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_7155632
_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 H10 Br2 O2'
_chemical_formula_sum            'C16 H10 Br2 O2'
_chemical_formula_weight         394.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-11-05
_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                 103.6158(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.16761(6)
_cell_length_b                   7.46338(4)
_cell_length_c                   28.10737(12)
_cell_measurement_reflns_used    22067
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      78.0400
_cell_measurement_theta_min      3.1950
_cell_volume                     2888.50(2)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(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 0.994
_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   -116.00 -17.00   1.00    3.00    --  -41.71 -38.00 -90.00   99
  2  \w   -116.00 -17.00   1.00    3.00    --  -41.71 -38.00   0.00   99
  3  \w     21.00 100.00   1.00    3.00    --   41.71-128.00 -73.00   79
  4  \w     38.00 142.00   1.00    9.00    --  114.00 -30.00  90.00  104
  5  \w     61.00 178.00   1.00    9.00    --  114.00  15.00-120.00  117
  6  \w     38.00 116.00   1.00    9.00    --  114.00-111.00 -30.00   78
  7  \w     88.00 178.00   1.00    9.00    --  114.00  45.00  90.00   90
  8  \w     38.00 147.00   1.00    9.00    --  114.00 -77.00 -30.00  109
  9  \w   -118.00  -9.00   1.00    3.00    --  -41.71 -77.00-180.00  109
 10  \w      9.00 118.00   1.00    3.00    --   41.71  77.00  90.00  109
 11  \w     -4.00  83.00   1.00    3.00    --   41.71 -99.00  30.00   87
 12  \w     85.00 178.00   1.00    9.00    --  114.00  61.00  30.00   93
 13  \w     32.00 109.00   1.00    9.00    --  114.00 -95.00 150.00   77
 14  \w     81.00 178.00   1.00    9.00    --  114.00  77.00 120.00   97
 15  \w     38.00 142.00   1.00    9.00    --  114.00 -30.00 -30.00  104
 16  \w     86.00 178.00   1.00    9.00    --  114.00  30.00   0.00   92
 17  \w     86.00 178.00   1.00    9.00    --  114.00  30.00 -60.00   92
 18  \w   -114.00 -63.00   1.00    3.00    --  -41.71-142.00 115.00   51
 19  \w   -118.00  -9.00   1.00    3.00    --  -41.71 -77.00 -90.00  109
 20  \w    -70.00  31.00   1.00    3.00    --  -41.71  57.00 150.00  101
 21  \w     85.00 178.00   1.00    9.00    --  114.00  61.00 -60.00   93
 22  \w     85.00 178.00   1.00    9.00    --  114.00  61.00-120.00   93
 23  \w     81.00 178.00   1.00    9.00    --  114.00  77.00  90.00   97
 24  \w     85.00 178.00   1.00    9.00    --  114.00  61.00  60.00   93
 25  \w     85.00 178.00   1.00    9.00    --  114.00  61.00   0.00   93
 26  \w     32.00 109.00   1.00    9.00    --  114.00 -95.00-120.00   77
 27  \w     18.00  98.00   1.00    3.00    --   41.71-125.00 -30.00   80
 28  \w     14.00 115.00   1.00    3.00    --   41.71  57.00  30.00  101
 29  \w      9.00 118.00   1.00    3.00    --   41.71  77.00-180.00  109
 30  \w     38.00 116.00   1.00    9.00    --  114.00-111.00 120.00   78
 31  \w     81.00 178.00   1.00    9.00    --  114.00  77.00 150.00   97
 32  \w     42.00 143.00   1.00    9.00    --  114.00 -61.00 150.00  101
 33  \w     85.00 178.00   1.00    9.00    --  114.00  61.00 -30.00   93
 34  \w     81.00 178.00   1.00    9.00    --  114.00  77.00 -90.00   97
 35  \w     85.00 178.00   1.00    9.00    --  114.00  61.00-150.00   93
 36  \w     14.00  56.00   1.00    3.00    --   41.71  57.00 -30.00   42
;
_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      -0.0435549000
_diffrn_orient_matrix_UB_12      -0.0061635000
_diffrn_orient_matrix_UB_13      0.0453024000
_diffrn_orient_matrix_UB_21      -0.1030343000
_diffrn_orient_matrix_UB_22      0.0083571000
_diffrn_orient_matrix_UB_23      -0.0334914000
_diffrn_orient_matrix_UB_31      -0.0028302000
_diffrn_orient_matrix_UB_32      -0.2060907000
_diffrn_orient_matrix_UB_33      -0.0027177000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0448
_diffrn_reflns_av_unetI/netI     0.0177
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            27581
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.157
_diffrn_reflns_theta_min         3.236
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.105
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.09216
_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    1.812
_exptl_crystal_description       block
_exptl_crystal_F_000             1536
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.678
_refine_diff_density_min         -0.678
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     181
_refine_ls_number_reflns         3075
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0306
_refine_ls_R_factor_gt           0.0304
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0474P)^2^+5.2427P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0799
_refine_ls_wR_factor_ref         0.0801
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3051
_reflns_number_total             3075
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob00991g2.cif
_cod_data_source_block           adg4
_cod_database_code               7155632
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;

There is a B alert for a short contact in the Platon cifcheck.
This is a halogen bond
O1 - Br10_$1 3.0467 (0.0015)  Angstroms

Symmetry operator used to generate symmetry equivalent atoms in 
above contact were $1 1.5-X,1.5-Y,1.5-Z

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:
 C8(H8), C9(H9), C11(H11), C14(H14), C16(H16), C17(H17)
;
_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 7.876
_oxdiff_exptl_absorpt_empirical_full_min 0.674