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_1569912
_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         'C44 H48 Li O3, C16 H32 Li O4'
_chemical_formula_sum            'C60 H80 Li2 O7'
_chemical_formula_weight         927.12
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-04-05
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.5976(13)
_cell_length_b                   17.2486(14)
_cell_length_c                   19.3869(16)
_cell_measurement_reflns_used    9526
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.72
_cell_measurement_theta_min      2.39
_cell_volume                     5215.8(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 0.998
_diffrn_measured_fraction_theta_max 0.996
_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  0.0676
_diffrn_reflns_av_unetI/netI     0.0401
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            238473
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        17.311
_diffrn_reflns_theta_max         24.864
_diffrn_reflns_theta_min         1.103
_diffrn_source                   synchrotron
_diffrn_source_current           103.0
_diffrn_source_power             103.0
_diffrn_source_voltage           1000.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.040
_exptl_absorpt_correction_T_max  0.6718
_exptl_absorpt_correction_T_min  0.4727
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.1176 before and 0.0781 after correction.
The Ratio of minimum to maximum transmission is 0.7036.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.181
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    none
_exptl_crystal_description       plate
_exptl_crystal_F_000             2008
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.407
_refine_diff_density_min         -0.284
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.1(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     853
_refine_ls_number_reflns         26236
_refine_ls_number_restraints     801
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0581
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0918P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1397
_refine_ls_wR_factor_ref         0.1425
_reflns_Friedel_coverage         0.932
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.972
_reflns_number_gt                21932
_reflns_number_total             26236
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04251k2.cif
_cod_data_source_block           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 1569912--1569917.cif.
;
_cod_database_code               1569912
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.996
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.1(12)
 -0.1(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 O6-C56 \\sim O6X-C56X
 with sigma of 0.02
 O6-C53 \\sim O6X-C53X
 with sigma of 0.02
 C54-C55 \\sim C54X-C55X
 with sigma of 0.02
 C54-C53 \\sim C54X-C53X
 with sigma of 0.02
 C55-C56 \\sim C55X-C56X
 with sigma of 0.02
 O6-C54 \\sim O6X-C54X
 with sigma of 0.04
 O6-C55 \\sim O6X-C55X
 with sigma of 0.04
 C54-C56 \\sim C54X-C56X
 with sigma of 0.04
 C55-C53 \\sim C55X-C53X
 with sigma of 0.04
 C56-C53 \\sim C56X-C53X
 with sigma of 0.04
 O7-C60 \\sim O7X-C60X
 with sigma of 0.02
 O7-C57 \\sim O7X-C57X
 with sigma of 0.02
 C60-C59 \\sim C60X-C59X
 with sigma of 0.02
 C59-C58 \\sim C59X-C58X
 with sigma of 0.02
 C58-C57 \\sim C58X-C57X
 with sigma of 0.02
 O7-C59 \\sim O7X-C59X
 with sigma of 0.04
 O7-C58 \\sim O7X-C58X
 with sigma of 0.04
 C60-C58 \\sim C60X-C58X
 with sigma of 0.04
 C60-C57 \\sim C60X-C57X
 with sigma of 0.04
 C59-C57 \\sim C59X-C57X
 with sigma of 0.04
 O4-C48 \\sim O4X-C48X
 with sigma of 0.02
 O4-C45 \\sim O4X-C45X
 with sigma of 0.02
 C46-C47 \\sim C46X-C47X
 with sigma of 0.02
 C46-C45 \\sim C46X-C45X
 with sigma of 0.02
 C47-C48 \\sim C47X-C48X
 with sigma of 0.02
 O4-C46 \\sim O4X-C46X
 with sigma of 0.04
 O4-C47 \\sim O4X-C47X
 with sigma of 0.04
 C46-C48 \\sim C46X-C48X
 with sigma of 0.04
 C47-C45 \\sim C47X-C45X
 with sigma of 0.04
 C48-C45 \\sim C48X-C45X
 with sigma of 0.04
 O3-C41 \\sim O3X-C41X
 with sigma of 0.02
 O3-C44 \\sim O3X-C44X
 with sigma of 0.02
 C41-C42 \\sim C41X-C42X
 with sigma of 0.02
 C43-C44 \\sim C43X-C44X
 with sigma of 0.02
 C43-C42 \\sim C43X-C42X
 with sigma of 0.02
 O3-C43 \\sim O3X-C43X
 with sigma of 0.04
 O3-C42 \\sim O3X-C42X
 with sigma of 0.04
 C41-C43 \\sim C41X-C43X
 with sigma of 0.04
 C41-C44 \\sim C41X-C44X
 with sigma of 0.04
 C44-C42 \\sim C44X-C42X
 with sigma of 0.04
 O5-C52 \\sim O5X-C52X
 with sigma of 0.02
 O5-C49 \\sim O5X-C49X
 with sigma of 0.02
 C51-C52 \\sim C51X-C52X
 with sigma of 0.02
 C51-C50 \\sim C51X-C50X
 with sigma of 0.02
 C50-C49 \\sim C50X-C49X
 with sigma of 0.02
 O5-C51 \\sim O5X-C51X
 with sigma of 0.04
 O5-C50 \\sim O5X-C50X
 with sigma of 0.04
 C51-C49 \\sim C51X-C49X
 with sigma of 0.04
 C52-C50 \\sim C52X-C50X
 with sigma of 0.04
 C52-C49 \\sim C52X-C49X
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
O7 \\sim C60 \\sim C59 \\sim C58 \\sim C57 \\sim O7X \\sim C57X \\sim C58X
\\sim C59X \\sim C60X \\sim O6 \\sim C54 \\sim C55 \\sim C56 \\sim C53 \\sim
O6X \\sim C56X \\sim C55X \\sim C54X \\sim C53X: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
O4 \\sim C46 \\sim C47 \\sim C48 \\sim C45 \\sim O4X \\sim C48X \\sim C47X
\\sim C46X \\sim C45X: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O3 \\sim C41 \\sim C43 \\sim C44 \\sim C42 \\sim O3X \\sim C41X \\sim C43X
\\sim C44X \\sim C42X: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O5 \\sim C51 \\sim C52 \\sim C50 \\sim C49 \\sim O5X \\sim C51X \\sim C52X
\\sim C50X \\sim C49X: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
5. Others
 Sof(O6X)=Sof(C56X)=Sof(H56C)=Sof(H56D)=Sof(C55X)=Sof(H55C)=Sof(H55D)=
 Sof(C54X)=Sof(H54C)=Sof(H54D)=Sof(C53X)=Sof(H53C)=Sof(H53D)=1-FVAR(1)
 Sof(O6)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=
 Sof(H56A)=Sof(H56B)=Sof(C53)=Sof(H53A)=Sof(H53B)=FVAR(1)
 Sof(O7X)=Sof(C57X)=Sof(H57C)=Sof(H57D)=Sof(C58X)=Sof(H58C)=Sof(H58D)=
 Sof(C59X)=Sof(H59C)=Sof(H59D)=Sof(C60X)=Sof(H60C)=Sof(H60D)=1-FVAR(2)
 Sof(O7)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C58)=
 Sof(H58A)=Sof(H58B)=Sof(C57)=Sof(H57A)=Sof(H57B)=FVAR(2)
 Sof(O4X)=Sof(C48X)=Sof(H48C)=Sof(H48D)=Sof(C47X)=Sof(H47C)=Sof(H47D)=
 Sof(C46X)=Sof(H46C)=Sof(H46D)=Sof(C45X)=Sof(H45C)=Sof(H45D)=1-FVAR(3)
 Sof(O4)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(C48)=
 Sof(H48A)=Sof(H48B)=Sof(C45)=Sof(H45A)=Sof(H45B)=FVAR(3)
 Sof(O3X)=Sof(C41X)=Sof(H41C)=Sof(H41D)=Sof(C43X)=Sof(H43C)=Sof(H43D)=
 Sof(C44X)=Sof(H44C)=Sof(H44D)=Sof(C42X)=Sof(H42C)=Sof(H42D)=1-FVAR(4)
 Sof(O3)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C44)=
 Sof(H44A)=Sof(H44B)=Sof(C42)=Sof(H42A)=Sof(H42B)=FVAR(4)
 Sof(O5X)=Sof(C51X)=Sof(H51C)=Sof(H51D)=Sof(C52X)=Sof(H52C)=Sof(H52D)=
 Sof(C50X)=Sof(H50C)=Sof(H50D)=Sof(C49X)=Sof(H49C)=Sof(H49D)=1-FVAR(5)
 Sof(O5)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C50)=
 Sof(H50A)=Sof(H50B)=Sof(C49)=Sof(H49A)=Sof(H49B)=FVAR(5)
6.a Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C41(H41A,H41B), C35(H35A,H35B), C39(H39A,H39B), C43(H43A,
 H43B), C37(H37A,H37B), C34(H34A,H34B), C36(H36A,H36B), C38(H38A,H38B),
 C44(H44A,H44B), C40(H40A,H40B), C42(H42A,H42B), C51(H51A,H51B), C60(H60A,H60B),
  C46(H46A,H46B), C59(H59A,H59B), C54(H54A,H54B), C47(H47A,H47B), C55(H55A,
 H55B), C48(H48A,H48B), C56(H56A,H56B), C52(H52A,H52B), C50(H50A,H50B),
 C58(H58A,H58B), C45(H45A,H45B), C49(H49A,H49B), C53(H53A,H53B), C57(H57A,H57B),
  C56X(H56C,H56D), C55X(H55C,H55D), C54X(H54C,H54D), C53X(H53C,H53D), C57X(H57C,
 H57D), C58X(H58C,H58D), C59X(H59C,H59D), C60X(H60C,H60D), C48X(H48C,H48D),
 C47X(H47C,H47D), C46X(H46C,H46D), C45X(H45C,H45D), C41X(H41C,H41D), C43X(H43C,
 H43D), C44X(H44C,H44D), C42X(H42C,H42D), C51X(H51C,H51D), C52X(H52C,H52D),
 C50X(H50C,H50D), C49X(H49C,H49D)
6.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C10(H10), C29(H29), C1(H1), C5(H5), C23(H23), C27(H27), C31(H31),
 C13(H13), C14(H14), C15(H15), C16(H16), C22(H22), C24(H24), C18(H18), C26(H26),
  C32(H32), C30(H30), C7(H7), C11(H11), C19(H19), C2(H2), C4(H4), C21(H21)
;
_shelx_res_checksum              60197
_olex2_submission_special_instructions 'No special instructions were received'