Stereoselective synthesis of spirocyclohexadiene-pyrazolones via organic base and/or hydrogen bonding assisted [3 + 3] annulation reactions
Sun, Bing-Bing; Zhang, Jun-Qi; Chen, Jun-Bo; Fan, Wei-Tai; Yu, Jie-Qiang; Hu, Jia-Ming; Wang, Xing-Wang; Organic Chemistry Frontiers 6 (2019) 1842–; doi:10.1039/C8QO01391H

data_1554580
_publ_section_title
;
 Stereoselective synthesis of spirocyclohexadiene-pyrazolones via organic
 base and/or hydrogen bonding assisted [3 + 3] annulation reactions
;
_journal_issue                   11
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1842
_journal_paper_doi               10.1039/C8QO01391H
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H23 Cl N4 O, C2 H3 N'
_chemical_formula_sum            'C35 H26 Cl N5 O'
_chemical_formula_weight         568.06
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-01-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-01-30 deposited with the CCDC.	2019-04-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.351(2)
_cell_length_b                   11.9996(17)
_cell_length_c                   21.215(3)
_cell_measurement_reflns_used    4144
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.55
_cell_measurement_theta_min      2.47
_cell_volume                     2889.6(8)
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0685
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            11645
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.339
_diffrn_reflns_theta_min         2.470
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.170
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5492
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1153 before and 0.0545 after correction. The Ratio of minimum to maximum transmission is 0.7365. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       block
_exptl_crystal_F_000             1184
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.317
_refine_diff_density_min         -0.279
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 1911 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     386
_refine_ls_number_reflns         7159
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0864
_refine_ls_R_factor_gt           0.0640
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0882P)^2^+1.7407P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1786
_refine_ls_wR_factor_ref         0.1920
_reflns_Friedel_coverage         0.781
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                5563
_reflns_number_total             7159
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8qo01391h2.cif
_cod_data_source_block           b180129b_0m_a
_cod_original_cell_volume        2889.7(8)
_cod_database_code               1554580
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.905
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N4-H4A = N4-H4B
 0.8 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C24(H24)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23),
  C27(H27), C28(H28), C29(H29), C30(H30)
3.c Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C)
;
_olex2_submission_special_instructions 'No special instructions were received'