H), C1I(H1I), C1K(H1K), C1L(H1L),
  C1M(H1M), C1N(H1N), C1O(H1O), C1P(H1P), C1Q(H1Q), C1R(H1R), C1S(H1S)
7.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C11(H11), C12(H12), C14(H14), C18(H18), C27(H27), C31(H31), C32(H32),
 C34(H34), C38(H38), C53(H53), C58(H58), C59(H59), C61(H61), C62(H62), C73(H73),
  C78(H78), C79(H79), C81(H81), C82(H82), C82A(H82A), C81A(H81A), C79A(H79A),
 C78A(H78A), C93(H93), C98(H98), C99(H99), C101(H101), C102(H102), C113(H113),
 C118(H118), C119(H119), C121(H121), C122(H122), C178(H178), C179(H179),
 C181(H181), C182(H182), C133(H133), C138(H138), C139(H139), C141(H141),
 C142(H142), C153(H153), C158(H158), C159(H159), C161(H161), C162(H162)
7.c Fitted hexagon refined as free rotating group:
 C77A(C82A,C81A,C80A,C79A,C78A), C177(C178,C179,C180,C181,C182)
7.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C42(H42A,H42B,
 H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C56(H56A,H56B,H56C), C64(H64A,
 H64B,H64C), C65(H65A,H65B,H65C), C76(H76A,H76B,H76C), C84(H84A,H84B,H84C),
 C85(H85A,H85B,H85C), C84A(H84D,H84E,H84F), C85A(H85D,H85E,H85F), C96(H96A,H96B,
 H96C), C104(H10A,H10B,H10C), C105(H10D,H10E,H10F), C204(H20A,H20B,H20C),
 C205(H20D,H20E,H20F), C116(H11A,H11B,H11C), C124(H12A,H12B,H12C), C125(H12D,
 H12E,H12F), C184(H18A,H18B,H18C), C185(H18D,H18E,H18F), C136(H13A,H13B,H13C),
 C144(H14A,H14B,H14C), C145(H14D,H14E,H14F), C156(H15A,H15B,H15C), C214(H21A,
 H21B,H21C), C215(H21D,H21E,H21F), C164(H16B,H16C,H16D), C165(H16E,H16F,H16G)
;
_shelx_res_checksum              18668
_olex2_submission_special_instructions 'No special instructions were received'