Kekulé diradicaloids derived from a classical N-heterocyclic carbene.
Rottschäfer, Dennis; Neumann, Beate; Stammler, Hans-Georg; Andrada, Diego M.; Ghadwal, Rajendra S.; Chemical science 9 (2018) 4970–4976; doi:10.1039/c8sc01209a

data_1549303
_publ_section_title
;
 Kekul\'e diradicaloids derived from a classical N-heterocyclic carbene.
;
_journal_issue                   22
_journal_name_full               'Chemical science'
_journal_page_first              4970
_journal_page_last               4976
_journal_paper_doi               10.1039/c8sc01209a
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         '2(Br), 3.22(C H4 O), C66 H84 N4'
_chemical_formula_sum            'C69.21 H96.87 Br2 N4 O3.22'
_chemical_formula_weight         1196.21
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-17
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-02-28 deposited with the CCDC.
2018-04-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.674(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.3343(2)
_cell_length_b                   17.7848(3)
_cell_length_c                   20.1423(4)
_cell_measurement_reflns_used    33245
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      26.3630
_cell_measurement_theta_min      2.0270
_cell_volume                     3327.41(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.15e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.15e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.15e (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0951
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_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     -4.00  94.00   1.00    8.00    --   24.94  77.00 120.00   98
  2  \w    -46.00  47.00   1.00    8.00    --   24.94 -38.00-180.00   93
  3  \w    -20.00  65.00   1.00    8.00    --   24.94 -99.00 -60.00   85
  4  \w    -47.00  63.00   1.00    8.00    --   24.94 -19.00  60.00  110
  5  \w     -4.00  94.00   1.00    8.00    --   24.94  77.00 -30.00   98
  6  \w     -4.00  94.00   1.00    8.00    --   24.94  77.00-150.00   98
  7  \w      3.00  96.00   1.00    8.00    --   24.94  38.00-180.00   93
  8  \w    -43.00  43.00   1.00    8.00    --   24.94 -57.00   0.00   86
  9  \w      6.00  93.00   1.00    8.00    --   24.94  57.00  90.00   87
 10  \w     -6.00  75.00   1.00    8.00    --   24.94-116.00 150.86   81
 11  \w    -97.00 -35.00   1.00    8.00    --  -23.50-178.00 -60.00   62
 12  \w    -95.00  48.00   1.00    8.00    --  -23.50   0.00-180.00  143
 13  \w    -95.00  48.00   1.00    8.00    --  -23.50   0.00-150.00  143
 14  \w      6.00  93.00   1.00    8.00    --   24.94  57.00 -90.00   87
 15  \w      6.00  93.00   1.00    8.00    --   24.94  57.00  30.00   87
 16  \w     14.00  95.00   1.00    8.00    --   24.94-149.00  57.00   81
 17  \w      5.00  82.00   1.00    8.00    --   24.94-129.00 -65.41   77
 18  \w    -44.00  54.00   1.00    8.00    --   24.94 -77.00  30.00   98
 19  \w    -20.00  65.00   1.00    8.00    --   24.94 -99.00   0.00   85
 20  \w     34.00 100.00   1.00    8.00    --   24.94-178.00 -60.00   66
 21  \w    -95.00  48.00   1.00    8.00    --  -23.50   0.00 -90.00  143
 22  \w    -95.00  48.00   1.00    8.00    --  -23.50   0.00 -60.00  143
 23  \w    -95.00  11.00   1.00    8.00    --  -23.50   0.00 -30.00  106
 24  \w    -95.00  48.00   1.00    8.00    --  -23.50   0.00-120.00  143
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0252004000
_diffrn_orient_matrix_UB_12      -0.0368200000
_diffrn_orient_matrix_UB_13      -0.0057554000
_diffrn_orient_matrix_UB_21      -0.0181906000
_diffrn_orient_matrix_UB_22      0.0047823000
_diffrn_orient_matrix_UB_23      -0.0347760000
_diffrn_orient_matrix_UB_31      0.0697476000
_diffrn_orient_matrix_UB_32      0.0145566000
_diffrn_orient_matrix_UB_33      -0.0031640000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0684
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            192850
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.080
_diffrn_reflns_theta_min         1.531
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.265
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.506
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.15e (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.194
_exptl_crystal_description       block
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.417
_exptl_crystal_size_mid          0.113
_exptl_crystal_size_min          0.108
_refine_diff_density_max         0.676
_refine_diff_density_min         -1.484
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.173
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     374
_refine_ls_number_reflns         9771
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.173
_refine_ls_R_factor_all          0.0918
_refine_ls_R_factor_gt           0.0733
_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^)+(0.0100P)^2^+7.9834P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1365
_refine_ls_wR_factor_ref         0.1430
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7860
_reflns_number_total             9771
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01209a2.cif
_cod_data_source_block           rottschaefer51
_cod_depositor_comments
'Adding full bibliography for 1549300--1549303.cif.'
_cod_database_code               1549303
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C68 H92 Br N4 O2'
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_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, All O(H) groups
2. Others
 Sof(O2)=Sof(H2)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B)
3.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20), C29(H29), C30(H30),
 C32(H32), C33(H33)
3.d Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2)
;
_shelx_res_checksum              18747
_olex2_date_sample_data_collection 2017-11-08
_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 1.217
_oxdiff_exptl_absorpt_empirical_full_min 0.896