Cu<sub>4</sub>Ti<sub>4</sub>-oxo clusters functionalized by <i>in situ</i> - generated 2,2'-biphenolate ligands from the oxidative coupling of phenols.
Liu, Xiao-Xue; Wang, Zi-Rui; Chen, Guang-Hui; Li, Qiao-Hong; Tao, Jun; Zhang, Lei; Dalton transactions (Cambridge, England : 2003) 52 (2023) 1857–1860; doi:10.1039/d2dt03756d

data_7712173
_publ_section_title
;
 Cu<sub>4</sub>Ti<sub>4</sub>-oxo clusters functionalized by <i>in
 situ</i> - generated 2,2'-biphenolate ligands from the oxidative coupling
 of phenols.
;
_journal_issue                   7
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1857
_journal_page_last               1860
_journal_paper_doi               10.1039/d2dt03756d
_journal_volume                  52
_journal_year                    2023
_chemical_formula_moiety
'C8 H12 Cu1 N4, C72 H51 O16 Ti4, 0.333(C6 H9 N3)'
_chemical_formula_sum            'C82 H66 Cu N5 O16 Ti4'
_chemical_formula_weight         1632.53
_space_group_crystal_system      trigonal
_space_group_IT_number           158
_space_group_name_Hall           'P 3 -2"c'
_space_group_name_H-M_alt        'P 3 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-12-15
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-12-22 deposited with the CCDC.	2022-12-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            2
_cell_length_a                   13.05240(10)
_cell_length_b                   13.05240(10)
_cell_length_c                   24.5902(2)
_cell_measurement_reflns_used    69483
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      60.6650
_cell_measurement_theta_min      3.1240
_cell_volume                     3628.05(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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     50.00  76.00   0.50    0.23    --   73.53  77.00  30.00   52
  2  \w     50.00  76.00   0.50    0.23    --   73.53  77.00  90.00   52
  3  \w     50.00 147.00   0.50    0.23    --   73.53  77.00 150.00  194
  4  \w    115.00 141.00   0.50    0.23    --   73.53  77.00  30.00   52
  5  \w    113.00 139.00   0.50    0.23    --   73.53  77.00  60.00   52
  6  \w    114.00 147.00   0.50    0.23    --   73.53  77.00 -60.00   66
  7  \w     50.00  94.00   0.50    0.23    --   73.53  77.00 -60.00   88
  8  \w     50.00  83.00   0.50    0.23    --   73.53  77.00 -90.00   66
  9  \w     50.00  75.00   0.50    0.23    --   73.53  77.00-120.00   50
 10  \w     50.00  75.00   0.50    0.23    --   73.53  77.00-150.00   50
 11  \w     50.00  83.00   0.50    0.23    --   73.53  77.00-180.00   66
 12  \w     51.00 114.00   0.50    0.23    --   73.53  75.00 -27.89  126
 13  \w     51.00  77.00   0.50    0.23    --   73.53  74.00 -75.44   52
 14  \w     50.00  75.00   0.50    0.23    --   73.53  77.00   0.00   50
 15  \w     51.00  77.00   0.50    0.23    --   73.53  73.00 -63.19   52
 16  \w     51.00  76.00   0.50    0.23    --   73.53  75.00  15.40   50
 17  \w     51.00  80.00   0.50    0.23    --   73.53  73.00  49.84   58
 18  \w     50.00  82.00   0.50    0.23    --   73.53  77.00  60.00   64
 19  \w     50.00  75.00   0.50    0.23    --   73.53  77.00 120.00   50
 20  \w     51.00  78.00   0.50    0.23    --   73.53  73.00 113.43   54
 21  \w     52.00  78.00   0.50    0.23    --   73.53  71.00 172.38   52
 22  \w     52.00 103.00   0.50    0.23    --   73.53  72.00 126.57  102
 23  \w    106.00 140.00   0.50    0.23    --   73.53  71.00 172.38   68
 24  \w    100.00 147.00   0.50    0.23    --   73.53  73.00 -63.19   94
 25  \w    122.00 147.00   0.50    0.23    --   73.53  73.00-116.88   50
 26  \w    105.00 146.00   0.50    0.23    --   73.53  57.00-120.00   82
 27  \w     59.00 103.00   0.50    0.23    --   73.53  48.00 -86.64   88
 28  \w     57.00  82.00   0.50    0.23    --   73.53  57.00-120.00   50
 29  \w     51.00  79.00   0.50    0.23    --   73.53  73.00-116.88   56
 30  \w     59.00 147.00   0.50    0.23    --   73.53  41.00 -29.00  176
 31  \w     59.00 140.00   0.50    0.23    --   73.53  38.00 150.00  162
 32  \w     41.00  66.00   0.50    0.05    --   -0.62  38.00  60.00   50
 33  \w    -14.00  40.00   0.50    0.05    --   -0.62  38.00  60.00  108
 34  \w    -12.00  32.00   0.50    0.05    --   -0.62  41.00 -29.00   88
 35  \w     38.00  68.00   0.50    0.05    --   -0.62  41.00 -29.00   60
 36  \w     47.00  73.00   0.50    0.05    --   -0.62  38.00-120.00   52
 37  \w    -15.00  31.00   0.50    0.05    --   -0.62  38.00-120.00   92
 38  \w    -91.00  -9.00   0.50    0.23    --  -74.78  57.00 -30.00  164
 39  \w    -90.00  -2.00   0.50    0.23    --  -74.78  57.00 -90.00  176
 40  \w    -72.00  -3.00   0.50    0.23    --  -74.78  41.00 -29.00  138
 41  \w   -148.00 -51.00   0.50    0.23    --  -74.78 -77.00  60.00  194
 42  \w   -147.00 -51.00   0.50    0.23    --  -74.78 -77.00 -90.00  192
 43  \w    -77.00 -51.00   0.50    0.23    --  -74.78 -78.00-127.32   52
 44  \w    -76.00 -51.00   0.50    0.23    --  -74.78 -77.00-180.00   50
 45  \w   -119.00 -94.00   0.50    0.23    --  -74.78 -77.00-180.00   50
 46  \w    -77.00 -52.00   0.50    0.23    --  -74.78 -74.00  -3.18   50
 47  \w    -78.00 -53.00   0.50    0.23    --  -74.78 -73.00 -23.50   50
 48  \w   -143.00-118.00   0.50    0.23    --  -74.78 -73.00 -23.50   50
 49  \w   -147.00 -54.00   0.50    0.23    --  -74.78 -69.00  32.65  186
 50  \w    -77.00 -51.00   0.50    0.23    --  -74.78 -76.00  79.15   52
 51  \w    -77.00 -52.00   0.50    0.23    --  -74.78 -74.00 139.88   50
 52  \w    -82.00 -57.00   0.50    0.23    --  -74.78 -62.00 141.35   50
 53  \w   -124.00 -64.00   0.50    0.23    --  -74.78 -41.00 177.00  120
 54  \w   -148.00-123.00   0.50    0.23    --  -74.78 -62.00 141.35   50
 55  \w   -123.00 -80.00   0.50    0.23    --  -74.78 -76.00  79.15   86
 56  \w    -64.00 -31.00   0.50    0.05    --   -0.62 -41.00 177.00   66
 57  \w    -73.00  15.00   0.50    0.05    --   -0.62 -77.00 120.00  176
 58  \w    -67.00   6.00   0.50    0.05    --   -0.62 -57.00  30.00  146
 59  \w    -24.00  12.00   0.50    0.05    --   -0.62 -41.00 177.00   72
 60  \w   -108.00 -23.00   0.50    0.23    --  -74.78 125.00 -60.00  170
 61  \w    -90.00 -34.00   0.50    0.23    --  -74.78 125.00 -30.00  112
 62  \w    -62.00  22.00   0.50    0.05    --   -0.62 -77.00 -60.00  168
 63  \w     14.00  39.00   0.50    0.05    --   -0.62-112.00-101.97   50
 64  \w     20.00 108.00   0.50    0.23    --   73.53-125.00  90.00  176
 65  \w     82.00 108.00   0.50    0.23    --   73.53-125.00-120.00   52
 66  \w     63.00  99.00   0.50    0.23    --   73.53-125.00-180.00   72
 67  \w     28.00  54.00   0.50    0.23    --   73.53-125.00-180.00   52
 68  \w     27.00  71.00   0.50    0.23    --   73.53-125.00-120.00   88
 69  \w      1.00  90.00   0.50    0.23    --   73.53 -57.00  90.00  178
 70  \w      1.00 106.00   0.50    0.23    --   73.53 -99.00 120.00  210
 71  \w     25.00  64.00   0.50    0.23    --   73.53 -41.00 177.00   78
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0529
_diffrn_reflns_av_unetI/netI     0.0173
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            112846
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         60.796
_diffrn_reflns_theta_min         3.125
_exptl_absorpt_coefficient_mu    4.251
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74272
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.494
_exptl_crystal_description       block
_exptl_crystal_F_000             1676
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.307
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.381(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     329
_refine_ls_number_reflns         5554
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0265
_refine_ls_R_factor_gt           0.0262
_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^)+(0.0313P)^2^+1.2527P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0635
_refine_ls_wR_factor_ref         0.0636
_reflns_Friedel_coverage         0.997
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                5511
_reflns_number_total             5554
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03756d2.cif
_cod_data_source_block           ptc-333
_cod_depositor_comments
'Adding full bibliography for 7712172--7712174.cif.'
_cod_original_cell_volume        3628.05(6)
_cod_database_code               7712173
_shelx_shelxl_version_number     2018/1
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.619(5)
 0.381(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3. Others
 Fixed Sof: H22A(0.33333) H22B(0.33333) H22C(0.33333) H5(0.75) H6(0.25)
 H26A(0.33333) H26B(0.33333) H26C(0.33333)
4.a Ternary CH refined with riding coordinates:
 O5(H5), O6(H6)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5A), C8(H8), C9(H9), C10(H10), C12(H12), C14(H14), C16(H16),
 C17(H17), C19(H19), C20(H20), C21(H21), C23(H23), C25(H25), C27(H27), C29(H29)
4.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C30(H30A,H30B,H30C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              33456
_shelx_hkl_checksum              31395
_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
;