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_7042694
_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         'C38 H32 Hf I3 N P2, C7 H8'
_chemical_formula_sum            'C45 H40 Hf I3 N P2'
_chemical_formula_weight         1215.91
_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/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_sb68
_audit_creation_date             2016-07-06
_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                 101.9429(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3761(2)
_cell_length_b                   17.07238(16)
_cell_length_c                   20.1630(3)
_cell_measurement_reflns_used    38775
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      31.8460
_cell_measurement_theta_min      3.4140
_cell_volume                     4168.01(10)
_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, 2009-15); 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 0.962
_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    -42.00  48.00   0.50   15.00    --   27.02 -57.00 -30.00  180
  2  \w     -3.00  97.00   0.50   15.00    --   27.02  77.00   0.00  200
  3  \w    -20.00  69.00   0.50   15.00    --   27.02 -99.00 -90.00  178
  4  \w    -20.00  69.00   0.50   15.00    --   27.02 -99.00  90.00  178
  5  \w    -45.00  53.00   0.50   15.00    --   27.02 -38.00-150.00  196
  6  \w      2.00  99.00   0.50   15.00    --   27.02  38.00-120.00  194
  7  \w    -42.00  48.00   0.50   15.00    --   27.02 -57.00 150.00  180
  8  \w     -3.00  97.00   0.50   15.00    --   27.02  77.00-180.00  200
  9  \w     -3.00  97.00   0.50   15.00    --   27.02  77.00 -90.00  200
 10  \w      7.00  96.00   0.50   15.00    --   27.02  57.00 120.00  178
 11  \w     -3.00  97.00   0.50   15.00    --   27.02  77.00  90.00  200
 12  \w    -20.00  31.00   0.50   15.00    --   27.02 -99.00 -30.00  102
 13  \w    -42.00  48.00   0.50   15.00    --   27.02 -57.00 120.00  180
;
_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      -0.0214492000
_diffrn_orient_matrix_UB_12      -0.0057092000
_diffrn_orient_matrix_UB_13      -0.0351017000
_diffrn_orient_matrix_UB_21      -0.0032839000
_diffrn_orient_matrix_UB_22      0.0411518000
_diffrn_orient_matrix_UB_23      -0.0048286000
_diffrn_orient_matrix_UB_31      0.0544128000
_diffrn_orient_matrix_UB_32      0.0002419000
_diffrn_orient_matrix_UB_33      -0.0061178000
_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  0.0639
_diffrn_reflns_av_unetI/netI     0.0575
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            111112
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.372
_diffrn_reflns_theta_min         2.920
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.834
_exptl_absorpt_correction_T_max  0.912
_exptl_absorpt_correction_T_min  0.717
_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
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.938
_exptl_crystal_description       block
_exptl_crystal_F_000             2312
_exptl_crystal_size_max          0.103
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.056
_refine_diff_density_max         2.483
_refine_diff_density_min         -1.400
_refine_diff_density_rms         0.197
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.161
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         14368
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.161
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0298P)^2^+14.9794P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0917
_refine_ls_wR_factor_ref         0.0946
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10980
_reflns_number_total             14368
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt00413c2.cif
_cod_data_source_block           ba_sb68_4
_cod_original_cell_volume        4168.04(10)
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               7042694
_audit_block_refno               2738
_audit_block_usercomment         'sb-dh45,block, yellow'
_shelx_estimated_absorpt_t_max   0.644
_shelx_estimated_absorpt_t_min   0.644
_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), C52(H52), C53(H53), C54(H54),
  C55(H55), C56(H56)
2.c Idealised Me refined as rotating group:
 C57(H57A,H57B,H57C)
;
_shelx_res_checksum              97734
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            12.3761(2)
_cell_oxdiff_length_b            17.07238(16)
_cell_oxdiff_length_c            20.1630(3)
_cell_oxdiff_angle_alpha         90.0061(10)
_cell_oxdiff_angle_beta          101.9429(13)
_cell_oxdiff_angle_gamma         90.0098(11)
_cell_oxdiff_volume              4168.04(10)
_cell_oxdiff_measurement_reflns_used 38775
_oxdiff_exptl_absorpt_empirical_full_min 0.880
_oxdiff_exptl_absorpt_empirical_full_max 1.121
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_twin_items               2
_oxdiff_twin_integration_method  simultaneous
_twin_special_details
;
Component 2 rotated by 4.5797\%
 around [-0.06 1.00 -0.00] (reciprocal) or [-0.12 0.99 -0.02] (direct)
Computed twin ratios:
Twin 1: 83.41% (11395 common observations, 1174 merged)
Twin 2: 16.59% (1872 common observations, 1174 merged)
;