Pyrazolates advance cerium chemistry: a Ce(III)/Ce(IV) redox equilibrium with benzoquinone.
Werner, Daniel; Deacon, Glen B.; Junk, Peter C.; Anwander, Reiner; Dalton transactions (Cambridge, England : 2003)  (2017) –; doi:10.1039/c7dt00635g

data_7043771
_publ_section_title
;
 Pyrazolates advance cerium chemistry: a Ce(III)/Ce(IV) redox equilibrium
 with benzoquinone.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/c7dt00635g
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C65 H87 Ce3 N18 O6, 1.5(C4 H8 O)'
_chemical_formula_sum            'C71 H99 Ce3 N18 O7.5'
_chemical_formula_weight         1745.04
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-03-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.02.23 svn.r3390 for OlexSys, GUI svn.r5320)
;
_audit_update_record
;
2017-03-06 deposited with the CCDC.
2017-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   16.2907(16)
_cell_length_b                   20.1796(19)
_cell_length_c                   23.505(2)
_cell_measurement_reflns_used    9667
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.819
_cell_measurement_theta_min      2.196
_cell_volume                     7727.0(12)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0555
_diffrn_reflns_av_unetI/netI     0.0485
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            91067
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         28.34
_diffrn_reflns_theta_min         1.33
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.800
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6939
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0773 before and 0.0589 after correction.
The Ratio of minimum to maximum transmission is 0.9305.
The \l/2 correction factor is 0.0000.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.500
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3540
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.148
_refine_diff_density_min         -0.423
_refine_diff_density_rms         0.109
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.016(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     945
_refine_ls_number_reflns         19260
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.0410
_refine_ls_R_factor_gt           0.0322
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0366P)^2^+4.2398P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0795
_refine_ls_wR_factor_ref         0.0838
_reflns_number_gt                17292
_reflns_number_total             19260
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c7dt00635g2.cif
_cod_data_source_block           5aTHF
_cod_original_cell_volume        7727.0(13)
_cod_original_formula_sum        'C71 H99 Ce3 N18 O7.50'
_cod_database_code               7043771
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C69-C70
 1.5 with sigma of 0.01
 C69-C68
 1.5 with sigma of 0.01
 C68-C67
 1.5 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C69) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C68) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.001
Uanis(C67) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.001
4. Others
 Fixed Sof: H58A(0.5) H58B(0.5) H58C(0.5) H58D(0.5) H60A(0.5) H60B(0.5)
 H60C(0.5) H60D(0.5) O8(0.5) C67(0.5) H67A(0.5) H67B(0.5) C70(0.5) H70B(0.5)
 H70A(0.5) C68(0.5) H68A(0.5) H68B(0.5) C69(0.5) H69A(0.5) H69B(0.5) C62(0.4)
 H62A(0.5) H62B(0.5) C59(0.6) H59A(0.5) H59B(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C58(H58A,H58B), C58(H58C,H58D), C63(H63A,H63B), C61(H61A,H61B), C65(H65A,
 H65B), C64(H64A,H64B), C66(H66A,H66B), C60(H60A,H60B), C60(H60C,H60D),
 C72(H72A,H72B), C74(H74A,H74B), C71(H71A,H71B), C73(H73A,H73B), C67(H67A,H67B),
  C70(H70B,H70A), C68(H68A,H68B), C69(H69A,H69B), C62(H62A,H62B), C59(H59A,H59B)
5.b Me refined with riding coordinates:
 C37(H37A,H37B,H37C)
5.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C7(H7), C10(H10), C24(H24), C14(H14), C8(H8), C45(H45), C25(H25),
 C19(H19), C9(H9), C26(H26), C50(H50), C3(H3), C40(H40), C30(H30), C35(H35),
 C55(H55)
5.d Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C17(H17A,H17B,H17C), C48(H48A,H48B,H48C), C21(H21A,H21B,
 H21C), C32(H32A,H32B,H32C), C1(H1A,H1B,H1C), C28(H28A,H28B,H28C), C5(H5A,H5B,
 H5C), C12(H12A,H12B,H12C), C52(H52A,H52B,H52C), C38(H38A,H38B,H38C), C42(H42A,
 H42B,H42C), C16(H16A,H16B,H16C), C43(H43A,H43B,H43C), C53(H53A,H53B,H53C),
 C33(H33A,H33B,H33C), C57(H57A,H57B,H57C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_publcif_funding_html
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