Divergent synthesis of pyrrolidone fused pyrimido[1,2-<i>b</i>]indazole through selective trapping of an enone intermediate by 1<i>H</i>-indazol-3-amine.
Shen, Xi; Yu, Zhi-Cheng; Zhou, You; Wu, Yan-Dong; Wu, An-Xin; Chemical communications (Cambridge, England) 60 (2024) 9781–9784; doi:10.1039/d4cc03483j

data_7133481
_publ_section_title
;
 Divergent synthesis of pyrrolidone fused pyrimido[1,2-<i>b</i>]indazole
 through selective trapping of an enone intermediate by
 1<i>H</i>-indazol-3-amine.
;
_journal_issue                   72
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9781
_journal_page_last               9784
_journal_paper_doi               10.1039/d4cc03483j
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C30 H20 F N4 O2, C2 H6 O S'
_chemical_formula_sum            'C32 H26 F N4 O3 S'
_chemical_formula_weight         565.63
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2023-08-31
_audit_creation_method
; 
Olex2 1.2 
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506) 
;
_audit_update_record
;
2024-07-03 deposited with the CCDC.	2024-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.371(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.761(2)
_cell_length_b                   11.663(2)
_cell_length_c                   19.570(3)
_cell_measurement_reflns_used    3089
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      22.63
_cell_measurement_theta_min      2.42
_cell_volume                     2779.8(8)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0644
_diffrn_reflns_av_unetI/netI     0.0575
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            19231
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.702
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.165
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6710
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2008/1 (Bruker,2008)'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.352
_exptl_crystal_description       block
_exptl_crystal_F_000             1180
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.627
_refine_diff_density_min         -0.509
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     387
_refine_ls_number_reflns         4899
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.1187
_refine_ls_R_factor_gt           0.0702
_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^)+(0.0760P)^2^+2.4177P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1588
_refine_ls_wR_factor_ref         0.1845
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3049
_reflns_number_total             4899
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc03483j2.cif
_cod_data_source_block           t_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7133480--7133481.cif.'
_cod_original_cell_volume        2779.6(8)
_cod_database_code               7133481
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.949
_olex2_refinement_description
; 
1. Fixed Uiso 
 At 1.2 times of: 
  All C(H) groups, All N(H) groups 
 At 1.5 times of: 
  All C(H,H,H) groups, All O(H) groups 
2. Restrained distances 
 S1-O3 \\sim S1A-O3A 
 with sigma of 0.02 
 S1-C31 \\sim S1A-C31A 
 with sigma of 0.02 
 O3-C31 \\sim O3A-C31A 
 with sigma of 0.04 
 S1-C32 \\sim S1A-C32A 
 with sigma of 0.02 
 O3-C32 \\sim O3A-C32A 
 with sigma of 0.04 
 C32-C31 \\sim C32A-C31A 
 with sigma of 0.04 
3. Uiso/Uaniso restraints and constraints 
Uanis(S1) = Uanis(S1A) 
Uanis(C32) = Uanis(C31A) 
Uanis(O3) = Uanis(O3A) 
Uanis(C32A) = Uanis(C31) 
4. Others 
 Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(C32A)=Sof(H32D)=Sof(H32E)= 
 Sof(H32F)=Sof(O3A)=Sof(S1A)=1-FVAR(1) 
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)= 
 Sof(O3)=Sof(S1)=FVAR(1) 
5.a Riding coordinates: 
 C32A(H32D,H32E,H32F) 
5.b Aromatic/amide H refined with riding coordinates: 
 C2(H2), C3(H3), C4(H4), C5(H5), C12(H12), C13(H13), C14(H14), C15(H15), 
 C16(H16), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), 
  C29(H29), C30(H30), N1(H1) 
5.c Idealised Me refined as rotating group: 
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C31A(H31D,H31E,H31F) 
5.d Idealised tetrahedral OH refined as rotating group: 
 O2(H2A) 
;
_olex2_submission_special_instructions 'No special instructions were received'