Unusual and Tunable Negative Linear Compressibility in the Metal-Organic Framework MFM-133(M) (M = Zr, Hf).
Yan, Yong; O'Connor, Alice E; Kanthasamy, Gopikkaa; Atkinson, George; Allan, David R.; Blake, Alexander J.; Schröder, Martin; Journal of the American Chemical Society 140 (2018) 3952–3958; doi:10.1021/jacs.7b11747

data_4131836
_publ_section_title
;
 Unusual and Tunable Negative Linear Compressibility in the Metal-Organic
 Framework MFM-133(M) (M = Zr, Hf).
;
_journal_issue                   11
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3952
_journal_page_last               3958
_journal_paper_doi               10.1021/jacs.7b11747
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C88 H72 Hf6 O32'
_chemical_formula_sum            'C88 H72 Hf6 O32'
_chemical_formula_weight         2708.36
_space_group_crystal_system      tetragonal
_space_group_IT_number           128
_space_group_name_Hall           '-P 4 2n'
_space_group_name_H-M_alt        'P 4/m n c'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-02-05
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.465(2)
_cell_length_b                   19.465(2)
_cell_length_c                   32.371(5)
_cell_measurement_reflns_used    1524
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      21.3200
_cell_measurement_theta_min      1.8840
_cell_volume                     12265(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.737
_diffrn_measured_fraction_theta_max 0.737
_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   -105.00 -85.00   0.20    0.20    --   20.00  70.00 155.77  100
  2  \w   -105.00 -74.00   0.20    0.20    --   20.00  70.00 -24.23  155
  3  \w   -106.00 -66.00   0.20    0.20    --  -20.00 -70.00-155.77  200
  4  \w   -106.00 -66.00   0.20    0.20    --  -20.00 -70.00  24.23  200
  5  \w   -150.00 -94.00   0.20    0.20    --  -20.00  70.00 -24.23  280
  6  \w   -146.60 -94.00   0.20    0.20    --  -20.00  70.00 155.77  263
  7  \w    -96.00 -30.00   0.20    0.20    --   20.00 -70.00  24.23  330
  8  \w    -96.00 -30.00   0.20    0.20    --   20.00 -70.00-155.77  330
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dectris-CrysAlisPro-abstract goniometer imported dectris images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0014124000
_diffrn_orient_matrix_UB_12      0.0295240000
_diffrn_orient_matrix_UB_13      0.0117227000
_diffrn_orient_matrix_UB_21      0.0257472000
_diffrn_orient_matrix_UB_22      -0.0141130000
_diffrn_orient_matrix_UB_23      0.0118798000
_diffrn_orient_matrix_UB_31      0.0242569000
_diffrn_orient_matrix_UB_32      0.0134676000
_diffrn_orient_matrix_UB_33      -0.0132054000
_diffrn_radiation_monochromator  synchrotron
_diffrn_radiation_probe          x-ray
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.7718
_diffrn_reflns_av_unetI/netI     0.4696
_diffrn_reflns_Laue_measured_fraction_full 0.737
_diffrn_reflns_Laue_measured_fraction_max 0.737
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            24509
_diffrn_reflns_point_group_measured_fraction_full 0.737
_diffrn_reflns_point_group_measured_fraction_max 0.737
_diffrn_reflns_theta_full        22.743
_diffrn_reflns_theta_max         22.743
_diffrn_reflns_theta_min         1.883
_diffrn_source                   synchrotron
_exptl_absorpt_coefficient_mu    2.327
_exptl_absorpt_correction_type   none
_exptl_crystal_density_diffrn    0.733
_exptl_crystal_F_000             2568
_refine_diff_density_max         5.145
_refine_diff_density_min         -3.066
_refine_diff_density_rms         0.373
_refine_ls_extinction_coef       0.009(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.244
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     77
_refine_ls_number_reflns         3425
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      3.305
_refine_ls_R_factor_all          0.4150
_refine_ls_R_factor_gt           0.2877
_refine_ls_shift/su_max          0.320
_refine_ls_shift/su_mean         0.053
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.5240
_refine_ls_wR_factor_ref         0.6662
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1034
_reflns_number_total             3425
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            HfMOF_All.cif
_cod_data_source_block           HfMOF_9.1kbar
_cod_original_cell_volume        12264(3)
_cod_database_code               4131836
_chemical_oxdiff_formula         'C88 H72 Hf6 O32'
_reflns_odcompleteness_completeness 53.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.50
_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
2. Restrained distances
 O13-C12
 1.41 with sigma of 0.01
 C12-O1
 1.41 with sigma of 0.01
 C6-C12 = C9-C3
 1.41 with sigma of 0.02
 C6-C12 = C9-C3
 1.41 with sigma of 0.01
 C9-C3 = C6-C12
 1.41 with sigma of 0.01
 Hf1-O13 = Hf2-O1
 2.11 with sigma of 0.02
 O1-C12 = O13-C12
 1.41 with sigma of 0.02
 C9-C15 = C9-C10
 1.41 with sigma of 0.02
 C10-C11 = C16-C17
 1.45 with sigma of 0.005
 C4-C5 = C7-C8
 1.39 with sigma of 0.01
 C6-C12 \\sim C9-C3
 with sigma of 0.01
 C9-C3 \\sim C6-C12
 with sigma of 0.01
 C11-C10 \\sim C16-C15 \\sim C17-C15
 with sigma of 0.01
 C9-C17 \\sim C15-C17 \\sim C9-C11 \\sim C11-C9D
 with sigma of 0.005
 C3-C7 \\sim C8-C6 \\sim C7-C5 \\sim C6-C4 \\sim C5-C3 \\sim C4-C8
 with sigma of 0.01
3. Restrained planarity
 C12, C6, C5, C4, C3, C9, C8, C7
 with sigma of 0.01
 C9, C3, C8, C7, C6, C12, C5, C4
 with sigma of 0.01
 C9, C3, C8, C4
 with sigma of 0.01
 C17, C15, C16, C10, C9, C11
 with sigma of 0.01
4. Rigid bond restraints
 C6, Hf2, Hf1, C8, C3, C5, C4, C7, C9, C10, C11, C12, C15, C16, C17, O1, O4,
 O13, O19, O20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C6 \\sim Hf2 \\sim Hf1 \\sim C8 \\sim C3 \\sim C5 \\sim C4 \\sim C7 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C15 \\sim C16 \\sim C17 \\sim O1 \\sim O4
\\sim O13 \\sim O19 \\sim O20: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
6. Others
 Fixed Sof: C16(0.5) C15(0.5) C15D(0.00001) C9D(0.00001) C10(0.5) C11(0.5)
 H11A(0.5) H11B(0.5) H11C(0.5)
 Fixed Uiso: C15D(0.05) C9D(0.05)
7.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8)
7.b Fitted hexagon refined as free rotating group:
 C9(C16,C15,C15D,C9D,C10)
7.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C17(H,HA,HB)
;
_shelx_res_checksum              21210
_shelx_hkl_checksum              1003
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.290
_oxdiff_exptl_absorpt_empirical_full_min 0.674