Asymmetric [3 + 2] spiroannulation of pyrazolone-derived Morita–Baylis–Hillman carbonates with alkynyl ketones: facile access to spiro[cyclopentadiene-pyrazolone] scaffolds
Wang, Baomin; Wei, Xingfu; Huang, Yue; Wang, Wenyao; Wei, Shiqiang; Qu, Jingping; Chemical Communications  (2022) –; doi:10.1039/D2CC02963D

data_7130431
_publ_section_title
;
 Asymmetric [3 + 2] spiroannulation of pyrazolone-derived
 Morita--Baylis--Hillman carbonates with alkynyl ketones: facile access to
 spiro[cyclopentadiene-pyrazolone] scaffolds
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC02963D
_journal_year                    2022
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C28 H19 Br N2 O4'
_chemical_formula_sum            'C27 H19 Br N3 O4'
_chemical_formula_weight         529.36
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-07-13 deposited with the CCDC.	2022-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.5080(5)
_cell_length_b                   12.3736(6)
_cell_length_c                   20.7192(11)
_cell_measurement_reflns_used    9923
_cell_measurement_temperature    295.0
_cell_measurement_theta_max      22.794
_cell_measurement_theta_min      2.357
_cell_volume                     2437.6(2)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      295.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0760
_diffrn_reflns_av_unetI/netI     0.0534
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            47283
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         1.966
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.725
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5422
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1266 before and 0.0880 after correction.
The Ratio of minimum to maximum transmission is 0.7271.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.442
_exptl_crystal_description       block
_exptl_crystal_F_000             1076
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.355
_refine_diff_density_min         -1.187
_refine_diff_density_rms         0.145
_refine_ls_abs_structure_details
;
 Flack x determined using 1265 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.044(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     317
_refine_ls_number_reflns         5592
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0963
_refine_ls_R_factor_gt           0.0581
_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^)+(0.0747P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1227
_refine_ls_wR_factor_ref         0.1405
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                3778
_reflns_number_total             5592
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc02963d2.cif
_cod_data_source_block           1
_cod_database_code               7130431
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.782
_shelx_estimated_absorpt_t_min   0.713
_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.a Aromatic/amide H refined with riding coordinates:
 C009(H009), C00F(H00F), C00H(H00H), C00I(H00I), C00J(H00J), C00K(H00K),
 C00L(H00L), C00Q(H00Q), C00R(H00R), C00S(H00S), C00U(H00U), C00V(H00V),
 C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z)
2.b Idealised Me refined as rotating group:
 C00T(H00A,H00B,H00C)
;
_shelx_res_checksum              54035
_shelx_hkl_checksum              25359
_olex2_submission_special_instructions 'No special instructions were received'