Divergent Construction of Macrocyclic Alkynes via Catalytic Metal Carbene C(sp2)–H Insertion and the Buchner Reaction
Zeng, Qian; Dong, Kuiyong; Pei, Chao; Dong, Shanliang; Hu, Wenhao; Qiu, Lihua; Xu, Xinfang; ACS Catalysis  (2019) 10773–; doi:10.1021/acscatal.9b04199

data_4515238
_publ_section_title
;
 Divergent Construction of Macrocyclic Alkynes via Catalytic Metal Carbene
 C(sp2)--H Insertion and the Buchner Reaction
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              10773
_journal_paper_doi               10.1021/acscatal.9b04199
_journal_year                    2019
_chemical_formula_moiety         'C19 H16 Cl N O2'
_chemical_formula_sum            'C19 H16 Cl N O2'
_chemical_formula_weight         325.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-12-15
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.271(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.1685(3)
_cell_length_b                   19.6127(8)
_cell_length_c                   19.5534(6)
_cell_measurement_reflns_used    6846
_cell_measurement_temperature    275.21(10)
_cell_measurement_theta_max      29.7880
_cell_measurement_theta_min      3.6890
_cell_volume                     3107.4(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      275.21(10)
_diffrn_detector_area_resol_mean 10.4471
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.901
_diffrn_measurement_details
;
  1 omega  -62.00  -37.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       13.8077  -38.0000  -60.0000 25

  2 omega  -13.00   20.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       13.8077  -38.0000  -60.0000 33

  3 omega  -91.00  -64.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.5889 -178.0000   30.0000 27

  4 omega  -16.00   23.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.5889  -99.0000 -120.0000 39

  5 omega  -23.00   27.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.5889  -99.0000  -30.0000 50

  6 omega  -43.00   44.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.5889   57.0000 -120.0000 87

  7 omega  -48.00   64.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.5889   77.0000   60.0000 112
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0424455000
_diffrn_orient_matrix_UB_12      0.0083101000
_diffrn_orient_matrix_UB_13      0.0283671000
_diffrn_orient_matrix_UB_21      -0.0090230000
_diffrn_orient_matrix_UB_22      0.0341112000
_diffrn_orient_matrix_UB_23      -0.0119524000
_diffrn_orient_matrix_UB_31      -0.0759982000
_diffrn_orient_matrix_UB_32      -0.0086897000
_diffrn_orient_matrix_UB_33      -0.0197547000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0417
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.901
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            30913
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.901
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.385
_diffrn_reflns_theta_min         2.844
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.255
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76976
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.393
_exptl_crystal_description       plate
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.324
_refine_diff_density_min         -0.475
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     417
_refine_ls_number_reflns         8453
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0844
_refine_ls_R_factor_gt           0.0512
_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^)+(0.0435P)^2^+1.5041P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1068
_refine_ls_wR_factor_ref         0.1251
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5856
_reflns_number_total             8453
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04199_si_004.cif
_cod_data_source_block           g181212c
_cod_depositor_comments
;

2020-08-05
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_cell_volume        3107.38(19)
_cod_original_formula_moiety     '2(C19 H16 Cl N O2)'
_cod_original_formula_sum        'C38 H32 Cl2 N2 O4'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     651.55
_cod_database_code               4515238
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H N O Cl'
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.914
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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 Ternary CH refined with riding coordinates:
 C21(H21), C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C37(H37A,H37B), C9(H9A,H9B), C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C24(H24), C26(H26), C27(H27), C30(H30), C31(H31), C32(H32),
 C33(H33), C4(H4), C5(H5), C7(H7), C8(H8), C11(H11), C12(H12), C13(H13),
 C14(H14)
2.d Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              46907
_shelx_hkl_checksum              30127
_olex2_submission_special_instructions 'No special instructions were received'