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_4131846
_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                   18.8445(13)
_cell_length_b                   18.8445(13)
_cell_length_c                   32.896(3)
_cell_measurement_reflns_used    3989
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      13.6940
_cell_measurement_theta_min      1.9540
_cell_volume                     11681.9(16)
_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)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1592
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.929
_diffrn_measured_fraction_theta_max 0.929
_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      4.00  64.00   1.00   90.00    --   26.49   0.00 150.00   60
  2  \w     -5.00  43.00   1.00   90.00    --   26.49 -53.00  17.00   48
  3  \w    -49.00 -16.00   1.00   90.00    --   26.49 134.00 123.00   33
  4  \w    -30.00   5.00   1.00   90.00    --   26.49  39.00 -12.00   35
  5  \w    -25.00  13.00   1.00   90.00    --   26.49  13.00  -3.00   38
  6  \w      8.00  67.00   1.00   90.00    --   26.49 -97.00-143.00   59
  7  \w    -28.00 -17.00   1.00   90.00    --   26.49  97.00 -35.00   11
  8  \w    -57.00  -1.00   1.00   90.00    --  -28.05  53.00 -17.00   56
  9  \w     -8.00  15.00   1.00   90.00    --  -28.05 -81.00  29.00   23
 10  \w      3.00  26.00   1.00   90.00    --  -28.05 -97.00  35.00   23
 11  \w    -19.00  13.00   1.00   90.00    --  -28.05 -53.00  17.00   32
 12  \w     -6.00  27.00   1.00   90.00    --  -28.05 -97.00-143.00   33
 13  \w    -20.00  11.00   1.00   90.00    --   26.49  81.00 151.00   31
 14  \w     -7.00  52.00   1.00   90.00    --   26.49 -37.00-180.00   59
 15  \w    -29.00 -16.00   1.00   90.00    --   26.49  97.00 -35.00   13
 16  \w     17.00  70.00   1.00   90.00    --   26.49-114.00  44.00   53
 17  \w    -52.00   3.00   1.00   90.00    --  -28.05  39.00 167.00   55
 18  \w    -25.00  29.00   1.00   90.00    --  -28.05 -39.00  12.00   54
 19  \w    -28.00  25.00   1.00   90.00    --  -28.05 -39.00-167.00   53
 20  \w     15.00  37.00   1.00   90.00    --  -28.05-114.00  44.00   22
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0015817000
_diffrn_orient_matrix_UB_12      0.0329298000
_diffrn_orient_matrix_UB_13      0.0103506000
_diffrn_orient_matrix_UB_21      -0.0357958000
_diffrn_orient_matrix_UB_22      -0.0068698000
_diffrn_orient_matrix_UB_23      0.0054443000
_diffrn_orient_matrix_UB_31      0.0116231000
_diffrn_orient_matrix_UB_32      -0.0168176000
_diffrn_orient_matrix_UB_33      0.0181124000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.4995
_diffrn_reflns_av_unetI/netI     0.1539
_diffrn_reflns_Laue_measured_fraction_full 0.929
_diffrn_reflns_Laue_measured_fraction_max 0.929
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            22462
_diffrn_reflns_point_group_measured_fraction_full 0.929
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        13.732
_diffrn_reflns_theta_max         13.732
_diffrn_reflns_theta_min         1.967
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.686
_exptl_absorpt_correction_T_max  0.839
_exptl_absorpt_correction_T_min  0.813
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    0.770
_exptl_crystal_F_000             2568
_exptl_crystal_size_max          0.117
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.052
_refine_diff_density_max         2.958
_refine_diff_density_min         -2.428
_refine_diff_density_rms         0.404
_refine_ls_extinction_coef       0.0007(5)
_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   1.824
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     75
_refine_ls_number_reflns         888
_refine_ls_number_restraints     88
_refine_ls_restrained_S_all      12.224
_refine_ls_R_factor_all          0.2108
_refine_ls_R_factor_gt           0.1723
_refine_ls_shift/su_max          0.784
_refine_ls_shift/su_mean         0.049
_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          0.4220
_refine_ls_wR_factor_ref         0.4635
_reflns_Friedel_coverage         0.000
_reflns_number_gt                667
_reflns_number_total             888
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            HfMOF_All.cif
_cod_data_source_block           hfmof_39.2kbar
_cod_original_cell_volume        11681.8(19)
_cod_database_code               4131846
_chemical_oxdiff_formula         'C88 H72 Hf6 O32'
_chemical_oxdiff_usercomment     'HFMOF at 39.2 KBAR'
_reflns_odcompleteness_completeness 15.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Same fragment restrains
{C16, C15, C15D, C9D, C10, C9} sigma for 1-2: 0.01, 1-3: 0.04
as
{C9, C16, C15, C15D, C9D, C10}
7. Others
 Fixed Sof: C16(0.5) C15(0.5) C15D(0.00001) C9D(0.00001) C10(0.5) H11A(0.5)
 H11B(0.5) H11C(0.5)
 Fixed Uiso: C15D(0.05) C9D(0.05)
8.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8)
8.b Fitted hexagon refined as free rotating group:
 C9(C16,C15,C15D,C9D,C10)
8.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C17(H,HA,HB)
;
_shelx_res_checksum              67046
_shelx_hkl_checksum              73857
_shelx_shelxl_version_number     2014/7
_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 2.070
_oxdiff_exptl_absorpt_empirical_full_min 0.589