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_7155634
_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_formula_moiety         'C16 H8 Br4 O2'
_chemical_formula_sum            'C16 H8 Br4 O2'
_chemical_formula_weight         551.86
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-11-22
_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                 101.0480(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.84858(5)
_cell_length_b                   15.11182(7)
_cell_length_c                   13.51546(9)
_cell_measurement_reflns_used    16640
_cell_measurement_temperature    175(2)
_cell_measurement_theta_max      77.9180
_cell_measurement_theta_min      3.2980
_cell_volume                     1573.310(17)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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      175(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2833
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -66.00  33.00   1.00    2.50    --  -41.71  38.00-120.00   99
  2  \w   -118.00  -9.00   1.00    2.50    --  -41.71 -77.00-150.00  109
  3  \w   -122.00  -1.00   1.00    2.50    --  -41.71 -19.00  60.00  121
  4  \w     38.00 147.00   1.00   10.00    --  114.00 -77.00   0.00  109
  5  \w     85.00 178.00   1.00   10.00    --  114.00  61.00  90.00   93
  6  \w     38.00 116.00   1.00   10.00    --  114.00-111.00-180.00   78
  7  \w     41.00 140.00   1.00   10.00    --  114.00 -45.00 150.00   99
  8  \w     86.00 178.00   1.00   10.00    --  114.00  30.00 150.00   92
  9  \w     38.00 147.00   1.00   10.00    --  114.00 -77.00-180.00  109
 10  \w     38.00 116.00   1.00   10.00    --  114.00-111.00  60.00   78
 11  \w     88.00 178.00   1.00   10.00    --  114.00  45.00   0.00   90
 12  \w     38.00 116.00   1.00   10.00    --  114.00-111.00 -90.00   78
 13  \w     81.00 178.00   1.00   10.00    --  114.00  77.00-150.00   97
 14  \w     88.00 178.00   1.00   10.00    --  114.00  45.00  30.00   90
 15  \w     88.00 178.00   1.00   10.00    --  114.00  45.00 -30.00   90
 16  \w   -118.00  -9.00   1.00    2.50    --  -41.71 -77.00  60.00  109
 17  \w   -115.00 -14.00   1.00    2.50    --  -41.71 -57.00 -60.00  101
 18  \w     18.00  98.00   1.00    2.50    --   41.71-125.00  60.00   80
 19  \w    -30.00  70.00   1.00    2.50    --   41.71 -57.00  60.00  100
 20  \w     85.00 178.00   1.00   10.00    --  114.00  61.00  30.00   93
 21  \w     85.00 178.00   1.00   10.00    --  114.00  61.00  60.00   93
 22  \w     85.00 178.00   1.00   10.00    --  114.00  61.00-180.00   93
 23  \w     85.00 178.00   1.00   10.00    --  114.00  61.00 150.00   93
 24  \w     85.00 159.00   1.00   10.00    --  114.00  61.00 -90.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0052641000
_diffrn_orient_matrix_UB_12      0.0910208000
_diffrn_orient_matrix_UB_13      -0.0518749000
_diffrn_orient_matrix_UB_21      -0.1528771000
_diffrn_orient_matrix_UB_22      0.0277531000
_diffrn_orient_matrix_UB_23      0.0496318000
_diffrn_orient_matrix_UB_31      0.1288542000
_diffrn_orient_matrix_UB_32      0.0365494000
_diffrn_orient_matrix_UB_33      0.0912864000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0218
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            21338
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.889
_diffrn_reflns_theta_min         4.435
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.522
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.19944
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    2.330
_exptl_crystal_description       block
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.445
_refine_diff_density_min         -0.896
_refine_diff_density_rms         0.148
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.173
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         3343
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.173
_refine_ls_R_factor_all          0.0257
_refine_ls_R_factor_gt           0.0251
_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^)+(0.0357P)^2^+0.9267P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0636
_refine_ls_wR_factor_ref         0.0640
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3283
_reflns_number_total             3343
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob00991g2.cif
_cod_data_source_block           adg5
_cod_original_cell_volume        1573.310(16)
_cod_database_code               7155634
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.12
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C5(H5A,H5B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C11(H11), C14(H14), C16(H16)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.408
_oxdiff_exptl_absorpt_empirical_full_min 0.707