From closed-shell edge-extended kekulenes to open-shell carbonylated cycloarene diradicaloid.
Chang, Dongdong; Zhu, Jiangyu; Sun, Yutao; Chi, Kai; Qiao, Yanjun; Wang, Teng; Zhao, Yan; Liu, Yunqi; Lu, Xuefeng; Chemical science 14 (2023) 6087–6094; doi:10.1039/d3sc01295f

data_1569184
_publ_section_title
;
 From closed-shell edge-extended kekulenes to open-shell carbonylated
 cycloarene diradicaloid.
;
_journal_issue                   22
_journal_name_full               'Chemical science'
_journal_page_first              6087
_journal_page_last               6094
_journal_paper_doi               10.1039/d3sc01295f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C112 H108 O4, C7 H8'
_chemical_formula_sum            'C119 H116 O4'
_chemical_formula_weight         1610.11
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-25
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_audit_update_record
;
2023-04-28 deposited with the CCDC.	2023-05-15 downloaded from the CCDC.
;
_cell_angle_alpha                103.9550(10)
_cell_angle_beta                 92.8870(10)
_cell_angle_gamma                99.0390(10)
_cell_formula_units_Z            1
_cell_length_a                   8.6954(2)
_cell_length_b                   15.6090(3)
_cell_length_c                   17.0505(4)
_cell_measurement_reflns_used    9881
_cell_measurement_temperature    173
_cell_measurement_theta_max      68.236
_cell_measurement_theta_min      2.962
_cell_volume                     2208.59(9)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       '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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0497
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            52235
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.343
_diffrn_reflns_theta_min         2.682
_exptl_absorpt_coefficient_mu    0.543
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6603
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1021 before and 0.0604 after correction.
The Ratio of minimum to maximum transmission is 0.8768.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.211
_exptl_crystal_description       plate
_exptl_crystal_F_000             862
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.394
_refine_diff_density_min         -0.251
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     583
_refine_ls_number_reflns         8079
_refine_ls_number_restraints     76
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0630
_refine_ls_R_factor_gt           0.0456
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0642P)^2^+0.5987P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1159
_refine_ls_wR_factor_ref         0.1264
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6137
_reflns_number_total             8079
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01295f2.cif
_cod_data_source_block           a_CCDC1
_cod_depositor_comments
'Adding full bibliography for 1569181--1569184.cif.'
_cod_original_cell_volume        2208.59(8)
_cod_database_code               1569184
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.854
_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
 C57-C63 \\sim C57-C59
 with sigma of 0.04
 C59-C60 \\sim C60-C61 \\sim C61-C62 \\sim C62-C63
 with sigma of 0.02
 C63-C61 \\sim C59-C63 \\sim C60-C62 \\sim C59-C61
 with sigma of 0.04
3. Restrained planarity
 C57, C59, C60, C61, C62, C63
 with sigma of 0.1
4. Rigid bond restraints
 C58
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C58, C57, C59, C60, C61, C62, C63
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C58: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C57 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
6. Rigid body (RIGU) restrains
 C58
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C57, C59, C60, C61, C62, C63
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
7. Others
 Fixed Sof: C58(0.5) C57(0.5) H57A(0.5) H57B(0.5) H57C(0.5) C59(0.5) H59(0.5)
 C60(0.5) H60(0.5) C61(0.5) H61(0.5) C62(0.5) H62(0.5) C63(0.5) H63(0.5)
8.a Free rotating group:
 C57(C59,C60,C61,C62,C63)
8.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C10(H10A,H10B), C17(H17A,H17B), C16(H16A,H16B), C11(H11A,
 H11B), C12(H12A,H12B)
8.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C29(H29), C7(H7), C41(H41), C26(H26), C25(H25), C21(H21), C49(H49),
 C48(H48), C51(H51), C42(H42), C52(H52), C24(H24), C4(H4), C39(H39), C1(H1),
 C38(H38), C2(H2), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63)
8.d Idealised Me refined as rotating group:
 C55(H55A,H55B,H55C), C46(H46A,H46B,H46C), C45(H45A,H45B,H45C), C54(H54A,H54B,
 H54C), C56(H56A,H56B,H56C), C44(H44A,H44B,H44C), C18(H18A,H18B,H18C), C13(H13A,
 H13B,H13C), C57(H57A,H57B,H57C)
;
_shelx_res_checksum              42840
_shelx_hkl_checksum              88688
_olex2_submission_special_instructions 'No special instructions were received'