Nickel(II)-catalyzed asymmetric thio-Claisen rearrangement of α-diazo pyrazoleamides with thioindoles.
Yang, Wei; Lin, Xiaobin; Zhang, Yongyan; Cao, Weidi; Liu, Xiaohua; Feng, Xiaoming; Chemical communications (Cambridge, England) 56 (2020) 10002–10005; doi:10.1039/d0cc04590j

data_7126952
_publ_section_title
;
 Nickel(II)-catalyzed asymmetric thio-Claisen rearrangement of \a-diazo
 pyrazoleamides with thioindoles.
;
_journal_issue                   69
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10002
_journal_page_last               10005
_journal_paper_doi               10.1039/d0cc04590j
_journal_volume                  56
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C50 H82 N4 Ni O10, 2(B F4)'
_chemical_formula_sum            'C50 H82 B2 F8 N4 Ni O10'
_chemical_formula_weight         1131.52
_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     iterative
_audit_creation_date             2019-08-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-23 deposited with the CCDC.	2020-07-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5480(4)
_cell_length_b                   22.1219(7)
_cell_length_c                   22.7290(8)
_cell_measurement_reflns_used    9844
_cell_measurement_temperature    183(2)
_cell_measurement_theta_max      68.46
_cell_measurement_theta_min      4.29
_cell_volume                     5806.4(3)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      183.29
_diffrn_measured_fraction_theta_full 0.997
_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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0339
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            43485
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.498
_diffrn_reflns_theta_min         2.787
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.179
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6421
_exptl_crystal_colour            COLOUELESS
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             2400
_refine_diff_density_max         0.578
_refine_diff_density_min         -0.375
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 3957 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     692
_refine_ls_number_reflns         10629
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0600
_refine_ls_R_factor_gt           0.0549
_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^)+(0.0943P)^2^+2.5193P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1541
_refine_ls_wR_factor_ref         0.1605
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                9617
_reflns_number_total             10629
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc04590j2.cif
_cod_data_source_block           cu_yw_20190820_4_0m_a
_cod_depositor_comments
'Adding full bibliography for 7126952--7126954.cif.'
_cod_database_code               7126952
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C12) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F4) = Uanis(F4A)
Uanis(F3) = Uanis(F3A)
Uanis(F2) = Uanis(F2A)
Uanis(F7) = Uanis(F7A)
Uanis(C12) = Uanis(C2)
3. Others
 Sof(F2A)=Sof(F3A)=Sof(F4A)=1-FVAR(1)
 Sof(F2)=Sof(F3)=Sof(F4)=FVAR(1)
 Sof(F7A)=1-FVAR(2)
 Sof(F7)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C00U(H00U), C00Z(H00Z), C01E(H01F), C01G(H01J), C01S(H01S), C014(H014)
4.b Secondary CH2 refined with riding coordinates:
 C00M(H00A,H00B), C00O(H00C,H00D), C00R(H00E,H00F), C00T(H00G,H00H), C00V(H00I,
 H00J), C01B(H01A,H01B), C01J(H01L,H01M), C01Z(H01X,H01Y), C2(H2A,H2B), C6(H6A,
 H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C010(H01Z,H),
 C11(H11A,H11B), C12(H12A,H12B), C015(H01,HA), C016(H0AA,HB), C018(H1AA,HC),
 C019(H2AA,HD), C023(H02G,H02H)
4.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N4(H4), C00K(H00K), C00N(H00N), C00Q(H00Q), C01H(H01K), C012(H012),
 C017(H017)
4.d Idealised Me refined as rotating group:
 C01D(H01C,H01D,H01E), C01F(H01G,H01H,H01I), C01P(H01N,H01O,H01P), C01V(H01Q,
 H01R,H01T), C01X(H01U,H01V,H01W), C3(H3A,H3B,H3C), C020(H02A,H02B,H02C),
 C021(H02D,H02E,H02F)
;
_shelx_res_checksum              14356
_shelx_hkl_checksum              13195
_olex2_submission_special_instructions 'No special instructions were received'