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_1549302
_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         'C66 H84 N4, C4 H8 O'
_chemical_formula_sum            'C70 H92 N4 O'
_chemical_formula_weight         1005.47
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-23
_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                70.870(4)
_cell_angle_beta                 84.424(3)
_cell_angle_gamma                76.360(3)
_cell_formula_units_Z            1
_cell_length_a                   9.3970(3)
_cell_length_b                   11.5574(5)
_cell_length_c                   15.1108(6)
_cell_measurement_reflns_used    11350
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.9740
_cell_measurement_theta_min      3.0880
_cell_volume                     1506.40(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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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    -94.00  -4.00   1.00    1.00    --  -24.12 -77.00 -90.00   90
  2  \w    -95.00 -65.00   1.00    1.00    --  -24.12 -38.00-180.00   30
  3  \w   -102.00 -34.00   1.00    1.00    --  -24.12 178.00 -90.00   68
  4  \w    -50.00   4.00   1.00    1.00    --  -24.12 -77.00 150.00   54
  5  \w    -68.00  -4.00   1.00    1.00    --  -24.12 -77.00  90.00   64
  6  \w    -42.00 -15.00   1.00    1.00    --  -24.12 -19.00-180.00   27
  7  \w    -82.00 -54.00   1.00    1.00    --  -24.12 -19.00-180.00   28
  8  \w    -35.00  -8.00   1.00    1.00    --  -24.12 -77.00   0.00   27
  9  \w   -101.00   6.00   1.00    1.00    --  -24.12 -19.00  60.00  107
 10  \w    -79.00 -54.00   1.00    1.00    --  -24.12 -77.00 150.00   25
 11  \w    -94.00 -61.00   1.00    1.00    --  -24.12 -77.00   0.00   33
 12  \w    -61.00 -13.00   1.00    1.00    --  -24.12 -38.00-180.00   48
 13  \w   -100.00 -73.00   1.00    1.00    --  -24.12 -19.00 -30.00   27
 14  \w    -55.00  -6.00   1.00    1.00    --  -24.12 -19.00 -30.00   49
 15  \w    -65.00 -18.00   1.00    1.00    --  -24.12 103.00-118.00   47
 16  \w    -73.00 -10.00   1.00    1.00    --  -24.12 -57.00 -30.00   63
 17  \w    -92.00 -56.00   1.00    1.00    --  -24.12-178.00-180.00   36
 18  \w    -98.00 -36.00   1.00    1.00    --  -24.12-178.00  90.00   62
 19  \w   -109.00 -34.00   1.00    1.00    --  -24.12 178.00   0.00   75
 20  \w      3.00  33.00   1.00    1.00    --   24.12  38.00 -90.00   30
 21  \w     20.00  57.00   1.00    1.00    --   24.12  57.00   0.00   37
 22  \w     36.00  63.00   1.00    1.00    --   24.12 -99.00  60.00   27
 23  \w     76.00 101.00   1.00    1.00    --   24.12  19.00  60.00   25
 24  \w     -7.00  43.00   1.00    1.00    --   24.12  19.00  60.00   50
 25  \w     48.00  73.00   1.00    1.00    --   24.12-116.00-128.30   25
 26  \w     86.00 111.00   1.00    1.33    --  111.00  61.00-180.00   25
 27  \w     85.00 112.00   1.00    1.33    --  111.00  61.00-120.00   27
 28  \w     94.00 121.00   1.00    1.33    --  111.00-125.00   0.00   27
 29  \w    115.00 177.00   1.00    1.33    --  111.00  61.00-180.00   62
 30  \w     81.00 112.00   1.00    1.33    --  111.00  77.00 -60.00   31
 31  \w     50.00 137.00   1.00    1.33    --  111.00 -77.00-120.00   87
 32  \w     84.00 110.00   1.00    1.33    --  111.00  66.00-170.20   26
 33  \w     44.00  77.00   1.00    1.33    --  111.00-125.00   0.00   33
 34  \w    134.00 161.00   1.00    1.33    --  111.00  77.00 150.00   27
 35  \w     42.00 113.00   1.00    1.33    --  111.00-125.00-180.00   71
 36  \w     81.00 107.00   1.00    1.33    --  111.00  77.00 150.00   26
 37  \w    113.00 178.00   1.00    1.33    --  111.00  77.00   0.00   65
 38  \w     86.00 113.00   1.00    1.33    --  111.00  61.00 -90.00   27
 39  \w     85.00 111.00   1.00    1.33    --  111.00  60.00  10.47   26
 40  \w     88.00 143.00   1.00    1.33    --  111.00  49.00   2.27   55
 41  \w     86.00 111.00   1.00    1.33    --  111.00  61.00 120.00   25
 42  \w    131.00 158.00   1.00    1.33    --  111.00  77.00  90.00   27
 43  \w     82.00 107.00   1.00    1.33    --  111.00  77.00  90.00   25
 44  \w     85.00 111.00   1.00    1.33    --  111.00  61.00  30.00   26
 45  \w     85.00 111.00   1.00    1.33    --  111.00  61.00 -30.00   26
 46  \w     81.00 108.00   1.00    1.33    --  111.00  77.00   0.00   27
 47  \w     85.00 111.00   1.00    1.33    --  111.00  61.00 150.00   26
 48  \w     81.00 107.00   1.00    1.33    --  111.00  77.00-150.00   26
 49  \w     85.00 112.00   1.00    1.33    --  111.00  61.00   0.00   27
 50  \w    124.00 151.00   1.00    1.33    --  111.00  45.00 -60.00   27
 51  \w     81.00 107.00   1.00    1.33    --  111.00  77.00 120.00   26
 52  \w    116.00 176.00   1.00    1.33    --  111.00  77.00 120.00   60
 53  \w     89.00 115.00   1.00    1.33    --  111.00  45.00 -60.00   26
 54  \w     41.00  94.00   1.00    1.33    --  111.00 -77.00  60.00   53
 55  \w    115.00 140.00   1.00    1.33    --  111.00 -77.00  60.00   25
 56  \w     89.00 116.00   1.00    1.33    --  111.00  45.00 -30.00   27
 57  \w     33.00  98.00   1.00    1.33    --  111.00 -94.00-150.00   65
 58  \w     89.00 121.00   1.00    1.33    --  111.00  45.00  60.00   32
 59  \w    133.00 160.00   1.00    1.33    --  111.00  65.00-128.53   27
 60  \w    132.00 177.00   1.00    1.33    --  111.00  62.00 -22.85   45
 61  \w    122.00 172.00   1.00    1.33    --  111.00  77.00  30.00   50
 62  \w     85.00 111.00   1.00    1.33    --  111.00  61.00  90.00   26
 63  \w     81.00 108.00   1.00    1.33    --  111.00  77.00  30.00   27
 64  \w    114.00 175.00   1.00    1.33    --  111.00  77.00-120.00   61
 65  \w     81.00 108.00   1.00    1.33    --  111.00  77.00-120.00   27
 66  \w     41.00 109.00   1.00    1.33    --  111.00 -94.00  30.00   68
 67  \w     84.00 110.00   1.00    1.33    --  111.00  65.00-128.53   26
 68  \w     85.00 122.00   1.00    1.33    --  111.00  61.00-150.00   37
 69  \w     89.00 143.00   1.00    1.33    --  111.00  45.00 120.00   54
 70  \w    122.00 176.00   1.00    1.33    --  111.00  77.00  60.00   54
 71  \w     89.00 134.00   1.00    1.33    --  111.00  45.00-180.00   45
 72  \w     89.00 116.00   1.00    1.33    --  111.00  45.00-150.00   27
 73  \w    151.00 176.00   1.00    1.33    --  111.00  45.00-150.00   25
 74  \w     92.00 119.00   1.00    1.33    --  111.00  45.00  30.00   27
 75  \w     85.00 143.00   1.00    1.33    --  111.00  61.00 -60.00   58
 76  \w     94.00 119.00   1.00    1.33    --  111.00-125.00-120.00   25
 77  \w     89.00 115.00   1.00    1.33    --  111.00  45.00 -90.00   26
 78  \w     89.00 123.00   1.00    1.33    --  111.00  45.00  90.00   34
 79  \w     81.00 107.00   1.00    1.33    --  111.00  77.00  60.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0362254000
_diffrn_orient_matrix_UB_12      0.0000593000
_diffrn_orient_matrix_UB_13      -0.1016568000
_diffrn_orient_matrix_UB_21      -0.1647963000
_diffrn_orient_matrix_UB_22      0.0306327000
_diffrn_orient_matrix_UB_23      -0.0196330000
_diffrn_orient_matrix_UB_31      -0.0017315000
_diffrn_orient_matrix_UB_32      0.1412455000
_diffrn_orient_matrix_UB_33      -0.0305041000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0269
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            25880
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.127
_diffrn_reflns_theta_min         3.096
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.488
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.600
_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            'metallic green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.108
_exptl_crystal_description       plate
_exptl_crystal_F_000             548
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.167
_exptl_crystal_size_min          0.026
_refine_diff_density_max         0.468
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.041
_refine_ls_extinction_coef       0.0023(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     337
_refine_ls_number_reflns         5928
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0563
_refine_ls_R_factor_gt           0.0483
_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^)+(0.0645P)^2^+0.5839P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1243
_refine_ls_wR_factor_ref         0.1314
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5051
_reflns_number_total             5928
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01209a2.cif
_cod_data_source_block           rottschaefer57
_cod_depositor_comments
'Adding full bibliography for 1549300--1549303.cif.'
_cod_original_cell_volume        1506.40(10)
_cod_database_code               1549302
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C66 H84 N4'
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.844
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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
Uanis(C10B) = Uanis(C10A)
Uanis(C12B) = Uanis(C12A)
Uanis(C11B) = Uanis(C11A)
3. Others
 Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C12B)=
 Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(1)
 Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C12A)=
 Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C10A(H10A), C10B(H10B), C13(H13), C22(H22), C25(H25)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B)
4.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)
4.d Idealised Me refined as rotating group:
 C11A(H11A,H11B,H11C), C11B(H11D,H11E,H11F), C12A(H12A,H12B,H12C), C12B(H12D,
 H12E,H12F), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C23(H23A,H23B,H23C),
 C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              37085
_shelx_fab_checksum              73800
_olex2_date_sample_data_collection 2017-11-23
_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 1.181
_oxdiff_exptl_absorpt_empirical_full_min 0.878