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_7230065
_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         'C21 H18 Cl N O2 S'
_chemical_formula_sum            'C21 H18 Cl N O2 S'
_chemical_formula_weight         383.87
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_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                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.08143(9)
_cell_length_b                   9.08409(11)
_cell_length_c                   29.0369(3)
_cell_measurement_reflns_used    18135
_cell_measurement_temperature    294(2)
_cell_measurement_theta_max      73.6170
_cell_measurement_theta_min      4.8540
_cell_volume                     1867.90(4)
_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    'SHELXS-97 (Sheldrick, 1990)'
_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    2.00   27.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5455  -99.0000  -90.0000 25

  2 omega   34.00   98.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -45.0000 -180.0000 64

  3 omega   25.00   96.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -95.0000 -150.0000 71

  4 omega   36.00   78.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -45.0000  -30.0000 42

  5 omega   55.00   85.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -30.0000   90.0000 30

  6 omega   34.00   77.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5455 -125.0000  150.0000 43

  7 omega  -43.00   14.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5455   38.0000  150.0000 57

  8 omega   50.00   88.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5455   77.0000  150.0000 38

  9 omega  106.00  177.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  125.0000 -150.0000 71

 10 omega -104.00  -19.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955  -38.0000   60.0000 85

 11 omega  -33.00   -8.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955  -77.0000  -30.0000 25

 12 omega -120.00   -2.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955  -19.0000  150.0000 118

 13 omega -107.00  -60.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955  -77.0000  -30.0000 47

 14 omega  -49.00   33.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.7955   38.0000 -120.0000 82

 15 omega    5.00   30.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.7955   88.0000  112.0905 25

 16 omega   24.00   95.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.7955 -125.0000    0.0000 71

 17 omega    8.00   33.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       42.0000   82.0000  -40.8064 25

 18 omega   18.00   43.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000   36.1259 25

 19 omega   16.00   41.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   82.0000   91.7644 25

 20 omega   21.00   47.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   79.0000 -116.3879 26

 21 omega   21.00   46.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   79.0000  156.8730 25

 22 omega   31.00   57.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  -59.9348 26

 23 omega   29.00   64.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   75.0000 -146.2639 35

 24 omega  109.00  134.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  -59.9348 25

 25 omega   30.00   70.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   75.0000  -89.0240 40

 26 omega   33.00   77.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  174.3629 44

 27 omega  100.00  126.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  102.2897 26

 28 omega   34.00   82.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   76.0000  -26.5652 48

 29 omega   33.00   59.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  102.2897 26

 30 omega  110.00  140.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  174.3629 30

 31 omega   38.00   79.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   77.0000  115.5086 41

 32 omega  118.00  144.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   75.0000   49.9610 26

 33 omega   38.00   67.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   75.0000   49.9610 29

 34 omega   42.00   80.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   76.0000   18.5036 38

 35 omega   75.00  106.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000 -180.0000 31

 36 omega   75.00  163.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  150.0000 88

 37 omega   75.00  170.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000   90.0000 95

 38 omega   58.00   95.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -45.0000  -90.0000 37

 39 omega   75.00  101.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  -30.0000 26

 40 omega   72.00   98.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410 -125.0000   90.0000 26

 41 omega   76.00  143.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000    0.0000 67

 42 omega   34.00   67.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410 -125.0000   90.0000 33

 43 omega   75.00  178.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  -60.0000 103

 44 omega   79.00  122.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000 -120.0000 43

 45 omega   31.00  111.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410 -101.0000  -52.0000 80

 46 omega   79.00  104.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000   60.0000 25

 47 omega   78.00  117.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000    0.0000 39

 48 omega   75.00  104.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000 -150.0000 29

 49 omega   78.00  156.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000 -150.0000 78

 50 omega   42.00  121.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410 -125.0000 -180.0000 79

 51 omega   75.00  146.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  -90.0000 71

 52 omega  148.00  175.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000 -120.0000 27

 53 omega   75.00  152.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000   30.0000 77

 54 omega   78.00  104.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000 -180.0000 26

 55 omega   79.00  124.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   61.0000  150.0000 45

 56 omega  122.00  149.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  120.0000 27

 57 omega   75.00  130.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000 -120.0000 55

 58 omega   75.00  101.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  120.0000 26

 59 omega   75.00  143.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000   60.0000 68

 60 omega  118.00  143.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410   77.0000  -30.0000 25

 61 omega   84.00  109.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -95.0000 -150.0000 25

 62 omega   84.00  109.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      107.1410  -95.0000  120.0000 25
;
_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      0.0598143000
_diffrn_orient_matrix_UB_12      -0.0179338000
_diffrn_orient_matrix_UB_13      -0.0507045000
_diffrn_orient_matrix_UB_21      0.0662621000
_diffrn_orient_matrix_UB_22      0.1615083000
_diffrn_orient_matrix_UB_23      -0.0009226000
_diffrn_orient_matrix_UB_31      0.1983507000
_diffrn_orient_matrix_UB_32      -0.0485259000
_diffrn_orient_matrix_UB_33      0.0156195000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0701
_diffrn_reflns_av_unetI/netI     0.0232
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            30484
_diffrn_reflns_theta_full        66.99
_diffrn_reflns_theta_max         66.99
_diffrn_reflns_theta_min         5.10
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.975
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37839
_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    1.365
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             800
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.143
_refine_diff_density_min         -0.246
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.005(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3334
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0345
_refine_ls_R_factor_gt           0.0337
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0611P)^2^+0.2179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0923
_refine_ls_wR_factor_ref         0.0935
_reflns_number_gt                3241
_reflns_number_total             3334
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c7ra12136a2.cif
_cod_data_source_block           3ag
_cod_original_cell_volume        1867.89(4)
_cod_database_code               7230065
_chemical_oxdiff_formula         'C H O N S'
_reflns_odcompleteness_completeness 99.90
_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), C6(H6), C8(H8), C10(H10), C11(H11), C13(H13), C14(H14), C16(H16),
 C17(H17), C19(H19), C20(H20)
2.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C)
;
_olex2_submission_special_instructions 'No special instructions were received'