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_7042695
_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_sum            'C41.75 H41 Cl3 N P2 Zr'
_chemical_formula_weight         816.26
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_sb64
_audit_creation_date             2016-05-24
_audit_creation_method
;
Olex2 1.2
(compiled Mar  2 2017 14:00:58 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2017-03-17 deposited with the CCDC.
2017-04-05 downloaded from the CCDC.
;
_cell_angle_alpha                80.0131(11)
_cell_angle_beta                 88.4840(10)
_cell_angle_gamma                72.8933(10)
_cell_formula_units_Z            4
_cell_length_a                   11.44486(13)
_cell_length_b                   17.6843(2)
_cell_length_c                   19.9828(3)
_cell_measurement_reflns_used    111747
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.5070
_cell_measurement_theta_min      3.7360
_cell_volume                     3805.61(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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 0.992
_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    -72.00  26.00   1.00    1.00    --    0.00 -38.00 -60.00   98
  2  \w    -72.00  26.00   1.00    1.00    --    0.00 -38.00-150.00   98
  3  \w    -21.00  69.00   1.00    1.00    --    0.00  57.00 -90.00   90
  4  \w    -69.00  21.00   1.00    1.00    --    0.00 -57.00 120.00   90
  5  \w    -37.00  11.00   1.00    1.00    --   10.00 109.00 -14.08   48
  6  \w    -43.00  -1.00   1.00    1.00    --   14.00 124.00  30.85   42
  7  \w    -21.00  11.00   1.00    1.00    --   26.00 109.00 150.31   32
  8  \w    -21.00   6.00   1.00    4.00    --   30.00 115.00 -89.57   27
  9  \w     -9.00  18.00   1.00    4.00    --   34.00 101.00 103.10   27
 10  \w    -10.00  17.00   1.00    4.00    --   34.00 103.00  -1.18   27
 11  \w      5.00  32.00   1.00    4.00    --   42.00  90.00 -92.04   27
 12  \w      6.00  33.00   1.00    4.00    --   42.00  88.00  65.56   27
 13  \w     15.00  47.00   1.00    4.00    --   46.00  79.00-155.91   32
 14  \w     13.00  45.00   1.00    4.00    --   46.00  82.00  42.99   32
 15  \w     13.00  40.00   1.00    4.00    --   46.00  83.00 -44.93   27
 16  \w     13.00  45.00   1.00    4.00    --   46.00  82.00 115.72   32
 17  \w     13.00  40.00   1.00    4.00    --   46.00  83.00  86.22   27
 18  \w     13.00  45.00   1.00    4.00    --   46.00  82.00-110.75   32
 19  \w     13.00  45.00   1.00    4.00    --   46.00  82.00 -88.29   32
 20  \w     13.00  45.00   1.00    4.00    --   46.00  82.00 164.97   32
 21  \w     18.00  46.00   1.00    4.00    --   50.00  81.00  -5.69   28
 22  \w     19.00  49.00   1.00    4.00    --   50.00  78.00-146.91   30
 23  \w     18.00  46.00   1.00    4.00    --   50.00  80.00 173.78   28
 24  \w     19.00  49.00   1.00    4.00    --   50.00  78.00 -51.45   30
 25  \w     18.00  46.00   1.00    4.00    --   50.00  81.00 -94.71   28
 26  \w     18.00  46.00   1.00    4.00    --   50.00  80.00-149.72   28
 27  \w     24.00 124.00   1.00    4.00    --   54.00  77.00  23.31  100
 28  \w      1.00  96.00   1.00    4.00    --   54.00 -99.00 150.00   95
 29  \w    -15.00  75.00   1.00    4.00    --   54.00 -57.00 -90.00   90
 30  \w     23.00  49.00   1.00    4.00    --   54.00  78.00-120.28   26
 31  \w    -15.00  75.00   1.00    4.00    --   54.00 -57.00-180.00   90
 32  \w     25.00 124.00   1.00    4.00    --   54.00  75.00 143.51   99
 33  \w     27.00 123.00   1.00    4.00    --   54.00  72.00  87.46   96
 34  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 120.00  100
 35  \w     23.00 111.00   1.00    4.00    --   54.00-125.00  90.00   88
 36  \w     24.00 124.00   1.00    4.00    --   54.00  77.00  90.00  100
 37  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 150.00  100
 38  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -90.00  100
 39  \w     23.00  49.00   1.00    4.00    --   54.00  78.00-178.76   26
 40  \w     24.00 124.00   1.00    4.00    --   54.00  77.00   0.00  100
 41  \w     29.00 128.00   1.00    4.00    --   58.00  76.00  37.06   99
 42  \w     29.00 128.00   1.00    4.00    --   58.00  76.00-122.19   99
 43  \w     30.00 128.00   1.00    4.00    --   58.00  74.00 -16.03   98
 44  \w     29.00 128.00   1.00    4.00    --   58.00  76.00 157.58   99
 45  \w     28.00 128.00   1.00    4.00    --   58.00  77.00  56.34  100
 46  \w     29.00 128.00   1.00    4.00    --   58.00  75.00-178.21   99
 47  \w     30.00 128.00   1.00    4.00    --   58.00  74.00-102.32   98
 48  \w     28.00 128.00   1.00    4.00    --   58.00  77.00 -77.28  100
 49  \w     29.00 128.00   1.00    4.00    --   58.00  75.00 -44.64   99
 50  \w     28.00 128.00   1.00    4.00    --   58.00  77.00  10.69  100
 51  \w     29.00 128.00   1.00    4.00    --   58.00  76.00-152.76   99
 52  \w     28.00 128.00   1.00    4.00    --   58.00  77.00 -60.32  100
 53  \w     34.00 131.00   1.00    4.00    --   62.00  73.00  85.64   97
 54  \w     33.00 132.00   1.00    4.00    --   62.00  75.00  93.39   99
 55  \w     34.00 132.00   1.00    4.00    --   62.00  74.00 -79.18   98
 56  \w     32.00 132.00   1.00    4.00    --   62.00  77.00 179.50  100
 57  \w     33.00 132.00   1.00    4.00    --   62.00  76.00   3.34   99
 58  \w     34.00 132.00   1.00    4.00    --   62.00  74.00 -49.00   98
 59  \w     33.00 132.00   1.00    4.00    --   62.00  76.00 123.54   99
 60  \w     39.00 135.00   1.00    4.00    --   66.00  72.00 -70.13   96
 61  \w     36.00 136.00   1.00    4.00    --   66.00  77.00 126.57  100
 62  \w     40.00 135.00   1.00    4.00    --   66.00  70.00  61.92   95
 63  \w     39.00 135.00   1.00    4.00    --   66.00  71.00 160.87   96
 64  \w     36.00 136.00   1.00    4.00    --   66.00  77.00-126.61  100
 65  \w     47.00 138.00   1.00    4.00    --   70.00  65.00 -29.88   91
 66  \w     46.00 138.00   1.00    4.00    --   70.00  67.00  89.68   92
 67  \w     43.00 139.00   1.00    4.00    --   70.00  71.00-141.14   96
 68  \w     40.00 140.00   1.00    4.00    --   70.00  77.00  28.11  100
 69  \w     44.00 144.00   1.00    4.00    --   74.00  77.00 -21.01  100
 70  \w     45.00 144.00   1.00    4.00    --   74.00  75.00 -96.59   99
 71  \w     47.00 143.00   1.00    4.00    --   74.00  72.00 -78.60   96
 72  \w     50.00 142.00   1.00    4.00    --   74.00  68.00-159.62   92
 73  \w     52.00 144.00   1.00    4.00    --   74.00  50.00  49.59   92
 74  \w     50.00 142.00   1.00    4.00    --   74.00  68.00 141.44   92
 75  \w     49.00 148.00   1.00    4.00    --   78.00  76.00  48.65   99
 76  \w     53.00 146.00   1.00    4.00    --   78.00  69.00-172.71   93
 77  \w     56.00 148.00   1.00    4.00    --   78.00  49.00 -78.07   92
 78  \w     55.00 146.00   1.00    4.00    --   78.00  66.00  -3.28   91
 79  \w     52.00 152.00   1.00    8.00    --   82.00  77.00  99.37  100
 80  \w     55.00 151.00   1.00    8.00    --   82.00  72.00 153.47   96
 81  \w     53.00 152.00   1.00    8.00    --   82.00  76.00  74.51   99
 82  \w     53.00 152.00   1.00    8.00    --   82.00  75.00 -67.00   99
 83  \w     58.00 156.00   1.00    8.00    --   86.00  74.00  68.50   98
 84  \w     65.00 154.00   1.00    8.00    --   86.00  60.00 108.12   89
 85  \w     64.00 154.00   1.00    8.00    --   86.00  61.00  45.84   90
 86  \w     56.00 156.00   1.00    8.00    --   86.00  77.00 140.45  100
 87  \w     62.00 154.00   1.00    8.00    --   86.00  67.00-124.16   92
 88  \w     63.00 159.00   1.00    8.00    --   90.00  71.00 -22.41   96
 89  \w     69.00 159.00   1.00    8.00    --   90.00  55.00 -22.27   90
 90  \w     62.00 160.00   1.00    8.00    --   90.00  74.00 -17.10   98
 91  \w     69.00 162.00   1.00    8.00    --   94.00  69.00 132.69   93
 92  \w     64.00 164.00   1.00    8.00    --   94.00  77.00  27.36  100
 93  \w     65.00 164.00   1.00    8.00    --   94.00  75.00-178.65   99
 94  \w     71.00 167.00   1.00    8.00    --   98.00  72.00 135.68   96
 95  \w     75.00 169.00   1.00    8.00    --   98.00  46.00 126.78   94
 96  \w     75.00 166.00   1.00    8.00    --   98.00  65.00 -52.84   91
 97  \w     81.00 172.00   1.00    8.00    --  102.00  53.00 101.91   91
 98  \w     75.00 171.00   1.00    8.00    --  102.00  72.00   3.67   96
 99  \w     85.00 176.00   1.00    8.00    --  106.00  53.00-109.96   91
100  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 -30.00  100
101  \w     78.00 178.00   1.00    8.00    --  108.00  77.00  30.00  100
102  \w     78.00 178.00   1.00    8.00    --  108.00  77.00  90.00  100
103  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 -60.00  100
104  \w     78.00 178.00   1.00    8.00    --  108.00  77.00-180.00  100
105  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 -90.00  100
106  \w     78.00 178.00   1.00    8.00    --  108.00  77.00-150.00  100
107  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 120.00  100
108  \w     78.00 178.00   1.00    8.00    --  108.00  77.00-120.00  100
109  \w     36.00 116.00   1.00    8.00    --  108.00-111.00-180.00   80
110  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 150.00  100
111  \w     36.00 116.00   1.00    8.00    --  108.00-111.00   0.00   80
112  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 -30.00   90
113  \w     78.00 178.00   1.00    8.00    --  108.00  77.00  60.00  100
114  \w    100.00 178.00   1.00    8.00    --  108.00 111.00 150.00   78
115  \w     41.00 131.00   1.00    8.00    --  108.00 -64.00  60.00   90
116  \w     36.00 146.00   1.00    8.00    --  108.00 -92.00-150.00  110
117  \w     36.00 116.00   1.00    8.00    --  108.00-111.00  90.00   80
118  \w     83.00 178.00   1.00    8.00    --  108.00  41.00 -61.88   95
119  \w     78.00 178.00   1.00    8.00    --  108.00  77.00  19.15  100
120  \w     82.00 178.00   1.00    8.00    --  108.00  38.00  90.00   96
121  \w     82.00 178.00   1.00    8.00    --  108.00  38.00 -90.00   96
122  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 120.00   90
123  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 -60.00   90
124  \w     85.00 175.00   1.00    8.00    --  108.00  64.00-150.00   90
125  \w     85.00 175.00   1.00    8.00    --  108.00  64.00-180.00   90
126  \w     85.00 175.00   1.00    8.00    --  108.00  64.00  90.00   90
127  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 -90.00   90
128  \w     82.00 178.00   1.00    8.00    --  108.00  38.00-120.00   96
129  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 150.00   90
130  \w     78.00 178.00   1.00    8.00    --  108.00  77.00   0.00  100
131  \w     85.00 175.00   1.00    8.00    --  108.00  64.00-120.00   90
132  \w     38.00 138.00   1.00    8.00    --  108.00 -77.00-120.00  100
133  \f    120.00 240.00   1.00    1.00   0.00   0.00 -60.00    --   120
134  \f      0.00 120.00   1.00    1.00   0.00   0.00  60.00    --   120
135  \f    240.00 360.00   1.00    1.00   0.00   0.00 -40.00    --   120
136  \f    120.00 240.00   1.00    1.00   0.00   0.00  60.00    --   120
137  \f      0.00 120.00   1.00    1.00   0.00   0.00 -60.00    --   120
138  \f    120.00 240.00   1.00    1.00   0.00   0.00  40.00    --   120
139  \f      0.00 120.00   1.00    1.00   0.00   0.00  40.00    --   120
140  \f      0.00 120.00   1.00    1.00   0.00   0.00 -40.00    --   120
141  \f    120.00 240.00   1.00    1.00   0.00   0.00 -40.00    --   120
142  \f    120.00 240.00   1.00    4.00  54.00  54.00 -40.00    --   120
143  \f      0.00 120.00   1.00    4.00  54.00  54.00  60.00    --   120
144  \f      0.00 120.00   1.00    4.00  54.00  54.00 -60.00    --   120
145  \f      0.00 120.00   1.00    4.00  54.00  54.00  40.00    --   120
146  \f    120.00 240.00   1.00    4.00  54.00  54.00  40.00    --   120
147  \f      0.00 120.00   1.00    4.00  54.00  54.00 -40.00    --   120
148  \f    240.00 355.00   1.00    4.00  54.00  54.00 -40.00    --   115
149  \f    120.00 240.00   1.00    4.00  54.00  54.00  60.00    --   120
150  \f    120.00 240.00   1.00    4.00  54.00  54.00 -60.00    --   120
151  \f      0.00 270.00   1.00    0.50   0.00   0.00   0.00    --   270
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0521505000
_diffrn_orient_matrix_UB_12      -0.0632522000
_diffrn_orient_matrix_UB_13      -0.0456826000
_diffrn_orient_matrix_UB_21      0.0945141000
_diffrn_orient_matrix_UB_22      0.0436883000
_diffrn_orient_matrix_UB_23      -0.0269369000
_diffrn_orient_matrix_UB_31      0.0905335000
_diffrn_orient_matrix_UB_32      -0.0515339000
_diffrn_orient_matrix_UB_33      0.0576152000
_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  0.0374
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            219388
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.780
_diffrn_reflns_theta_min         3.764
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.332
_exptl_absorpt_correction_T_max  0.798
_exptl_absorpt_correction_T_min  0.560
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1678
_exptl_crystal_size_max          0.174
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.049
_refine_diff_density_max         0.745
_refine_diff_density_min         -0.645
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     811
_refine_ls_number_reflns         14522
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0251
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0253P)^2^+3.0191P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0601
_refine_ls_wR_factor_ref         0.0611
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13711
_reflns_number_total             14522
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt00413c2.cif
_cod_data_source_block           ba_sb64_sq
_cod_original_cell_volume        3805.61(8)
_cod_database_code               7042695
_audit_block_refno               2723
_chemical_oxdiff_formula         'C41.75 H41 Cl3 N1 P2 Zr1'
_chemical_oxdiff_usercomment     'sb_dh36_2, irregular, yellow'
_shelx_estimated_absorpt_t_max   0.618
_shelx_estimated_absorpt_t_min   0.618
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_shelxl_version_number           2016/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C20(H20A,H20B), C51(H51A,H51B), C70(H70A,H70B)
2.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), C54(H54), C55(H55), C56(H56),
  C57(H57), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C65(H65),
 C66(H66), C67(H67), C68(H68), C69(H69), C73(H73), C74(H74), C75(H75), C76(H76),
  C78(H78), C79(H79), C80(H80), C81(H81), C82(H82), C84(H84), C85(H85),
 C86(H86), C87(H87), C88(H88)
;
_shelx_fab_checksum              66118
_audit_block_usercomment         'sb_dh36_2, irregular, yellow'
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.194
_oxdiff_exptl_absorpt_empirical_full_min 0.829
_shelx_res_checksum              45457
_cell_oxdiff_length_a            11.44486(13)
_cell_oxdiff_length_b            17.6843(2)
_cell_oxdiff_length_c            19.9828(3)
_cell_oxdiff_angle_alpha         80.0131(11)
_cell_oxdiff_angle_beta          88.4840(10)
_cell_oxdiff_angle_gamma         72.8933(10)
_cell_oxdiff_volume              3805.61(8)
_cell_oxdiff_measurement_reflns_used 111747