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_7042692
_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            'C62 H69 B N P2 Zr'
_chemical_formula_weight         992.15
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_ms34
_audit_creation_date             2017-01-30
_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                67.552(2)
_cell_angle_beta                 66.932(2)
_cell_angle_gamma                66.047(3)
_cell_formula_units_Z            4
_cell_length_a                   17.3823(5)
_cell_length_b                   17.7265(5)
_cell_length_c                   21.7567(5)
_cell_measurement_reflns_used    36614
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      30.4910
_cell_measurement_theta_min      3.0150
_cell_volume                     5435.2(3)
_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    'SIR2014 (Giacovazzo et al., 2014)'
_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 0.995
_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    -44.00   5.00   0.50   20.00    --   26.43 -79.00 -31.30   98
  2  \w     31.00  58.00   0.50   20.00    --   26.43 -79.00 -31.30   54
  3  \w      0.00  27.00   0.50   20.00    --   26.43 -79.00  45.44   54
  4  \w     33.00  58.00   0.50   20.00    --   26.43 -79.00  45.44   50
  5  \w    -38.00  58.00   0.50   20.00    --   26.43 -80.00  28.84  192
  6  \w    -44.00  58.00   0.50   20.00    --   26.43 -79.00 122.51  204
  7  \w     31.00  58.00   0.50   20.00    --   26.43 -80.00  76.22   54
  8  \w     -4.00  56.00   0.50   20.00    --   26.43  77.00  30.00  120
  9  \w     -4.00  54.00   0.50   20.00    --   26.43  77.00 -90.00  116
 10  \w     -4.00  32.00   0.50   20.00    --   26.43  77.00 150.00   72
 11  \w     69.00  95.00   0.50   20.00    --   26.43  77.00 150.00   52
 12  \w     14.00  95.00   0.50   20.00    --   26.43  57.00 -30.00  162
 13  \w     15.00  42.00   0.50   20.00    --   26.43  57.00  90.00   54
 14  \w     67.00  95.00   0.50   20.00    --   26.43  57.00-120.00   56
 15  \w     30.00  56.00   0.50   20.00    --   26.43 -77.00 -90.00   52
 16  \w      2.00  37.00   0.50   20.00    --   26.43  38.00 -30.00   70
 17  \w      7.00  58.00   0.50   20.00    --   26.43  77.00-180.00  102
 18  \w     70.00  97.00   0.50   20.00    --   26.43  77.00-180.00   54
 19  \w      2.00  99.00   0.50   20.00    --   26.43  38.00 120.00  194
 20  \w    -28.00  55.00   0.50   20.00    --   26.43 -77.00-120.00  166
 21  \w     24.00  56.00   0.50   20.00    --   26.43 -77.00 -60.00   64
 22  \w     60.00  86.00   0.50   20.00    --   26.43  77.00   0.00   52
 23  \w    -44.00  58.00   0.50   20.00    --   26.43 -80.00-162.10  204
 24  \w      1.00  99.00   0.50   20.00    --   26.43  38.00   0.00  196
 25  \w      5.00  95.00   0.50   20.00    --   26.43  57.00 120.00  180
 26  \w      1.00  99.00   0.50   20.00    --   26.43  38.00-120.00  196
 27  \w    -42.00  47.00   0.50   20.00    --   26.43 -57.00  90.00  178
 28  \w    -42.00  47.00   0.50   20.00    --   26.43 -57.00   0.00  178
 29  \w    -44.00  58.00   0.50   20.00    --   26.43 -80.00-162.10  204
 30  \w    -42.00 -17.00   0.50   20.00    --   26.43 -57.00 -90.00   50
 31  \w    -42.00  47.00   0.50   20.00    --   26.43 -57.00-150.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Agilent 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      0.0279539000
_diffrn_orient_matrix_UB_12      0.0256663000
_diffrn_orient_matrix_UB_13      -0.0114792000
_diffrn_orient_matrix_UB_21      0.0371615000
_diffrn_orient_matrix_UB_22      -0.0361274000
_diffrn_orient_matrix_UB_23      -0.0053629000
_diffrn_orient_matrix_UB_31      -0.0011867000
_diffrn_orient_matrix_UB_32      0.0098920000
_diffrn_orient_matrix_UB_33      -0.0344948000
_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  0.0928
_diffrn_reflns_av_unetI/netI     0.0625
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            243662
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.577
_diffrn_reflns_theta_min         2.595
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.300
_exptl_absorpt_correction_T_max  0.984
_exptl_absorpt_correction_T_min  0.950
_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            'dark yellow'
_exptl_crystal_density_diffrn    1.212
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2092
_exptl_crystal_size_max          0.248
_exptl_crystal_size_mid          0.181
_exptl_crystal_size_min          0.068
_refine_diff_density_max         1.394
_refine_diff_density_min         -0.525
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1035
_refine_ls_number_reflns         33234
_refine_ls_number_restraints     57
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0758
_refine_ls_R_factor_gt           0.0506
_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^)+(0.0580P)^2^+0.1560P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1148
_refine_ls_wR_factor_ref         0.1247
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23925
_reflns_number_total             33234
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt00413c2.cif
_cod_data_source_block           ba_ms34_sq
_cod_database_code               7042692
_audit_block_refno               2438
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.971
_reflns_odcompleteness_completeness 99.89
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 C101, C102, C103, C104, C105, C106, C201, C202, C203, C204, C205
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Ternary CH refined with riding coordinates:
 C26(H26), C76(H76)
3.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C57(H57A,H57B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C23(H23),
  C24(H24), C25(H25), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
 C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C53(H53), C54(H54), C55(H55),
  C56(H56), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C65(H65),
 C66(H66), C67(H67), C68(H68), C69(H69), C72(H72), C73(H73), C74(H74), C75(H75),
  C78(H78), C79(H79), C80(H80), C81(H81), C82(H82), C84(H84), C85(H85),
 C86(H86), C87(H87), C88(H88), C101(H101), C102(H102), C103(H103), C104(H104),
 C105(H105), C106(H106), C201(H201), C202(H202), C203(H203), C204(H204),
 C205(H205), C206(H206)
3.d Fitted hexagon refined as free rotating group:
 C101(C102,C103,C104,C105,C106), C201(C202,C203,C204,C205,C206)
3.e Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C90(H90A,H90B,
 H90C), C92(H92A,H92B,H92C), C94(H94A,H94B,H94C)
;
_shelx_fab_checksum              5524
_audit_block_usercomment         'MS606 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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.229
_oxdiff_exptl_absorpt_empirical_full_min 0.754
_shelx_res_checksum              18906
_cell_oxdiff_length_a            17.3823(5)
_cell_oxdiff_length_b            17.7265(5)
_cell_oxdiff_length_c            21.7567(5)
_cell_oxdiff_angle_alpha         67.552(2)
_cell_oxdiff_angle_beta          66.932(2)
_cell_oxdiff_angle_gamma         66.047(3)
_cell_oxdiff_volume              5435.2(2)
_cell_oxdiff_measurement_reflns_used 36614