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_7042698
_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         'C44 H50 Hf N4 P2'
_chemical_formula_sum            'C44 H50 Hf N4 P2'
_chemical_formula_weight         875.31
_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_Int_Tables_number      2
_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_sb57
_audit_creation_date             2016-04-11
_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                81.2172(11)
_cell_angle_beta                 85.5974(9)
_cell_angle_gamma                61.4891(12)
_cell_formula_units_Z            2
_cell_length_a                   12.47419(13)
_cell_length_b                   12.67913(18)
_cell_length_c                   14.64329(19)
_cell_measurement_reflns_used    52008
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      32.0980
_cell_measurement_theta_min      3.3040
_cell_volume                     2011.26(5)
_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 0.998
_diffrn_measured_fraction_theta_max 0.967
_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     -4.00  97.00   0.50   20.00    --   26.43  77.00-120.00  202
  2  \w      1.00  99.00   0.50   20.00    --   26.43  38.00 150.00  196
  3  \w      5.00  95.00   0.50   20.00    --   26.43  57.00   0.00  180
  4  \w    -42.00  47.00   0.50   20.00    --   26.43 -57.00 -30.00  178
  5  \w    -42.00  47.00   0.50   20.00    --   26.43 -57.00 120.00  178
  6  \w     -4.00  97.00   0.50   20.00    --   26.43  77.00  90.00  202
  7  \w    -20.00  68.00   0.50   20.00    --   26.43 -99.00 -90.00  176
  8  \w    -46.00  52.00   0.50   20.00    --   26.43 -38.00  30.00  196
  9  \w     -4.00  97.00   0.50   20.00    --   26.43  77.00  30.00  202
 10  \w    -20.00  68.00   0.50   20.00    --   26.43 -99.00-150.00  176
 11  \w    -20.00  68.00   0.50   20.00    --   26.43 -99.00 -60.00  176
 12  \w      1.00  99.00   0.50   20.00    --   26.43  38.00 -30.00  196
 13  \w     -4.00  97.00   0.50   20.00    --   26.43  77.00-180.00  202
 14  \w     -4.00  97.00   0.50   20.00    --   26.43  77.00 -60.00  202
 15  \w      6.00  88.00   0.50   20.00    --   26.43-132.00 114.45  164
 16  \f      0.00 120.00   0.50   20.00  26.43  26.43  40.00    --   240
 17  \f      0.00 120.00   0.50   20.00  26.43  26.43 -60.00    --   240
 18  \f      0.00 120.00   0.50   20.00  26.43  26.43  60.00    --   240
 19  \f    120.00 240.00   0.50   20.00  26.43  26.43 -40.00    --   240
 20  \f    120.00 240.00   0.50   20.00  26.43  26.43  40.00    --   240
 21  \f    120.00 240.00   0.50   20.00  26.43  26.43 -60.00    --   240
 22  \f    120.00 240.00   0.50   20.00  26.43  26.43  60.00    --   240
 23  \f    240.00 360.00   0.50   20.00  26.43  26.43 -40.00    --   240
 24  \f    240.00 360.00   0.50   20.00  26.43  26.43  40.00    --   240
 25  \f    240.00 310.00   0.50   20.00  26.43  26.43 -60.00    --   140
 26  \f      0.00 120.00   0.50   20.00  26.43  26.43 -40.00    --   240
;
_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      -0.0025937000
_diffrn_orient_matrix_UB_12      0.0379168000
_diffrn_orient_matrix_UB_13      -0.0416707000
_diffrn_orient_matrix_UB_21      0.0641211000
_diffrn_orient_matrix_UB_22      -0.0230768000
_diffrn_orient_matrix_UB_23      0.0014332000
_diffrn_orient_matrix_UB_31      0.0083116000
_diffrn_orient_matrix_UB_32      -0.0464233000
_diffrn_orient_matrix_UB_33      -0.0257653000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0388
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            128166
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.437
_diffrn_reflns_theta_min         3.155
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.708
_exptl_absorpt_correction_T_max  0.863
_exptl_absorpt_correction_T_min  0.757
_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            'light yellow'
_exptl_crystal_density_diffrn    1.445
_exptl_crystal_description       irregular
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.158
_exptl_crystal_size_mid          0.106
_exptl_crystal_size_min          0.079
_refine_diff_density_max         1.360
_refine_diff_density_min         -0.748
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     466
_refine_ls_number_reflns         13994
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0237
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0198P)^2^+1.7199P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0514
_refine_ls_wR_factor_ref         0.0527
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12875
_reflns_number_total             13994
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt00413c2.cif
_cod_data_source_block           ba_sb57
_cod_database_code               7042698
_audit_block_refno               2698
_audit_block_usercomment         sb_dh_04
_chemical_oxdiff_formula         'C44 H50 N4 P Hf'
_chemical_oxdiff_usercomment     sb_dh_04
_shelx_estimated_absorpt_t_max   0.773
_shelx_estimated_absorpt_t_min   0.773
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C20(H20A,H20B)
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)
2.c Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              57004
_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 1.104
_oxdiff_exptl_absorpt_empirical_full_min 0.906
_cell_oxdiff_length_a            12.47419(13)
_cell_oxdiff_length_b            12.67913(18)
_cell_oxdiff_length_c            14.64329(19)
_cell_oxdiff_angle_alpha         81.2172(11)
_cell_oxdiff_angle_beta          85.5974(9)
_cell_oxdiff_angle_gamma         61.4891(12)
_cell_oxdiff_volume              2011.26(4)
_cell_oxdiff_measurement_reflns_used 52008