Stereoselective [4 + 3] annulation of azadienes and ethyl 4-bromo-3-oxobutanoate: construction of benzindeno-fused azepine derivatives.
Shen, Jinhui; Yu, Aimin; Meng, Xiangtai; Organic & biomolecular chemistry 19 (2021) 9026–9030; doi:10.1039/d1ob01749g

data_7158326
_publ_section_title
;
 Stereoselective [4 + 3] annulation of azadienes and ethyl
 4-bromo-3-oxobutanoate: construction of benzindeno-fused azepine
 derivatives.
;
_journal_issue                   41
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9026
_journal_page_last               9030
_journal_paper_doi               10.1039/d1ob01749g
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         '2(C29 H29 N O5 S)'
_chemical_formula_sum            'C58 H58 N2 O10 S2'
_chemical_formula_weight         1007.18
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-08-03
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-09-07 deposited with the CCDC.	2021-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                81.9160(10)
_cell_angle_beta                 82.2550(10)
_cell_angle_gamma                78.7780(10)
_cell_formula_units_Z            2
_cell_length_a                   11.71540(10)
_cell_length_b                   12.19970(10)
_cell_length_c                   18.5760(2)
_cell_measurement_reflns_used    15397
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.0440
_cell_measurement_theta_min      2.4230
_cell_volume                     2562.51(4)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0221
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            24249
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.212
_diffrn_reflns_theta_min         2.417
_exptl_absorpt_coefficient_mu    1.450
_exptl_crystal_density_diffrn    1.305
_exptl_crystal_description       block
_exptl_crystal_F_000             1064
_refine_diff_density_max         0.220
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.031
_refine_ls_extinction_coef       0.00200(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     712
_refine_ls_number_reflns         8960
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0447
_refine_ls_R_factor_gt           0.0397
_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^)+(0.0571P)^2^+0.4334P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1099
_refine_ls_wR_factor_ref         0.1133
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7774
_reflns_number_total             8960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob01749g2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7158322--7158326.cif.'
_cod_database_code               7158326
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C3-C2
 1.45 with sigma of 0.02
 H01I-C01I
 1.45 with sigma of 0.02
3. Rigid bond restraints
 C2, C7, C3, C6, O00N, O6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O00E, C1, C4, C5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C01U, C01V
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
4. Uiso/Uaniso restraints and constraints
C7 \\sim O6: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C3: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
1.7A
C2 \\sim C7: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
5. Rigid body (RIGU) restrains
 O00N, C6, C7, C012
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6, C3, C2, C012
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H1BC)=Sof(H1BD)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=1-FVAR(1)
 Sof(H1AA)=Sof(H1AB)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(1)
 Sof(O6)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=1-FVAR(2)
 Sof(O00N)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C00I(H00I), C00J(H00J), C00L(H00L), C00R(H00R), C00X(H00X), C013(H013)
7.b Secondary CH2 refined with riding coordinates:
 C00Q(H00A,H00B), C01F(H01A,H01B), C6(H6A,H6B), C1(H1BC,H1BD), C1(H1AA,H1AB),
 C3(H3A,H3B)
7.c Aromatic/amide H refined with riding coordinates:
 C00S(H00S), C00T(H00T), C00V(H00V), C00W(H00W), C00Y(H00Y), C014(H014),
 C016(H016), C017(H017), C018(H018), C019(H019), C01A(H01N), C01C(H01R),
 C01D(H01D), C01G(H01G), C01I(H01I), C01J(H01J), C01K(H01K), C01L(H01L),
 C01M(H01U), C01O(H01O), C01P(H01P), C01Q(H01Q), C01R(H01Z), C01S(H01S),
 C01T(H01T), C01V(H01V)
7.d Idealised Me refined as rotating group:
 C01N(H01W,H01X,H01Y), C01Y(H01F,H01H,H01M), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C),
 C7(H7A,H7B,H7C), C2(H2A,H2B,H2C)
7.e Idealised tetrahedral OH refined as rotating group:
 O003(H003), O008(H008)
;
_shelx_res_checksum              44123
_olex2_submission_special_instructions 'No special instructions were received'