A photochemical ring expansion of 6- to 8-membered nitrogen heterocycles by [1,3]-sigmatropic rearrangement.
Manning, Morgan A.; Sun, Wei; Light, Mark E.; Harrowven, David C.; Chemical communications (Cambridge, England) 57 (2021) 4556–4559; doi:10.1039/d1cc00393c

data_7128108
_publ_section_title
;
 A photochemical ring expansion of 6- to 8-membered nitrogen heterocycles
 by [1,3]-sigmatropic rearrangement.
;
_journal_issue                   37
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4556
_journal_page_last               4559
_journal_paper_doi               10.1039/d1cc00393c
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'C30 H29 N O5'
_chemical_formula_sum            'C30 H29 N O5'
_chemical_formula_weight         483.54
_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
_audit_creation_date             2020-08-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-08-27 deposited with the CCDC.	2021-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                97.518(2)
_cell_angle_beta                 90.336(2)
_cell_angle_gamma                92.213(2)
_cell_formula_units_Z            8
_cell_length_a                   8.7874(2)
_cell_length_b                   17.8436(4)
_cell_length_c                   31.3137(6)
_cell_measurement_reflns_used    24004
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.4370
_cell_measurement_theta_min      2.3160
_cell_volume                     4863.82(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -85.00  18.50   0.50    6.71    --   -8.00 -44.00 139.76  207
  2  \w    -41.00  75.50   0.50    6.71    --   -9.10  38.00   0.00  233
  3  \w    -40.00  79.50   0.50    6.71    --   -9.10  60.00-150.00  239
  4  \w    -39.00 -12.00   0.50    6.71    --   -9.10  60.00-180.00   54
  5  \w     46.00  75.50   0.50    6.71    --   -9.10  60.00-180.00   59
  6  \w    -39.00  76.50   0.50    6.71    --   -9.10  38.00 150.00  231
  7  \w    -84.00  19.50   0.50    6.71    --   -9.10 -60.00 -60.00  207
  8  \w    -40.00  68.00   0.50    6.71    --   -9.10  60.00 -90.00  216
  9  \w    -40.00  73.50   0.50    6.71    --   -9.10  60.00  60.00  227
 10  \w    -77.00   4.00   0.50    6.71    --   -9.10 -60.00  90.00  162
;
_diffrn_measurement_device       'four-circle \k diffractometer'
_diffrn_measurement_device_type  'Rigaku AFC12 FRE-VHF'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroMesh'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0632129000
_diffrn_orient_matrix_UB_12      0.0079008000
_diffrn_orient_matrix_UB_13      0.0142867000
_diffrn_orient_matrix_UB_21      -0.0502905000
_diffrn_orient_matrix_UB_22      0.0080931000
_diffrn_orient_matrix_UB_23      0.0174881000
_diffrn_orient_matrix_UB_31      -0.0009433000
_diffrn_orient_matrix_UB_32      -0.0385003000
_diffrn_orient_matrix_UB_33      0.0034845000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'Confocal mirrors, VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1015
_diffrn_reflns_av_unetI/netI     0.0659
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            150262
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.499
_diffrn_reflns_theta_min         1.856
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FR-E+ SuperBright'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    0.090
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67364
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.37a (Rigaku Oxford Diffraction, 2019)
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    1.321
_exptl_crystal_description       prism
_exptl_crystal_F_000             2048
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of Et2O and petrol  by slow evaporation'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.169
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.595
_refine_diff_density_min         -0.433
_refine_diff_density_rms         0.161
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1313
_refine_ls_number_reflns         24636
_refine_ls_number_restraints     1164
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.1475
_refine_ls_R_factor_gt           0.1215
_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^)+(0.1679P)^2^+10.4008P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2961
_refine_ls_wR_factor_ref         0.3138
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18851
_reflns_number_total             24636
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc00393c2.cif
_cod_data_source_block           2020sot0013_r1_100k
_cod_depositor_comments
'Adding full bibliography for 7128107--7128108.cif.'
_cod_database_code               7128108
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C21 H27 N1 O5'
_chemical_oxdiff_usercomment     MM/8910/44
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.979
_diffrn_measurement_device_type2 'Rigaku AFC12 (Right)'
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Ternary CH refined with riding coordinates:
 C104(H104), C114(H114), C204(H204), C214(H214), C304(H304), C314(H314),
 C404(H404), C414(H414)
3.b Secondary CH2 refined with riding coordinates:
 C124(H12B,H12A), C224(H22A,H22B), C324(H32A,H32B), C424(H42A,H42B)
3.c Aromatic/amide H refined with riding coordinates:
 C106(H106), C107(H107), C109(H109), C116(H116), C117(H117), C118(H118),
 C119(H119), C120(H120), C126(H126), C127(H127), C128(H128), C129(H129),
 C130(H130), C206(H206), C207(H207), C209(H209), C216(H216), C217(H217),
 C218(H218), C219(H219), C220(H220), C226(H226), C227(H227), C228(H228),
 C229(H229), C230(H230), C306(H306), C307(H307), C309(H309), C316(H316),
 C317(H317), C318(H318), C319(H319), C320(H320), C326(H326), C327(H327),
 C328(H328), C329(H329), C330(H330), C406(H406), C407(H407), C409(H409),
 C416(H416), C417(H417), C418(H418), C419(H419), C420(H420), C426(H426),
 C427(H427), C428(H428), C429(H429), C430(H430)
3.d Idealised Me refined as rotating group:
 C101(H10A,H10B,H10C), C121(H12C,H12D,H12E), C122(H12I,H12J,H12K), C123(H12F,
 H12G,H12H), C201(H20A,H20B,H20C), C221(H22C,H22D,H22E), C222(H22I,H22J,H22K),
 C223(H22F,H22G,H22H), C301(H30A,H30B,H30C), C321(H32C,H32D,H32E), C322(H32I,
 H32J,H32K), C323(H32F,H32G,H32H), C401(H40A,H40B,H40C), C421(H42F,H42G,H42H),
 C422(H42I,H42J,H42K), C423(H42C,H42D,H42E)
;
_shelx_res_checksum              26062
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with silicon oil'
_olex2_submission_original_sample_id MM/8910/44
_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 2.062
_oxdiff_exptl_absorpt_empirical_full_min 0.440