Two-Dimensional Metal–Organic Layers Constructed from Hf6/Hf12-oxo Clusters and Trigonal Pyramidal Phosphine Oxide Ligand
Chen, Jiawei; Ye, Zhi; Chen, Peican; Hu, Huihui; Zhang, Shuhong; Xu, Han; Cao, Lingyun; Wang, Cheng; Dalton Transactions  (2022) –; doi:10.1039/D2DT01239A

data_7710642
_publ_section_title
;
 Two-Dimensional Metal--Organic Layers Constructed from Hf6/Hf12-oxo
 Clusters and Trigonal Pyramidal Phosphine Oxide Ligand
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01239A
_journal_year                    2022
_chemical_formula_moiety         'C48 H34 O35 P2 Zr6, C3 H7 N O'
_chemical_formula_sum            'C51 H41 N O36 P2 Zr6'
_chemical_formula_weight         1853.11
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-03-17
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-03-17 deposited with the CCDC.	2022-06-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.129(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.8571(3)
_cell_length_b                   17.8537(2)
_cell_length_c                   26.4192(6)
_cell_measurement_reflns_used    15398
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.3390
_cell_measurement_theta_min      3.0960
_cell_volume                     9408.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.943
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -69.00  31.00   1.00    8.00    --  -43.34  85.00-177.00  100
  2  \w      3.00  68.00   1.00    8.00    --   43.34 -85.00  63.00   65
  3  \w    -77.00 -50.00   1.00   30.00    --  -96.00  85.00-177.00   27
  4  \w   -171.00-107.00   1.00   30.00    --  -96.00 -85.00  63.00   64
  5  \w    102.00 178.00   1.00   30.00    --  108.01  85.00-177.00   76
  6  \w     58.00 138.00   1.00   30.00    --  108.01 -85.00  63.00   80
  7  \w   -100.00 -73.00   1.00    8.00    --  -43.34-125.00-150.00   27
  8  \w    -23.00  36.00   1.00    8.00    --  -43.34  37.00 -60.00   59
  9  \w    -25.00  34.00   1.00    8.00    --  -43.34  19.00 -90.00   59
 10  \w    -50.00 -23.00   1.00   30.00    --  -96.00  45.00 150.00   27
 11  \w   -156.00-129.00   1.00   30.00    --  -96.00 -94.00 120.00   27
 12  \w   -128.00-101.00   1.00   30.00    --  -96.00 -94.00 120.00   27
 13  \w    -70.00 -45.00   1.00   30.00    --  -96.00  61.00 -60.00   25
 14  \w    -99.00 -35.00   1.00   30.00    --  -96.00  77.00  30.00   64
 15  \w    -66.00 -24.00   1.00   30.00    --  -96.00  61.00  30.00   42
 16  \w    -51.00 -22.00   1.00   30.00    --  -96.00  45.00-150.00   29
 17  \w    -71.00 -24.00   1.00   30.00    --  -96.00  61.00 150.00   47
 18  \w    -45.00 -19.00   1.00   30.00    --  -96.00  45.00 -60.00   26
 19  \w    -51.00 -19.00   1.00   30.00    --  -96.00  45.00 -30.00   32
 20  \w    -50.00 -24.00   1.00   30.00    --  -96.00  45.00 -90.00   26
 21  \w    -47.00 -19.00   1.00   30.00    --  -96.00  45.00-180.00   28
 22  \w    -45.00 -20.00   1.00   30.00    --  -96.00  45.00  30.00   25
 23  \w     37.00  68.00   1.00   30.00    --  108.01 -61.00  90.00   31
 24  \w     67.00 108.00   1.00   30.00    --  108.01 -94.00 -60.00   41
 25  \w     41.00  66.00   1.00   30.00    --  108.01 -61.00  60.00   25
 26  \w     33.00  58.00   1.00   30.00    --  108.01 -94.00 -60.00   25
 27  \w     43.00 106.00   1.00   30.00    --  108.01 -94.00-120.00   63
 28  \w     41.00  66.00   1.00   30.00    --  108.01 -61.00-120.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0119840000
_diffrn_orient_matrix_UB_12      0.0414271000
_diffrn_orient_matrix_UB_13      0.0463164000
_diffrn_orient_matrix_UB_21      0.0350148000
_diffrn_orient_matrix_UB_22      -0.0639823000
_diffrn_orient_matrix_UB_23      0.0406029000
_diffrn_orient_matrix_UB_31      0.0677967000
_diffrn_orient_matrix_UB_32      0.0404179000
_diffrn_orient_matrix_UB_33      0.0169093000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0614
_diffrn_reflns_av_unetI/netI     0.0585
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            64914
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.554
_diffrn_reflns_theta_min         3.080
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.177
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73184
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.308
_exptl_crystal_description       block
_exptl_crystal_F_000             3648
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.728
_refine_diff_density_min         -1.450
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     903
_refine_ls_number_reflns         18175
_refine_ls_number_restraints     972
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0655
_refine_ls_R_factor_gt           0.0507
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0513P)^2^+28.9531P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1191
_refine_ls_wR_factor_ref         0.1254
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14415
_reflns_number_total             18175
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01239a2.cif
_cod_data_source_block           exp_9101_auto_sq
_cod_database_code               7710642
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Zr6 C20 O30 N2'
_shelx_estimated_absorpt_t_max   0.836
_shelx_estimated_absorpt_t_min   0.524
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O29-C49 = O35-C49
 1.27 with sigma of 0.01
 O17-C25 \\sim O33-C25
 with sigma of 0.01
 O35-C49 \\sim O9-C51
 with sigma of 0.02
 O29-O35 \\sim O29-O9
 with sigma of 0.04
 O29-C49 \\sim O29-C51
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(O35) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(O17) \\sim Ueq, Uanis(O33)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O37) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
5. Others
 Fixed Sof: O35(0.32) C49(0.32) H49(0.32) C51(0.18) H51(0.18) O9(0.18)
 C13(0.5) H13(0.5) O37(0.5)
6.a Ternary CH refined with riding coordinates:
 O6(H6), O8(H8), O14(H14), O20(H20)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C16(H16), C26(H26), C30(H30), C38(H38), C46(H46), C48(H48), C50(H50),
 C52(H52), C53(H53), C27(H27), C7(H7), C15(H15), C31(H31), C2(H2), C33(H33),
 C17(H17), C35(H35), C9(H9), C37(H37), C19(H19), C39(H39), C5(H5), C41(H41),
 C21(H21), C43(H43), C11(H11), C45(H45), C23(H23), C49(H49), C25(H25), C51(H51),
  C13(H13)
6.c Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              66134
_shelx_fab_checksum              24254
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.784
_oxdiff_exptl_absorpt_empirical_full_min 0.672