Synthesis and structures of cobalt-expanded zirconium- and cerium-oxo clusters as precursors for mixed-metal oxide thin films.
Seiß, Maximilian; Lorenz, Jonas; Schmitz, Sebastian; Moors, Marco; Börner, Martin; Monakhov, Kirill Yu; Dalton transactions (Cambridge, England : 2003) 53 (2024) 8454–8462; doi:10.1039/d4dt00328d

data_7715828
_publ_section_title
;
 Synthesis and structures of cobalt-expanded zirconium- and cerium-oxo
 clusters as precursors for mixed-metal oxide thin films.
;
_journal_issue                   19
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              8454
_journal_page_last               8462
_journal_paper_doi               10.1039/d4dt00328d
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C57 H107 Ce3 Co2 N3 O24, C2 H3 N'
_chemical_formula_sum            'C59 H110 Ce3 Co2 N4 O24'
_chemical_formula_weight         1797.72
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-23
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-01-25 deposited with the CCDC.	2024-04-25 downloaded from the CCDC.
;
_cell_angle_alpha                66.8650(10)
_cell_angle_beta                 75.4190(10)
_cell_angle_gamma                79.6030(10)
_cell_formula_units_Z            2
_cell_length_a                   14.8820(2)
_cell_length_b                   15.2696(2)
_cell_length_c                   19.4127(3)
_cell_measurement_reflns_used    66447
_cell_measurement_temperature    180
_cell_measurement_theta_max      71.01
_cell_measurement_theta_min      3.57
_cell_volume                     3909.46(10)
_computing_cell_refinement
;
X-Area Recipe 1.37.0.0 (STOE, 2021)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.186.0 (STOE, 2022)
;
_computing_data_reduction
;
X-Area Integrate 2.5.3.0 (STOE, 2021)
X-Area LANA 2.7.5.0 (STOE, 2022)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material
;
STOE & Cie GmbH, X-Area, software package for collecting single-crystal or
multi-domain crystal data on STOE area-detector diffractometers, for image 
processing, for the correction and scaling of reflection intensities and 
for outlier rejection, version 2.1, Darmstadt 2022
;
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      180
_diffrn_detector                 Pilatus300K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 300K'
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_details
;
 3989 frames, detector distance = 60 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0272
_diffrn_reflns_av_unetI/netI     0.0256
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            63541
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         71.065
_diffrn_reflns_theta_min         3.573
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    17.049
_exptl_absorpt_correction_T_max  0.0369
_exptl_absorpt_correction_T_min  0.0101
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens in: F. R. Ahmed (Editor), "Crystallographic Computing", Munksgaard,
Copenhagen (1970), 255 - 270. Afterwards scaling of reflection intensities was
performed within STOE LANA. J. Koziskova, F. Hahn, J. Richter, J. Kozisek, Acta
Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Finally a spherical absorption correction was done within STOE LANA.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.527
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1824
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_exptl_crystal_size_rad          0.050
_refine_diff_density_max         1.473
_refine_diff_density_min         -0.693
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     912
_refine_ls_number_reflns         14579
_refine_ls_number_restraints     226
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0597P)^2^+5.5298P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0954
_refine_ls_wR_factor_ref         0.1015
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12503
_reflns_number_total             14579
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00328d2.cif
_cod_data_source_block           sv-1419
_cod_depositor_comments
'Adding full bibliography for 7715827--7715828.cif.'
_cod_database_code               7715828
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.483
_shelx_estimated_absorpt_t_min   0.342
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N4-C58
 1.14 with sigma of 0.02
 C58-N4
 1.137 with sigma of 0.01
 C58-C59
 1.456 with sigma of 0.01
 C59-N4
 2.593 with sigma of 0.02
 N5-C60
 1.14 with sigma of 0.02
 C60-N5
 1.137 with sigma of 0.01
 C60-C61
 1.456 with sigma of 0.01
 C61-N5
 2.593 with sigma of 0.02
 N4-C59
 2.59 with sigma of 0.04
 N5-C61
 2.59 with sigma of 0.04
 C17-C18 \\sim C17-C19 \\sim C17-C20
 with sigma of 0.02
 C17-C18A \\sim C17-C19A \\sim C17-C20A
 with sigma of 0.02
 C18-C19 \\sim C18-C20 \\sim C19-C20
 with sigma of 0.02
 C18A-C19A \\sim C18A-C20A \\sim C19A-C20A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C17 \\sim C18 \\sim C19 \\sim C20: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
N4 \\sim C58 \\sim C59: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C17 \\sim C18A \\sim C19A \\sim C20A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
N5 \\sim C60 \\sim C61: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C31 \\sim C32 \\sim C35 \\sim C33 \\sim C34: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C7 \\sim C10 \\sim C9 \\sim C8: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C17, C18, C19, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17, C18A, C19A, C20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C58, C59
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N5, C60, C61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31, C32, C35, C33, C34
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, C10, C9, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
 Fixed Sof: N4(0.25) C58(0.25) C59(0.25) H59A(0.25) H59B(0.25) H59C(0.25)
 N5(0.75) C60(0.75) C61(0.75) H61A(0.75) H61B(0.75) H61C(0.75)
6.a Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,
 H40B), C41(H41A,H41B), C42(H42A,H42B), C44(H44A,H44B), C45(H45A,H45B),
 C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B),
  C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B)
6.b Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C28(H28A,
 H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C43(H43A,H43B,H43C), C51(H51A,H51B,
 H51C), C59(H59A,H59B,H59C), C61(H61A,H61B,H61C), C18A(H18D,H18E,H18F),
 C19A(H19D,H19E,H19F), C20A(H20D,H20E,H20F)
;
_shelx_res_checksum              43548
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '60.0 mm'
_stoe_detector_pixelsize_x       '0.172 mm'
_stoe_detector_pixelsize_y       '0.172 mm'
_stoe_detector_size_x            '8.4 cm'
_stoe_detector_size_y            '10.6 cm'
_stoe_evaluation_integration_a   4.0
_stoe_evaluation_integration_b   0.5
_stoe_evaluation_integration_ems 0.008
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 6
_stoe_evaluation_lana_bos_l_odd_max 3
_stoe_evaluation_lana_completeness 96.3
_stoe_evaluation_lana_dxs_max_order -
_stoe_evaluation_lana_dys_max_order -
_stoe_evaluation_lana_fs_max_order 8
_stoe_evaluation_lana_max_2theta_available 142.2
_stoe_evaluation_lana_max_2theta_desired 142.2
_stoe_evaluation_lana_mean_redundancy 4.4
_stoe_evaluation_lana_number_refls_after_or 63558
_stoe_evaluation_lana_number_refls_outliers 12952
_stoe_evaluation_lana_number_refls_total 76510
_stoe_evaluation_lana_number_refls_unique 14579
_stoe_evaluation_lana_number_refls_written 63558
_stoe_evaluation_lana_or_c1      0.035
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      0.7
_stoe_evaluation_lana_point_group -1
_stoe_evaluation_lana_table
;
2Theta          13.9   29.1   44.3   59.5   74.7   89.9  105.1  120.3  135.5
<Resolution>    5.30   2.94   2.02   1.55   1.25   1.09   0.97   0.89   0.84
N(total)         544   2233   4510   5801  12827  15770  15319  13275   6231
<Redundancy>     3.8    4.0    3.8    3.0    5.1    5.4    4.9    4.2    3.0
Complet. [%%]   100.0  100.0  100.0   99.8   99.8   99.7   99.2   97.9   78.4
<I/sigma>      105.5   65.6   40.8   24.3   12.6   11.5    8.9    7.7    7.3
R(int)         0.013  0.014  0.014  0.019  0.033  0.033  0.042  0.058  0.065
;
_stoe_measurement_identifier     SV-1419
_stoe_measurement_max_exposure_per_frame '3.0 s'
_stoe_measurement_mean_exposure_per_frame '2.7 s'
_stoe_measurement_min_exposure_per_frame '2.0 s'
_stoe_measurement_total_exposure_time '3.0 h'
_stoe_measurement_total_frame_number 3989
_stoe_measurement_total_run_number 72
_stoe_measurement_tube_power     '30.0 W'