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_1569916
_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
'2(C18 H36 K N2 O6), C32 H24, 0.346(C6 H14), 1.308(C4 H8 O)'
_chemical_formula_sum            'C75.31 H111.31 K2 N4 O13.31'
_chemical_formula_weight         1363.82
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-04-04
_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                 114.1120(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.9901(8)
_cell_length_b                   18.2207(6)
_cell_length_c                   20.0657(7)
_cell_measurement_reflns_used    9134
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.84
_cell_measurement_theta_min      2.25
_cell_volume                     7338.3(4)
_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 0.995
_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  0.0639
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            322345
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        17.311
_diffrn_reflns_theta_max         22.861
_diffrn_reflns_theta_min         1.053
_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    0.082
_exptl_absorpt_correction_T_max  0.7108
_exptl_absorpt_correction_T_min  0.6185
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.1151 before and 0.0633 after correction.
The Ratio of minimum to maximum transmission is 0.8701.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.234
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    none
_exptl_crystal_description       block
_exptl_crystal_F_000             2942.5
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.853
_refine_diff_density_min         -0.604
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1464
_refine_ls_number_reflns         29401
_refine_ls_number_restraints     2154
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0619
_refine_ls_R_factor_gt           0.0471
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0732P)^2^+1.3582P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1339
_refine_ls_wR_factor_ref         0.1426
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22858
_reflns_number_total             29401
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04251k2.cif
_cod_data_source_block           5
_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_sg_symbol_H-M      'P 21/c'
_cod_database_code               1569916
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.990
_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. Uiso/Uaniso restraints and constraints
O11X \\sim O10X \\sim O12X \\sim O10 \\sim O9 \\sim O7 \\sim O8 \\sim O8X \\sim
O11 \\sim O12 \\sim O7X \\sim N4X \\sim C60X \\sim C61X \\sim C67X \\sim C66X
\\sim C64X \\sim C65X \\sim C60 \\sim C61 \\sim C58 \\sim C59 \\sim C52 \\sim
C53 \\sim C54 \\sim C55 \\sim C54X \\sim C55X \\sim C64 \\sim C65 \\sim C66
\\sim C67 \\sim C52X \\sim C53X \\sim C56X \\sim C62X \\sim C68X \\sim C59X
\\sim C63X \\sim C62 \\sim C57 \\sim C51 \\sim C56 \\sim C63 \\sim C68 \\sim
C51X \\sim O9X \\sim N3X \\sim N4 \\sim N3 \\sim C58X \\sim C57X: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C75 \\sim C74 \\sim C73 \\sim C77 \\sim O14 \\sim C76 \\sim C79 \\sim C78:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O13 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim O13X \\sim C72X \\sim C71X
\\sim C70X \\sim C69X: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C6X \\sim C30X \\sim C29X \\sim C25X \\sim C28X \\sim C26X \\sim C24X \\sim
C31X \\sim C27X \\sim C23X \\sim C32X \\sim C20X \\sim C3X \\sim C19X \\sim
C21X \\sim C2X \\sim C4X \\sim C18X \\sim C22X \\sim C1X \\sim C5X \\sim C17X
\\sim C16X \\sim C7X \\sim C15X \\sim C8X \\sim C12X \\sim C9X \\sim C11X \\sim
C13X \\sim C10X \\sim C14X \\sim C6 \\sim C1 \\sim C2 \\sim C3 \\sim C5 \\sim
C7 \\sim C4 \\sim C32 \\sim C8 \\sim C31 \\sim C9 \\sim C28 \\sim C10 \\sim C14
\\sim C27 \\sim C29 \\sim C11 \\sim C13 \\sim C26 \\sim C30 \\sim C12 \\sim C25
\\sim C15 \\sim C24 \\sim C16 \\sim C23 \\sim C17 \\sim C20 \\sim C18 \\sim C22
\\sim C19 \\sim C21: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
3. Others
 Sof(C67X)=Sof(H67C)=Sof(H67D)=Sof(O10X)=Sof(O8X)=Sof(O9X)=Sof(O11X)=Sof(O7X)=
 Sof(O12X)=Sof(N3X)=Sof(N4X)=Sof(C60X)=Sof(H60C)=Sof(H60D)=Sof(C61X)=Sof(H61C)=
 Sof(H61D)=Sof(C54X)=Sof(H54C)=Sof(H54D)=Sof(C55X)=Sof(H55C)=Sof(H55D)=
 Sof(C58X)=Sof(H58C)=Sof(H58D)=Sof(C59X)=Sof(H59C)=Sof(H59D)=Sof(C64X)=
 Sof(H64C)=Sof(H64D)=Sof(C65X)=Sof(H65C)=Sof(H65D)=Sof(C52X)=Sof(H52C)=
 Sof(H52D)=Sof(C53X)=Sof(H53C)=Sof(H53D)=Sof(C66X)=Sof(H66C)=Sof(H66D)=
 Sof(C51X)=Sof(H51C)=Sof(H51D)=Sof(C57X)=Sof(H57C)=Sof(H57D)=Sof(C63X)=
 Sof(H63C)=Sof(H63D)=Sof(C56X)=Sof(H56C)=Sof(H56D)=Sof(C62X)=Sof(H62C)=
 Sof(H62D)=Sof(C68X)=Sof(H68C)=Sof(H68D)=1-FVAR(1)
 Sof(O7)=Sof(O8)=Sof(O9)=Sof(O10)=Sof(O11)=Sof(O12)=Sof(N3)=Sof(N4)=Sof(C51)=
 Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=
 Sof(H56B)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(C59)=
 Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C61)=Sof(H61A)=Sof(H61B)=
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=
 Sof(H64B)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(C67)=
 Sof(H67A)=Sof(H67B)=Sof(C68)=Sof(H68A)=Sof(H68B)=FVAR(1)
 Sof(C22)=Sof(H22)=Sof(C30X)=Sof(H30X)=Sof(C1X)=Sof(H1X)=Sof(C2X)=Sof(H2X)=
 Sof(C6X)=Sof(C3X)=Sof(C5X)=Sof(H5X)=Sof(C7X)=Sof(H7X)=Sof(C4X)=Sof(H4X)=
 Sof(C32X)=Sof(H32X)=Sof(C8X)=Sof(H8X)=Sof(C31X)=Sof(H31X)=Sof(C9X)=Sof(C28X)=
 Sof(C10X)=Sof(H10X)=Sof(C14X)=Sof(H14X)=Sof(C29X)=Sof(H29X)=Sof(C27X)=
 Sof(H27X)=Sof(C11X)=Sof(H11X)=Sof(C13X)=Sof(H13X)=Sof(C26X)=Sof(H26X)=
 Sof(C12X)=Sof(C25X)=Sof(C15X)=Sof(H15X)=Sof(C24X)=Sof(H24X)=Sof(C16X)=
 Sof(H16X)=Sof(C23X)=Sof(H23X)=Sof(C17X)=Sof(C20X)=Sof(C18X)=Sof(H18X)=
 Sof(C19X)=Sof(H19X)=Sof(C21X)=Sof(H21X)=1-FVAR(2)
 Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=
 Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(C10)=Sof(H10)=Sof(C11)=
 Sof(H11)=Sof(C12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=
 Sof(C21)=Sof(H21)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(C26)=
 Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=
 Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C22X)=Sof(H22X)=FVAR(2)
 Sof(O13X)=Sof(C72X)=Sof(H72C)=Sof(H72D)=Sof(C71X)=Sof(H71C)=Sof(H71D)=
 Sof(C70X)=Sof(H70C)=Sof(H70D)=Sof(C69X)=Sof(H69C)=Sof(H69D)=1-FVAR(3)
 Sof(O13)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(C71)=
 Sof(H71A)=Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=FVAR(3)
 Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(O14)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(C79)=
 Sof(H79A)=Sof(H79B)=Sof(C78)=Sof(H78A)=Sof(H78B)=1-FVAR(4)
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C73)=Sof(H73A)=
 Sof(H73B)=Sof(H73C)=FVAR(4)
4.a Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,
 H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B),
 C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B),
  C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,
 H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B),
 C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,H60B),
  C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,
 H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B),
 C70(H70A,H70B), C71(H71A,H71B), C72(H72A,H72B), C75(H75A,H75B), C74(H74A,H74B),
  C67X(H67C,H67D), C60X(H60C,H60D), C61X(H61C,H61D), C54X(H54C,H54D), C55X(H55C,
 H55D), C58X(H58C,H58D), C59X(H59C,H59D), C64X(H64C,H64D), C65X(H65C,H65D),
 C52X(H52C,H52D), C53X(H53C,H53D), C66X(H66C,H66D), C51X(H51C,H51D), C57X(H57C,
 H57D), C63X(H63C,H63D), C56X(H56C,H56D), C62X(H62C,H62D), C68X(H68C,H68D),
 C72X(H72C,H72D), C71X(H71C,H71D), C70X(H70C,H70D), C77(H77A,H77B), C76(H76A,
 H76B), C79(H79A,H79B), C78(H78A,H78B), C69X(H69C,H69D)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C7(H7), C8(H8), C10(H10), C11(H11), C13(H13),
 C14(H14), C15(H15), C16(H16), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23),
  C24(H24), C26(H26), C27(H27), C29(H29), C30(H30), C31(H31), C32(H32),
 C30X(H30X), C1X(H1X), C2X(H2X), C5X(H5X), C7X(H7X), C4X(H4X), C32X(H32X),
 C8X(H8X), C31X(H31X), C10X(H10X), C14X(H14X), C29X(H29X), C27X(H27X),
 C11X(H11X), C13X(H13X), C26X(H26X), C15X(H15X), C24X(H24X), C16X(H16X),
 C23X(H23X), C18X(H18X), C22X(H22X), C19X(H19X), C21X(H21X)
4.c Idealised Me refined as rotating group:
 C73(H73A,H73B,H73C)
;
_shelx_res_checksum              70147
_olex2_submission_special_instructions 'No special instructions were received'