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_7042693
_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 I3 N P2 Zr, 1.5(C H2 Cl2)'
_chemical_formula_sum            'C39.5 H35 Cl3 I3 N P2 Zr'
_chemical_formula_weight         1163.89
_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_ms21
_audit_creation_date             2017-03-16
_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                104.1686(10)
_cell_angle_beta                 96.0145(9)
_cell_angle_gamma                116.0700(14)
_cell_formula_units_Z            2
_cell_length_a                   12.32855(16)
_cell_length_b                   12.57691(19)
_cell_length_c                   15.78601(14)
_cell_measurement_reflns_used    69205
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      28.9060
_cell_measurement_theta_min      2.7560
_cell_volume                     2067.45(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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 0.999
_diffrn_measured_fraction_theta_max 0.964
_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     10.00  49.00   0.50   15.00    --   18.69 -77.00  30.00   78
  2  \w     -3.00  53.00   0.50   15.00    --   18.69  57.00 150.00  112
  3  \w     -2.00  25.00   0.50   15.00    --   18.69  57.00  30.00   54
  4  \w    -50.00  49.00   0.50   15.00    --   18.69 -77.00   0.00  198
  5  \w    -10.00  89.00   0.50   15.00    --   18.69  77.00-120.00  198
  6  \w    -47.00  49.00   0.50   15.00    --   18.69 -77.00 120.00  192
  7  \w    -47.00  49.00   0.50   15.00    --   18.69 -77.00 -60.00  192
  8  \w     19.00  77.00   0.50   15.00    --   18.69  57.00  60.00  116
  9  \w      3.00  69.00   0.50   15.00    --   18.69  77.00 -30.00  132
 10  \w    -29.00  49.00   0.50   15.00    --   18.69 -77.00-120.00  156
 11  \w     -3.00  40.00   0.50   15.00    --   18.69  57.00-150.00   86
 12  \w    -46.00  49.00   0.50   15.00    --   18.69 -77.00-180.00  190
 13  \w     21.00  47.00   0.50   15.00    --   18.69 -77.00  60.00   52
 14  \w    -43.00   6.00   0.50   15.00    --   18.69 -77.00  30.00   98
 15  \w    -11.00  89.00   0.50   15.00    --   18.69  77.00-150.00  200
 16  \w    -50.00  40.00   0.50   15.00    --   18.69 -57.00  90.00  180
 17  \w    -51.00  49.00   0.50   15.00    --   18.69 -77.00 -30.00  200
 18  \w    -11.00  89.00   0.50   15.00    --   18.69  77.00   0.00  200
 19  \w    -51.00  49.00   0.50   15.00    --   18.69 -77.00-150.00  200
 20  \w    -50.00  40.00   0.50   15.00    --   18.69 -57.00   0.00  180
 21  \w    -51.00  49.00   0.50   15.00    --   18.69 -77.00 -90.00  200
 22  \w     -3.00  87.00   0.50   15.00    --   18.69  57.00 -30.00  180
 23  \w     -3.00  87.00   0.50   15.00    --   18.69  57.00  90.00  180
 24  \w    -51.00  49.00   0.50   15.00    --   18.69 -77.00-180.00  200
 25  \w    -54.00  63.00   0.50   15.00    --   18.69 -19.00 150.00  234
 26  \w    -54.00  92.00   0.50   15.00    --   18.69   0.00   0.00  292
 27  \w    -54.00  92.00   0.50   15.00    --   18.69   0.00 120.00  292
 28  \w    -54.00  92.00   0.50   15.00    --   18.69   0.00 240.00  292
 29  \f      0.00 120.00   0.50   15.00  40.00  18.69   0.00    --   240
 30  \f      0.00 120.00   0.50   15.00  18.69  18.69 -20.00    --   240
 31  \f      0.00 120.00   0.50   15.00  18.69  18.69  20.00    --   240
 32  \f      0.00 120.00   0.50   15.00  18.69  18.69 -40.00    --   240
 33  \f      0.00 120.00   0.50   15.00  18.69  18.69  40.00    --   240
 34  \f      0.00 120.00   0.50   15.00  18.69  18.69 -60.00    --   240
 35  \f      0.00 120.00   0.50   15.00  18.69  18.69  60.00    --   240
 36  \w    -51.00  49.00   0.50   15.00    --   18.69 -77.00  90.00  200
 37  \f    120.00 217.00   0.50   15.00  40.00  18.69   0.00    --   194
;
_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      0.0446627000
_diffrn_orient_matrix_UB_12      0.0323545000
_diffrn_orient_matrix_UB_13      -0.0220877000
_diffrn_orient_matrix_UB_21      0.0436373000
_diffrn_orient_matrix_UB_22      0.0372617000
_diffrn_orient_matrix_UB_23      0.0421879000
_diffrn_orient_matrix_UB_31      0.0215101000
_diffrn_orient_matrix_UB_32      -0.0444298000
_diffrn_orient_matrix_UB_33      -0.0039527000
_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  0.0402
_diffrn_reflns_av_unetI/netI     0.0198
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            146604
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.070
_diffrn_reflns_theta_min         2.598
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.806
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.522
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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    1.870
_exptl_crystal_description       needle
_exptl_crystal_F_000             1118
_exptl_crystal_size_max          0.206
_exptl_crystal_size_mid          0.076
_exptl_crystal_size_min          0.043
_refine_diff_density_max         0.951
_refine_diff_density_min         -0.673
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     479
_refine_ls_number_reflns         10645
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0271
_refine_ls_R_factor_gt           0.0221
_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^)+(0.0185P)^2^+1.9629P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0456
_refine_ls_wR_factor_ref         0.0471
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9648
_reflns_number_total             10645
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt00413c2.cif
_cod_data_source_block           ba_ms21
_cod_original_cell_volume        2067.44(5)
_cod_original_formula_sum        'C39.50 H35 Cl3 I3 N P2 Zr'
_cod_database_code               7042693
_audit_block_refno               2196
_chemical_oxdiff_formula         'C39.5 H35 Cl3 I3 N P2 Zr'
_chemical_oxdiff_usercomment     'MS461, needle, yellow'
_shelx_estimated_absorpt_t_max   0.767
_shelx_estimated_absorpt_t_min   0.767
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Restrained distances
 C39A-Cl1A \\sim C39A-Cl2 \\sim C39B-Cl1B \\sim C39B-Cl2
 with sigma of 0.02
 Cl2-Cl1A \\sim Cl2-Cl1B
 with sigma of 0.02
3. Others
 Sof(C39B)=Sof(H39C)=Sof(H39D)=Sof(Cl1B)=1-FVAR(1)
 Sof(C39A)=Sof(H39A)=Sof(H39B)=Sof(Cl1A)=FVAR(1)
 Fixed Sof: Cl3(0.5) Cl4(0.5) C40(0.5) H40A(0.5) H40B(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C20(H20A,H20B), C39A(H39A,H39B), C39B(H39C,H39D), C40(H40A,H40B)
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)
;
_audit_block_usercomment         'MS461, needle, 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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.164
_oxdiff_exptl_absorpt_empirical_full_min 0.813
_shelx_res_checksum              88660
_cell_oxdiff_length_a            12.32855(16)
_cell_oxdiff_length_b            12.57691(19)
_cell_oxdiff_length_c            15.78601(14)
_cell_oxdiff_angle_alpha         104.1686(10)
_cell_oxdiff_angle_beta          96.0145(9)
_cell_oxdiff_angle_gamma         116.0700(14)
_cell_oxdiff_volume              2067.45(4)
_cell_oxdiff_measurement_reflns_used 69205