Dehydrogenative coupling of 4-substituted pyridines mediated by a zirconium(ii) synthon: reaction pathways and dead ends.
Merz, Lukas S.; Wadepohl, Hubert; Clot, Eric; Gade, Lutz H.; Chemical science 9 (2018) 5223–5232; doi:10.1039/c8sc01025k

data_1554589
_publ_section_title
;
 Dehydrogenative coupling of 4-substituted pyridines mediated by a
 zirconium(ii) synthon: reaction pathways and dead ends.
;
_journal_issue                   23
_journal_name_full               'Chemical science'
_journal_page_first              5223
_journal_page_last               5232
_journal_paper_doi               10.1039/c8sc01025k
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C52 H78 Cl N3 P2 Zr'
_chemical_formula_sum            'C52 H78 Cl N3 P2 Zr'
_chemical_formula_weight         933.78
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_lm21
_audit_creation_date             2017-02-28
_audit_creation_method
;
Olex2 1.2
(compiled Aug 10 2017 17:44:14 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-02-28 deposited with the CCDC.
2018-05-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.0656(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.10234(18)
_cell_length_b                   13.69809(19)
_cell_length_c                   31.6606(4)
_cell_measurement_reflns_used    22934
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.4240
_cell_measurement_theta_min      3.5070
_cell_volume                     5247.75(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-17); encifer 1.5.2 (CCDC, 2016)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_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    -30.00  70.00   1.00    1.50    --    0.00  77.00 -90.00  100
  2  \w    -69.00  21.00   1.00    1.50    --    0.00 -57.00 120.00   90
  3  \w    -21.00  69.00   1.00    1.50    --    0.00  57.00 120.00   90
  4  \w    -21.00  69.00   1.00    1.50    --    0.00  57.00 150.00   90
  5  \w    -59.00  38.00   1.00    1.50    --   10.00 -73.00   0.09   97
  6  \w    -35.00  10.00   1.00    1.50    --   14.00 111.00 -73.67   45
  7  \w    -35.00  -1.00   1.00    1.50    --   22.00 124.00 -38.30   34
  8  \w     -9.00  18.00   1.00    4.50    --   34.00 101.00 111.32   27
  9  \w     -1.00  26.00   1.00    4.50    --   38.00  94.00 -32.50   27
 10  \w      6.00  33.00   1.00    4.50    --   42.00  88.00-114.72   27
 11  \w      5.00  33.00   1.00    4.50    --   42.00  89.00 161.43   28
 12  \w      5.00  32.00   1.00    4.50    --   42.00  90.00  83.77   27
 13  \w     13.00  40.00   1.00    4.50    --   46.00  83.00 -29.36   27
 14  \w     12.00  38.00   1.00    4.50    --   46.00  84.00-133.09   26
 15  \w     13.00  40.00   1.00    4.50    --   46.00  83.00 -49.85   27
 16  \w     12.00  38.00   1.00    4.50    --   46.00  84.00  54.11   26
 17  \w     12.00  38.00   1.00    4.50    --   46.00  84.00-154.13   26
 18  \w     18.00  46.00   1.00    4.50    --   50.00  80.00  42.78   28
 19  \w     17.00  45.00   1.00    4.50    --   50.00  82.00 130.18   28
 20  \w     21.00 120.00   1.00    4.50    --   50.00  76.00 -77.38   99
 21  \w     17.00  45.00   1.00    4.50    --   50.00  82.00 141.45   28
 22  \w     18.00  46.00   1.00    4.50    --   50.00  81.00  96.49   28
 23  \w     24.00 124.00   1.00    4.50    --   54.00  77.00 -30.00  100
 24  \w     24.00 104.00   1.00    4.50    --   54.00  77.00  60.00   80
 25  \w     24.00  85.00   1.00    4.50    --   54.00-125.00-120.00   61
 26  \w     30.00  57.00   1.00    4.50    --   54.00  77.00 -90.00   27
 27  \w     25.00  52.00   1.00    4.50    --   54.00  77.00 -60.00   27
 28  \w     24.00  57.00   1.00    4.50    --   54.00  77.00-120.00   33
 29  \w      1.00  94.00   1.00    4.50    --   54.00 -99.00 -30.00   93
 30  \w     24.00  51.00   1.00    4.50    --   54.00  77.00-180.00   27
 31  \w     24.00  51.00   1.00    4.50    --   54.00  77.00-150.00   27
 32  \w     24.00  51.00   1.00    4.50    --   54.00  77.00-165.94   27
 33  \w      1.00  96.00   1.00    4.50    --   54.00 -99.00 120.00   95
 34  \w     23.00  48.00   1.00    4.50    --   54.00  78.00  20.06   25
 35  \w     28.00  59.00   1.00    4.50    --   58.00  77.00 -98.36   31
 36  \w     29.00  55.00   1.00    4.50    --   58.00  76.00  -2.45   26
 37  \w     29.00  54.00   1.00    4.50    --   58.00  77.00 137.45   25
 38  \w     31.00  59.00   1.00    4.50    --   58.00  76.00-141.14   28
 39  \w     35.00  61.00   1.00    4.50    --   58.00  66.00 108.12   26
 40  \w     28.00  54.00   1.00    4.50    --   58.00  77.00 116.93   26
 41  \w     33.00  60.00   1.00    4.50    --   58.00  74.00  12.40   27
 42  \w     32.00  59.00   1.00    4.50    --   58.00  74.00 179.87   27
 43  \w     41.00 131.00   1.00    4.50    --   62.00  56.00  18.48   90
 44  \w     32.00  59.00   1.00    4.50    --   62.00  77.00 -54.55   27
 45  \w     41.00 116.00   1.00    4.50    --   62.00  54.00 107.63   75
 46  \w     43.00  70.00   1.00    4.50    --   62.00  61.00-170.13   27
 47  \w     44.00  76.00   1.00    4.50    --   62.00  61.00  37.90   32
 48  \w     37.00  64.00   1.00    4.50    --   62.00  69.00 107.26   27
 49  \w     36.00  63.00   1.00    4.50    --   66.00  77.00-162.01   27
 50  \w     43.00  70.00   1.00    4.50    --   66.00  70.00 139.08   27
 51  \w    110.00 135.00   1.00    4.50    --   66.00  71.00 -68.25   25
 52  \w     40.00  67.00   1.00    4.50    --   66.00  71.00 -68.25   27
 53  \w     46.00  94.00   1.00    4.50    --   70.00  67.00  -2.84   48
 54  \w     49.00 113.00   1.00    4.50    --   70.00  64.00 -99.79   64
 55  \w     42.00  76.00   1.00    4.50    --   70.00  73.00  37.37   34
 56  \w     45.00  70.00   1.00    4.50    --   70.00  70.00-152.98   25
 57  \w     47.00  74.00   1.00    4.50    --   70.00  65.00 -60.86   27
 58  \w     44.00  70.00   1.00    4.50    --   70.00  70.00  91.80   26
 59  \w     48.00  73.00   1.00    4.50    --   70.00  66.00 -37.16   25
 60  \w    106.00 133.00   1.00    4.50    --   70.00  73.00  37.37   27
 61  \w    106.00 132.00   1.00    4.50    --   70.00  66.00 -37.16   26
 62  \w     46.00  72.00   1.00    4.50    --   70.00  68.00-177.81   26
 63  \w     46.00  73.00   1.00    4.50    --   74.00  74.00 -94.26   27
 64  \w     51.00  77.00   1.00    4.50    --   74.00  65.00  87.71   26
 65  \w     88.00 122.00   1.00    4.50    --   74.00  77.00-141.95   34
 66  \w     45.00  79.00   1.00    4.50    --   74.00  77.00-141.95   34
 67  \w     89.00 116.00   1.00    4.50    --   74.00  68.00-167.37   27
 68  \w     50.00  76.00   1.00    4.50    --   74.00  68.00-167.37   26
 69  \w     48.00 108.00   1.00    4.50    --   74.00  72.00 107.23   60
 70  \w     46.00  72.00   1.00    4.50    --   74.00  74.00  -5.59   26
 71  \w     58.00  85.00   1.00    4.50    --   78.00  57.00  90.84   27
 72  \w     59.00  84.00   1.00    4.50    --   78.00  60.00  95.35   25
 73  \w    123.00 148.00   1.00    4.50    --   78.00  76.00 -76.27   25
 74  \w     49.00  75.00   1.00    4.50    --   78.00  76.00 -76.27   26
 75  \w     51.00 147.00   1.00    4.50    --   78.00  72.00 130.77   96
 76  \w     96.00 151.00   1.00    7.50    --   82.00  74.00-158.00   55
 77  \w     54.00  90.00   1.00    7.50    --   82.00  74.00-158.00   36
 78  \w     54.00  79.00   1.00    7.50    --   82.00  75.00 -12.71   25
 79  \w     54.00 152.00   1.00    7.50    --   82.00  74.00  26.36   98
 80  \w     52.00  82.00   1.00    7.50    --   82.00  77.00  -4.17   30
 81  \w     63.00  90.00   1.00    7.50    --   82.00  67.00 -98.99   27
 82  \w     58.00 148.00   1.00    7.50    --   86.00  74.00 167.07   90
 83  \w     60.00  91.00   1.00    7.50    --   86.00  70.00 -22.90   31
 84  \w     63.00 118.00   1.00    7.50    --   86.00  66.00 104.12   55
 85  \w     66.00  93.00   1.00    7.50    --   86.00  58.00-123.18   27
 86  \w     61.00  88.00   1.00    7.50    --   90.00  76.00 -74.45   27
 87  \w    104.00 129.00   1.00    7.50    --   90.00  56.00 -30.44   25
 88  \w     69.00  95.00   1.00    7.50    --   90.00  56.00 -30.44   26
 89  \w     63.00  89.00   1.00    7.50    --   90.00  71.00 142.31   26
 90  \w     72.00  97.00   1.00    7.50    --   90.00  64.00-102.99   25
 91  \w     85.00 112.00   1.00    7.50    --   90.00  51.00  11.96   27
 92  \w     67.00 138.00   1.00    7.50    --   90.00  69.00 -24.59   71
 93  \w     60.00  86.00   1.00    7.50    --   90.00  77.00-125.10   26
 94  \w     64.00  90.00   1.00    7.50    --   90.00  70.00  87.98   26
 95  \w     72.00  98.00   1.00    7.50    --   94.00  61.00 -73.70   26
 96  \w     75.00 102.00   1.00    7.50    --   94.00  51.00 -39.39   27
 97  \w     71.00 101.00   1.00    7.50    --   94.00  64.00 133.77   30
 98  \w     76.00 104.00   1.00    7.50    --   98.00  62.00 120.42   28
 99  \w    138.00 165.00   1.00    7.50    --   98.00  77.00  32.20   27
100  \w     68.00  94.00   1.00    7.50    --   98.00  77.00  32.20   26
101  \w     69.00  96.00   1.00    7.50    --   98.00  76.00-138.57   27
102  \w     81.00 107.00   1.00    7.50    --  102.00  58.00 158.83   26
103  \w     82.00 107.00   1.00    7.50    --  102.00  56.00 163.34   25
104  \w     82.00 107.00   1.00    7.50    --  102.00  57.00 153.75   25
105  \w     85.00 112.00   1.00    7.50    --  108.00  64.00  60.00   27
106  \w     85.00 111.00   1.00    7.50    --  108.00  64.00-180.00   26
107  \w    141.00 175.00   1.00    7.50    --  108.00  77.00   0.00   34
108  \w     78.00 104.00   1.00    7.50    --  108.00  77.00   0.00   26
109  \w    147.00 175.00   1.00    7.50    --  108.00  77.00 -90.00   28
110  \w     78.00 105.00   1.00    7.50    --  108.00  77.00 -90.00   27
111  \w     79.00 176.00   1.00    7.50    --  108.00  77.00  30.00   97
112  \w     85.00 112.00   1.00    7.50    --  108.00-111.00 -90.00   27
113  \w     57.00  84.00   1.00    7.50    --  108.00-111.00 -90.00   27
114  \w     86.00 155.00   1.00    7.50    --  108.00  64.00   0.00   69
115  \w    113.00 175.00   1.00    7.50    --  108.00  77.00 150.00   62
116  \w     78.00 109.00   1.00    7.50    --  108.00  77.00 150.00   31
117  \w     78.00 104.00   1.00    7.50    --  108.00  77.00  90.00   26
118  \w     86.00 112.00   1.00    7.50    --  108.00-111.00 120.00   26
119  \w     42.00  69.00   1.00    7.50    --  108.00-111.00 120.00   27
120  \w    141.00 178.00   1.00    7.50    --  108.00  77.00-120.00   37
121  \w     79.00 106.00   1.00    7.50    --  108.00  77.00-120.00   27
122  \w    110.00 170.00   1.00    7.50    --  108.00  77.00 -30.00   60
123  \w     78.00 104.00   1.00    7.50    --  108.00  77.00-180.00   26
124  \w     78.00 104.00   1.00    7.50    --  108.00  77.00 -30.00   26
125  \w    121.00 176.00   1.00    7.50    --  108.00  77.00  60.00   55
126  \w     79.00 106.00   1.00    7.50    --  108.00  77.00  60.00   27
127  \w    114.00 172.00   1.00    7.50    --  108.00  77.00 120.00   58
128  \w     78.00 104.00   1.00    7.50    --  108.00  77.00 120.00   26
129  \w     78.00 171.00   1.00    7.50    --  108.00  77.00 -60.00   93
130  \w     85.00 161.00   1.00    7.50    --  108.00  64.00 -90.00   76
131  \w     38.00 138.00   1.00    7.50    --  108.00 -77.00-180.00  100
132  \w     39.00 135.00   1.00    7.50    --  108.00 -77.00   0.00   96
133  \w     37.00 116.00   1.00    7.50    --  108.00-111.00   0.00   79
134  \w     54.00 113.00   1.00    7.50    --  108.00-111.00-180.00   59
135  \w     79.00 106.00   1.00    7.50    --  108.00  75.00-137.61   27
136  \w     82.00 109.00   1.00    7.50    --  108.00  77.00-150.00   27
137  \w     85.00 113.00   1.00    7.50    --  108.00  38.00   0.00   28
138  \w     83.00 116.00   1.00    7.50    --  108.00  38.00-150.00   33
139  \w     81.00 177.00   1.00    7.50    --  108.00  71.00-162.59   96
140  \w     86.00 153.00   1.00    7.50    --  108.00  64.00-120.00   67
141  \w     85.00 112.00   1.00    7.50    --  108.00  64.00 150.00   27
142  \w     83.00 123.00   1.00    7.50    --  108.00  38.00  90.00   40
143  \w     82.00 108.00   1.00    7.50    --  108.00  70.00-177.88   26
144  \w     85.00 126.00   1.00    7.50    --  108.00  64.00 120.00   41
145  \w     86.00 111.00   1.00    7.50    --  108.00  64.00 -60.00   25
146  \w     86.00 111.00   1.00    7.50    --  108.00  64.00 -30.00   25
147  \w     85.00 168.00   1.00    7.50    --  108.00  64.00  90.00   83
148  \w    117.00 178.00   1.00    7.50    --  108.00  77.00-180.00   61
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0013465000
_diffrn_orient_matrix_UB_12      0.0065240000
_diffrn_orient_matrix_UB_13      0.0485670000
_diffrn_orient_matrix_UB_21      0.0550384000
_diffrn_orient_matrix_UB_22      -0.1011866000
_diffrn_orient_matrix_UB_23      0.0031493000
_diffrn_orient_matrix_UB_31      0.1147690000
_diffrn_orient_matrix_UB_32      0.0486944000
_diffrn_orient_matrix_UB_33      0.0000494000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0908
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            136700
_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         70.963
_diffrn_reflns_theta_min         3.516
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.014
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.657
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
 a multifaceted crystal model (Busing & Levy, 1957).
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.182
_exptl_crystal_description       plate
_exptl_crystal_F_000             1992
_exptl_crystal_size_max          0.149
_exptl_crystal_size_mid          0.107
_exptl_crystal_size_min          0.011
_refine_diff_density_max         0.854
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.165
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     552
_refine_ls_number_reflns         10072
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.165
_refine_ls_R_factor_all          0.0645
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0165P)^2^+16.6322P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1104
_refine_ls_wR_factor_ref         0.1153
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8403
_reflns_number_total             10072
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01025k3.cif
_cod_data_source_block           ga_lm21
_cod_original_cell_volume        5247.76(13)
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               1554589
_audit_block_refno               2829
_audit_block_usercomment         'LM098, plate, black'
_shelx_estimated_absorpt_t_max   0.753
_shelx_estimated_absorpt_t_min   0.753
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_shelxl_version_number           2018/1
_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 Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C30(H30), C33(H33)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C9(H9), C11(H11), C36(H36), C37(H37), C39(H39), C42(H42),
 C44(H44), C45(H45)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C47(H47A,H47B,
 H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C51(H51A,H51B,H51C), C52(H52A,
 H52B,H52C), C53(H53A,H53B,H53C)
;
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.264
_oxdiff_exptl_absorpt_empirical_full_min 0.799
_shelx_res_checksum              51879
_cell_oxdiff_length_a            12.1047(2)
_cell_oxdiff_length_b            13.6960(2)
_cell_oxdiff_length_c            31.6591(6)
_cell_oxdiff_angle_alpha         90.0054(14)
_cell_oxdiff_angle_beta          91.0507(15)
_cell_oxdiff_angle_gamma         90.0426(14)
_cell_oxdiff_volume              5247.76(16)
_cell_oxdiff_measurement_reflns_used 22934