Fluorescent phenoxy benzoxazole complexes of zirconium and hafnium: synthesis, structure and photo-physical behaviour.
Kuhlmann, Lisa; Methling, Rafael; Simon, Jasmin; Neumann, Beate; Stammler, Hans-Georg; Strassert, Cristian A.; Mitzel, Norbert W.; Dalton transactions (Cambridge, England : 2003) 47 (2018) 11245–11252; doi:10.1039/c8dt01757c

data_7047156
_publ_section_title
;
 Fluorescent phenoxy benzoxazole complexes of zirconium and hafnium:
 synthesis, structure and photo-physical behaviour.
;
_journal_issue                   32
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11245
_journal_page_last               11252
_journal_paper_doi               10.1039/c8dt01757c
_journal_volume                  47
_journal_year                    2018
_chemical_formula_moiety         'C42 H38 Hf N2 O6'
_chemical_formula_sum            'C42 H38 Hf N2 O6'
_chemical_formula_weight         845.23
_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_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-11-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.07 svn.r3352 for OlexSys, GUI svn.r5261)
;
_audit_update_record
;
2018-01-11 deposited with the CCDC.
2018-07-26 downloaded from the CCDC.
;
_cell_angle_alpha                90.0
_cell_angle_beta                 106.436(3)
_cell_angle_gamma                90.0
_cell_formula_units_Z            4
_cell_length_a                   10.1170(2)
_cell_length_b                   29.0237(7)
_cell_length_c                   12.8277(3)
_cell_measurement_reflns_used    77999
_cell_measurement_temperature    99.99(14)
_cell_measurement_theta_max      32.0890
_cell_measurement_theta_min      2.1610
_cell_volume                     3612.71(15)
_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
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0951
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_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      3.00  93.00   0.75    8.00    --   24.87  38.00   0.00  120
  2  \w     47.00  90.50   0.75    8.00    --   24.87  57.00  90.00   58
  3  \w      7.00  90.25   0.75    8.00    --   24.87  38.00 -90.00  111
  4  \w     -7.00  31.25   0.75    8.00    --   24.87 -99.00-180.00   51
  5  \w    -10.00  16.25   0.75    8.00    --  -23.50  57.00  60.00   35
  6  \w     37.00  94.00   0.75    8.00    --   24.87 178.00 -30.00   76
  7  \w     35.00  61.25   0.75    8.00    --   24.87 178.00-150.00   35
  8  \w    -61.00 -35.50   0.75    8.00    --  -23.50-178.00  90.00   34
  9  \w    -62.00 -35.00   0.75    8.00    --  -23.50-178.00 120.00   36
 10  \w     34.00 100.00   0.75    8.00    --   24.87-178.00 120.00   88
 11  \w     52.75  85.00   0.75    8.00    --   24.87-133.00  17.27   43
 12  \w     -4.00  90.50   0.75    8.00    --   24.87  77.00  30.00  126
 13  \w     23.50  85.00   0.75    8.00    --   24.87-133.00 179.43   82
 14  \w     -4.00  93.50   0.75    8.00    --   24.87  77.00 150.00  130
 15  \w     -4.00  41.00   0.75    8.00    --   24.87  77.00 -90.00   60
 16  \w     65.00  91.25   0.75    8.00    --   24.87  77.00 -90.00   35
 17  \w     35.00  68.00   0.75    8.00    --   24.87 178.00 150.00   44
 18  \w    -44.00  33.25   0.75    8.00    --   24.87 -57.00 -60.00  103
 19  \w      7.00  34.00   0.75    8.00    --   24.87-133.00  17.27   36
 20  \w    -95.00  46.75   0.75    8.00    --  -23.50   0.00 -60.00  189
 21  \w    -85.00  -9.25   0.75    8.00    --  -23.50 135.00-163.61  101
 22  \w    -95.00  46.75   0.75    8.00    --  -23.50   0.00   0.00  189
 23  \w    -95.00  46.75   0.75    8.00    --  -23.50   0.00 -30.00  189
 24  \w    -92.00  -5.00   0.75    8.00    --  -23.50 -57.00-120.00  116
 25  \w    -97.00 -36.25   0.75    8.00    --  -23.50-178.00 150.00   81
 26  \w    -65.00  19.00   0.75    8.00    --  -23.50 100.00  18.08  112
 27  \w    -95.00  46.75   0.75    8.00    --  -23.50   0.00-180.00  189
 28  \w    -95.00  46.75   0.75    8.00    --  -23.50   0.00-150.00  189
 29  \w    -95.00  46.75   0.75    8.00    --  -23.50   0.00-120.00  189
 30  \w    -95.00  46.75   0.75    8.00    --  -23.50   0.00 -90.00  189
 31  \w    -10.00  71.00   0.75    8.00    --   24.87-111.00-104.34  108
 32  \w     -4.00  92.75   0.75    8.00    --   24.87  77.00-180.00  129
 33  \w      6.00  93.00   0.75    8.00    --   24.87  57.00  90.00  116
 34  \w    -44.00  52.75   0.75    8.00    --   24.87 -77.00-150.00  129
 35  \w    -95.00 -68.00   0.75    8.00    --  -23.50   0.00  60.00   36
 36  \w    -95.00  46.75   0.75    8.00    --  -23.50   0.00  30.00  189
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0554486000
_diffrn_orient_matrix_UB_12      0.0099995000
_diffrn_orient_matrix_UB_13      0.0404184000
_diffrn_orient_matrix_UB_21      -0.0472405000
_diffrn_orient_matrix_UB_22      0.0090837000
_diffrn_orient_matrix_UB_23      0.0262719000
_diffrn_orient_matrix_UB_31      0.0060446000
_diffrn_orient_matrix_UB_32      -0.0203603000
_diffrn_orient_matrix_UB_33      0.0316297000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0448
_diffrn_reflns_av_unetI/netI     0.0814
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            349734
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         32.276
_diffrn_reflns_theta_min         1.798
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.924
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.433
_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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.554
_exptl_crystal_description       block
_exptl_crystal_F_000             1696
_exptl_crystal_recrystallization_method
'non-merohedrically twinned by a rotation of 2.9 deg. around [-0.43 0.01 -0.90] (reciprocal) or [-0.69 0.00 -0.72] (direct), ratio 52:48. Both domains were taken into account during data reduction and refinement'
_exptl_crystal_size_max          0.347
_exptl_crystal_size_mid          0.142
_exptl_crystal_size_min          0.043
_refine_diff_density_max         1.736
_refine_diff_density_min         -1.086
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     467
_refine_ls_number_reflns         28958
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0323
_refine_ls_R_factor_gt           0.0260
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0343P)^2^+2.1227P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0664
_refine_ls_wR_factor_ref         0.0672
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24765
_reflns_number_total             28958
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 2.9070\% 
 around [-0.43 0.01 -0.90] (reciprocal) or [-0.69 0.00 -0.72] (direct)
;
_cod_data_source_file            c8dt01757c2.cif
_cod_data_source_block           compound5
_cod_depositor_comments
'Adding full bibliography for 7047149--7047158.cif.'
_cod_original_cell_volume        3612.74(15)
_cod_database_code               7047156
_chemical_oxdiff_formula         C43H43HfN4O4
_cell_oxdiff_angle_alpha         89.9284(12)
_cell_oxdiff_angle_beta          106.4191(16)
_cell_oxdiff_angle_gamma         90.0900(12)
_cell_oxdiff_length_a            10.11650(19)
_cell_oxdiff_length_b            29.0286(3)
_cell_oxdiff_length_c            12.8251(2)
_cell_oxdiff_measurement_reflns_used 77999
_cell_oxdiff_volume              3612.74(10)
_olex2_date_sample_data_collection 2016-10-11
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5217(4) 0.4783(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C8(H8), C13(H13), C14(H14), C15(H15),
 C16(H16), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C25(H25), C30(H30),
  C31(H31), C32(H32), C33(H33)
3.b Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,
 H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C)
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.094
_oxdiff_exptl_absorpt_empirical_full_min 0.673
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_shelx_shelxl_version_number     2016/4