Crystallographic evidence for global aromaticity in the di-anion and tetra-anion of a cyclophane hydrocarbon.
Stawski, Wojciech; Zhu, Yikun; Wei, Zheng; Petrukhina, Marina A.; Anderson, Harry L.; Chemical science 14 (2023) 14109–14114; doi:10.1039/d3sc04251k

data_1569915
_publ_section_title
;
 Crystallographic evidence for global aromaticity in the di-anion and
 tetra-anion of a cyclophane hydrocarbon.
;
_journal_issue                   48
_journal_name_full               'Chemical science'
_journal_page_first              14109
_journal_page_last               14114
_journal_paper_doi               10.1039/d3sc04251k
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C64 H88 Li4 O8'
_chemical_formula_sum            'C64 H88 Li4 O8'
_chemical_formula_weight         1013.10
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-03-30
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-26 deposited with the CCDC.	2023-09-20 downloaded from the CCDC.
;
_cell_angle_alpha                89.457(2)
_cell_angle_beta                 89.6290(10)
_cell_angle_gamma                76.211(2)
_cell_formula_units_Z            2
_cell_length_a                   12.0087(15)
_cell_length_b                   12.8316(16)
_cell_length_c                   19.699(3)
_cell_measurement_reflns_used    9613
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      19.23
_cell_measurement_theta_min      2.28
_cell_volume                     2947.8(7)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector
;
DECTRIS PILATUS3 X 1M(CdTe) pixel array detector
;
_diffrn_detector_area_resol_mean 30
_diffrn_detector_type            'CMOS pixel array detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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     0.49594
_diffrn_reflns_av_R_equivalents  0.0950
_diffrn_reflns_av_unetI/netI     0.0618
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            147996
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        17.311
_diffrn_reflns_theta_max         19.348
_diffrn_reflns_theta_min         1.140
_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    0.039
_exptl_absorpt_correction_T_max  0.744354
_exptl_absorpt_correction_T_min  0.716827
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
TWINABS-2012/1 (Bruker, 2012) was used for absorption correction.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.141
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    none
_exptl_crystal_description       block
_exptl_crystal_F_000             1096
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.561
_refine_diff_density_min         -0.381
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     881
_refine_ls_number_reflns         14678
_refine_ls_number_restraints     711
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.1205
_refine_ls_R_factor_gt           0.0889
_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^)+(0.1150P)^2^+3.1720P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2372
_refine_ls_wR_factor_ref         0.2628
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11203
_reflns_number_total             14678
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04251k2.cif
_cod_data_source_block           6
_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 1569912--1569917.cif.
;
_cod_original_cell_volume        2947.7(6)
_cod_database_code               1569915
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.995
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.800(5)
 0.200(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
3. Restrained distances
 C57-C58 \\sim C57-C58X
 with sigma of 0.02
 C60-C59 \\sim C60-C59X
 with sigma of 0.02
 C58-C59 \\sim C58X-C59X
 with sigma of 0.02
 C57-C59 \\sim C57-C59X
 with sigma of 0.04
 C60-C58 \\sim C60-C58X
 with sigma of 0.04
 O2-C37 \\sim O2-C37X
 with sigma of 0.02
 O2-C40 \\sim O2-C40X
 with sigma of 0.02
 C37-C38 \\sim C37X-C38X
 with sigma of 0.02
 C40-C39 \\sim C40X-C39X
 with sigma of 0.02
 C38-C39 \\sim C38X-C39X
 with sigma of 0.02
 O2-C38 \\sim O2-C38X
 with sigma of 0.04
 O2-C39 \\sim O2-C39X
 with sigma of 0.04
 C37-C39 \\sim C37X-C39X
 with sigma of 0.04
 C40-C38 \\sim C40X-C38X
 with sigma of 0.04
 O1-C33 \\sim O1-C33X
 with sigma of 0.02
 O1-C36 \\sim O1-C36X
 with sigma of 0.02
 C33-C34 \\sim C33X-C34X
 with sigma of 0.02
 C36-C35 \\sim C36X-C35X
 with sigma of 0.02
 C34-C35 \\sim C34X-C35X
 with sigma of 0.02
 O1-C34 \\sim O1-C34X
 with sigma of 0.04
 O1-C35 \\sim O1-C35X
 with sigma of 0.04
 C33-C35 \\sim C33X-C35X
 with sigma of 0.04
 C36-C34 \\sim C36X-C34X
 with sigma of 0.04
 C42-C43 \\sim C42-C43X
 with sigma of 0.02
 C44-C43 \\sim C44-C43X
 with sigma of 0.02
 O6-C56 \\sim O6X-C56X
 with sigma of 0.02
 O6-C53 \\sim O6X-C53X
 with sigma of 0.02
 O6-Li3 \\sim O6X-Li3
 with sigma of 0.02
 C56-C55 \\sim C56X-C55X
 with sigma of 0.02
 C55-C54 \\sim C55X-C54X
 with sigma of 0.02
 C53-C54 \\sim C53X-C54X
 with sigma of 0.02
 O6-C55 \\sim O6X-C55X
 with sigma of 0.04
 O6-C54 \\sim O6X-C54X
 with sigma of 0.04
 C56-C53 \\sim C56X-C53X
 with sigma of 0.04
 C56-C54 \\sim C56X-C54X
 with sigma of 0.04
 C56-Li3 \\sim C56X-Li3
 with sigma of 0.04
 C55-C53 \\sim C55X-C53X
 with sigma of 0.04
 C53-Li3 \\sim C53X-Li3
 with sigma of 0.04
 O8-C61 \\sim O9-C61X
 with sigma of 0.02
 O8-C64 \\sim O9-C64X
 with sigma of 0.02
 O8-Li4 \\sim O9-Li4
 with sigma of 0.02
 C61-C62 \\sim C61X-C62X
 with sigma of 0.02
 C64-C63 \\sim C64X-C63X
 with sigma of 0.02
 C62-C63 \\sim C62X-C63X
 with sigma of 0.02
 O8-C62 \\sim O9-C62X
 with sigma of 0.04
 O8-C63 \\sim O9-C63X
 with sigma of 0.04
 C61-C64 \\sim C61X-C64X
 with sigma of 0.04
 C61-C63 \\sim C61X-C63X
 with sigma of 0.04
 C61-Li4 \\sim C61X-Li4
 with sigma of 0.04
 C64-C62 \\sim C64X-C62X
 with sigma of 0.04
 C64-Li4 \\sim C64X-Li4
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
O7 \\sim C57 \\sim C60 \\sim C58 \\sim C59 \\sim C59X \\sim C58X: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O2 \\sim C37 \\sim C40 \\sim C38 \\sim C39 \\sim C37X \\sim C40X \\sim C39X
\\sim C38X: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
O1 \\sim C33 \\sim C36 \\sim C34 \\sim C35 \\sim C34X \\sim C35X \\sim C33X
\\sim C36X: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C41 \\sim C42 \\sim C44 \\sim C43 \\sim C43X \\sim O3: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O6 \\sim C56 \\sim C55 \\sim C53 \\sim C54 \\sim O6X \\sim C53X \\sim C54X
\\sim C56X \\sim C55X: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O8 \\sim C61 \\sim C64 \\sim C62 \\sim C63 \\sim O9 \\sim C61X \\sim C64X \\sim
C62X \\sim C63X: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
5. Others
 Sof(H57C)=Sof(H57D)=Sof(H60C)=Sof(H60D)=Sof(C59X)=Sof(H59C)=Sof(H59D)=
 Sof(C58X)=Sof(H58C)=Sof(H58D)=1-FVAR(1)
 Sof(H57A)=Sof(H57B)=Sof(H60A)=Sof(H60B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(C59)=
 Sof(H59A)=Sof(H59B)=FVAR(1)
 Sof(C37X)=Sof(H37C)=Sof(H37D)=Sof(C40X)=Sof(H40C)=Sof(H40D)=Sof(C39X)=
 Sof(H39C)=Sof(H39D)=Sof(C38X)=Sof(H38C)=Sof(H38D)=1-FVAR(2)
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C38)=Sof(H38A)=
 Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=FVAR(2)
 Sof(C34X)=Sof(H34C)=Sof(H34D)=Sof(C35X)=Sof(H35C)=Sof(H35D)=Sof(C33X)=
 Sof(H33C)=Sof(H33D)=Sof(C36X)=Sof(H36C)=Sof(H36D)=1-FVAR(3)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C34)=Sof(H34A)=
 Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=FVAR(3)
 Sof(H42C)=Sof(H42D)=Sof(H44C)=Sof(H44D)=Sof(C43X)=Sof(H43C)=Sof(H43D)=1-FVAR(4)
 Sof(H42A)=Sof(H42B)=Sof(H44A)=Sof(H44B)=Sof(C43)=Sof(H43A)=Sof(H43B)=FVAR(4)
 Sof(O6X)=Sof(C53X)=Sof(H53C)=Sof(H53D)=Sof(C54X)=Sof(H54C)=Sof(H54D)=
 Sof(C56X)=Sof(H56C)=Sof(H56D)=Sof(C55X)=Sof(H55C)=Sof(H55D)=1-FVAR(5)
 Sof(O6)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C53)=
 Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=FVAR(5)
 Sof(O9)=Sof(C61X)=Sof(H61C)=Sof(H61D)=Sof(C64X)=Sof(H64C)=Sof(H64D)=Sof(C62X)=
 Sof(H62C)=Sof(H62D)=Sof(C63X)=Sof(H63C)=Sof(H63D)=1-FVAR(6)
 Sof(O8)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(C62)=
 Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=FVAR(6)
6.a Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C45(H45A,H45B), C41(H41A,H41B), C49(H49A,H49B), C48(H48A,
 H48B), C51(H51A,H51B), C57(H57A,H57B), C57(H57C,H57D), C60(H60A,H60B),
 C60(H60C,H60D), C50(H50A,H50B), C52(H52A,H52B), C64(H64A,H64B), C33(H33A,H33B),
  C62(H62A,H62B), C42(H42A,H42B), C42(H42C,H42D), C44(H44A,H44B), C44(H44C,
 H44D), C37(H37A,H37B), C56(H56A,H56B), C55(H55A,H55B), C36(H36A,H36B),
 C53(H53A,H53B), C46(H46A,H46B), C47(H47A,H47B), C63(H63A,H63B), C54(H54A,H54B),
  C40(H40A,H40B), C38(H38A,H38B), C39(H39A,H39B), C43(H43A,H43B), C34(H34A,
 H34B), C58(H58A,H58B), C35(H35A,H35B), C59(H59A,H59B), C59X(H59C,H59D),
 C58X(H58C,H58D), C37X(H37C,H37D), C40X(H40C,H40D), C39X(H39C,H39D), C38X(H38C,
 H38D), C34X(H34C,H34D), C35X(H35C,H35D), C33X(H33C,H33D), C36X(H36C,H36D),
 C43X(H43C,H43D), C53X(H53C,H53D), C54X(H54C,H54D), C56X(H56C,H56D), C55X(H55C,
 H55D), C61X(H61C,H61D), C64X(H64C,H64D), C62X(H62C,H62D), C63X(H63C,H63D)
6.b Aromatic/amide H refined with riding coordinates:
 C26(H26), C2(H2), C14(H14), C30(H30), C1(H1), C21(H21), C27(H27), C23(H23),
 C13(H13), C7(H7), C22(H22), C29(H29), C4(H4), C5(H5), C8(H8), C32(H32),
 C11(H11), C10(H10), C15(H15), C31(H31), C18(H18), C19(H19), C24(H24), C16(H16)
;
_shelx_res_checksum              32696
_olex2_submission_special_instructions 'No special instructions were received'