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_1572827
_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 Hf6 O32 P12, 1.45[CH2Cl2]'
_chemical_formula_sum            'C73.45 H78.9 Cl2.9 Hf6 O32 P12'
_chemical_formula_weight         3019.05
_chemical_name_systematic        Hf6-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             2023-09-14
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-05-28 deposited with the CCDC.	2024-09-20 downloaded from the CCDC.
;
_cell_angle_alpha                89.932(2)
_cell_angle_beta                 99.740(2)
_cell_angle_gamma                115.133(2)
_cell_formula_units_Z            2
_cell_length_a                   14.3934(3)
_cell_length_b                   15.1871(3)
_cell_length_c                   24.9430(5)
_cell_measurement_reflns_used    142830
_cell_measurement_temperature    150
_cell_measurement_theta_max      56.22
_cell_measurement_theta_min      3.00
_cell_volume                     4849.75(19)
_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 0.991
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_details
;
 5577 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  0.0541
_diffrn_reflns_av_unetI/netI     0.0306
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            69963
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        53.597
_diffrn_reflns_theta_max         55.904
_diffrn_reflns_theta_min         4.168
_diffrn_source                   'Metal Jet D2+'
_diffrn_source_current           3.57
_diffrn_source_power             0.250
_diffrn_source_voltage           70
_exptl_absorpt_coefficient_mu    9.992
_exptl_absorpt_correction_T_max  0.0003
_exptl_absorpt_correction_T_min  0.0001
_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    2.067
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2874
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and pentane by solvent layering.'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.173
_exptl_crystal_size_min          0.16
_exptl_crystal_size_rad          0.170
_refine_diff_density_max         3.035
_refine_diff_density_min         -1.265
_refine_diff_density_rms         0.226
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     976
_refine_ls_number_reflns         18736
_refine_ls_number_restraints     793
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0984
_refine_ls_R_factor_gt           0.0899
_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^)+(0.1000P)^2^+35.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2276
_refine_ls_wR_factor_ref         0.2348
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14870
_reflns_number_total             18736
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03859b4.cif
_cod_data_source_block           Hf6O8H4(OOP(H)Ph)12
_cod_depositor_comments
'Adding full bibliography for 1572827--1572828.cif.'
_cod_original_formula_sum        'C73.45 H78.90 Cl2.90 Hf6 O32 P12'
_cod_database_code               1572827
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.298
_shelx_estimated_absorpt_t_min   0.266
_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
 Cl2-C9 \\sim Cl1-C9
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C62 \\sim C30 \\sim C3 \\sim C69 \\sim C17 \\sim C57: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C14 \\sim C24 \\sim C22 \\sim C20 \\sim C18 \\sim C16: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C34 \\sim C36 \\sim C38 \\sim C40 \\sim C42 \\sim C44: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C46 \\sim C63 \\sim C2 \\sim C65 \\sim C33 \\sim C71: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C1 \\sim C4 \\sim C12 \\sim C8 \\sim C6 \\sim C10: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C39 \\sim C5 \\sim C41 \\sim C21 \\sim C43 \\sim C11: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C68 \\sim C70 \\sim C72 \\sim C73 \\sim C37 \\sim C19: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C25 \\sim C51 \\sim C13 \\sim C53 \\sim C27 \\sim C55: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C1 \\sim C12 \\sim C10 \\sim C8 \\sim C6 \\sim C4: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C32 \\sim C28 \\sim C26 \\sim C66 \\sim C35 \\sim C47: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C29 \\sim C23 \\sim C59 \\sim C64 \\sim C31 \\sim C15: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C58 \\sim C60 \\sim C50 \\sim C52 \\sim C54 \\sim C56: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C25) = Uanis(C51) = Uanis(C13) = Uanis(C53) = Uanis(C27) = Uanis(C55)
4. Rigid body (RIGU) restrains
 C62, C30, C3, C69, C17, C57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14, C24, C22, C20, C18, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34, C36, C38, C40, C42, C44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C46, C63, C2, C65, C33, C71
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C4, C12, C8, C6, C10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, C5, C41, C21, C43, C11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C68, C70, C72, C73, C37, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C25, C51, C13, C53, C27, C55
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C12, C10, C8, C6, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C32, C28, C26, C66, C35, C47
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C23, C59, C64, C31, C15
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C54, C56, C58, C60, C50, C52
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl1(0.2) Cl2(0.2) C9(0.2) H9A(0.2) H9B(0.2)
6.a Riding coordinates:
 P74(H74), P77(H77), P79(H79), P81(H81), P83(H83), P85(H85), P76(H76),
 P80(H80), P75(H75), P82(H82), P78(H78), P84(H84)
6.b Ternary CH refined with riding coordinates:
 O26(H26), O17(H17), O19(H19), O5(H5)
6.c Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
6.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C8(H8), C10(H10), C12(H12), C16(H16), C18(H18), C20(H20),
 C22(H22), C24(H24), C66(H66), C35(H35), C47(H47), C32(H32), C28(H28), C30(H30),
  C36(H36), C38(H38), C40(H40), C42(H42), C44(H44), C46(H46), C49(H49), C7(H7),
 C45(H45), C67(H67), C61(H61), C52(H52), C54(H54), C56(H56), C58(H58), C60(H60),
  C70(H70), C72(H72), C73(H73), C37(H37), C19(H19A), C5(H5A), C41(H41),
 C21(H21), C43(H43), C11(H11), C3(H3), C51(H51), C13(H13), C53(H53), C27(H27),
 C55(H55), C57(H57), C15(H15), C31(H31), C59(H59), C23(H23), C29(H29), C63(H63),
  C2(H2), C33(H33), C17(H17A), C69(H69), C71(H71)
6.e Fitted hexagon refined as free rotating group:
 C1(C4,C6,C8,C10,C12), C14(C16,C18,C20,C22,C24), C26(C66,C35,C47,C32,C28),
 C34(C36,C38,C40,C42,C44), C48(C49,C7,C45,C67,C61), C50(C52,C54,C56,C58,C60),
 C68(C70,C72,C73,C37,C19), C39(C5,C41,C21,C43,C11), C25(C51,C13,C53,C27,C55),
 C15(C31,C64,C59,C23,C29)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              17436
_shelx_hkl_checksum              81700
_shelx_fab_checksum              23958
_olex2_date_sample_data_collection 2023-09-05
_olex2_date_sample_submission    2023-08-14
_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_150K
_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 6
_stoe_evaluation_lana_bos_l_odd_max 3
_stoe_evaluation_lana_completeness 98.0
_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 111.9
_stoe_evaluation_lana_max_2theta_desired 111.9
_stoe_evaluation_lana_mean_redundancy 3.7
_stoe_evaluation_lana_number_refls_after_or 69974
_stoe_evaluation_lana_number_refls_outliers 25937
_stoe_evaluation_lana_number_refls_total 95911
_stoe_evaluation_lana_number_refls_unique 18744
_stoe_evaluation_lana_number_refls_written 69974
_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          13.7   25.3   36.9   48.5   60.1   71.7   83.3   94.9  106.5
<Resolution>    4.98   2.95   2.09   1.59   1.34   1.14   1.01   0.91   0.84
N(total)         283    916   1985   9145  17034  17805  18557  18161  12025
<Redundancy>     1.7    1.7    1.8    4.0    5.4    4.4    4.0    3.6    2.7
Complet. [%%]    95.3   93.6   96.4   99.9  100.0  100.0   99.9   99.3   92.5
<I/sigma>      108.3  100.0   50.0   58.8   27.8   21.4   13.3    7.7    6.4
R(int)         0.028  0.024  0.035  0.045  0.057  0.067  0.100  0.139  0.169
;
_stoe_measurement_identifier     ARUP207b_150K
_stoe_measurement_max_exposure_per_frame '5.0 s'
_stoe_measurement_mean_exposure_per_frame '4.4 s'
_stoe_measurement_min_exposure_per_frame '1.0 s'
_stoe_measurement_total_exposure_time '6.8 h'
_stoe_measurement_total_frame_number 5577
_stoe_measurement_total_run_number 26
_stoe_measurement_tube_power     '250 W'