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_7042691
_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         'C45 H38 Cl N P2 Zr, C4 H10 O'
_chemical_formula_sum            'C49 H48 Cl N O P2 Zr'
_chemical_formula_weight         855.49
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_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 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_sb55
_audit_creation_date             2016-04-05
_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                 91.1112(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1149(2)
_cell_length_b                   12.1996(2)
_cell_length_c                   28.4817(4)
_cell_measurement_reflns_used    20092
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      29.8050
_cell_measurement_theta_min      3.3080
_cell_volume                     4208.72(11)
_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 0.997
_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  48.00   0.50   17.50    --   26.87  57.00-180.00   76
  2  \w     59.00  96.00   0.50   17.50    --   26.87  57.00-180.00   74
  3  \w      7.00  52.00   0.50   17.50    --   26.87  57.00 -30.00   90
  4  \w     55.00  96.00   0.50   17.50    --   26.87  57.00 -30.00   82
  5  \w    -20.00  69.00   0.50   17.50    --   26.87 -99.00 -60.00  178
  6  \w     -3.00  35.00   0.50   17.50    --   26.87  77.00-150.00   76
  7  \w     59.00  97.00   0.50   17.50    --   26.87  77.00-150.00   76
  8  \w    -18.00   9.00   0.50   17.50    --   26.87 -99.00   0.00   54
  9  \w     39.00  66.00   0.50   17.50    --   26.87 -99.00   0.00   54
 10  \w     -1.00  25.00   0.50   17.50    --   26.87  77.00  60.00   52
 11  \w    -42.00 -16.00   0.50   17.50    --   26.87 -57.00-180.00   52
 12  \w     -1.00  45.00   0.50   17.50    --   26.87 -57.00-180.00   92
 13  \w     -3.00  26.00   0.50   17.50    --   26.87  77.00 -60.00   58
 14  \w    -35.00   6.00   0.50   17.50    --   26.87 -77.00  90.00   82
 15  \w      6.00  37.00   0.50   17.50    --   26.87  77.00  90.00   62
 16  \w      6.00  31.00   0.50   17.50    --   26.87  57.00  30.00   50
 17  \w      3.00  30.00   0.50   17.50    --   26.87  38.00 -60.00   54
 18  \w     70.00  99.00   0.50   17.50    --   26.87  38.00 -60.00   58
 19  \w    -17.00  64.00   0.50   17.50    --   26.87 -99.00  30.00  162
 20  \w      3.00  99.00   0.50   17.50    --   26.87  38.00 150.00  192
 21  \w    -12.00  72.00   0.50   17.50    --   26.87-106.00 143.00  168
 22  \w    -17.00  16.00   0.50   17.50    --   26.87 -99.00-150.00   66
 23  \w     25.00  51.00   0.50   17.50    --   26.87 -99.00-150.00   52
 24  \w      1.00  90.00   0.50   17.50    --   26.87  38.00  90.00  178
;
_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      -0.0085155000
_diffrn_orient_matrix_UB_12      0.0167111000
_diffrn_orient_matrix_UB_13      0.0235062000
_diffrn_orient_matrix_UB_21      -0.0213137000
_diffrn_orient_matrix_UB_22      -0.0526549000
_diffrn_orient_matrix_UB_23      0.0052705000
_diffrn_orient_matrix_UB_31      0.0538874000
_diffrn_orient_matrix_UB_32      -0.0181094000
_diffrn_orient_matrix_UB_33      0.0063207000
_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  0.0825
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            106852
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.555
_diffrn_reflns_theta_min         3.175
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.438
_exptl_absorpt_correction_T_max  0.975
_exptl_absorpt_correction_T_min  0.960
_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            yellow
_exptl_crystal_density_diffrn    1.350
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1776
_exptl_crystal_size_max          0.121
_exptl_crystal_size_mid          0.091
_exptl_crystal_size_min          0.075
_refine_diff_density_max         1.816
_refine_diff_density_min         -0.756
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     501
_refine_ls_number_reflns         12873
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0677
_refine_ls_R_factor_gt           0.0470
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0521P)^2^+4.3808P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1104
_refine_ls_wR_factor_ref         0.1204
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9920
_reflns_number_total             12873
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt00413c2.cif
_cod_data_source_block           ba_sb55
_cod_original_cell_volume        4208.73(12)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7042691
_audit_block_refno               2690
_audit_block_usercomment         'sb_dh16, irregular, yellow'
_chemical_oxdiff_formula         'C49 H48 Cl1 N1 O1 P2 Zr'
_chemical_oxdiff_usercomment     'sb_dh16, irregular, yellow'
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.957
_reflns_odcompleteness_completeness 99.85
_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. Restrained distances
 O51-C51 \\sim O51-C53
 with sigma of 0.005
 C51-C52 \\sim C53-C54
 with sigma of 0.005
 O51-C52 \\sim O51-C54
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 O51, C51, C52, C53, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C45(H45A,H45B), C51(H51A,H51B), C53(H53A,H53B)
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), C40(H40), C41(H41), C42(H42),
  C43(H43), C44(H44)
4.c Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C54(H54A,H54B,H54C)
;
_shelx_res_checksum              57774
_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 1.146
_oxdiff_exptl_absorpt_empirical_full_min 0.901
_cell_oxdiff_length_a            12.1122(2)
_cell_oxdiff_length_b            12.2008(2)
_cell_oxdiff_length_c            28.4853(5)
_cell_oxdiff_angle_alpha         90.0316(15)
_cell_oxdiff_angle_beta          91.1040(15)
_cell_oxdiff_angle_gamma         90.0684(15)
_cell_oxdiff_volume              4208.73(13)
_cell_oxdiff_measurement_reflns_used 20092