Atomically precise surface chemistry of zirconium and hafnium metal oxo clusters beyond carboxylate ligands.
Unniram Parambil, Ajmal Roshan; Pokratath, Rohan; Parammal, Muhammed Jibin; Dhaene, Evert; Van den Eynden, Dietger; Balog, Sandor; Prescimone, Alessandro; Infante, Ivan; Shahgaldian, Patrick; De Roo, Jonathan; Chemical science 15 (2024) 17380–17396; doi:10.1039/d4sc03859b

data_1572828
_publ_section_title
;
 Atomically precise surface chemistry of zirconium and hafnium metal oxo
 clusters beyond carboxylate ligands.
;
_journal_issue                   42
_journal_name_full               'Chemical science'
_journal_page_first              17380
_journal_page_last               17396
_journal_paper_doi               10.1039/d4sc03859b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C72 H76 O32 P12 Zr6, 1[CH2Cl2]'
_chemical_formula_sum            'C73 H78 Cl2 O32 P12 Zr6'
_chemical_formula_weight         2457.21
_chemical_name_systematic        Zr6-phenylphosphinate
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-05-28 deposited with the CCDC.	2024-09-20 downloaded from the CCDC.
;
_cell_angle_alpha                89.897(2)
_cell_angle_beta                 80.487(2)
_cell_angle_gamma                64.685(2)
_cell_formula_units_Z            2
_cell_length_a                   14.4003(3)
_cell_length_b                   15.2252(4)
_cell_length_c                   24.9863(6)
_cell_measurement_reflns_used    156099
_cell_measurement_temperature    150
_cell_measurement_theta_max      56.12
_cell_measurement_theta_min      2.81
_cell_volume                     4869.4(2)
_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  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150
_diffrn_detector                 Pilatus300K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 300K'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_details
;
 7913 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    '1.2 0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34143
_diffrn_reflns_av_R_equivalents  0.0713
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            91695
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        53.597
_diffrn_reflns_theta_max         55.813
_diffrn_reflns_theta_min         3.004
_diffrn_source                   'Metal Jet D2+'
_diffrn_source_current           3.57
_diffrn_source_power             0.250
_diffrn_source_voltage           70
_exptl_absorpt_coefficient_mu    5.402
_exptl_absorpt_correction_T_max  0.0179
_exptl_absorpt_correction_T_min  0.0050
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.676
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2452
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and hexane  by solvent layering'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.197
_exptl_crystal_size_min          0.17
_exptl_crystal_size_rad          0.200
_refine_diff_density_max         2.005
_refine_diff_density_min         -1.778
_refine_diff_density_rms         0.202
_refine_ls_extinction_coef       0.00014(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1127
_refine_ls_number_reflns         18798
_refine_ls_number_restraints     333
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0972
_refine_ls_R_factor_gt           0.0871
_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^)+(0.1418P)^2^+28.5759P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2444
_refine_ls_wR_factor_ref         0.2570
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15770
_reflns_number_total             18798
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03859b4.cif
_cod_data_source_block           Zr6O8H4(OOP(H)Ph)12
_cod_depositor_comments
'Adding full bibliography for 1572827--1572828.cif.'
_cod_database_code               1572828
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.460
_shelx_estimated_absorpt_t_min   0.383
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All P(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 Cl3-C73 \\sim Cl6-C73
 with sigma of 0.02
 Cl4-C11 \\sim Cl1-C11
 with sigma of 0.02
 Cl5-C37 \\sim Cl2-C37
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C41 \\sim C21 \\sim C43 \\sim C8 \\sim C45 \\sim C23: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C18 \\sim C20 \\sim C22 \\sim C24 \\sim C26 \\sim C28: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C72 \\sim C74 \\sim C75 \\sim C19 \\sim C39 \\sim C7: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C67 \\sim C61 \\sim C65 \\sim C66 \\sim C6 \\sim C46: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C72) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C73) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Cl4) = Uanis(Cl1)
Uanis(Cl2) = Uanis(Cl5)
Uanis(C11) = Uanis(C37)
4. Rigid body (RIGU) restrains
 C41, C21, C43, C8, C45, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18, C20, C22, C24, C26, C28
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C72, C74, C75, C19, C39, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6, C46, C61, C67, C65, C66
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl1(0.25) Cl4(0.25) C11(0.25) H11A(0.25) H11B(0.25) Cl6(0.25)
 Cl3(0.25) C73(0.25) H73A(0.25) H73B(0.25) Cl2(0.2) Cl5(0.2) C37(0.2) H37A(0.2)
 H37B(0.2)
6.a Riding coordinates:
 P1(H1), P4(H4), P6(H6), P8(H8), P10(H10), P12(H12), P3(H3), P7(H7), P2(H2),
 P9(H9), P5(H5), P11(H11)
6.b Ternary CH refined with riding coordinates:
 O1(H1A), O6(H6A), O14(H14), O24(H24)
6.c Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C73(H73A,H73B), C37(H37A,H37B)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1B), C76(H76), C20(H20), C22(H22), C24(H24A), C26(H26), C28(H28),
 C34(H34), C36(H36), C38(H38), C40(H40), C42(H42), C44(H44), C46(H46), C48(H48),
  C50(H50), C52(H52), C54(H54), C56(H56), C58(H58), C60(H60), C62(H62),
 C64(H64), C66(H66), C68(H68), C70(H70), C74(H74), C75(H75), C19(H19), C39(H39),
  C7(H7A), C21(H21), C43(H43), C8(H8A), C45(H45), C23(H23), C47(H47), C49(H49),
 C25(H25), C51(H51), C13(H13), C53(H53), C27(H27), C55(H55), C9(H9A), C57(H57),
 C29(H29), C59(H59), C15(H15), C61(H61), C31(H31), C63(H63), C10(H10A),
 C65(H65), C33(H33), C67(H67), C17(H17), C69(H69), C35(H35), C71(H71)
6.e Fitted hexagon refined as free rotating group:
 C18(C20,C22,C24,C26,C28), C72(C74,C75,C19,C39,C7), C41(C21,C43,C8,C45,C23)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              10029
_shelx_hkl_checksum              59858
_shelx_fab_checksum              24767
_olex2_date_sample_submission    2023-07-12
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id ARUP207
_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   8.0
_stoe_evaluation_integration_b   0.1
_stoe_evaluation_integration_ems 0.014
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 4
_stoe_evaluation_lana_bos_l_odd_max 1
_stoe_evaluation_lana_completeness 98.3
_stoe_evaluation_lana_dxs_max_order 1
_stoe_evaluation_lana_dys_max_order 1
_stoe_evaluation_lana_fs_max_order 3
_stoe_evaluation_lana_max_2theta_available 111.7
_stoe_evaluation_lana_max_2theta_desired 111.7
_stoe_evaluation_lana_mean_redundancy 4.9
_stoe_evaluation_lana_number_refls_after_or 91725
_stoe_evaluation_lana_number_refls_outliers 38362
_stoe_evaluation_lana_number_refls_total 130087
_stoe_evaluation_lana_number_refls_unique 18807
_stoe_evaluation_lana_number_refls_written 91725
_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          11.6   23.4   35.2   47.0   58.8   70.6   82.4   94.2  106.0
<Resolution>    5.97   3.17   2.18   1.62   1.37   1.16   1.02   0.92   0.85
N(total)         486   1514   3183  10631  23055  23637  25365  24948  17268
<Redundancy>     2.8    2.5    2.5    4.8    7.4    5.8    5.2    4.7    3.5
Complet. [%%]    99.2  100.0   99.1   99.9  100.0   99.9   99.9   99.6   92.3
<I/sigma>      258.5  129.5   73.3   61.1   30.0   22.7   15.4    9.2    7.4
R(int)         0.083  0.066  0.061  0.062  0.068  0.066  0.076  0.102  0.115
;
_stoe_measurement_identifier     ARUP207_150K
_stoe_measurement_max_exposure_per_frame '1.0 s'
_stoe_measurement_mean_exposure_per_frame '0.9 s'
_stoe_measurement_min_exposure_per_frame '0.5 s'
_stoe_measurement_total_exposure_time '119 min'
_stoe_measurement_total_frame_number 7913
_stoe_measurement_total_run_number 37
_stoe_measurement_tube_power     '250 W'