Programmable synthesis of multiply arylated cubanes through C–H metalation and arylation
Okude, Ryo; Mori, Genki; Yagi, Akiko; Itami, Kenichiro; Chemical Science 11 (2020) 7672–7675; doi:10.1039/D0SC01909G

data_1557903
_publ_section_title
;
 Programmable synthesis of multiply arylated cubanes through C--H
 metalation and arylation
;
_journal_issue                   29
_journal_name_full               'Chemical Science'
_journal_page_first              7672
_journal_page_last               7675
_journal_paper_doi               10.1039/D0SC01909G
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C37 H29 F9 N2 O, C6 H6'
_chemical_formula_sum            'C43 H35 F9 N2 O'
_chemical_formula_weight         766.73
_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             2020-02-21
_audit_creation_method
;
Olex2 1.3
(compiled 2019.11.21 svn.r41b79517 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2020-03-30 deposited with the CCDC.	2020-04-24 downloaded from the CCDC.
;
_cell_angle_alpha                86.6000(10)
_cell_angle_beta                 88.6120(10)
_cell_angle_gamma                81.4120(10)
_cell_formula_units_Z            2
_cell_length_a                   9.75710(10)
_cell_length_b                   10.10370(10)
_cell_length_c                   19.2300(3)
_cell_measurement_reflns_used    19760
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      29.6980
_cell_measurement_theta_min      2.8570
_cell_volume                     1870.97(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      123(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.901
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -103.00  77.00   0.50    5.00    --  -13.00  45.00 264.00  360
  2  \w   -103.00  60.00   0.50    5.00    --  -13.00  45.00 122.00  326
  3  \w    -86.00  45.00   0.50    5.00    --  -13.00  45.00 158.00  262
  4  \w     16.00  61.00   0.50    5.00    --  -13.00  45.00 193.00   90
  5  \w      4.50  63.00   0.50    5.00    --  -13.00  45.00  16.00  117
  6  \w   -103.00  58.50   0.50    5.00    --  -13.00  45.00 -19.00  323
  7  \w    -71.00 -25.00   0.50    5.00    --  -13.00  45.00  51.00   92
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0564128000
_diffrn_orient_matrix_UB_12      0.0248757000
_diffrn_orient_matrix_UB_13      0.0218754000
_diffrn_orient_matrix_UB_21      0.0439861000
_diffrn_orient_matrix_UB_22      -0.0111114000
_diffrn_orient_matrix_UB_23      0.0292552000
_diffrn_orient_matrix_UB_31      0.0170087000
_diffrn_orient_matrix_UB_32      0.0656849000
_diffrn_orient_matrix_UB_33      -0.0055894000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.901
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            37233
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.901
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.766
_diffrn_reflns_theta_min         2.348
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.112
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90047
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.39a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.361
_exptl_crystal_description       block
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.467
_refine_diff_density_min         -0.413
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     583
_refine_ls_number_reflns         9620
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0610
_refine_ls_R_factor_gt           0.0465
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0585P)^2^+0.6829P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1209
_refine_ls_wR_factor_ref         0.1286
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7619
_reflns_number_total             9620
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc01909g2.cif
_cod_data_source_block           4b
_cod_depositor_comments
;Adding full bibliography for 1557900--1557907.cif.

 Adding full bibliography for 1557900--1557907.cif.
;
_cod_database_code               1557903
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 90.11
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.70
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F7A-F9A
 2.2 with sigma of 0.01
 F9A-F8A
 2.2 with sigma of 0.01
 F8A-F7A
 2.2 with sigma of 0.01
 F9-C25 = F8A-C25 = F8-C25 = F7A-C25 = F7-C25 = F9A-C25
 1.35 with sigma of 0.01
 F9-F8
 2.2 with sigma of 0.01
 F8-F7
 2.2 with sigma of 0.01
 F7-F9
 2.2 with sigma of 0.01
 C51A-C50A = C55A-C50A = C55A-C54A = C54A-C53A = C53A-C52A = C52A-C51A
 1.39 with sigma of 0.01
 C55A-C53A
 2.42 with sigma of 0.01
 C53A-C51A
 2.42 with sigma of 0.01
 C55A-C51A
 2.42 with sigma of 0.01
 C50A-C52A
 2.42 with sigma of 0.01
 C52A-C54A
 2.42 with sigma of 0.01
 C54A-C50A
 2.42 with sigma of 0.01
 C52-C51 = C51-C50 = C55-C50 = C55-C54 = C54-C53 = C53-C52
 1.39 with sigma of 0.01
 C55-C51
 2.42 with sigma of 0.01
 C51-C53
 2.42 with sigma of 0.01
 C53-C55
 2.42 with sigma of 0.01
 C50-C54
 2.42 with sigma of 0.01
 C54-C52
 2.42 with sigma of 0.01
 C52-C50
 2.42 with sigma of 0.01
3. Restrained planarity
 C50A, C55A, C54A, C53A, C52A, C51A
 with sigma of 0.02
 C50, C51, C55, C52, C53, C54
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(F8A) \\sim Ueq, Uanis(F7A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
5. Others
 Sof(F8A)=Sof(F7A)=Sof(F9A)=1-FVAR(1)
 Sof(F7)=Sof(F9)=Sof(F8)=FVAR(1)
 Sof(C50A)=Sof(H50A)=Sof(C55A)=Sof(H55A)=Sof(C54A)=Sof(H54A)=Sof(C53A)=
 Sof(H53A)=Sof(C52A)=Sof(H52A)=Sof(C51A)=Sof(H51A)=1-FVAR(2)
 Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C55)=Sof(H55)=Sof(C52)=Sof(H52)=
 Sof(C53)=Sof(H53)=Sof(C54)=Sof(H54)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C4(H4), C2(H2), C6(H6), C41(H41), C43(H43)
6.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C13(H13), C14(H14), C30(H30), C24(H24), C23(H23), C11(H11),
 C31(H31), C20(H20), C34(H34), C33(H33), C21(H21), C50(H50), C51(H51), C55(H55),
  C52(H52), C53(H53), C54(H54), C50A(H50A), C55A(H55A), C54A(H54A), C53A(H53A),
 C52A(H52A), C51A(H51A)
6.c Idealised Me refined as rotating group:
 C46(H46A,H46B,H46C), C42(H42A,H42B,H42C), C45(H45A,H45B,H45C), C44(H44A,H44B,
 H44C)
;
_shelx_res_checksum              6728
_shelx_hkl_checksum              56834
_olex2_exptl_crystal_mounting_method mesh
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.769
_oxdiff_exptl_absorpt_empirical_full_min 0.713