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_7042696
_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            'C47 H45 Cl N O0.5 P2 Zr'
_chemical_formula_weight         820.45
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_sb71
_audit_creation_date             2016-08-08
_audit_creation_method
;
Olex2 1.2
(compiled Dec 12 2016 15:58:59 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2017-03-17 deposited with the CCDC.
2017-04-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.1276(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.9791(3)
_cell_length_b                   11.12020(16)
_cell_length_c                   38.2266(5)
_cell_measurement_reflns_used    29506
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      31.8860
_cell_measurement_theta_min      3.2530
_cell_volume                     7916.1(2)
_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 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     -3.00  99.00   0.50   25.00    --   28.16  77.00-150.00  204
  2  \w      7.00  97.00   0.50   25.00    --   28.16  57.00 -30.00  180
  3  \w    -20.00  72.00   0.50   25.00    --   28.16 -99.00 120.00  184
  4  \w    -44.00  56.00   0.50   25.00    --   28.16 -38.00 -30.00  200
  5  \w     -3.00  99.00   0.50   25.00    --   28.16  77.00 120.00  204
  6  \w    -44.00  56.00   0.50   25.00    --   28.16 -38.00  60.00  200
  7  \w     -3.00  99.00   0.50   25.00    --   28.16  77.00  30.00  204
  8  \w    -43.00  60.00   0.50   25.00    --   28.16 -77.00 -90.00  206
  9  \w    -41.00  50.00   0.50   25.00    --   28.16 -57.00-180.00  182
 10  \w     -3.00  99.00   0.50   25.00    --   28.16  77.00 -90.00  204
 11  \w      1.00 101.00   0.50   25.00    --   28.16  38.00-180.00  200
 12  \w    -20.00  72.00   0.50   25.00    --   28.16 -99.00-180.00  184
 13  \w      1.00  49.00   0.50   25.00    --   28.16  38.00 120.00   96
 14  \w    -20.00  72.00   0.50   25.00    --   28.16 -99.00   0.00  184
;
_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      -0.0240834000
_diffrn_orient_matrix_UB_12      0.0060659000
_diffrn_orient_matrix_UB_13      -0.0165751000
_diffrn_orient_matrix_UB_21      -0.0180189000
_diffrn_orient_matrix_UB_22      -0.0531432000
_diffrn_orient_matrix_UB_23      0.0035709000
_diffrn_orient_matrix_UB_31      -0.0233713000
_diffrn_orient_matrix_UB_32      0.0347519000
_diffrn_orient_matrix_UB_33      0.0083727000
_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  0.0562
_diffrn_reflns_av_unetI/netI     0.0338
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -57
_diffrn_reflns_number            125681
_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         32.287
_diffrn_reflns_theta_min         2.982
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.462
_exptl_absorpt_correction_T_max  0.991
_exptl_absorpt_correction_T_min  0.959
_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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       plate
_exptl_crystal_F_000             3400
_exptl_crystal_size_max          0.190
_exptl_crystal_size_mid          0.134
_exptl_crystal_size_min          0.027
_refine_diff_density_max         1.483
_refine_diff_density_min         -0.404
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     467
_refine_ls_number_reflns         13622
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0479
_refine_ls_R_factor_gt           0.0342
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0353P)^2^+7.7814P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0759
_refine_ls_wR_factor_ref         0.0810
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11129
_reflns_number_total             13622
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt00413c2.cif
_cod_data_source_block           ba_sb71_sq
_cod_original_formula_sum        'C47 H45 Cl N O0.50 P2 Zr'
_cod_database_code               7042696
_audit_block_refno               2751
_shelx_estimated_absorpt_t_max   0.955
_shelx_estimated_absorpt_t_min   0.955
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C40-H40 \\sim C44-H44
 with sigma of 0.02
 C41-H41 \\sim C43-H43
 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C20(H20A,H20B)
3.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)
3.c Idealised Me refined as rotating group:
 C45(H45A,H45B,H45C)
;
_shelx_fab_checksum              34286
_audit_block_usercomment         'sb561, plate, green'
_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 1.109
_oxdiff_exptl_absorpt_empirical_full_min 0.894
_shelx_res_checksum              3616
_cell_oxdiff_length_a            18.9789(4)
_cell_oxdiff_length_b            11.11995(18)
_cell_oxdiff_length_c            38.2295(8)
_cell_oxdiff_angle_alpha         90.0350(15)
_cell_oxdiff_angle_beta          101.1396(17)
_cell_oxdiff_angle_gamma         89.9771(15)
_cell_oxdiff_volume              7916.1(3)
_cell_oxdiff_measurement_reflns_used 29506