Substituent Effects in the Crystallization of Zr−Hydroxamate Metal−Organic Frameworks
Liu, Yuxin; Shao, Zhen-Wu; Duan, Xiangping; Xiong, Chaozhi; Li, Xiaoting; Liu, Chong; CrystEngComm  (2026) –; doi:10.1039/D6CE00114A

data_7251805
_publ_section_title
;
 Substituent effects in the crystallization of Zr-hydroxamate
 metal--organic frameworks
;
_journal_issue                   14
_journal_name_full               CrystEngComm
_journal_page_first              2120
_journal_page_last               2124
_journal_paper_doi               10.1039/D6CE00114A
_journal_volume                  28
_journal_year                    2026
_chemical_formula_moiety
'C16 H8 Cl4 N4 O8 Zr, 2(Cl), C4 H10 O2, 2.5[CH3CH2OH]'
_chemical_formula_sum            'C22 H22 Cl6 N6 O10 Zr'
_chemical_formula_weight         834.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           72
_space_group_name_Hall           '-I 2 2c'
_space_group_name_H-M_alt        'I b a m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2026-02-03 deposited with the CCDC.	2026-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.3299(7)
_cell_length_b                   17.5645(7)
_cell_length_c                   14.9948(9)
_cell_measurement_reflns_used    13690
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.5940
_cell_measurement_theta_min      3.8360
_cell_volume                     4037.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_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   -119.00 -34.00   0.50    1.00    --  -45.68 -11.00 -64.00  170
  2  \w    -21.00   5.00   0.50    1.00    --  -45.68  11.00 108.00   52
  3  \w     -4.00  23.00   0.50    1.00    --   45.68 -11.00 -64.00   54
  4  \w     66.00 120.00   0.50    1.00    --   45.68  11.00 108.00  108
  5  \w   -172.00 -92.00   0.50    3.00    -- -102.76 -11.00 -64.00  160
  6  \w     86.00 175.00   0.50    3.00    --  102.76  11.00 108.00  178
  7  \w    -83.00 -38.00   0.50    1.00    --  -45.68 -38.00  60.00   90
  8  \w    -40.00  23.00   0.50    1.00    --  -45.68  38.00  60.00  126
  9  \w    -24.00  66.00   0.50    1.00    --   45.68 -77.00 -60.00  180
 10  \w    -26.00  54.00   0.50    1.00    --   45.68 -57.00-180.00  160
 11  \w   -168.00 -90.00   0.50    3.00    -- -102.76 -45.00  30.00  156
 12  \w   -141.00 -81.00   0.50    3.00    -- -102.76 -77.00  90.00  120
 13  \w   -100.00 -31.00   0.50    3.00    -- -102.76  77.00-150.00  138
 14  \w    -69.00 -31.00   0.50    3.00    -- -102.76  61.00-180.00   76
 15  \w   -111.00 -64.00   0.50    3.00    -- -102.76 125.00 -90.00   94
 16  \w    -62.00 -36.00   0.50    3.00    -- -102.76 140.00 168.57   52
 17  \w    -72.00 -46.00   0.50    3.00    -- -102.76 125.00 150.00   52
 18  \w   -108.00 -75.00   0.50    3.00    -- -102.76 125.00 150.00   66
 19  \w    -97.00 -34.00   0.50    3.00    -- -102.76 125.00-150.00  126
 20  \w    -67.00 -36.00   0.50    3.00    -- -102.76  61.00 150.00   62
 21  \w   -123.00 -85.00   0.50    3.00    -- -102.76 140.00 168.57   76
 22  \w     68.00  98.00   0.50    3.00    --  102.76 -95.00   0.00   60
 23  \w     51.00 111.00   0.50    3.00    --  102.76-125.00  30.00  120
 24  \w    116.00 176.00   0.50    3.00    --  102.76  15.00  30.00  120
 25  \w     32.00 105.00   0.50    3.00    --  102.76 -95.00  30.00  146
 26  \w    145.00 174.00   0.50    3.00    --  102.76  15.00 -60.00   58
 27  \w     92.00 126.00   0.50    3.00    --  102.76  15.00 -60.00   68
 28  \w     42.00  73.00   0.50    3.00    --  102.76 -61.00-120.00   62
 29  \w     80.00 111.00   0.50    3.00    --  102.76-125.00 150.00   62
 30  \w     36.00  83.00   0.50    3.00    --  102.76 -95.00-120.00   94
 31  \w     38.00  84.00   0.50    3.00    --  102.76 -95.00  90.00   92
 32  \w     46.00  75.00   0.50    3.00    --  102.76-125.00 150.00   58
 33  \w     34.00  59.00   0.50    3.00    --  102.76 -61.00-180.00   50
 34  \w     43.00 112.00   0.50    3.00    --  102.76-125.00 -30.00  138
 35  \w     58.00 112.00   0.50    3.00    --  102.76-125.00-150.00  108
 36  \w     95.00 158.00   0.50    3.00    --  102.76  61.00 150.00  126
 37  \w     31.00  77.00   0.50    3.00    --  102.76 -95.00 -30.00   92
 38  \w     55.00  80.00   0.50    3.00    --  102.76 -77.00-120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0570760000
_diffrn_orient_matrix_UB_12      0.0180628000
_diffrn_orient_matrix_UB_13      0.1287360000
_diffrn_orient_matrix_UB_21      -0.1086177000
_diffrn_orient_matrix_UB_22      0.0075248000
_diffrn_orient_matrix_UB_23      -0.0013836000
_diffrn_orient_matrix_UB_31      -0.0748238000
_diffrn_orient_matrix_UB_32      -0.1319046000
_diffrn_orient_matrix_UB_33      -0.0406606000
_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  0.2266
_diffrn_reflns_av_unetI/netI     0.0890
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            21903
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        65.058
_diffrn_reflns_theta_max         65.058
_diffrn_reflns_theta_min         5.902
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.322
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47261
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.140a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.373
_exptl_crystal_description       block
_exptl_crystal_F_000             1672
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.001
_refine_diff_density_min         -1.238
_refine_diff_density_rms         0.223
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.183
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     149
_refine_ls_number_reflns         1776
_refine_ls_number_restraints     101
_refine_ls_restrained_S_all      1.187
_refine_ls_R_factor_all          0.1374
_refine_ls_R_factor_gt           0.1355
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1229P)^2^+201.6341P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3377
_refine_ls_wR_factor_ref         0.3380
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1728
_reflns_number_total             1776
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ce00114a2.cif
_cod_data_source_block           SUM-1-Cl
_cod_depositor_comments
'Adding full bibliography for 7251803--7251805.cif.'
_cod_database_code               7251805
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Zr Cl'
_chemical_oxdiff_usercomment     'C H O N Zr Cl'
_cell_oxdiff_angle_alpha         101.359(3)
_cell_oxdiff_angle_beta          114.488(4)
_cell_oxdiff_angle_gamma         112.818(3)
_cell_oxdiff_length_a            13.8513(6)
_cell_oxdiff_length_b            13.8569(4)
_cell_oxdiff_length_c            13.8623(5)
_cell_oxdiff_measurement_reflns_used 13682
_cell_oxdiff_volume              2018.75(13)
_shelx_estimated_absorpt_t_max   0.571
_shelx_estimated_absorpt_t_min   0.518
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N4-C10
 1.46 with sigma of 0.02
 N4-C1
 1.45 with sigma of 0.02
 C2-O1
 1.22 with sigma of 0.02
 C2-N4
 1.36 with sigma of 0.02
 C2-C10
 2.45 with sigma of 0.04
 C2-C1
 2.46 with sigma of 0.04
 N4-C1 \\sim N4-C10
 with sigma of 0.02
 Cl1-C3 \\sim Cl2-C7
 with sigma of 0.02
 C9-C6 \\sim C9-C5
 with sigma of 0.02
 C6-C3 \\sim C5-C7
 with sigma of 0.02
 C6-C8 \\sim C5-C4
 with sigma of 0.02
 Cl1-C6 \\sim Cl2-C5
 with sigma of 0.04
 C9-C3 \\sim C9-C7
 with sigma of 0.04
 C9-C8 \\sim C9-C4
 with sigma of 0.04
 C3-C8 \\sim C7-C4
 with sigma of 0.04
3. Restrained planarity
 C2, O1, N4, C1, C10
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C2 \\sim O1 \\sim N4 \\sim C1 \\sim C10: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C6) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Cl2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C5) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 C2, O1, N4, C1, C10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Cl2)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(C7)=1-FVAR(1)
 Sof(Cl1)=Sof(C3)=Sof(C6)=Sof(C8)=Sof(H8)=FVAR(1)
 Fixed Sof: H1B(0.5) H1C(0.5) H1A(0.5) H10A(0.5) H10B(0.5) H10C(0.5)
7.a Riding coordinates:
 C1(H1B,H1C,H1A), C10(H10A,H10B,H10C)
7.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C4(H4), C8(H8), C2(H2)
;
_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 2.536
_oxdiff_exptl_absorpt_empirical_full_min 0.551