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_1569914
_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         'C60 H80 Na2 O7'
_chemical_formula_sum            'C60 H80 Na2 O7'
_chemical_formula_weight         959.22
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-03-31
_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                 90.3280(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.8448(5)
_cell_length_b                   16.1337(4)
_cell_length_c                   18.5018(5)
_cell_measurement_reflns_used    9548
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.28
_cell_measurement_theta_min      2.51
_cell_volume                     5326.6(2)
_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 0.999
_diffrn_measured_fraction_theta_max 0.943
_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  0.0539
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            359467
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        17.311
_diffrn_reflns_theta_max         31.281
_diffrn_reflns_theta_min         1.109
_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    0.046
_exptl_absorpt_correction_T_max  0.6751
_exptl_absorpt_correction_T_min  0.6340
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.1639 before and 0.0622 after correction.
The Ratio of minimum to maximum transmission is 0.9391.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.196
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    none
_exptl_crystal_description       plate
_exptl_crystal_F_000             2072
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.636
_refine_diff_density_min         -0.562
_refine_diff_density_rms         0.071
_refine_ls_extinction_coef       0.0570(16)
_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   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     821
_refine_ls_number_reflns         48338
_refine_ls_number_restraints     885
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0396
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0668P)^2^+0.4311P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1146
_refine_ls_wR_factor_ref         0.1252
_reflns_Friedel_coverage         0.000
_reflns_number_gt                39095
_reflns_number_total             48338
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04251k2.cif
_cod_data_source_block           3
_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/n'
_cod_database_code               1569914
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.995
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C46X-C45X = C46-C45 = C47X-C46X = C47-C46 = C48-C47 = C48X-C47X
 1.54 with sigma of 0.02
 O4A-C48X = O4-C48 = O4A-C45X = O4-C45
 1.43 with sigma of 0.02
 O2-C37 \\sim O2X-C37X
 with sigma of 0.02
 O2-C40 \\sim O2X-C40X
 with sigma of 0.02
 C37-C38 \\sim C37X-C38X
 with sigma of 0.02
 C38-C39 \\sim C38X-C39X
 with sigma of 0.02
 C39-C40 \\sim C39X-C40X
 with sigma of 0.02
 O2-C38 \\sim O2X-C38X
 with sigma of 0.04
 O2-C39 \\sim O2X-C39X
 with sigma of 0.04
 C37-C39 \\sim C37X-C39X
 with sigma of 0.04
 C37-C40 \\sim C37X-C40X
 with sigma of 0.04
 C38-C40 \\sim C38X-C40X
 with sigma of 0.04
 O1-C33 \\sim O1X-C33X
 with sigma of 0.02
 O1-C36 \\sim O1X-C36X
 with sigma of 0.02
 C33-C34 \\sim C33X-C34X
 with sigma of 0.02
 C34-C35 \\sim C34X-C35X
 with sigma of 0.02
 C35-C36 \\sim C35X-C36X
 with sigma of 0.02
 O1-C34 \\sim O1X-C34X
 with sigma of 0.04
 O1-C35 \\sim O1X-C35X
 with sigma of 0.04
 C33-C35 \\sim C33X-C35X
 with sigma of 0.04
 C33-C36 \\sim C33X-C36X
 with sigma of 0.04
 C34-C36 \\sim C34X-C36X
 with sigma of 0.04
 O6-C53 \\sim O6X-C53X
 with sigma of 0.02
 O6-C56 \\sim O6X-C56X
 with sigma of 0.02
 C53-C54 \\sim C53X-C54X
 with sigma of 0.02
 C54-C55 \\sim C54X-C55X
 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
 C53-C55 \\sim C53X-C55X
 with sigma of 0.04
 C53-C56 \\sim C53X-C56X
 with sigma of 0.04
 C54-C56 \\sim C54X-C56X
 with sigma of 0.04
 C49-C50 \\sim C49-C50X
 with sigma of 0.02
 C50-C51 \\sim C50X-C51
 with sigma of 0.02
 C50-C51 \\sim C50-C51X
 with sigma of 0.02
 C51-C52 \\sim C51X-C52
 with sigma of 0.02
 C51-C50X \\sim C51X-C50X
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O6 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim O6X \\sim C53X \\sim C54X
\\sim C55X \\sim C56X \\sim O1 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim
C36X \\sim O1X \\sim C33X \\sim C34X \\sim C35X \\sim O2 \\sim C37 \\sim C38
\\sim C39 \\sim C40 \\sim C40X \\sim C39X \\sim O2X \\sim C37X \\sim C38X \\sim
O4 \\sim C45 \\sim C46 \\sim C47 \\sim C48: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O4 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C45X \\sim O4A \\sim C48X
\\sim C47X \\sim C46X: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O5 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C50X: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O5 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C50X \\sim C51X: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O2 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C40X \\sim C39X \\sim O2X
\\sim C37X \\sim C38X: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C39) = Uanis(C39X)
4. Rigid body (RIGU) restrains
 O2, C37, C38, C39, C40, C40X, C39X, O2X, C37X, C38X
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5, C49, C50, C51, C52, C50X, C51X
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O4, C45, C46, C47, C48, C45X, O4A, C48X, C47X, C46X
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C40X)=Sof(H40C)=Sof(H40D)=Sof(C39X)=Sof(H39C)=Sof(H39D)=Sof(O2X)=
 Sof(C37X)=Sof(H37C)=Sof(H37D)=Sof(C38X)=Sof(H38C)=Sof(H38D)=1-FVAR(1)
 Sof(O2)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=
 Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=FVAR(1)
 Sof(C36X)=Sof(H36C)=Sof(H36D)=Sof(O1X)=Sof(C33X)=Sof(H33C)=Sof(H33D)=
 Sof(C34X)=Sof(H34C)=Sof(H34D)=Sof(C35X)=Sof(H35C)=Sof(H35D)=1-FVAR(2)
 Sof(O1)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=
 Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=FVAR(2)
 Sof(O6X)=Sof(C53X)=Sof(H53C)=Sof(H53D)=Sof(C54X)=Sof(H54C)=Sof(H54D)=
 Sof(C55X)=Sof(H55C)=Sof(H55D)=Sof(C56X)=Sof(H56C)=Sof(H56D)=1-FVAR(3)
 Sof(O6)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=
 Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=FVAR(3)
 Sof(C45X)=Sof(H45C)=Sof(H45D)=Sof(O4A)=Sof(C48X)=Sof(H48C)=Sof(H48D)=
 Sof(C47X)=Sof(H47C)=Sof(H47D)=Sof(C46X)=Sof(H46C)=Sof(H46D)=1-FVAR(4)
 Sof(O4)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(C47)=
 Sof(H47A)=Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=FVAR(4)
 Sof(H49C)=Sof(H49D)=Sof(C50X)=Sof(H50C)=Sof(H50D)=1-FVAR(5)
 Sof(H49A)=Sof(H49B)=Sof(C50)=Sof(H50A)=Sof(H50B)=FVAR(5)
 Sof(H52C)=Sof(H52D)=Sof(C51X)=Sof(H51C)=Sof(H51D)=1-FVAR(6)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H52A)=Sof(H52B)=FVAR(6)
6.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), C49(H49C,H49D), C50(H50A,
 H50B), C51(H51A,H51B), C52(H52A,H52B), C52(H52C,H52D), C53(H53A,H53B),
 C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B),
  C59(H59A,H59B), C60(H60A,H60B), C40X(H40C,H40D), C39X(H39C,H39D), C37X(H37C,
 H37D), C38X(H38C,H38D), C36X(H36C,H36D), C33X(H33C,H33D), C34X(H34C,H34D),
 C35X(H35C,H35D), C53X(H53C,H53D), C54X(H54C,H54D), C55X(H55C,H55D), C56X(H56C,
 H56D), C45X(H45C,H45D), C48X(H48C,H48D), C47X(H47C,H47D), C46X(H46C,H46D),
 C50X(H50C,H50D), C51X(H51C,H51D)
6.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)
;
_shelx_res_checksum              19689
_olex2_submission_special_instructions 'No special instructions were received'