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_7043773
_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 La3 N18 O6, 2(C4 H8 O)'
_chemical_formula_sum            'C73 H103 La3 N18 O8'
_chemical_formula_weight         1777.46
_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     heavy
_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                   16.3220(6)
_cell_length_b                   20.2156(6)
_cell_length_c                   23.5719(7)
_cell_measurement_reflns_used    9870
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.802
_cell_measurement_theta_min      2.357
_cell_volume                     7777.8(4)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.969
_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  0.0361
_diffrn_reflns_av_unetI/netI     0.0547
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            58920
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         28.20
_diffrn_reflns_theta_min         1.33
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.683
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6960
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0456 before and 0.0409 after correction. The Ratio of minimum to maximum transmission is 0.9334. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.518
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3608
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.752
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.100
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.019(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     944
_refine_ls_number_reflns         18196
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0424
_refine_ls_R_factor_gt           0.0291
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0186P)^2^+1.6780P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0493
_refine_ls_wR_factor_ref         0.0539
_reflns_number_gt                15714
_reflns_number_total             18196
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c7dt00635g2.cif
_cod_data_source_block           5aLa
_cod_database_code               7043773
_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
 C68-C69
 1.51 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C68) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C67) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C66) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C69) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
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) C59B(0.5) H59A(0.5) H59B(0.5) C59(0.5) H59C(0.5) H59D(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C62(H62A,H62B), C61(H61A,H61B), C65(H65A,H65B), C63(H63A,H63B), C58(H58A,
 H58B), C58(H58C,H58D), C64(H64A,H64B), C60(H60A,H60B), C60(H60C,H60D),
 C70(H70A,H70B), C73(H73A,H73B), C69(H69A,H69B), C68(H68A,H68B), C66(H66A,H66B),
  C67(H67A,H67B), C72(H72A,H72B), C71(H71A,H71B), C59B(H59A,H59B), C59(H59C,
 H59D)
5.b Me refined with riding coordinates:
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C)
5.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C24(H24), C30(H30), C26(H26), C7(H7), C10(H10), C13(H13), C8(H8),
 C23(H23), C18(H18), C55(H55), C25(H25), C50(H50), C45(H45), C35(H35), C3(H3),
 C40(H40)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C57(H57A,H57B,
 H57C), C11(H11A,H11B,H11C), C15(H15A,H15B,H15C), C47(H47A,H47B,H47C), C48(H48A,
 H48B,H48C), C32(H32A,H32B,H32C), C5(H5A,H5B,H5C), C33(H33A,H33B,H33C),
 C43(H43A,H43B,H43C), C52(H52A,H52B,H52C), C28(H28A,H28B,H28C), C53(H53A,H53B,
 H53C), C42(H42A,H42B,H42C)
;
_olex2_submission_original_sample_id 5aLa
_olex2_submission_special_instructions 'No special instructions were received'
_publcif_funding_html
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