Selective C(sp(2))-H Halogenation of "Click" 4-Aryl-1,2,3-triazoles.
Goitia, Asier; Gómez-Bengoa, Enrique; Correa, Arkaitz; Organic letters 19 (2017) 962–965; doi:10.1021/acs.orglett.7b00275

data_1545240
_publ_section_title
;
 Selective C(sp(2))-H Halogenation of &quot;Click&quot;
 4-Aryl-1,2,3-triazoles.
;
_journal_issue                   4
_journal_name_full               'Organic letters'
_journal_page_first              962
_journal_page_last               965
_journal_paper_doi               10.1021/acs.orglett.7b00275
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C46 H32 N8 O4 Pd2, 2.5(O), C O2, C O'
_chemical_formula_sum            'C48 H32 N8 O9.5 Pd2'
_chemical_formula_weight         1085.61
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-12-07
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.1286(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.39008(13)
_cell_length_b                   16.17413(10)
_cell_length_c                   18.85694(14)
_cell_measurement_reflns_used    22734
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.9980
_cell_measurement_theta_min      4.0010
_cell_volume                     4551.90(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector_area_resol_mean 5.2012
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  1 omega -119.00   -9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
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  2 omega -114.00  -89.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
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  3 omega    2.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.3256 -125.0000  -90.0000 88

  4 omega  -35.00   -5.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   30.0000 -150.0000 30

  5 omega   33.00   58.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  120.0000 25

  6 omega   82.00  117.00   1.0000    4.0000
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  7 omega   44.00   75.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
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  8 omega   37.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000  -60.0000 72

  9 omega   31.00   58.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  -60.0000 27

 10 omega   24.00   98.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000  120.0000 74

 11 omega   42.00   68.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000   30.0000 26

 12 omega  132.00  158.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  125.0000  -90.0000 26

 13 omega   39.00   65.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000 -150.0000 26

 14 omega   32.00   64.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000 -120.0000 32

 15 omega   30.00   69.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000 -180.0000 39

 16 omega   84.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000   30.0000 25

 17 omega   69.00   94.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000  -60.0000 25

 18 omega   38.00   73.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000  150.0000 35

 19 omega  -69.00    9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3256   57.0000 -180.0000 78

 20 omega -132.00  -40.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   15.0000   60.0000 92

 21 omega -151.00 -113.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000 -125.0000 -180.0000 38

 22 omega   32.00   63.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  -30.0000 31

 23 omega   97.00  122.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000  120.0000 25

 24 omega   60.00   86.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000  -90.0000 26

 25 omega   34.00   82.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000  120.0000 48

 26 omega  103.00  143.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   61.0000 -120.0000 40

 27 omega   37.00   63.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -77.0000  -90.0000 26

 28 omega   94.00  121.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -77.0000  -90.0000 27

 29 omega   31.00   69.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
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 30 omega  115.00  142.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   45.0000    0.0000 27

 31 omega  130.00  158.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   45.0000  -90.0000 28

 32 omega   88.00  121.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000  -90.0000 33

 33 omega   59.00   96.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
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 34 omega   40.00   67.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
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 35 omega   56.00   95.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
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 36 omega  107.00  150.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
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 37 omega   33.00   59.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000    0.0000 26
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1007080000
_diffrn_orient_matrix_UB_12      -0.0160555000
_diffrn_orient_matrix_UB_13      0.0317094000
_diffrn_orient_matrix_UB_21      -0.0151199000
_diffrn_orient_matrix_UB_22      -0.0930679000
_diffrn_orient_matrix_UB_23      -0.0157389000
_diffrn_orient_matrix_UB_31      0.0170210000
_diffrn_orient_matrix_UB_32      0.0124641000
_diffrn_orient_matrix_UB_33      -0.0764318000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0394
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            39610
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.996
_diffrn_reflns_theta_min         3.648
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.943
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64334
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.584
_exptl_crystal_description
;
;
_exptl_crystal_F_000             2176
_refine_diff_density_max         3.208
_refine_diff_density_min         -1.054
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     678
_refine_ls_number_reflns         8628
_refine_ls_number_restraints     138
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0602
_refine_ls_R_factor_gt           0.0567
_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^)+(0.0938P)^2^+17.6254P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1568
_refine_ls_wR_factor_ref         0.1608
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7986
_reflns_number_total             8628
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b00275_si_002.cif
_cod_data_source_block           a20160425_acn538
_cod_depositor_comments          'Adding full bibliography for 1545240.cif.'
_cod_original_formula_sum        'C48 H32 N8 O9.50 Pd2'
_cod_database_code               1545240
_chemical_oxdiff_formula         C10H10N2O2
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C35-H35B = C35-H35A = C35-H35C
 0.96 with sigma of 0.01
 H35B-H35A
 1.56 with sigma of 0.02
 H35B-H35C
 1.56 with sigma of 0.02
 H35C-H35A
 1.56 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C44) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C6AA) \\sim Ueq, Uanis(C5AA)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C7AA) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C46) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C4AA) \\sim Ueq, Uanis(C3AA)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C48, C54, C1AA, C65, C10, C60, C11, C59, C14, C39, C2AA
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C14)=Sof(H14)=Sof(C1AA)=Sof(H1AA)=
 Sof(C2AA)=Sof(H2AA)=1-FVAR(1)
 Sof(C39)=Sof(H39)=Sof(C54)=Sof(H54)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=
 Sof(C65)=Sof(H65)=FVAR(1)
 Sof(C46)=Sof(H46)=Sof(C6AA)=Sof(H6AA)=Sof(C7AA)=Sof(H7AA)=Sof(C5AA)=Sof(H5AA)=
 Sof(C4AA)=Sof(H4AA)=1-FVAR(2)
 Sof(C44)=Sof(H44)=Sof(C51)=Sof(H51)=Sof(C53)=Sof(H53)=Sof(C67)=Sof(H67)=
 Sof(C3AA)=Sof(H3AA)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C26(H26), C27(H27), C31(H31), C32(H32), C33(H33),
 C37(H37), C39(H39), C44(H44), C45(H45), C46(H46), C49(H49), C51(H51), C52(H52),
  C53(H53), C54(H54), C56(H56), C57(H57), C59(H59), C60(H60), C61(H61),
 C62(H62), C64(H64), C65(H65), C67(H67), C10(H10), C11(H11), C14(H14),
 C1AA(H1AA), C2AA(H2AA), C6AA(H6AA), C7AA(H7AA), C5AA(H5AA), C4AA(H4AA),
 C3AA(H3AA)
6.b Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-12-01
_olex2_submission_special_instructions 'No special instructions were received'