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_7715827
_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         'C88 H168 Co6 O58 Zr6'
_chemical_formula_sum            'C88 H168 Co6 O58 Zr6'
_chemical_formula_weight         3055.11
_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
_audit_creation_date             2024-01-22
_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                90
_cell_angle_beta                 112.1870(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.0807(2)
_cell_length_b                   20.8326(3)
_cell_length_c                   20.2215(2)
_cell_measurement_reflns_used    83254
_cell_measurement_temperature    180
_cell_measurement_theta_max      71.06
_cell_measurement_theta_min      3.65
_cell_volume                     6272.67(14)
_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)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
 5538 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  0.0311
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            95970
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         71.308
_diffrn_reflns_theta_min         3.649
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    10.708
_exptl_absorpt_correction_T_max  0.0543
_exptl_absorpt_correction_T_min  0.0222
_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            purple
_exptl_crystal_density_diffrn    1.618
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3124
_exptl_crystal_size_max          0.158
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.093
_exptl_crystal_size_rad          0.066
_refine_diff_density_max         0.822
_refine_diff_density_min         -0.696
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     806
_refine_ls_number_reflns         12024
_refine_ls_number_restraints     556
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0592
_refine_ls_R_factor_gt           0.0500
_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^)+(0.0551P)^2^+15.7711P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1199
_refine_ls_wR_factor_ref         0.1267
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10328
_reflns_number_total             12024
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00328d2.cif
_cod_data_source_block           sv-0992
_cod_depositor_comments
'Adding full bibliography for 7715827--7715828.cif.'
_cod_database_code               7715827
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 C13-C14
 1.54 with sigma of 0.02
 C41-C42
 1.54 with sigma of 0.02
 C42-C43
 1.54 with sigma of 0.02
 C42-C44
 1.54 with sigma of 0.02
 C30-C31
 1.54 with sigma of 0.02
 C42-C43A
 1.54 with sigma of 0.02
 C42-C44A
 1.54 with sigma of 0.02
 C30-C32
 1.54 with sigma of 0.02
 C25-C26
 1.54 with sigma of 0.02
 C26-C27
 1.54 with sigma of 0.02
 C26-C28
 1.54 with sigma of 0.02
 C14-C15 = C14-C15A
 1.54 with sigma of 0.02
 C14-C16 = C14-C16A
 1.54 with sigma of 0.02
 C41-C44
 2.51 with sigma of 0.04
 C41-C43
 2.51 with sigma of 0.04
 C29-C31
 2.51 with sigma of 0.04
 C41-C44A
 2.51 with sigma of 0.04
 C41-C43A
 2.51 with sigma of 0.04
 C29-C32
 2.51 with sigma of 0.04
 C13-C14 \\sim C14-C15 \\sim C14-C16
 with sigma of 0.02
 C13-C14 \\sim C14-C15A \\sim C14-C16A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O25 \\sim O26 \\sim C37 \\sim C39 \\sim C38 \\sim C40: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
O25 \\sim O26 \\sim C39A \\sim C38A \\sim C40A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
O21 \\sim O22 \\sim C30 \\sim C32 \\sim C29 \\sim C31: within 2A with sigma of
0.05 and sigma for terminal atoms of 0.1 within 2A
O27 \\sim O28 \\sim C41 \\sim C42 \\sim C44 \\sim C43: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
O27 \\sim O28 \\sim C41 \\sim C42 \\sim C43A \\sim C44A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
O19 \\sim O20 \\sim C26 \\sim C28 \\sim C25 \\sim C27: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C13 \\sim C14 \\sim C16A \\sim C15A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C13 \\sim C14 \\sim C15 \\sim C16: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C22 \\sim C24 \\sim C21 \\sim C23: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O11 \\sim C9 \\sim O12 \\sim C10 \\sim C12 \\sim C11: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 O25, O26, C37, C39, C38, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O25, O26, C39A, C38A, C40A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O21, O22, C30, C32, C29, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O27, O28, C41, C42, C44, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O27, O28, C41, C42, C43A, C44A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O19, O20, C26, C28, C25, C27
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13, O14, C13, C14, C15, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13, C14, C16A, C15A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O17, O18, C22, C24, C21, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O23, O24, C34, C36, C33, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C10, C12, O12, C9, O11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H14A)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C15A)=Sof(H15D)=
 Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(H14)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=FVAR(1)
 Sof(H42A)=Sof(C43A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=Sof(C44A)=Sof(H44D)=
 Sof(H44E)=Sof(H44F)=1-FVAR(2)
 Sof(H42)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(H43C)=FVAR(2)
 Sof(C38A)=Sof(H38A)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40A)=
 Sof(H40D)=Sof(H40E)=Sof(H40F)=1-FVAR(3)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C38)=Sof(H38)=Sof(C40)=Sof(H40A)=
 Sof(H40B)=Sof(H40C)=FVAR(3)
 Fixed Sof: H1(0.5) H2(0.5) H3(0.5) H4(0.5)
6.a Rotating group:
 O29(H29A,H29B)
6.b Ternary CH refined with riding coordinates:
 O1(H1), O2(H2), O3(H3), O4(H4), O5(H5), O6(H6), C34(H34), C26(H26), C22(H22),
 C30(H30), C6(H6A), C10(H10), C42(H42), C42(H42A), C14(H14), C14(H14A),
 C18(H18), C38(H38), C2(H2A), C38A(H38A)
6.c Me refined with everything fixed:
 C43A(H43D,H43E,H43F)
6.d Tetrahedral OH refined with riding coordinates:
 O20(H20)
6.e Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C4(H4A,H4B,H4C), C20(H20A,H20B,H20C), C24(H24A,H24B,
 H24C), C28(H28A,H28B,H28C), C7(H7A,H7B,H7C), C32(H32A,H32B,H32C), C8(H8A,H8B,
 H8C), C36(H36A,H36B,H36C), C23(H23A,H23B,H23C), C11(H11A,H11B,H11C), C27(H27A,
 H27B,H27C), C12(H12A,H12B,H12C), C31(H31A,H31B,H31C), C35(H35A,H35B,H35C),
 C19(H19A,H19B,H19C), C40(H40A,H40B,H40C), C3(H3A,H3B,H3C), C44(H44A,H44B,H44C),
  C43(H43A,H43B,H43C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C16A(H16D,H16E,
 H16F), C15A(H15D,H15E,H15F), C44A(H44D,H44E,H44F), C39A(H39D,H39E,H39F),
 C40A(H40D,H40E,H40F)
;
_shelx_res_checksum              11348
_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   5.8
_stoe_evaluation_integration_b   -0.5
_stoe_evaluation_integration_ems 0.010
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 8
_stoe_evaluation_lana_bos_l_odd_max 5
_stoe_evaluation_lana_completeness 98.7
_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 142.7
_stoe_evaluation_lana_max_2theta_desired 142.7
_stoe_evaluation_lana_mean_redundancy 8.0
_stoe_evaluation_lana_number_refls_after_or 95970
_stoe_evaluation_lana_number_refls_outliers 20861
_stoe_evaluation_lana_number_refls_total 116831
_stoe_evaluation_lana_number_refls_unique 12024
_stoe_evaluation_lana_number_refls_written 95970
_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 2/m
_stoe_evaluation_lana_table
;
2Theta          14.2   29.4   44.6   59.8   75.0   90.2  105.4  120.6  135.8
<Resolution>    5.34   2.93   2.01   1.54   1.25   1.09   0.97   0.89   0.84
N(total)         777   3480   6666   8559  19011  24366  24151  20162   9659
<Redundancy>     7.0    7.7    6.9    5.4    9.2   10.3    9.4    7.8    4.6
Complet. [%%]   100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0   90.8
<I/sigma>      122.1   92.8   50.9   29.7   10.1   10.7    7.2    6.2    5.3
R(int)         0.011  0.013  0.015  0.019  0.050  0.045  0.069  0.083  0.121
;
_stoe_measurement_identifier     SV-0992
_stoe_measurement_max_exposure_per_frame '5.0 s'
_stoe_measurement_mean_exposure_per_frame '4.4 s'
_stoe_measurement_min_exposure_per_frame '3.0 s'
_stoe_measurement_total_exposure_time '6.8 h'
_stoe_measurement_total_frame_number 5538
_stoe_measurement_total_run_number 67
_stoe_measurement_tube_power     '30.0 W'