Asymmetric sequential annulation/aldol process of 4-isothiocyanato pyrazolones and allenones: access to novel spiro[pyrrole-pyrazolones] and spiro[thiopyranopyrrole-pyrazolones].
Wang, Wenyao; Bao, Xiaoze; Wei, Shiqiang; Nawaz, Shah; Qu, Jingping; Wang, Baomin; Chemical communications (Cambridge, England) 57 (2021) 363–366; doi:10.1039/d0cc07113g

data_7127555
_publ_section_title
;
 Asymmetric sequential annulation/aldol process of 4-isothiocyanato
 pyrazolones and allenones: access to novel spiro[pyrrole-pyrazolones] and
 spiro[thiopyranopyrrole-pyrazolones].
;
_journal_issue                   3
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              363
_journal_page_last               366
_journal_paper_doi               10.1039/d0cc07113g
_journal_volume                  57
_journal_year                    2021
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C36 H25 Br2 N3 O3 S'
_chemical_formula_sum            'C36 H25 Br2 N3 O3 S'
_chemical_formula_weight         739.47
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-09-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-09-27 deposited with the CCDC.	2020-12-02 downloaded from the CCDC.
;
_cell_angle_alpha                80.786(2)
_cell_angle_beta                 73.318(2)
_cell_angle_gamma                89.103(2)
_cell_formula_units_Z            2
_cell_length_a                   10.3636(9)
_cell_length_b                   11.3220(10)
_cell_length_c                   17.7474(15)
_cell_measurement_reflns_used    9989
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      27.435
_cell_measurement_theta_min      2.349
_cell_volume                     1968.0(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      200.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0400
_diffrn_reflns_av_unetI/netI     0.1066
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            34680
_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         27.484
_diffrn_reflns_theta_min         2.020
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    2.146
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5986
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014/3) was used for absorption correction.
wR2(int) was 0.1243 before and 0.0778 after correction.
The Ratio of minimum to maximum transmission is 0.8027.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_description       block
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_exptl_transmission_factor_max   0.7457
_exptl_transmission_factor_min   0.5986
_refine_diff_density_max         0.457
_refine_diff_density_min         -0.417
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 4191 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.057(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.984
_refine_ls_hydrogen_treatment    'riding mode'
_refine_ls_matrix_type           full
_refine_ls_number_parameters     719
_refine_ls_number_reflns         17915
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.984
_refine_ls_R_factor_all          0.0990
_refine_ls_R_factor_gt           0.0541
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0618P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1244
_refine_ls_wR_factor_ref         0.1401
_reflns_Friedel_coverage         0.985
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                11482
_reflns_number_total             17915
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc07113g2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7127555--7127556.cif.'
_cod_database_code               7127555
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.783
_shelx_estimated_absorpt_t_min   0.512
_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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C46(H46A,H46B), C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C53(H53), C52(H52), C50(H50), C49(H49), C13(H13), C14(H14), C16(H16),
 C17(H17), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C32(H32), C33(H33),
  C34(H34), C35(H35), C36(H36), C29(H29), C28(H28), C27(H27), C26(H26),
 C25(H25), C44(H44), C8(H8), C3(H3), C2(H2A), C6(H6), C5(H5), C65(H65),
 C64(H64), C63(H63), C62(H62), C61(H61), C41(H41), C42(H42), C38(H38), C39(H39)
2.c Fitted hexagon refined as free rotating group:
 C48(C53,C52,C51,C50,C49), C12(C13,C14,C15,C16,C17), C67(C68,C69,C70,C71,C72),
 C31(C32,C33,C34,C35,C36), C24(C29,C28,C27,C26,C25), C4(C3,C2,C1,C6,C5),
 C60(C65,C64,C63,C62,C61), C40(C41,C42,C37,C38,C39)
2.d Idealised Me refined as rotating group:
 C57(H57A,H57B,H57C), C21(H21A,H21B,H21C)
2.e Idealised tetrahedral OH refined as rotating group:
 O5(H5A), O2(H2)
;
_shelx_res_checksum              5869
_shelx_fab_checksum              65881
_olex2_submission_special_instructions 'No special instructions were received'