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_4347686
_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
'C53 H110 Ce Co3 N Na O29 P9, C2 H5 N O, 0.25(C6 H14)'
_chemical_formula_sum            'C56.5 H118.5 Ce Co3 N2 Na O30 P9'
_chemical_formula_weight         1924.66
_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   geom
_audit_creation_date             2016-01-05
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.619(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6774(4)
_cell_length_b                   24.5363(4)
_cell_length_c                   23.7102(7)
_cell_measurement_reflns_used    18462
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      29.2370
_cell_measurement_theta_min      3.4360
_cell_volume                     8739.5(4)
_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, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3587
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_details
;
  1 omega   -9.00   87.00   0.5000   80.0000
omega____ theta____ kappa____ phi______ frames
    -       15.8574   57.0000 -120.0000 192

  2 omega  -33.00   37.00   0.5000   80.0000
omega____ theta____ kappa____ phi______ frames
    -       15.8574  -77.0000  -30.0000 140

  3 omega  -20.00   96.00   0.5000   80.0000
omega____ theta____ kappa____ phi______ frames
    -       15.8574   77.0000   90.0000 232
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Mo at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0040437000
_diffrn_orient_matrix_UB_12      0.0227284000
_diffrn_orient_matrix_UB_13      -0.0190798000
_diffrn_orient_matrix_UB_21      -0.0027544000
_diffrn_orient_matrix_UB_22      0.0176103000
_diffrn_orient_matrix_UB_23      0.0231579000
_diffrn_orient_matrix_UB_31      0.0469315000
_diffrn_orient_matrix_UB_32      0.0029814000
_diffrn_orient_matrix_UB_33      0.0086993000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0592
_diffrn_reflns_av_unetI/netI     0.0617
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            49771
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         3.200
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Mo
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.312
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43723
_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            yellow
_exptl_crystal_density_diffrn    1.463
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3986
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.863
_refine_diff_density_min         -0.902
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.004
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     913
_refine_ls_number_reflns         16698
_refine_ls_number_restraints     186
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0882
_refine_ls_R_factor_gt           0.0655
_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^)+(0.0980P)^2^+11.2000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1681
_refine_ls_wR_factor_ref         0.1835
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12352
_reflns_number_total             16698
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b00480_si_001.cif
_cod_data_source_block           so113h
_cod_original_formula_sum        'C56.50 H118.50 Ce Co3 N2 Na O30 P9'
_cod_database_code               4347686
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C62-C61 = C62A-C61 = C64A-C63 = C64-C63 = C68-C67 = C68A-C67A
 1.52 with sigma of 0.02
 C32A-C31A = C22-C21 = C22A-C21A = C24-C23 = C24A-C23A = C28-C27 = C28A-C27A =
 C32-C31 = C30A-C29A = C26-C25 = C24A-C23A
 1.52 with sigma of 0.02
 C44A-C43A = C44-C43 = C46A-C45 = C46-C45A = C50A-C49A = C50-C49 = C42-C41 =
 C52-C51
 1.52 with sigma of 0.02
 C21-P3A = C29-P3
 2.65 with sigma of 0.03
 C6A-C8A
 2.45 with sigma of 0.03
 O16A-C31A \\sim O11-C21
 with sigma of 0.02
 P2A-O13A \\sim P2A-O14A \\sim P3-O15 \\sim P3-O16 \\sim P3A-O15A \\sim
P3A-O16A \\sim P1-O11 \\sim P1-O12
 \\sim P1A-O11A \\sim P1A-O12A \\sim P2-O13 \\sim P2-O14
 with sigma of 0.02
 O13-C25 \\sim O12A-C23A
 with sigma of 0.02
 P2A-O14A \\sim P2A-O13A \\sim P3-O15 \\sim P3-O16 \\sim P3A-O15A \\sim
P3A-O16A \\sim P1-O11 \\sim P1-O12
 \\sim P1A-O11A \\sim P1A-O12A \\sim P2-O14 \\sim P2-O13
 with sigma of 0.02
 C8-C7 \\sim C9-C8 \\sim C9-C10 \\sim C6-C10 \\sim C7-C6 \\sim C7A-C6A \\sim
C8A-C7A \\sim C9A-C8A \\sim C9A-
 C10A \\sim C6A-C10A
 with sigma of 0.02
 C4A-C3A \\sim C3A-C2A \\sim C2A-C1A \\sim C5A-C1A \\sim C5A-C4A \\sim C4-C3
\\sim C3-C2 \\sim C2-C1 \\sim C5-
 C1 \\sim C5-C4
 with sigma of 0.02
3. Others
 Fixed Sof: P1(0.82) P1A(0.18) P2(0.82) P2A(0.18) P3(0.82) P3A(0.18) O11(0.5)
 O11A(0.5) O12(0.5) O12A(0.33333) O13A(0.5) O13(0.66667) O14(0.5) O14A(0.5)
 O15(0.5) O15A(0.5) O16(0.5) O16A(0.5) O17(0.82) O17A(0.18) O18(0.82)
 O18A(0.18) O19(0.82) O19A(0.18) O22(0.5) O22A(0.5) O23(0.5) O23A(0.5) O25(0.5)
 O25A(0.5) C1(0.5) C1A(0.5) C2(0.5) C2A(0.5) C3(0.5) C3A(0.5) C4(0.5) C4A(0.5)
 C5(0.5) C5A(0.5) C6(0.65) C6A(0.35) C7(0.65) C7A(0.35) C8(0.65) C8A(0.35)
 C9(0.65) C9A(0.35) C10(0.65) C10A(0.35) C21A(0.5) C21(0.5) C22A(0.5) C22(0.6)
 C23(0.5) C23A(0.6) C24(0.5) C24A(0.6) C25(0.4) C25A(0.4) C26(0.4) C26A(0.2)
 C27(0.6) C27A(0.65) C28(0.8) C28A(0.65) C29A(0.5) C29(0.35) C30A(0.5)
 C30(0.35) C31A(0.5) C31(0.5) C32A(0.4) C32(0.5) C43(0.5) C43A(0.5) C44(0.5)
 C44A(0.5) C45(0.5) C45A(0.5) C46(0.5) C46A(0.5) C49(0.5) C49A(0.5) C50(0.5)
 C50A(0.5) C62(0.75) C62A(0.25) C64A(0.25) C64(0.75) C67(0.55) C67A(0.45)
 C68(0.55) C68A(0.45) C1S(0.5) C2S(0.5) C3S(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B), C47(H47A,H47B), C51(H51A,H51B), C65(H65A,H65B), C69(H69A,
 H69B), C71(H71A,H71B)
4.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15)
4.c X=CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B)
4.d Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C48(H48A,H48B,H48C), C52(H52A,H52B,H52C), C66(H66A,H66B,
 H66C), C70(H70A,H70B,H70C), C72(H72A,H72B,H72C), C82(H82A,H82B,H82C), C92(H92A,
 H92B,H92C)
;
_shelx_res_checksum              92578
_shelx_hkl_checksum              52301
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-12-18
_olex2_submission_special_instructions 'No special instructions were received'