Photochemical reactions of a diamidocarbene: cyclopropanation of bromonaphthalene, addition to pyridine, and activation of sp<sup>3</sup> C-H bonds.
Perera, Tharushi A.; Taylor, William V.; Gildner, M. Brenton; Reinheimer, Eric W.; Ito, Sho; Nelson, Anna; Yost, Shane R.; Hudnall, Todd W.; Chemical science 14 (2023) 7867–7874; doi:10.1039/d2sc05122b

data_1569162
_publ_section_title
;
 Photochemical reactions of a diamidocarbene: cyclopropanation of
 bromonaphthalene, addition to pyridine, and activation of sp<sup>3</sup>
 C-H bonds.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              7867
_journal_page_last               7874
_journal_paper_doi               10.1039/d2sc05122b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C58 H63 Br N4 O4'
_chemical_formula_sum            'C58 H63 Br N4 O4'
_chemical_formula_weight         960.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-15
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-08-16 deposited with the CCDC.	2023-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.4690(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.89710(10)
_cell_length_b                   23.3372(2)
_cell_length_c                   33.3618(3)
_cell_measurement_reflns_used    22348
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.9920
_cell_measurement_theta_min      3.5170
_cell_volume                     11587.68(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.1d (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.1d (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.1d (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -14.00  45.00   0.50    1.96    --   46.72 -19.00   0.00  118
  2  \w     28.00  98.00   0.50    7.83    --   99.96 -94.00   0.00  140
  3  \w     31.00  57.00   0.50    7.83    --   99.96 -30.00   0.00   52
  4  \w     26.00  54.00   0.50    7.83    --   99.96 -30.00  60.00   56
  5  \w     23.00  55.00   0.50    7.83    --   99.96 -30.00 120.00   64
  6  \w     25.00  51.00   0.50    7.83    --   99.96 -15.00 120.00   52
  7  \w     23.00  79.00   0.50    7.83    --   99.96 -45.00  60.00  112
  8  \w     25.00  50.00   0.50    7.83    --   99.96 -15.00   0.00   50
  9  \w     25.00  57.00   0.50    7.83    --   99.96 -30.00 -60.00   64
 10  \w     22.00  56.00   0.50    7.83    --   99.96 -30.00-120.00   68
 11  \w     22.00  54.00   0.50    7.83    --   99.96 -15.00 -90.00   64
 12  \w     29.00  54.00   0.50    7.83    --   99.96 -15.00-120.00   50
 13  \w     19.00  44.00   0.50    7.83    --   99.96 -15.00-150.00   50
 14  \w     68.00 113.00   0.50    7.83    --   99.96-111.00-180.00   90
 15  \w     17.00  43.00   0.50    7.83    --   99.96 -15.00  30.00   52
 16  \w     17.00  50.00   0.50    7.83    --   99.96 -15.00  90.00   66
 17  \w     20.00 112.00   0.50    7.83    --   99.96-111.00  60.00  184
 18  \w    -32.00  94.00   0.50    1.96    --   46.72   0.00-120.00  252
 19  \w    -68.00 -21.00   0.50    7.83    --  -84.50  61.00-180.00   94
 20  \w   -126.00 -86.00   0.50    1.96    --  -46.72 -99.00  90.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_unetI/netI     0.0313
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            31898
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         5.841
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.309
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.757
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.1d (Rigaku Oxford Diffraction, 2018)
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    1.101
_exptl_crystal_description       block
_exptl_crystal_F_000             4048
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.146
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.452
_refine_diff_density_min         -0.654
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     707
_refine_ls_number_reflns         10182
_refine_ls_number_restraints     114
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0541
_refine_ls_R_factor_gt           0.0518
_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^)+(0.0567P)^2^+25.9344P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1375
_refine_ls_wR_factor_ref         0.1389
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9552
_reflns_number_total             10182
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05122b2.cif
_cod_data_source_block           proc_notwin
_cod_depositor_comments
'Adding full bibliography for 1569160--1569162.cif.'
_cod_database_code               1569162
_shelx_shelxl_version_number     2014/7
_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. Uiso/Uaniso restraints and constraints
C5B \\sim C3A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C5A \\sim C2B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C11A \\sim C8B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C9A \\sim C10B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C10B \\sim C9B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C12A) = Uanis(C6B)
Uanis(C6A) = Uanis(C3B)
3. Rigid body (RIGU) restrains
 Br1A, C5A, C3A, C2A, C12A, C7A, C6A, C8A, C9A, C10A, C11A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Fixed Sof: Br1A(0.5) Br1B(0.5) C2B(0.5) H2B(0.5) C5B(0.5) H5B(0.5) C3B(0.5)
 H3B(0.5) C6B(0.5) H6B(0.5) C12B(0.5) C7B(0.5) C11B(0.5) C8B(0.5) H8B(0.5)
 C9B(0.5) H9B(0.5) C10B(0.5) H10B(0.5) C5A(0.5) H5A(0.5) C3A(0.5) H3A(0.5)
 C2A(0.5) H2A(0.5) C12A(0.5) C7A(0.5) C6A(0.5) H6A(0.5) C8A(0.5) H8A(0.5)
 C9A(0.5) H9A(0.5) C10A(0.5) H10A(0.5) C11A(0.5)
5.a Ternary CH refined with riding coordinates:
 C2B(H2B), C5B(H5B), C3B(H3B), C6B(H6B), C5A(H5A), C3A(H3A), C2A(H2A), C6A(H6A)
5.b Aromatic/amide H refined with riding coordinates:
 C40(H40), C17(H17), C38(H38), C15(H15), C52(H52), C31(H31), C29(H29),
 C54(H54), C8B(H8B), C9B(H9B), C10B(H10B), C8A(H8A), C9A(H9A), C10A(H10A)
5.c Idealised Me refined as rotating group:
 C44(H44A,H44B,H44C), C42(H42A,H42B,H42C), C49(H49A,H49B,H49C), C26(H26A,H26B,
 H26C), C56(H56A,H56B,H56C), C35(H35A,H35B,H35C), C58(H58A,H58B,H58C), C48(H48A,
 H48B,H48C), C33(H33A,H33B,H33C), C21(H21A,H21B,H21C), C25(H25A,H25B,H25C),
 C19(H19A,H19B,H19C), C43(H43A,H43B,H43C), C20(H20A,H20B,H20C), C57(H57A,H57B,
 H57C), C34(H34A,H34B,H34C)
;
_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
;