Stepwise reduction of an asymmetric π-expanded pyracylene towards the crystalline radical trianion.
Zhu, Yikun; Borstelmann, Jan; Neiss, Christian; Wei, Zheng; Görling, Andreas; Kivala, Milan; Petrukhina, Marina A.; Chemical science 16 (2025) 3211–3217; doi:10.1039/d4sc08255a

data_1573686
_publ_section_title
;
 Stepwise reduction of an asymmetric &#x3c0;-expanded pyracylene towards
 the crystalline radical trianion.
;
_journal_issue                   7
_journal_name_full               'Chemical science'
_journal_page_first              3211
_journal_page_last               3217
_journal_paper_doi               10.1039/d4sc08255a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
;
C102 H102, C12 H30 K O6, 2(C6 H14)
;
_chemical_formula_sum            'C126 H160 K O6'
_chemical_formula_weight         1809.63
_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_Hall           'C 2c -2'
_space_group_name_H-M_alt        'C m c 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-09-30
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-10-18 deposited with the CCDC.	2025-01-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.623(2)
_cell_length_b                   12.2818(9)
_cell_length_c                   36.081(3)
_cell_measurement_reflns_used    9963
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      17.15
_cell_measurement_theta_min      2.24
_cell_volume                     11797.7(16)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'APEX3 v.2017.3-0 (Bruker AXS Inc., 2017)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector
;
DECTRIS PILATUS3 X 2M(CdTe) pixel array detector
;
_diffrn_detector_area_resol_mean 30
_diffrn_detector_type            'CMOS pixel array detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Huber 4-circle diffractometer'
_diffrn_measurement_method       'phi rotation'
_diffrn_radiation_collimation    '0.2 mm sinlge-pinhole'
_diffrn_radiation_monochromator  'Si(111) & Si(311)'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.41328
_diffrn_reflns_av_R_equivalents  0.0790
_diffrn_reflns_av_unetI/netI     0.0716
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -51
_diffrn_reflns_number            227228
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        14.357
_diffrn_reflns_theta_max         17.232
_diffrn_reflns_theta_min         0.889
_diffrn_source                   synchrotron
_diffrn_source_current           103.0
_diffrn_source_power             103.0
_diffrn_source_type
'Insertion Device, Station 15 ID-B, APS, Argonne Nat'l Lab'
_diffrn_source_voltage           1000.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.035
_exptl_absorpt_correction_T_max  0.6372
_exptl_absorpt_correction_T_min  0.5430
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.1316 before and 0.0723 after correction.
The Ratio of minimum to maximum transmission is 0.8522.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.019
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    none
_exptl_crystal_description       block
_exptl_crystal_F_000             3932
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.735
_refine_diff_density_min         -0.497
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 7130 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(5)
_refine_ls_extinction_coef       0.0033(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     899
_refine_ls_number_reflns         18484
_refine_ls_number_restraints     1091
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0732
_refine_ls_R_factor_gt           0.0663
_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^)+(0.1332P)^2^+1.4497P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1843
_refine_ls_wR_factor_ref         0.1943
_reflns_Friedel_coverage         0.969
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                16184
_reflns_number_total             18484
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08255a2.cif
_cod_data_source_block           K_1_1
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1573686--1573688.cif.
;
_cod_database_code               1573686
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.997
_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
 O2-C55 = O2-C56 = O1-C54 = O1-C53 = O3-C58 = O3-C57 = O4-C59 = O4-C60
 1.43 with sigma of 0.02
 C57_$1-C57 = C60-C60_$1
 1.54 with sigma of 0.02
 C55-C54
 1.54 with sigma of 0.02
 O1A-C53A
 1.43 with sigma of 0.02
 C42-C43 \\sim C42-C43A
 with sigma of 0.02
 C43-C44 \\sim C43A-C44A
 with sigma of 0.02
 C43-C48 \\sim C43A-C48A
 with sigma of 0.02
 C44-C45 \\sim C44A-C45A
 with sigma of 0.02
 C46-C50 \\sim C46A-C50A
 with sigma of 0.04
 C45-C46 \\sim C45A-C46A
 with sigma of 0.02
 C45-C47 \\sim C45A-C47A
 with sigma of 0.04
 C46-C52 \\sim C46A-C52A
 with sigma of 0.04
 C46-C47 \\sim C46A-C47A
 with sigma of 0.02
 C46-C49 \\sim C46A-C49A
 with sigma of 0.02
 C50-C51 \\sim C50A-C51A
 with sigma of 0.04
 C47-C48 \\sim C47A-C48A
 with sigma of 0.02
 C45-C49 \\sim C45A-C49A
 with sigma of 0.04
 C49-C50 \\sim C49A-C50A
 with sigma of 0.02
 C49-C51 \\sim C49A-C51A
 with sigma of 0.02
 C49-C52 \\sim C49A-C52A
 with sigma of 0.02
 C46-C48 \\sim C46A-C48A
 with sigma of 0.04
 C46-C51 \\sim C46A-C51A
 with sigma of 0.04
 C47-C49 \\sim C47A-C49A
 with sigma of 0.04
 C42-C44 \\sim C42-C44A
 with sigma of 0.04
 C42-C48 \\sim C42-C48A
 with sigma of 0.04
 C43-C45 \\sim C43A-C45A
 with sigma of 0.04
 C43-C47 \\sim C43A-C47A
 with sigma of 0.04
 C50-C52 \\sim C50A-C52A
 with sigma of 0.04
 C44-C46 \\sim C44A-C46A
 with sigma of 0.04
 C51-C52 \\sim C51A-C52A
 with sigma of 0.04
 C44-C48 \\sim C44A-C48A
 with sigma of 0.04
 C32-C33 \\sim C32A-C33A
 with sigma of 0.02
 C39-C40 \\sim C39A-C40A
 with sigma of 0.04
 C35-C41 \\sim C35A-C41A
 with sigma of 0.04
 C32-C37 \\sim C32A-C37A
 with sigma of 0.02
 C34-C36 \\sim C34A-C36A
 with sigma of 0.04
 C1-C32 \\sim C1-C32A
 with sigma of 0.02
 C33-C34 \\sim C33A-C34A
 with sigma of 0.02
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 C40-C41 \\sim C40A-C41A
 with sigma of 0.04
 C35-C39 \\sim C35A-C39A
 with sigma of 0.04
 C35-C36 \\sim C35A-C36A
 with sigma of 0.02
 C35-C38 \\sim C35A-C38A
 with sigma of 0.02
 C36-C38 \\sim C36A-C38A
 with sigma of 0.04
 C36-C37 \\sim C36A-C37A
 with sigma of 0.02
 C34-C38 \\sim C34A-C38A
 with sigma of 0.04
 C38-C39 \\sim C38A-C39A
 with sigma of 0.02
 C38-C40 \\sim C38A-C40A
 with sigma of 0.02
 C35-C37 \\sim C35A-C37A
 with sigma of 0.04
 C35-C40 \\sim C35A-C40A
 with sigma of 0.04
 C1-C33 \\sim C1-C33A
 with sigma of 0.04
 C1-C37 \\sim C1-C37A
 with sigma of 0.04
 C32-C34 \\sim C32A-C34A
 with sigma of 0.04
 C32-C36 \\sim C32A-C36A
 with sigma of 0.04
 C39-C41 \\sim C39A-C41A
 with sigma of 0.04
 C33-C35 \\sim C33A-C35A
 with sigma of 0.04
 C33-C37 \\sim C33A-C37A
 with sigma of 0.04
 C38-C41 \\sim C38A-C41A
 with sigma of 0.02
 C24-C26 \\sim C24-C26A
 with sigma of 0.02
 C24-C27 \\sim C24-C27A
 with sigma of 0.02
 C24-C25 \\sim C24-C25A
 with sigma of 0.02
 C25A-C26A \\sim C26A-C27A \\sim C27A-C25A
 with sigma of 0.02
 O3-C57 \\sim O3A-C57A
 with sigma of 0.02
 O3-C58 \\sim O3A-C58A
 with sigma of 0.02
 K1-O3 \\sim K1-O3A
 with sigma of 0.02
 K1-C58 \\sim K1-C58A
 with sigma of 0.04
 C57-C58 \\sim C57A-C58A
 with sigma of 0.04
 K1-C57 \\sim K1-C57A
 with sigma of 0.04
 O4-C60 \\sim O4A-C60A
 with sigma of 0.02
 K1-O4 \\sim K1-O4A
 with sigma of 0.02
 C59-C60 \\sim C59A-C60A
 with sigma of 0.04
 K1-C59 \\sim K1-C59A
 with sigma of 0.04
 K1-C60 \\sim K1-C60A
 with sigma of 0.04
 O4-C59 \\sim O4A-C59A
 with sigma of 0.02
 O2-C54 \\sim O2A-C54A
 with sigma of 0.04
 O2-C55 \\sim O2A-C55A
 with sigma of 0.02
 K1-O1 \\sim K1-O1A
 with sigma of 0.02
 K1-O2 \\sim K1-O2A
 with sigma of 0.02
 C55-C56 \\sim C55A-C56A
 with sigma of 0.04
 C53-C54 \\sim C53A-C54A
 with sigma of 0.04
 C54-C55 \\sim C54A-C55A
 with sigma of 0.02
 O1-C53 \\sim O1A-C53A
 with sigma of 0.02
 O1-C54 \\sim O1A-C54A
 with sigma of 0.02
 K1-C55 \\sim K1-C55A
 with sigma of 0.04
 K1-C56 \\sim K1-C56A
 with sigma of 0.04
 O1-C55 \\sim O1A-C55A
 with sigma of 0.04
 O2-C56 \\sim O2A-C56A
 with sigma of 0.02
 K1-C53 \\sim K1-C53A
 with sigma of 0.04
 K1-C54 \\sim K1-C54A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim
C51 \\sim C52 \\sim C43A \\sim C44A \\sim C45A \\sim C46A \\sim C47A \\sim C48A
\\sim C49A \\sim C50A \\sim C51A \\sim C52A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim
C40 \\sim C41 \\sim C32A \\sim C38A \\sim C39A \\sim C40A \\sim C41A \\sim C34A
\\sim C35A \\sim C36A \\sim C33A \\sim C37A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C24 \\sim C25 \\sim C26 \\sim C27 \\sim C26A \\sim C25A \\sim C27A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O3 \\sim C57 \\sim C58 \\sim O3A \\sim C58A \\sim C57A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O4 \\sim C59 \\sim C60 \\sim C60A \\sim O4A \\sim C59A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O1 \\sim O2 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim O1A \\sim O2A \\sim
C53A \\sim C54A \\sim C55A \\sim C56A: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.02 within 2A
Uanis(C53A) = Uanis(C53)
4. Rigid body (RIGU) restrains
 O1, O2, C53, C54, C55, C56, O1A, O2A, C53A, C54A, C55A, C56A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(O1)+Sof(O2)+Sof(C53)+Sof(H53A)+Sof(H53B)+Sof(H53C)+Sof(C54)+Sof(H54A)+
 Sof(H54B)+Sof(C55)+Sof(H55A)+Sof(H55B)+Sof(C56)+Sof(H56A)+Sof(H56B)+Sof(H56C)]+
 1*[Sof(O1A)+Sof(O2A)+Sof(C53A)+Sof(H53D)+Sof(H53E)+Sof(H53F)+Sof(C54A)+
 Sof(H54C)+Sof(H54D)+Sof(C55A)+Sof(H55C)+Sof(H55D)+Sof(C56A)+Sof(H56D)+
 Sof(H56E)+Sof(H56F)]=0.5 with esd of 0
 Sof(C43A)=Sof(C44A)=Sof(H44A)=Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(C47A)=
 Sof(H47A)=Sof(C48A)=Sof(H48A)=Sof(C49A)=Sof(C50A)=Sof(H50D)=Sof(H50E)=
 Sof(H50F)=Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=Sof(C52A)=Sof(H52D)=
 Sof(H52E)=Sof(H52F)=1-FVAR(1)
 Sof(C43)=Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(C47)=Sof(H47)=
 Sof(C48)=Sof(H48)=Sof(C49)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C51)=
 Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=FVAR(1)
 Sof(C32A)=Sof(C38A)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40A)=
 Sof(H40D)=Sof(H40E)=Sof(H40F)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=
 Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(C36A)=Sof(H36A)=Sof(C33A)=Sof(H33A)=
 Sof(C37A)=Sof(H37A)=1-FVAR(2)
 Sof(C32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(C36)=Sof(H36)=
 Sof(C37)=Sof(H37)=Sof(C38)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=
 Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(2)
 Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C25A)=Sof(H25D)=Sof(H25E)=
 Sof(H25F)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(3)
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(3)
 Sof(O3A)=Sof(C58A)=Sof(H58D)=Sof(H58E)=Sof(H58F)=Sof(C57A)=Sof(H57C)=
 Sof(H57D)=1-FVAR(4)
 Sof(O3)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=
 FVAR(4)
 Sof(C60A)=Sof(H60A)=Sof(H60B)=Sof(O4A)=Sof(C59A)=Sof(H59A)=Sof(H59B)=
 Sof(H59C)=1-FVAR(5)
 Sof(O4)=Sof(C59)=Sof(H59D)=Sof(H59E)=Sof(H59F)=Sof(C60)=Sof(H60C)=Sof(H60D)=
 FVAR(5)
 Sof(O1)=Sof(O2)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C54)=Sof(H54A)=
 Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=
 FVAR(6)
 Sof(O1A)=Sof(O2A)=Sof(C53A)=Sof(H53D)=Sof(H53E)=Sof(H53F)=Sof(C54A)=Sof(H54C)=
 Sof(H54D)=Sof(C55A)=Sof(H55C)=Sof(H55D)=Sof(C56A)=Sof(H56D)=Sof(H56E)=
 Sof(H56F)=FVAR(7)
6.a Secondary CH2 refined with riding coordinates:
 C54(H54A,H54B), C55(H55A,H55B), C57(H57A,H57B), C60(H60C,H60D), C57A(H57C,
 H57D), C60A(H60A,H60B), C54A(H54C,H54D), C55A(H55C,H55D)
6.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C12(H12), C13(H13), C15(H15), C18(H18), C20(H20), C33(H33),
 C34(H34), C36(H36), C37(H37), C44(H44), C45(H45), C47(H47), C48(H48),
 C44A(H44A), C45A(H45A), C47A(H47A), C48A(H48A), C34A(H34A), C36A(H36A),
 C33A(H33A), C37A(H37A)
6.c Fitted hexagon refined as free rotating group:
 C43(C44,C45,C46,C47,C48), C43A(C44A,C45A,C46A,C47A,C48A)
6.d Idealised Me refined as rotating group:
 C53(H53A,H53B,H53C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C59(H59D,H59E,
 H59F), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,
 H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C50(H50A,H50B,H50C), C51(H51A,H51B,
 H51C), C52(H52A,H52B,H52C), C50A(H50D,H50E,H50F), C51A(H51D,H51E,H51F),
 C52A(H52D,H52E,H52F), C39A(H39D,H39E,H39F), C40A(H40D,H40E,H40F), C41A(H41D,
 H41E,H41F), C26A(H26D,H26E,H26F), C25A(H25D,H25E,H25F), C27A(H27D,H27E,H27F),
 C58A(H58D,H58E,H58F), C59A(H59A,H59B,H59C), C53A(H53D,H53E,H53F), C56A(H56D,
 H56E,H56F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              81108
_shelx_fab_checksum              58195
_olex2_submission_special_instructions 'No special instructions were received'