Benzylene-linked [PNP] scaffolds and their cyclometalated zirconium and hafnium complexes
Sietzen, Malte; Batke, Sonja; Antoni, Patrick W.; Wadepohl, Hubert; Ballmann, Joachim; Dalton Trans.  (2017) –; doi:10.1039/C7DT00413C

data_7042700
_publ_section_title
;
 Benzylene-linked [PNP] scaffolds and their cyclometalated zirconium and
 hafnium complexes
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT00413C
_journal_year                    2017
_chemical_formula_moiety         'C45 H38 Cl Hf N P2, C4 H10 O'
_chemical_formula_sum            'C49 H48 Cl Hf N O P2'
_chemical_formula_weight         942.76
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_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_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_sb60
_audit_creation_date             2016-04-27
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2017-03-17 deposited with the CCDC.
2017-04-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.9077(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.05585(7)
_cell_length_b                   12.17458(6)
_cell_length_c                   28.6103(2)
_cell_measurement_reflns_used    96329
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.6590
_cell_measurement_theta_min      3.9440
_cell_volume                     4196.95(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41p (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41p (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41p (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-15); encifer 1.5 (CCDC, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      perfluoro
_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    -32.00  73.00   1.00    2.00    --    0.00  27.00  69.00  105
  2  \w    -21.00  69.00   1.00    2.00    --    0.00  57.00  60.00   90
  3  \w    -26.00  72.00   1.00    2.00    --    0.00  38.00 -30.00   98
  4  \w    -70.00  30.00   1.00    2.00    --    0.00 -77.00   0.00  100
  5  \w    -30.00  70.00   1.00    2.00    --    0.00  77.00 120.00  100
  6  \w    -49.00  -4.00   1.00    2.00    --   10.00 128.00 126.38   45
  7  \w    -30.00  17.00   1.00    2.00    --   14.00 103.00   1.08   47
  8  \w    -32.00  -3.00   1.00    2.00    --   26.00 126.00  83.83   29
  9  \w    -29.00  -3.00   1.00    6.00    --   30.00 127.00  98.59   26
 10  \w     -9.00  18.00   1.00    6.00    --   34.00 102.00-161.50   27
 11  \w     -2.00  25.00   1.00    6.00    --   38.00  95.00 -84.03   27
 12  \w      6.00  33.00   1.00    6.00    --   42.00  88.00  71.85   27
 13  \w      5.00  32.00   1.00    6.00    --   42.00  90.00 175.47   27
 14  \w      5.00  32.00   1.00    6.00    --   42.00  90.00 -58.35   27
 15  \w     13.00  40.00   1.00    6.00    --   46.00  83.00 -66.99   27
 16  \w     13.00  40.00   1.00    6.00    --   46.00  83.00-123.99   27
 17  \w     12.00  38.00   1.00    6.00    --   46.00  84.00 146.72   26
 18  \w     18.00  46.00   1.00    6.00    --   50.00  81.00  82.80   28
 19  \w     18.00  46.00   1.00    6.00    --   50.00  80.00-128.82   28
 20  \w     18.00  46.00   1.00    6.00    --   50.00  81.00  54.18   28
 21  \w     17.00  45.00   1.00    6.00    --   50.00  82.00  17.52   28
 22  \w     17.00  45.00   1.00    6.00    --   50.00  82.00 102.38   28
 23  \w     18.00  46.00   1.00    6.00    --   50.00  80.00-162.43   28
 24  \w     18.00  46.00   1.00    6.00    --   50.00  80.00 -33.94   28
 25  \w     18.00  46.00   1.00    6.00    --   50.00  80.00-100.70   28
 26  \w     18.00  46.00   1.00    6.00    --   50.00  80.00 175.15   28
 27  \w     18.00  46.00   1.00    6.00    --   50.00  81.00 -82.24   28
 28  \w      1.00  96.00   1.00    6.00    --   54.00 -99.00-180.00   95
 29  \w     25.00 124.00   1.00    6.00    --   54.00  75.00 140.63   99
 30  \w     23.00  49.00   1.00    6.00    --   54.00  78.00  -9.04   26
 31  \w     24.00 124.00   1.00    6.00    --   54.00  77.00 -30.00  100
 32  \w     23.00  49.00   1.00    6.00    --   54.00  78.00 -78.64   26
 33  \w     24.00 124.00   1.00    6.00    --   54.00  77.00 150.00  100
 34  \w     26.00 124.00   1.00    6.00    --   54.00  74.00  25.69   98
 35  \w     26.00 124.00   1.00    6.00    --   54.00  74.00 116.42   98
 36  \w     23.00  49.00   1.00    6.00    --   54.00  78.00  39.76   26
 37  \w    -15.00  75.00   1.00    6.00    --   54.00 -57.00  90.00   90
 38  \w     24.00 124.00   1.00    6.00    --   54.00  77.00-120.00  100
 39  \w     24.00 124.00   1.00    6.00    --   54.00  77.00 -90.00  100
 40  \w     23.00  49.00   1.00    6.00    --   54.00  78.00 166.63   26
 41  \w     24.00 124.00   1.00    6.00    --   54.00  77.00  90.00  100
 42  \w     26.00 123.00   1.00    6.00    --   54.00  73.00-154.91   97
 43  \w     23.00 111.00   1.00    6.00    --   54.00-125.00 -30.00   88
 44  \w      1.00  96.00   1.00    6.00    --   54.00 -99.00   0.00   95
 45  \w     24.00 124.00   1.00    6.00    --   54.00  77.00-150.00  100
 46  \w     30.00 127.00   1.00    6.00    --   58.00  73.00 -73.66   97
 47  \w     28.00 128.00   1.00    6.00    --   58.00  77.00-124.07  100
 48  \w     29.00 128.00   1.00    6.00    --   58.00  75.00 -96.53   99
 49  \w     28.00 128.00   1.00    6.00    --   58.00  77.00  -4.26  100
 50  \w     30.00 128.00   1.00    6.00    --   58.00  74.00 179.14   98
 51  \w     28.00 128.00   1.00    6.00    --   58.00  77.00-169.60  100
 52  \w     29.00 128.00   1.00    6.00    --   58.00  76.00  89.06   99
 53  \w     29.00 128.00   1.00    6.00    --   58.00  76.00  59.52   99
 54  \w     33.00 132.00   1.00    6.00    --   62.00  75.00 -33.08   99
 55  \w     32.00 132.00   1.00    6.00    --   62.00  77.00-103.05  100
 56  \w     34.00 132.00   1.00    6.00    --   62.00  74.00 103.06   98
 57  \w     32.00 132.00   1.00    6.00    --   62.00  77.00-123.00  100
 58  \w     40.00 135.00   1.00    6.00    --   66.00  70.00 127.66   95
 59  \w     42.00 134.00   1.00    6.00    --   66.00  67.00-134.11   92
 60  \w     37.00 136.00   1.00    6.00    --   66.00  75.00  96.53   99
 61  \w     40.00 135.00   1.00    6.00    --   66.00  70.00 155.83   95
 62  \w     44.00 134.00   1.00    6.00    --   66.00  62.00 -86.14   90
 63  \w     44.00 134.00   1.00    6.00    --   66.00  61.00 -92.45   90
 64  \w     44.00 134.00   1.00    6.00    --   66.00  61.00 -60.68   90
 65  \w     36.00 136.00   1.00    6.00    --   66.00  77.00 -15.57  100
 66  \w     41.00 140.00   1.00    6.00    --   70.00  75.00 -40.69   99
 67  \w     46.00 138.00   1.00    6.00    --   70.00  68.00 163.46   92
 68  \w     42.00 139.00   1.00    6.00    --   70.00  73.00  70.69   97
 69  \w     41.00 140.00   1.00    6.00    --   70.00  75.00 109.42   99
 70  \w     47.00 138.00   1.00    6.00    --   70.00  66.00  16.66   91
 71  \w     44.00 139.00   1.00    6.00    --   70.00  70.00-178.06   95
 72  \w     53.00 142.00   1.00    6.00    --   74.00  60.00 -17.92   89
 73  \w     45.00 144.00   1.00    6.00    --   74.00  76.00 107.10   99
 74  \w     45.00 144.00   1.00    6.00    --   74.00  75.00  78.69   99
 75  \w     49.00 142.00   1.00    6.00    --   74.00  69.00  -7.87   93
 76  \w     46.00 144.00   1.00    6.00    --   74.00  74.00 -72.73   98
 77  \w     44.00 144.00   1.00    6.00    --   74.00  77.00-168.39  100
 78  \w     45.00 144.00   1.00    6.00    --   74.00  75.00  32.74   99
 79  \w     54.00 149.00   1.00    6.00    --   78.00  44.00 -61.86   95
 80  \w     50.00 147.00   1.00    6.00    --   78.00  73.00  63.85   97
 81  \w     50.00 147.00   1.00    6.00    --   78.00  73.00-137.38   97
 82  \w     55.00 146.00   1.00    6.00    --   78.00  65.00 135.98   91
 83  \w     57.00 147.00   1.00    6.00    --   78.00  54.00 -46.81   90
 84  \w     53.00 152.00   1.00   10.00    --   82.00  75.00 151.14   99
 85  \w     52.00 152.00   1.00   10.00    --   82.00  77.00 -91.27  100
 86  \w     58.00 150.00   1.00   10.00    --   82.00  67.00-139.43   92
 87  \w     57.00 154.00   1.00   10.00    --   82.00  39.00  54.99   97
 88  \w     61.00 151.00   1.00   10.00    --   82.00  56.00-153.84   90
 89  \w     62.00 154.00   1.00   10.00    --   86.00  68.00-103.32   92
 90  \w     61.00 122.00   1.00   10.00    --   86.00  69.00-148.39   61
 91  \w     63.00  89.00   1.00   10.00    --   86.00  65.00  28.12   26
 92  \w     66.00 104.00   1.00   10.00    --   90.00  67.00-101.17   38
 93  \w     67.00  94.00   1.00   10.00    --   90.00  46.00  79.98   27
 94  \w     70.00 142.00   1.00   10.00    --   90.00  59.00 -30.04   72
 95  \w     70.00  96.00   1.00   10.00    --   94.00  69.00  83.45   26
 96  \w     68.00 168.00   1.00   10.00    --   98.00  77.00 -26.01  100
 97  \w     69.00  95.00   1.00   10.00    --   98.00  75.00  44.32   26
 98  \w    100.00 125.00   1.00   10.00    --   98.00  75.00  82.87   25
 99  \w     69.00  98.00   1.00   10.00    --   98.00  75.00  82.87   29
100  \w     75.00 101.00   1.00   10.00    --   98.00  48.00 -32.26   26
101  \w     82.00 117.00   1.00   10.00    --  102.00  57.00 122.76   35
102  \w     79.00 105.00   1.00   10.00    --  102.00  66.00  63.94   26
103  \w     77.00 176.00   1.00   10.00    --  106.00  75.00 -67.95   99
104  \w     85.00 112.00   1.00   10.00    --  108.00  64.00-180.00   27
105  \w     85.00 112.00   1.00   10.00    --  108.00  64.00   0.00   27
106  \w     38.00 137.00   1.00   10.00    --  108.00 -77.00 -90.00   99
107  \w     85.00 152.00   1.00   10.00    --  108.00  64.00 150.00   67
108  \w     78.00 175.00   1.00   10.00    --  108.00  77.00 -60.00   97
109  \w     78.00 104.00   1.00   10.00    --  108.00  77.00 -90.00   26
110  \w     78.00 177.00   1.00   10.00    --  108.00  77.00  90.00   99
111  \w     85.00 175.00   1.00   10.00    --  108.00  64.00  30.00   90
112  \w     90.00 116.00   1.00   10.00    --  108.00-111.00-180.00   26
113  \w     37.00  62.00   1.00   10.00    --  108.00-111.00-180.00   25
114  \w     78.00 130.00   1.00   10.00    --  108.00  77.00-180.00   52
115  \w    113.00 178.00   1.00   10.00    --  108.00  77.00-120.00   65
116  \w     79.00 107.00   1.00   10.00    --  108.00  77.00-120.00   28
117  \w     78.00 177.00   1.00   10.00    --  108.00  77.00-150.00   99
118  \w    112.00 176.00   1.00   10.00    --  108.00  77.00 120.00   64
119  \w     85.00 111.00   1.00   10.00    --  108.00  64.00 -90.00   26
120  \w     79.00 108.00   1.00   10.00    --  108.00  77.00 120.00   29
121  \w    117.00 168.00   1.00   10.00    --  108.00  77.00   0.00   51
122  \w     78.00 108.00   1.00   10.00    --  108.00  77.00   0.00   30
123  \w     78.00 177.00   1.00   10.00    --  108.00  77.00 -30.00   99
124  \w     37.00 109.00   1.00   10.00    --  108.00-111.00  90.00   72
125  \w     78.00 104.00   1.00   10.00    --  108.00 -64.00-120.00   26
126  \w     46.00  72.00   1.00   10.00    --  108.00 -64.00-120.00   26
127  \w     78.00 178.00   1.00   10.00    --  108.00  77.00 150.00  100
128  \w     49.00 138.00   1.00   10.00    --  108.00 -77.00  90.00   89
129  \w     37.00 115.00   1.00   10.00    --  108.00-111.00 -90.00   78
130  \w     77.00 104.00   1.00   10.00    --  108.00-111.00  30.00   27
131  \w    147.00 173.00   1.00   10.00    --  108.00  72.00  78.23   26
132  \w     82.00 117.00   1.00   10.00    --  108.00  72.00  78.23   35
133  \w     86.00 113.00   1.00   10.00    --  108.00  62.00-121.89   27
134  \w     84.00 110.00   1.00   10.00    --  108.00  68.00 -85.62   26
135  \w     80.00 150.00   1.00   10.00    --  108.00  76.00-167.91   70
136  \w     85.00 112.00   1.00   10.00    --  108.00  77.00  60.00   27
137  \w     82.00 178.00   1.00   10.00    --  108.00  38.00  60.00   96
138  \w     85.00 149.00   1.00   10.00    --  108.00  38.00 -60.00   64
139  \w     85.00 113.00   1.00   10.00    --  108.00  38.00-150.00   28
140  \w     82.00 109.00   1.00   10.00    --  108.00  38.00-180.00   27
141  \w     86.00 111.00   1.00   10.00    --  108.00  64.00-120.00   25
142  \w     86.00 147.00   1.00   10.00    --  108.00  64.00-150.00   61
143  \w     81.00 108.00   1.00   10.00    --  108.00  77.00  30.00   27
144  \w     85.00 111.00   1.00   10.00    --  108.00  64.00 120.00   26
145  \w    131.00 157.00   1.00   10.00    --  108.00  64.00 -90.00   26
;
_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      -0.1210275000
_diffrn_orient_matrix_UB_12      -0.0084973000
_diffrn_orient_matrix_UB_13      -0.0186400000
_diffrn_orient_matrix_UB_21      0.0059216000
_diffrn_orient_matrix_UB_22      -0.1261104000
_diffrn_orient_matrix_UB_23      0.0039660000
_diffrn_orient_matrix_UB_31      -0.0407370000
_diffrn_orient_matrix_UB_32      0.0068012000
_diffrn_orient_matrix_UB_33      0.0503833000
_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  0.0411
_diffrn_reflns_av_unetI/netI     0.0140
_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       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            179970
_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         70.867
_diffrn_reflns_theta_min         3.668
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.187
_exptl_absorpt_correction_T_max  0.738
_exptl_absorpt_correction_T_min  0.628
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41p (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.492
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1904
_exptl_crystal_size_max          0.104
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.064
_refine_diff_density_max         1.411
_refine_diff_density_min         -0.706
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.118
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     501
_refine_ls_number_reflns         8028
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.140
_refine_ls_R_factor_all          0.0303
_refine_ls_R_factor_gt           0.0288
_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^)+(0.0282P)^2^+9.2216P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0693
_refine_ls_wR_factor_ref         0.0700
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7722
_reflns_number_total             8028
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt00413c2.cif
_cod_data_source_block           ba_sb60
_cod_original_cell_volume        4196.94(4)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7042700
_audit_block_refno               2711
_audit_block_usercomment         'sb_dh17, irregular, yellow'
_chemical_oxdiff_formula         'C49 H48 Cl1 Hf1 N1 O1 P2'
_chemical_oxdiff_usercomment     'sb_dh17, irregular, yellow'
_shelx_estimated_absorpt_t_max   0.577
_shelx_estimated_absorpt_t_min   0.577
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_shelxl_version_number           2014/7
_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. Restrained distances
 O51-C51 \\sim O51-C53
 with sigma of 0.005
 C51-C52 \\sim C53-C54
 with sigma of 0.005
 O51-C52 \\sim O51-C54
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 O51, C51, C52, C53, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C45(H45A,H45B), C51(H51A,H51B), C53(H53A,H53B)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C23(H23), C24(H24),
  C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
 C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C40(H40), C41(H41), C42(H42),
  C43(H43), C44(H44)
4.c Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C54(H54A,H54B,H54C)
;
_shelx_res_checksum              24144
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.205
_oxdiff_exptl_absorpt_empirical_full_min 0.864
_cell_oxdiff_length_a            12.05757(13)
_cell_oxdiff_length_b            12.17073(10)
_cell_oxdiff_length_c            28.6149(3)
_cell_oxdiff_angle_alpha         90.0070(8)
_cell_oxdiff_angle_beta          91.8888(9)
_cell_oxdiff_angle_gamma         90.0160(8)
_cell_oxdiff_volume              4196.94(8)
_cell_oxdiff_measurement_reflns_used 96329