Strained alkynes derived from 2,2′-dihydroxy-1,1′-biaryls; synthesis and copper-free cycloaddition with azides
Del Grosso, Alessandro; Galanopoulos, Lavrentis-Dimitrios; Chiu, Cookson K. C.; Clarkson, Guy J.; O′ Connor, Peter B.; Wills, Martin; Org. Biomol. Chem.  (2017) –; doi:10.1039/C7OB00991G

data_7155633
_publ_section_title
;
 Strained alkynes derived from 2,2&#x2032;-dihydroxy-1,1&#x2032;-biaryls;
 synthesis and copper-free cycloaddition with azides
;
_journal_name_full               'Org. Biomol. Chem.'
_journal_paper_doi               10.1039/C7OB00991G
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H19 N3 O2'
_chemical_formula_sum            'C23 H19 N3 O2'
_chemical_formula_weight         369.41
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-27
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-11-04 deposited with the CCDC.
2017-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.54430(10)
_cell_length_b                   19.2006(2)
_cell_length_c                   20.0739(2)
_cell_measurement_reflns_used    10595
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      77.6100
_cell_measurement_theta_min      4.5770
_cell_volume                     3678.67(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1417
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
  1 omega  -50.00   33.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109   38.0000  120.0000 83

  2 omega -115.00  -14.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109  -57.0000  -30.0000 101

  3 omega   57.00   98.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       41.7109 -125.0000   30.0000 41

  4 omega   41.00   71.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       41.7109 -125.0000 -120.0000 30

  5 omega   53.00   80.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -95.0000  150.0000 27

  6 omega   41.00   90.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -30.0000   60.0000 49

  7 omega   50.00   79.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000 -120.0000 29

  8 omega   63.00  138.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -61.0000  -60.0000 75

  9 omega   61.00   87.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -95.0000 -180.0000 26

 10 omega   59.00  147.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  178.0000  -30.0000 88

 11 omega   42.00   98.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000  120.0000 56

 12 omega   40.00  161.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -15.0000 -120.0000 121

 13 omega   92.00  157.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   45.0000  -90.0000 65

 14 omega  -50.00   33.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109   38.0000  -90.0000 83

 15 omega -118.00   -9.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109  -77.0000 -120.0000 109

 16 omega -115.00  -14.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109  -57.0000  120.0000 101
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0544165000
_diffrn_orient_matrix_UB_12      0.0534480000
_diffrn_orient_matrix_UB_13      0.0510604000
_diffrn_orient_matrix_UB_21      0.0239266000
_diffrn_orient_matrix_UB_22      -0.0529628000
_diffrn_orient_matrix_UB_23      0.0565137000
_diffrn_orient_matrix_UB_31      0.1500750000
_diffrn_orient_matrix_UB_32      0.0278289000
_diffrn_orient_matrix_UB_33      0.0094643000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0306
_diffrn_reflns_av_unetI/netI     0.0298
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            22984
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.023
_diffrn_reflns_theta_min         4.405
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.697
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54127
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_description       block
_exptl_crystal_F_000             1552
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.268
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 2943 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
The molecule have crystallised in an achiral space group
Flack x: -0.05(8) Shelx 2014
Hooft y: -0.03(8) Olex2

;
_refine_ls_abs_structure_Flack   -0.05(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     505
_refine_ls_number_reflns         7685
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.152
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0369
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0472P)^2^+0.6946P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0910
_refine_ls_wR_factor_ref         0.0938
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                7153
_reflns_number_total             7685
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob00991g2.cif
_cod_data_source_block           adg
_cod_original_cell_volume        3678.66(7)
_cod_database_code               7155633
_chemical_oxdiff_formula         'C20 H20 N2 O2'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;

SIMU restraints were used to give the nitrogens and benzylic carbons of one of the 
triazines (C107 N108 N109 N110 C111 C128) similar thermal parameters to chemically 
equivalent atoms.

1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
C227 \\sim C228 \\sim N208 \\sim N209 \\sim N210 \\sim C211 \\sim C212 \\sim
C207 \\sim C206: within 1.7A with sigma of 0.001 and sigma for terminal atoms
of 0.002
3.a Secondary CH2 refined with riding coordinates:
 C107(H10A,H10B), C112(H11A,H11B), C127(H12A,H12B), C207(H20A,H20B), C212(H21A,
 H21B), C227(H22A,H22B)
3.b Aromatic/amide H refined with riding coordinates:
 C101(H101), C102(H102), C103(H103), C104(H104), C105(H105), C115(H115),
 C116(H116), C117(H117), C118(H118), C121(H121), C122(H122), C123(H123),
 C124(H124), C201(H201), C202(H202), C203(H203), C204(H204), C205(H205),
 C215(H215), C216(H216), C217(H217), C218(H218), C221(H221), C222(H222),
 C223(H223), C224(H224)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'