Cyanomethylation and Cyclization of Aryl Alkynoates with Acetonitrile under Transition-Metal-Free Conditions: Synthesis of 3-Cyanomethylated Coumarins.
Yu, Yulan; Zhuang, Shengyi; Liu, Ping; Sun, Peipei; The Journal of organic chemistry 81 (2016) 11489–11495; doi:10.1021/acs.joc.6b02155

data_4037392
_publ_section_title
;
 Cyanomethylation and Cyclization of Aryl Alkynoates with Acetonitrile
 under Transition-Metal-Free Conditions: Synthesis of 3-Cyanomethylated
 Coumarins.
;
_journal_issue                   22
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              11489
_journal_page_last               11495
_journal_paper_doi               10.1021/acs.joc.6b02155
_journal_volume                  81
_journal_year                    2016
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C18 H12 Cl N O2'
_chemical_formula_sum            'C18 H12 Cl N O2'
_chemical_formula_weight         309.23
_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     direct
_audit_creation_date             2016-09-04
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.495(8)
_cell_length_b                   12.365(9)
_cell_length_c                   20.951(15)
_cell_measurement_reflns_used    5922
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      24.425
_cell_measurement_theta_min      2.418
_cell_volume                     2978(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_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      296.15
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_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  0.1175
_diffrn_reflns_av_unetI/netI     0.0910
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_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       14
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            18357
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.912
_exptl_absorpt_coefficient_mu    0.262
_exptl_absorpt_correction_T_max  0.8325
_exptl_absorpt_correction_T_min  0.7523
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_description       block
_exptl_crystal_F_000             1276
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         2.215
_refine_diff_density_min         -0.548
_refine_diff_density_rms         0.220
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.6(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.317
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     388
_refine_ls_number_reflns         5118
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.319
_refine_ls_R_factor_all          0.1843
_refine_ls_R_factor_gt           0.1494
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3343
_refine_ls_wR_factor_ref         0.3614
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                3569
_reflns_number_total             5118
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b02155_si_003.cif
_cod_data_source_block           22
_cod_depositor_comments
;

2020-06-08
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C36 H24 Cl2 N2 O4'
_cod_original_formula_weight         618.46
_cod_original_formula_moiety         'C18 H12 Cl N O2, C18 H12 Cl N O2'
_cod_original_formula_units_Z            4
_cod_database_code               4037392
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.4(3) 0.6(3)
2. 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
3. Uiso/Uaniso restraints and constraints
Uanis(C4) \\sim Ueq: with sigma of 0.008 and sigma for terminal atoms of 0.016
4.a Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B)
4.b Aromatic/amide H refined with riding coordinates:
 C26(H26), C29(H29), C32(H32), C36(H36), C35(H35), C33(H33), C27(H27), C3(H3),
 C7(H7), C11(H11), C14(H14), C18(H18), C17(H17), C15(H15), C4(H4)
4.c Fitted hexagon refined as free rotating group:
 C14(C13,C18,C17,C16,C15)
4.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              21761
_shelx_hkl_checksum              38543
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'