2,7-Diazabicyclo[2.2.1]heptanes: Novel Asymmetric Access and Controlled Bridge-Opening
Simpkins, N. S.; Peczkowski, Gary R.; Craven, Philip; Stead, Darren; Chemical Communications  (2019) –; doi:10.1039/C8CC10263E

data_7123127
_publ_section_title
;
 2,7-Diazabicyclo[2.2.1]heptanes: Novel Asymmetric Access and Controlled
 Bridge-Opening
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C8CC10263E
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H24 N2 O4 S'
_chemical_formula_sum            'C26 H24 N2 O4 S'
_chemical_formula_weight         460.53
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-19
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-11-21 deposited with the CCDC.    2019-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.9580(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.27000(10)
_cell_length_b                   11.16340(10)
_cell_length_c                   14.17310(10)
_cell_measurement_reflns_used    17885
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.6810
_cell_measurement_theta_min      3.9560
_cell_volume                     1141.79(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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 5.1768
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_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    -75.00  34.00   1.00    1.00    --  -42.02  77.00  60.00  109
  2  \w   -114.00 -14.00   1.00    1.00    --  -42.02 -57.00 150.00  100
  3  \w   -114.00 -14.00   1.00    1.00    --  -42.02 -57.00-120.00  100
  4  \w     17.00 116.00   1.00    1.00    --   42.02  38.00-120.00   99
  5  \w     23.00  98.00   1.00    1.00    --   42.02-125.00-150.00   75
  6  \w     94.00 178.00   1.00    1.00    --  105.92 125.00  60.00   84
  7  \w     94.00 178.00   1.00    1.00    --  105.92 125.00 150.00   84
  8  \w     73.00 178.00   1.00    1.00    --  105.92  77.00 -60.00  105
  9  \w     77.00 178.00   1.00    1.00    --  105.92  61.00-120.00  101
 10  \w     77.00 178.00   1.00    1.00    --  105.92  61.00 -90.00  101
 11  \w     80.00 178.00   1.00    1.00    --  105.92  45.00 -30.00   98
 12  \w     73.00 178.00   1.00    1.00    --  105.92  77.00-180.00  105
 13  \w     77.00 178.00   1.00    1.00    --  105.92  61.00 -60.00  101
 14  \w     73.00 178.00   1.00    1.00    --  105.92  77.00-120.00  105
 15  \w     73.00 178.00   1.00    1.00    --  105.92  77.00 -90.00  105
 16  \w     80.00 178.00   1.00    1.00    --  105.92  45.00 -90.00   98
 17  \w     77.00 178.00   1.00    1.00    --  105.92  61.00-150.00  101
 18  \w     80.00 178.00   1.00    1.00    --  105.92  45.00   0.00   98
 19  \w     94.00 178.00   1.00    1.00    --  105.92 125.00-150.00   84
 20  \w     80.00 178.00   1.00    1.00    --  105.92  45.00-120.00   98
 21  \w     73.00 178.00   1.00    1.00    --  105.92  77.00-150.00  105
 22  \w     34.00 135.00   1.00    1.00    --  105.92 -61.00 150.00  101
 23  \w     77.00 178.00   1.00    1.00    --  105.92  61.00 -92.78  101
 24  \w    -67.00  32.00   1.00    1.00    --  -42.02  38.00 -30.00   99
 25  \w   -114.00 -14.00   1.00    1.00    --  -42.02 -57.00  30.00  100
 26  \w   -118.00  -9.00   1.00    1.00    --  -42.02 -77.00 120.00  109
 27  \w   -118.00  -9.00   1.00    1.00    --  -42.02 -77.00   0.00  109
 28  \w      9.00 118.00   1.00    1.00    --   42.02  77.00 -60.00  109
 29  \w     80.00 146.00   1.00    1.00    --  105.92  45.00  60.00   66
 30  \w     77.00 178.00   1.00    1.00    --  105.92  61.00 120.00  101
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2134570000
_diffrn_orient_matrix_UB_12      0.0006994000
_diffrn_orient_matrix_UB_13      0.0152691000
_diffrn_orient_matrix_UB_21      0.0040377000
_diffrn_orient_matrix_UB_22      -0.0600719000
_diffrn_orient_matrix_UB_23      -0.0975860000
_diffrn_orient_matrix_UB_31      0.0007177000
_diffrn_orient_matrix_UB_32      0.1242205000
_diffrn_orient_matrix_UB_33      -0.0472810000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0209
_diffrn_reflns_av_unetI/netI     0.0147
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            21276
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.109
_diffrn_reflns_theta_min         6.132
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.556
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.716
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.340
_exptl_crystal_description       block
_exptl_crystal_F_000             484
_exptl_crystal_size_max          0.198
_exptl_crystal_size_mid          0.163
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.146
_refine_diff_density_min         -0.125
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 1976 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     345
_refine_ls_number_reflns         4388
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0231
_refine_ls_R_factor_gt           0.0227
_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^)+(0.0350P)^2^+0.1560P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0576
_refine_ls_wR_factor_ref         0.0582
_reflns_Friedel_coverage         0.857
_reflns_Friedel_fraction_full    0.960
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                4322
_reflns_number_total             4388
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc10263e3.cif
_cod_data_source_block           2f
_cod_database_code               7123127
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C26 H24 N2 O4 S1'
_shelx_estimated_absorpt_t_max   0.835
_shelx_estimated_absorpt_t_min   0.748
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 C6-C7 = C6-C7'
 1.5 with sigma of 0.01
 C11'-C10'
 1.43 with sigma of 0.02
3. Rigid bond restraints
 C7, S8, C9, C10, C11, C7', S8'
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C7 \\sim C7': within 2A with sigma of 0.004 and sigma for terminal atoms of
0.004
5. Others
 Sof(C7')=Sof(S8')=Sof(C9')=Sof(H9')=Sof(C10')=Sof(H10')=Sof(C11')=Sof(H11')=1-
 FVAR(1)
 Sof(C7)=Sof(S8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C16(H16A,H16B), C23(H23A,H23B)
6.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C9'(H9'), C10'(H10'), C11'(H11'), C18(H18),
 C19(H19), C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C27(H27), C28(H28),
  C29(H29)
6.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
;
_shelx_res_checksum              6282
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.114
_oxdiff_exptl_absorpt_empirical_full_min 0.951