Synthesis and Reactivity of a Bis-Strained Alkyne Derived from 1,1'-Biphenyl-2,2',6,6'-tetrol.
Knighton, Richard C.; Sharma, Krishna; Robertson, Naomi S.; Spring, David R.; Wills, Martin; ACS omega 4 (2019) 2160–2167; doi:10.1021/acsomega.8b03634

data_4514977
_publ_section_title
;
 Synthesis and Reactivity of a Bis-Strained Alkyne Derived from
 1,1'-Biphenyl-2,2',6,6'-tetrol.
;
_journal_issue                   1
_journal_name_full               'ACS omega'
_journal_page_first              2160
_journal_page_last               2167
_journal_paper_doi               10.1021/acsomega.8b03634
_journal_volume                  4
_journal_year                    2019
_chemical_formula_moiety         '3(C H Cl3), C34 H28 N6 O4'
_chemical_formula_sum            'C37 H31 Cl9 N6 O4'
_chemical_formula_weight         942.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.823(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.5961(2)
_cell_length_b                   25.9364(5)
_cell_length_c                   15.8162(3)
_cell_measurement_reflns_used    9013
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.3400
_cell_measurement_theta_min      4.3980
_cell_volume                     4114.22(14)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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      150.03(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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    -64.00  31.00   1.00    7.00    --  -42.11  37.00  90.00   95
  2  \w    -64.00  31.00   1.00    7.00    --  -42.11  37.00 -30.00   95
  3  \w     23.00  97.00   1.00    7.00    --   42.11-125.00  90.00   74
  4  \w     20.00 115.00   1.00    7.00    --   42.11  37.00-120.00   95
  5  \w     75.00 178.00   1.00   23.99    --  106.00  77.00-120.00  103
  6  \w     94.00 178.00   1.00   23.99    --  106.00 125.00 -60.00   84
  7  \w     25.00 109.00   1.00   23.99    --  106.00 -94.00 120.00   84
  8  \w     25.00 109.00   1.00   23.99    --  106.00 -94.00-150.00   84
  9  \w     34.00 121.00   1.00   23.99    --  106.00-125.00 120.00   87
 10  \w     34.00 121.00   1.00   23.99    --  106.00-125.00 -30.00   87
 11  \w     78.00 176.00   1.00   23.99    --  106.00  61.00  30.00   98
 12  \w     94.00 178.00   1.00   23.99    --  106.00 125.00-120.00   84
 13  \w     75.00 178.00   1.00   23.99    --  106.00  77.00 -60.00  103
 14  \w     83.00 109.00   1.00   23.99    --  106.00 -94.00 -60.00   26
 15  \w    105.00 178.00   1.00   23.99    --  106.00  77.00   0.00   73
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0202498000
_diffrn_orient_matrix_UB_12      -0.0584224000
_diffrn_orient_matrix_UB_13      -0.0076768000
_diffrn_orient_matrix_UB_21      0.0313950000
_diffrn_orient_matrix_UB_22      0.0088704000
_diffrn_orient_matrix_UB_23      -0.0874478000
_diffrn_orient_matrix_UB_31      0.1489638000
_diffrn_orient_matrix_UB_32      0.0060934000
_diffrn_orient_matrix_UB_33      0.0537198000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0556
_diffrn_reflns_av_unetI/netI     0.0424
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            32987
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.645
_diffrn_reflns_theta_min         4.408
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.005
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.00368
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (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    1.522
_exptl_crystal_description       block
_exptl_crystal_F_000             1920
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.922
_refine_diff_density_min         -1.012
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     589
_refine_ls_number_reflns         8223
_refine_ls_number_restraints     464
_refine_ls_restrained_S_all      2.359
_refine_ls_R_factor_all          0.1068
_refine_ls_R_factor_gt           0.0920
_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^)+(0.1533P)^2^+6.9245P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2501
_refine_ls_wR_factor_ref         0.2671
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6581
_reflns_number_total             8223
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao8b03634_si_003.cif
_cod_data_source_block           014rck17
_cod_database_code               4514977
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_usercomment
'014RCK17 colourless block 0.22 0.08 0.05 CHCl3/hexane Cu150K 4x4'
_shelx_estimated_absorpt_t_max   0.753
_shelx_estimated_absorpt_t_min   0.352
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Cl53-Cl54
 1.5 with sigma of 0.02
 Cl57-Cl55 \\sim Cl57-Cl54 \\sim Cl55-Cl54
 with sigma of 0.04
 C51-Cl57 \\sim C51-Cl55 \\sim C51-Cl54
 with sigma of 0.02
 Cl8-Cl47 \\sim Cl8-Cl49 \\sim Cl47-Cl49
 with sigma of 0.04
 C45-Cl8 \\sim C45-Cl47 \\sim C45-Cl49
 with sigma of 0.02
 Cl57-Cl55 \\sim Cl57-Cl54 \\sim Cl55-Cl54 \\sim Cl53-Cl56 \\sim Cl53-Cl5A
\\sim Cl56-Cl5A
 with sigma of 0.04
 Cl59-Cl61 \\sim Cl59-Cl63 \\sim Cl61-Cl63
 with sigma of 0.04
 C64-Cl59 \\sim C64-Cl61 \\sim C64-Cl63
 with sigma of 0.02
 Cl8-Cl47 \\sim Cl8-Cl49 \\sim Cl47-Cl49 \\sim Cl48-Cl8A \\sim Cl48-Cl50 \\sim
Cl8A-Cl50
 with sigma of 0.04
 C45-Cl8 \\sim C45-Cl47 \\sim C45-Cl49 \\sim C45-Cl48 \\sim C45-Cl8A \\sim
C45-Cl50
 with sigma of 0.02
 Cl57-Cl53 \\sim Cl55-Cl54 \\sim Cl55-Cl56 \\sim Cl54-Cl5A \\sim Cl56-Cl5A
 with sigma of 0.04
 C51-Cl57 \\sim C51-Cl55 \\sim C51-Cl54 \\sim C51-Cl53 \\sim C51-Cl56 \\sim
C51-Cl5A
 with sigma of 0.02
 Cl59-Cl61 \\sim Cl59-Cl63 \\sim Cl59-H64 \\sim Cl61-Cl63 \\sim Cl61-H64 \\sim
Cl63-H64 \\sim Cl62-
 Cl60 \\sim Cl62-Cl58 \\sim Cl60-Cl58
 with sigma of 0.04
 C64-Cl59 \\sim C64-Cl61 \\sim C64-Cl63 \\sim C64-H64 \\sim C64-Cl62 \\sim
C64-Cl60 \\sim C64-Cl58
 with sigma of 0.02
 Cl8-Cl47 \\sim Cl8-Cl49 \\sim Cl8-H45A \\sim Cl47-H45A \\sim Cl49-H45A \\sim
H45-Cl48 \\sim H45-Cl8A
 \\sim H45-Cl50 \\sim Cl48-Cl8A \\sim Cl48-Cl50 \\sim Cl8A-Cl50
 with sigma of 0.04
 C45-Cl8 \\sim C45-Cl47 \\sim C45-Cl49 \\sim C45-H45 \\sim C45-H45A \\sim
C45-Cl48 \\sim C45-Cl8A ~
 C45-Cl50
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl53 \\sim Cl54 \\sim Cl55 \\sim Cl56 \\sim Cl57: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
Cl8 \\sim C45 \\sim Cl47 \\sim Cl49 \\sim H45 \\sim H45A \\sim Cl48 \\sim Cl8A
\\sim Cl50: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C51 \\sim Cl57 \\sim Cl55 \\sim Cl54 \\sim Cl53 \\sim Cl56 \\sim Cl5A: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C64 \\sim Cl59 \\sim Cl61 \\sim Cl63 \\sim H64 \\sim Cl62 \\sim Cl60 \\sim
Cl58: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(Cl48) \\sim Ueq, Uanis(C45) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 C45, Cl50, Cl48, Cl8, Cl47, Cl8A, Cl49
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl63, Cl61, Cl59, C64
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl56, Cl55, C51, Cl54, Cl53, Cl57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl53, Cl54, C51, Cl57, Cl56, Cl55
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C64, Cl63, Cl59, Cl61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl50, Cl8A, Cl47, Cl48, Cl49, C45
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Cl53)=Sof(Cl56)=Sof(Cl5A)=1-FVAR(1)
 Sof(Cl57)=Sof(Cl55)=Sof(Cl54)=FVAR(1)
 Sof(H45A)=Sof(Cl48)=Sof(Cl8A)=Sof(Cl50)=1-FVAR(2)
 Sof(Cl8)=Sof(Cl47)=Sof(Cl49)=Sof(H45)=FVAR(2)
 Sof(Cl62)=Sof(Cl60)=Sof(Cl58)=1-FVAR(3)
 Sof(Cl59)=Sof(Cl61)=Sof(Cl63)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C64(H64), C51(H51), C45(H45), C45(H45A)
6.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C14(H14A,H14B), C38(H38A,H38B), C23(H23A,H23B), C28(H28A,
 H28B), C17(H17A,H17B)
6.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C4(H4), C2(H2), C40(H40), C11(H11), C30(H30), C10(H10), C44(H44),
 C3(H3), C43(H43), C31(H31), C41(H41), C34(H34), C32(H32), C42(H42), C33(H33)
;
_shelx_res_checksum              80061
_shelx_hkl_checksum              14517
_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 158.229
_oxdiff_exptl_absorpt_empirical_full_min 0.487