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_7047152
_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_absolute_configuration unk
_chemical_formula_moiety         'C68 H40 Hf N4 O8, 2(C H2 Cl2)'
_chemical_formula_sum            'C70 H44 Cl4 Hf N4 O8'
_chemical_formula_weight         1389.38
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-20
_audit_creation_method
;
  Olex2 1.2-ac2
  (compiled 2012.03.27 svn.r2268, GUI svn.r4156)
;
_audit_update_record
;
2018-01-11 deposited with the CCDC.
2018-07-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.08302(9)
_cell_length_b                   18.98014(13)
_cell_length_c                   27.6971(2)
_cell_measurement_reflns_used    94740
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.2510
_cell_measurement_theta_min      2.7730
_cell_volume                     6351.98(8)
_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 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9997
_diffrn_measured_fraction_theta_max 0.9959
_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    -59.00  33.00   1.00    2.04    --  -38.50  38.00 120.00   92
  2  \w   -116.00  -5.00   1.00    2.04    --  -38.50 -19.00 -30.00  111
  3  \w     57.00 127.00   1.00    2.04    --   43.20 178.00 -30.00   70
  4  \w     13.00 115.00   1.00    2.04    --   43.20  77.00   0.00  102
  5  \w     57.00 127.00   1.00    2.04    --   43.20 178.00  90.00   70
  6  \w     13.00 115.00   1.00    2.04    --   43.20  77.00-180.00  102
  7  \w     13.00 115.00   1.00    2.04    --   43.20  77.00 120.00  102
  8  \w     13.00 115.00   1.00    2.04    --   43.20  77.00 -60.00  102
  9  \w    -25.00  68.00   1.00    2.04    --   43.20 -57.00 -90.00   93
 10  \w     11.00  40.00   1.00    2.04    --   43.20  83.00  56.18   29
 11  \w     23.00 114.00   1.00    2.04    --   43.20  38.00 120.00   91
 12  \w     13.00 115.00   1.00    2.04    --   43.20  77.00-120.00  102
 13  \w      1.00  82.00   1.00    2.04    --   43.20 -99.00-180.00   81
 14  \w     23.00 114.00   1.00    2.04    --   43.20  38.00-150.00   91
 15  \w     82.00 178.00   1.00    8.18    --  111.00  72.00-151.42   96
 16  \w     81.00 178.00   1.00    8.18    --  111.00  76.00-104.60   97
 17  \w     84.00 178.00   1.00    8.18    --  111.00  65.00-111.47   94
 18  \w     84.00 178.00   1.00    8.18    --  111.00  63.00 124.17   94
 19  \w     81.00 178.00   1.00    8.18    --  111.00  77.00-180.00   97
 20  \w     40.00 141.00   1.00    8.18    --  111.00 -77.00  30.00  101
 21  \w     81.00 178.00   1.00    8.18    --  111.00  76.00 -68.10   97
 22  \w     81.00 178.00   1.00    8.18    --  111.00  77.00 -60.00   97
 23  \w     81.00 178.00   1.00    8.18    --  111.00  77.00  90.00   97
 24  \w     81.00 178.00   1.00    8.18    --  111.00  77.00 -90.00   97
 25  \w     41.00 122.00   1.00    8.18    --  111.00-125.00  30.00   81
 26  \w     81.00 178.00   1.00    8.18    --  111.00  77.00 150.00   97
 27  \w     81.00 178.00   1.00    8.18    --  111.00  76.00 -38.09   97
 28  \w     85.00 178.00   1.00    8.18    --  111.00  61.00-168.13   93
 29  \w     85.00 178.00   1.00    8.18    --  111.00  61.00 -60.00   93
 30  \w     82.00 178.00   1.00    8.18    --  111.00  73.00   5.27   96
 31  \w     85.00 178.00   1.00    8.18    --  111.00  61.00 -30.00   93
 32  \w     85.00 178.00   1.00    8.18    --  111.00  61.00 120.00   93
 33  \w     85.00 178.00   1.00    8.18    --  111.00  60.00 -93.38   93
 34  \w     85.00 178.00   1.00    8.18    --  111.00  62.00  35.35   93
 35  \w     81.00 178.00   1.00    8.18    --  111.00  77.00  30.00   97
 36  \w     81.00 178.00   1.00    8.18    --  111.00  77.00-150.00   97
 37  \w     81.00 178.00   1.00    8.18    --  111.00  77.00 120.00   97
 38  \w     85.00 178.00   1.00    8.18    --  111.00  61.00 150.00   93
 39  \w     81.00 178.00   1.00    8.18    --  111.00  77.00 -30.00   97
 40  \w     85.00 178.00   1.00    8.18    --  111.00  61.00  30.00   93
 41  \w     85.00 178.00   1.00    8.18    --  111.00  61.00   0.00   93
 42  \w     81.00 174.00   1.00    8.18    --  111.00  77.00  60.00   93
 43  \w     85.00 111.00   1.00    8.18    --  111.00  61.00-180.00   26
 44  \w     85.00 115.00   1.00    8.18    --  111.00  61.00  60.00   30
 45  \w     85.00 111.00   1.00    8.18    --  111.00  59.00  14.43   26
 46  \w     41.00 101.00   1.00    8.18    --  111.00-125.00-150.00   60
 47  \w     82.00 140.00   1.00    8.18    --  111.00 -77.00 -30.00   58
 48  \w     85.00 152.00   1.00    8.18    --  111.00  61.00-150.00   67
 49  \w     85.00 111.00   1.00    8.18    --  111.00  61.00-120.00   26
 50  \w     43.00 109.00   1.00    8.18    --  111.00 -94.00-120.00   66
 51  \w     41.00 121.00   1.00    8.18    --  111.00-125.00 150.00   80
 52  \w     85.00 111.00   1.00    8.18    --  111.00  61.00  90.00   26
 53  \w     51.00 137.00   1.00    8.18    --  111.00 -61.00-120.00   86
 54  \w     65.00 122.00   1.00    8.18    --  111.00-125.00-120.00   57
 55  \w     83.00 108.00   1.00    8.18    --  111.00  72.00  54.15   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0205329000
_diffrn_orient_matrix_UB_12      -0.0797918000
_diffrn_orient_matrix_UB_13      0.0048556000
_diffrn_orient_matrix_UB_21      0.1251043000
_diffrn_orient_matrix_UB_22      0.0136917000
_diffrn_orient_matrix_UB_23      0.0052222000
_diffrn_orient_matrix_UB_31      -0.0137192000
_diffrn_orient_matrix_UB_32      0.0056382000
_diffrn_orient_matrix_UB_33      0.0551636000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0474
_diffrn_reflns_av_unetI/netI     0.0171
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            184852
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.73
_diffrn_reflns_theta_min         2.82
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.063
_exptl_absorpt_correction_T_max  0.780
_exptl_absorpt_correction_T_min  0.453
_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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.451
_exptl_crystal_description       fragment
_exptl_crystal_F_000             2784
_exptl_crystal_size_max          0.213
_exptl_crystal_size_mid          0.139
_exptl_crystal_size_min          0.056
_refine_diff_density_max         1.965
_refine_diff_density_min         -1.244
_refine_diff_density_rms         0.089
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
 
 Highly disordered solvent in four voids were squeezed
 with the SQUEEZE procedure of Olex2 program 
 (Dolomanov, O.V.; Bourhis, L.J.; Gildea, R.J.; Howard, J.A.K.; 
 Puschmann, H., J. Appl. Cryst. (2009). 42, 339-341.)
 The sum formular and further calculations disregard this 
 electron density.

Miller array info: D:\Data\lisa37\struct\olex2_lisa37\lisa37.hkl:Iobs,SigIobs
Observation type: xray.intensity
Type of data: double, size=184852
Type of sigmas: double, size=184852
Number of Miller indices: 184852
Anomalous flag: True
Unit cell: (12.083, 18.9801, 27.6971, 90, 90, 90)
Space group: P 21 21 2 (No. 18)
Systematic absences: 148
Systematic absences not included in following:
Centric reflections: 18083
Resolution range: 15.6567 0.807313

use_set_completion: False
solvent_radius: 1.20
shrink_truncation_radius: 1.20
van der Waals radii:
    C    Cl     H    Hf     N     O
 1.70  1.75  1.09  2.00  1.55  1.52

Total solvent accessible volume / cell = 949.8 Ang^3 [15.0%]
Total electron count / cell = 264.4

gridding: (60,96,144)
Void #Grid points Vol/A^3 Vol/%  Centre of mass (frac)   Eigenvectors (frac)
   1        26653   204.1   3.2  (-0.000,-0.000, 0.453)  1  ( 0.980, 0.199, 0.000)
                                                         2  (-0.199, 0.980, 0.000)
                                                         3  ( 0.000, 0.000, 1.000)
   2        35362   270.8   4.3  (-0.000, 0.500, 0.104)  1  ( 0.966, 0.260, 0.000)
                                                         2  (-0.260, 0.966, 0.000)
                                                         3  ( 0.000, 0.000, 1.000)
   3        35362   270.8   4.3  ( 0.500,-0.000, 0.896)  1  ( 0.966,-0.260, 0.000)
                                                         2  ( 0.260, 0.966, 0.000)
                                                         3  ( 0.000, 0.000, 1.000)
   4        26653   204.1   3.2  ( 0.500, 0.500, 0.547)  1  ( 0.980,-0.199, 0.000)
                                                         2  ( 0.199, 0.980, 0.000)
                                                         3  ( 0.000, 0.000, 1.000)

Void  Vol/Ang^3  #Electrons
   1      204.1         58.5
   2      270.8         96.9
   3      270.8         97.7
   4      204.1         57.8

;
_refine_ls_abs_structure_Flack   0.481(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     786
_refine_ls_number_reflns         12561
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0342
_refine_ls_R_factor_gt           0.0334
_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^)+(0.0565P)^2^+8.9315P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0893
_refine_ls_wR_factor_ref         0.0902
_reflns_Friedel_coverage         0.815
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                12231
_reflns_number_total             12561
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt01757c2.cif
_cod_data_source_block           compound10
_cod_depositor_comments
'Adding full bibliography for 7047149--7047158.cif.'
_cod_original_cell_volume        6351.99(8)
_cod_database_code               7047152
_chemical_oxdiff_formula         'C70 H42 Cl4 Hf N4 O8 '
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_date_sample_data_collection 2016-07-06
_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 1.361
_oxdiff_exptl_absorpt_empirical_full_min 0.735
_shelx_res_checksum              45226
_shelxl_version_number           2014-3