Synthesis of δ- and α-Carbolines via Nickel-Catalyzed [2 + 2 + 2] Cycloaddition of Functionalized Alkyne-Nitriles with Alkynes.
Wang, Gaonan; You, Xu; Gan, Yi; Liu, Yuanhong; Organic letters 19 (2017) 110–113; doi:10.1021/acs.orglett.6b03385

data_1544929
_publ_section_title
;
 Synthesis of \d- and \a-Carbolines via Nickel-Catalyzed [2 + 2 + 2]
 Cycloaddition of Functionalized Alkyne-Nitriles with Alkynes.
;
_journal_issue                   1
_journal_name_full               'Organic letters'
_journal_page_first              110
_journal_page_last               113
_journal_paper_doi               10.1021/acs.orglett.6b03385
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C33 H25 N3 O4 S'
_chemical_formula_sum            'C33 H25 N3 O4 S'
_chemical_formula_weight         559.62
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-05-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.224(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6286(18)
_cell_length_b                   25.115(4)
_cell_length_c                   10.7465(18)
_cell_measurement_reflns_used    1234
_cell_measurement_temperature    130
_cell_measurement_theta_max      21.573
_cell_measurement_theta_min      2.541
_cell_volume                     2780.7(8)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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  0.0684
_diffrn_reflns_av_unetI/netI     0.1022
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            11501
_diffrn_reflns_point_group_measured_fraction_full 0.765
_diffrn_reflns_point_group_measured_fraction_max 0.765
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.670
_diffrn_reflns_theta_min         1.622
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.161
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6606
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0697 before and 0.0522 after correction.
The Ratio of minimum to maximum transmission is 0.8860.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.337
_exptl_crystal_description       block
_exptl_crystal_F_000             1168
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.238
_refine_diff_density_min         -0.279
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 767 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.22(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.807
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         4962
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      0.807
_refine_ls_R_factor_all          0.0989
_refine_ls_R_factor_gt           0.0497
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1119
_refine_ls_wR_factor_ref         0.1429
_reflns_Friedel_coverage         0.531
_reflns_Friedel_fraction_full    0.530
_reflns_Friedel_fraction_max     0.532
_reflns_number_gt                3313
_reflns_number_total             4962
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b03385_si_004.cif
_cod_data_source_block           mo_dm16329_0m
_cod_depositor_comments
;
Adding full bibliography for 1544929--1544930.cif.

2019-03-14
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '0.5(C33 H25 N3 O4 S)'
_cod_original_formula_sum        'C16.50 H12.50 N1.50 O2 S0.50'
_cod_original_formula_units_Z    8
_cod_original_formula_weight     279.81
_cod_database_code               1544929
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.981
_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
2.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C28(H28), C29(H29),
  C31(H31), C32(H32)
2.c Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C)
;
_shelx_res_checksum              41627
_shelx_hkl_checksum              31789
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'