A high-activity cobalt-based MOF catalyst for [2 + 2 + 2] cycloaddition of diynes and alkynes: insights into alkyne affinity and selectivity control
Xu, Fen; Si, Xiao-Ju; Wang, Xiao-Ning; Kou, Hao-Dong; Chen, Di-Ming; Liu, Chun-Sen; Du, Miao; RSC Advances 8 (2018) 4895–; doi:10.1039/C7RA12136A

data_7230061
_publ_section_title
;
 A high-activity cobalt-based MOF catalyst for [2&#x00A0;+ 2 + 2]
 cycloaddition of diynes and alkynes: insights into alkyne affinity and
 selectivity control
;
_journal_issue                   9
_journal_name_full               'RSC Advances'
_journal_page_first              4895
_journal_paper_doi               10.1039/C7RA12136A
_journal_volume                  8
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H21 N O2 S'
_chemical_formula_sum            'C22 H21 N O2 S'
_chemical_formula_weight         363.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-12-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-12-29 deposited with the CCDC.
2018-01-23 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 101.204(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   7.9693(2)
_cell_length_b                   6.1218(2)
_cell_length_c                   19.3280(5)
_cell_measurement_reflns_used    7272
_cell_measurement_temperature    294(2)
_cell_measurement_theta_max      73.3580
_cell_measurement_theta_min      4.6670
_cell_volume                     924.97(5)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      294(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3031
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -37.00   17.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5455   38.0000  -90.0000 54

  2 omega  -50.00   34.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5455   38.0000   30.0000 84

  3 omega  -95.00   -6.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5455  125.0000  120.0000 89

  4 omega  -67.00   31.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5455   19.0000  150.0000 98

  5 omega   23.00   49.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5455 -125.0000  -60.0000 26

  6 omega   53.00   91.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5455 -125.0000   30.0000 38

  7 omega   23.00   50.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5455 -125.0000  -30.0000 27

  8 omega   42.00   91.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -45.0000  -90.0000 49

  9 omega   49.00  104.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -95.0000  120.0000 55

 10 omega   42.00   90.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -30.0000   90.0000 48

 11 omega   25.00  109.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -95.0000   30.0000 84

 12 omega   44.00   90.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -30.0000   30.0000 46

 13 omega   47.00  139.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -77.0000 -180.0000 92

 14 omega   54.00  160.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   15.0000    0.0000 106

 15 omega   94.00  121.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410 -125.0000  -60.0000 27

 16 omega   84.00  171.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   30.0000   60.0000 87

 17 omega   42.00   70.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410 -125.0000  -60.0000 28

 18 omega   39.00   81.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -45.0000   90.0000 42

 19 omega   31.00   85.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -30.0000  150.0000 54

 20 omega   45.00   88.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -45.0000    0.0000 43

 21 omega   71.00  109.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410 -125.0000   30.0000 38

 22 omega    8.00   48.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       40.7955   77.0000 -180.0000 40

 23 omega    1.00   26.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.0000   90.0000    0.7496 25

 24 omega   -1.00   25.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.0000   94.0000  129.9724 26

 25 omega -100.00  -47.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955  -57.0000  -30.0000 53

 26 omega  -79.00  -53.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955  -38.0000   90.0000 26

 27 omega  -42.00  -16.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955  -38.0000   90.0000 26

 28 omega  -41.00  -13.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955  -57.0000  -30.0000 28

 29 omega  -40.00  -14.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955  -57.0000  150.0000 26

 30 omega -114.00  -88.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955  -38.0000   90.0000 26

 31 omega   18.00   45.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000   38.7730 27

 32 omega   19.00   44.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   81.0000 -112.1148 25

 33 omega   21.00   47.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   79.0000  164.2213 26

 34 omega   21.00   46.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   79.0000  100.8808 25

 35 omega   34.00   60.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   76.0000 -125.8833 26

 36 omega   34.00   68.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   75.0000  -26.7581 34

 37 omega   31.00   81.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   77.0000 -167.1431 50

 38 omega   33.00   64.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000   25.4504 31

 39 omega   33.00   72.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  -86.7803 39

 40 omega   88.00  130.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   77.0000   69.9721 42

 41 omega   37.00   71.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   77.0000   69.9721 34

 42 omega   47.00   94.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   72.0000  116.2167 47

 43 omega   76.00  153.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000 -150.0000 77

 44 omega   75.00  100.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000    0.0000 25

 45 omega  125.00  151.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  120.0000 26

 46 omega   75.00  114.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  120.0000 39

 47 omega   80.00  163.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000 -180.0000 83

 48 omega   83.00  147.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000  150.0000 64

 49 omega   80.00  105.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000  120.0000 25

 50 omega   75.00  100.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  -90.0000 25

 51 omega   76.00  101.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000 -180.0000 25

 52 omega   82.00  108.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000  -60.0000 26

 53 omega   75.00  100.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000   30.0000 25

 54 omega   75.00  101.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  150.0000 26

 55 omega   75.00  101.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  -60.0000 26

 56 omega  151.00  177.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000   60.0000 26

 57 omega   78.00  104.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000   60.0000 26

 58 omega   87.00  113.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000  -30.0000 26

 59 omega   80.00  111.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000   90.0000 31

 60 omega  117.00  173.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000   90.0000 56

 61 omega   75.00  128.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000 -120.0000 53

 62 omega   78.00  104.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  -30.0000 26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1632940000
_diffrn_orient_matrix_UB_12      -0.0187297000
_diffrn_orient_matrix_UB_13      -0.0311392000
_diffrn_orient_matrix_UB_21      0.1104180000
_diffrn_orient_matrix_UB_22      0.0245388000
_diffrn_orient_matrix_UB_23      0.0744462000
_diffrn_orient_matrix_UB_31      -0.0014526000
_diffrn_orient_matrix_UB_32      -0.2496345000
_diffrn_orient_matrix_UB_33      0.0096929000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0323
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            13752
_diffrn_reflns_theta_full        67.07
_diffrn_reflns_theta_max         67.07
_diffrn_reflns_theta_min         4.66
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.674
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54914
_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.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.305
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             384
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.086
_refine_diff_density_min         -0.169
_refine_diff_density_rms         0.027
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.002(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         3178
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0345
_refine_ls_R_factor_gt           0.0307
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0514P)^2^+0.0493P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0818
_refine_ls_wR_factor_ref         0.0845
_reflns_number_gt                2969
_reflns_number_total             3178
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c7ra12136a2.cif
_cod_data_source_block           3ad
_cod_original_cell_volume        924.97(4)
_cod_database_code               7230061
_chemical_oxdiff_formula         'C H O N S'
_reflns_odcompleteness_completeness 99.95
_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 C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C4(H4A,H4B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C8(H8), C10(H10), C11(H11), C13(H13), C14(H14), C17(H17),
 C18(H18), C20(H20), C21(H21)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C22(H22A,H22B,H22C)
;
_olex2_submission_special_instructions 'No special instructions were received'