Photochemically Switching Diamidocarbene Spin States Leads to Reversible Büchner Ring Expansions.
Perera, Tharushi A.; Reinheimer, Eric W.; Hudnall, Todd W.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b09264

data_4126557
_publ_section_title
;
 Photochemically Switching Diamidocarbene Spin States Leads to Reversible
 B\"uchner Ring Expansions.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b09264
_journal_year                    2017
_chemical_formula_moiety         'C30 H34 N2 O2'
_chemical_formula_sum            'C30 H34 N2 O2'
_chemical_formula_weight         454.59
_chemical_name_common            DAC-Benzene
_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             2017-08-04
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2016.03.30 svn.r3266 for Rigaku Oxford Diffraction, GUI svn.r5168)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.461(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.5160(2)
_cell_length_b                   20.1012(5)
_cell_length_c                   14.0241(4)
_cell_measurement_reflns_used    17355
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      77.1590
_cell_measurement_theta_min      3.7540
_cell_volume                     2393.40(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_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_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_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    -57.00   3.00   0.50    9.84    --  -49.30  19.00   0.00  120
  2  \w    -60.00  21.00   0.50    9.84    --  -49.30  57.00-150.00  162
  3  \w    -64.00 -32.00   0.50    9.84    --  -49.30 125.00-180.00   64
  4  \w   -120.00 -81.00   0.50    9.84    --  -49.30 -37.00-120.00   78
  5  \w   -107.00 -70.00   0.50    9.84    --  -49.30-125.00 -60.00   74
  6  \w    -95.00 -70.00   0.50    9.84    --  -49.30-125.00 -30.00   50
  7  \w     32.00 108.00   0.50   31.81    --  105.75 -19.00 -90.00  152
  8  \w    108.00 134.00   0.50   31.81    --  105.75  37.00-120.00   52
  9  \w     39.00 111.00   0.50   31.81    --  105.75 -37.00-150.00  144
 10  \w     71.00 110.00   0.50   31.81    --  105.75 -99.00-150.00   78
 11  \w     34.00 100.00   0.50   31.81    --  105.75 -99.00-120.00  132
 12  \w     33.00 113.00   0.50   31.81    --  105.75 -19.00-180.00  160
 13  \w    146.00 172.00   0.50   31.81    --  105.75 125.00  90.00   52
 14  \w    100.00 126.00   0.50   31.81    --  105.75 125.00  90.00   52
 15  \w     39.00 102.00   0.50   31.81    --  105.75 -37.00 120.00  126
 16  \w     69.00 101.00   0.50   31.81    --  105.75 -99.00 150.00   64
 17  \w     53.00 101.00   0.50   32.00    --  105.75 -57.00 -60.00   96
 18  \w   -121.00 -28.00   0.50   10.00    --  -49.17 -77.00 120.00  186
 19  \w   -121.00 -28.00   0.50   10.00    --  -49.17 -77.00   0.00  186
 20  \w   -121.00 -28.00   0.50   10.00    --  -49.17 -77.00-120.00  186
 21  \w   -120.00 -36.00   0.50   10.00    --  -49.17 -57.00  30.00  168
 22  \w     31.00  95.00   0.50   10.00    --   49.17-125.00 120.00  128
 23  \w     35.00  62.00   0.50   32.00    --  105.75 -57.00  30.00   54
 24  \w     98.00 148.00   0.50   32.00    --  105.75  19.00 -60.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1317518000
_diffrn_orient_matrix_UB_12      -0.0026734000
_diffrn_orient_matrix_UB_13      0.0816008000
_diffrn_orient_matrix_UB_21      0.1243397000
_diffrn_orient_matrix_UB_22      -0.0022115000
_diffrn_orient_matrix_UB_23      -0.0740647000
_diffrn_orient_matrix_UB_31      0.0084386000
_diffrn_orient_matrix_UB_32      0.0765869000
_diffrn_orient_matrix_UB_33      0.0007942000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0368
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            21277
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.585
_diffrn_reflns_theta_max         66.585
_diffrn_reflns_theta_min         5.657
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.614
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71036
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.30d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.262
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.144
_exptl_crystal_size_mid          0.128
_exptl_crystal_size_min          0.051
_refine_diff_density_max         0.361
_refine_diff_density_min         -0.443
_refine_diff_density_rms         0.060
_refine_ls_extinction_coef       0.00098(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     316
_refine_ls_number_reflns         4214
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0547
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0418P)^2^+3.6965P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1243
_refine_ls_wR_factor_ref         0.1335
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3812
_reflns_number_total             4214
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b09264_si_002.cif
_cod_data_source_block           2a
_cod_original_cell_volume        2393.40(10)
_cod_database_code               4126557
_chemical_oxdiff_formula         'C120 H136 N8 O8 '
_exptl_absorpt_special_details   none
_diffrn_oxdiff_ac3_digest_frames
;
01330b725b9561fc4cebbf1d9bc0c9a289000251e00
;
_diffrn_oxdiff_ac3_digest_hkl
;
01578e5a4ae45704b25bb85f33038d4808d804
;
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Aromatic/amide H refined with riding coordinates:
 C30(H30), C26(H26), C7(H7), C18(H18), C9(H9), C25(H25), C29(H29), C28(H28),
 C27(H27), C20(H20)
2.b Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C11(H11A,H11B,
 H11C), C15(H15A,H15B,H15C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C12(H12A,
 H12B,H12C)
;
_shelx_res_checksum              63933
_shelx_hkl_checksum              60639
_shelx_shelxl_version_number     2014/7
_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 2.522
_oxdiff_exptl_absorpt_empirical_full_min 0.701