Probing the Reactivity of the Ce═O Multiple Bond in a Cerium(IV) Oxo Complex.
So, Yat-Ming; Li, Yang; Au-Yeung, Ka-Chun; Wang, Guo-Cang; Wong, Kang-Long; Sung, Herman H. Y.; Arnold, Polly L.; Williams, Ian D.; Lin, Zhenyang; Leung, Wa-Hung; Inorganic chemistry 55 (2016) 10003–10012; doi:10.1021/acs.inorgchem.6b00480

data_4347684
_publ_section_title
;
 Probing the Reactivity of the Ce&#x2550;O Multiple Bond in a Cerium(IV)
 Oxo Complex.
;
_journal_issue                   20
_journal_name_full               'Inorganic chemistry'
_journal_page_first              10003
_journal_page_last               10012
_journal_paper_doi               10.1021/acs.inorgchem.6b00480
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety
'C38 H80 Ce Co2 N2 O20 P6, 2(C18 H B F15 O), C H2 Cl2'
_chemical_formula_sum            'C75 H84 B2 Ce Cl2 Co2 F30 N2 O22 P6'
_chemical_formula_weight         2471.76
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-06-09
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.1748(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.9526(3)
_cell_length_b                   15.35706(17)
_cell_length_c                   24.5163(3)
_cell_measurement_reflns_used    14350
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      75.3510
_cell_measurement_theta_min      4.6130
_cell_volume                     9764.1(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3587
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
  1 omega   33.00   90.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703  -30.0000    0.0000 57

  2 omega -117.00  -15.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9453  -37.0000 -150.0000 102

  3 omega  -71.00   33.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9453   57.0000  150.0000 104

  4 omega   36.00   98.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703  -45.0000   60.0000 62

  5 omega   80.00  178.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703   30.0000  -60.0000 98

  6 omega   77.00  178.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703   77.0000  150.0000 101

  7 omega   33.00   90.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703  -30.0000 -120.0000 57

  8 omega   33.00   90.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703  -30.0000 -180.0000 57

  9 omega -116.00   -9.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9453  -67.0000   44.0000 107

 10 omega    1.00   32.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9453  -99.0000  -90.0000 31
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0566507000
_diffrn_orient_matrix_UB_12      0.0282497000
_diffrn_orient_matrix_UB_13      0.0088760000
_diffrn_orient_matrix_UB_21      0.0167779000
_diffrn_orient_matrix_UB_22      -0.0716185000
_diffrn_orient_matrix_UB_23      -0.0396530000
_diffrn_orient_matrix_UB_31      -0.0062384000
_diffrn_orient_matrix_UB_32      0.0642644000
_diffrn_orient_matrix_UB_33      -0.0480029000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0401
_diffrn_reflns_av_unetI/netI     0.0549
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            40047
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.500
_diffrn_reflns_theta_max         67.496
_diffrn_reflns_theta_min         4.049
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Cu
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    8.731
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49189
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.681
_exptl_crystal_description       block
_exptl_crystal_F_000             4960
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.701
_refine_diff_density_min         -0.992
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1296
_refine_ls_number_reflns         17471
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0500P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0943
_refine_ls_wR_factor_ref         0.1008
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14364
_reflns_number_total             17471
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b00480_si_001.cif
_cod_data_source_block           ka43b
_cod_database_code               4347684
_chemical_oxdiff_formula         'Ce1 Cp2 Co2 P6 Et12 O18 O2 N2 B2 Ph6 F30 O2'
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H,H)
  groups, All O(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C20-C19
 1.52 with sigma of 0.02
 C20A-C19
 1.52 with sigma of 0.02
 C22-C21
 1.52 with sigma of 0.02
 C14A-C13 = C14-C13
 1.52 with sigma of 0.02
 C16A-C15 = C16-C15
 1.52 with sigma of 0.02
3. Others
 Fixed Sof: H13A(0.55) H13B(0.55) H13C(0.45) H13D(0.45) C14(0.55) H14A(0.55)
 H14B(0.55) H14C(0.55) C14A(0.45) H14D(0.45) H14E(0.45) H14F(0.45) H15A(0.65)
 H15B(0.65) H15C(0.35) H15D(0.35) C16(0.65) H16A(0.65) H16B(0.65) H16C(0.65)
 C16A(0.35) H16D(0.35) H16E(0.35) H16F(0.35) H19A(0.5) H19B(0.5) H19C(0.5)
 H19D(0.5) C20(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C20A(0.5) H20D(0.5) H20E(0.5)
 H20F(0.5) H1SA(0.5) H1SB(0.5) H2SA(0.5) H2SB(0.5) Cl2(0.34) Cl2A(0.2)
 Cl2B(0.46)
4.a Riding coordinates:
 O1S(H1SA,H1SB), O2S(H2SA,H2SB)
4.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C13(H13A,H13B), C13(H13C,H13D), C15(H15A,H15B), C15(H15C,
 H15D), C17(H17A,H17B), C19(H19A,H19B), C19(H19C,H19D), C21(H21A,H21B),
 C31(H31A,H31B), C33(H33A,H33B), C35(H35A,H35B), C37(H37A,H37B), C39(H39A,H39B),
  C41(H41A,H41B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9),
 C10(H10)
4.d X=CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B)
4.e Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C14A(H14D,H14E,H14F), C16(H16A,H16B,
 H16C), C16A(H16D,H16E,H16F), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C),
 C20A(H20D,H20E,H20F), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C26(H26A,H26B,
 H26C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C38(H38A,
 H38B,H38C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              16475
_shelx_hkl_checksum              12223
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'