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_4131840
_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                   19.1867(13)
_cell_length_b                   19.1867(13)
_cell_length_c                   32.543(3)
_cell_measurement_reflns_used    3422
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.7810
_cell_measurement_theta_min      1.9410
_cell_volume                     11980.0(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.1592
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.586
_diffrn_measured_fraction_theta_max 0.586
_diffrn_measurement_details
;
  1 omega    4.00   58.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870    0.0000  150.0000 54

  2 omega   -5.00   43.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870  -53.0000   17.0000 48

  3 omega  -49.00  -16.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870  134.0000  123.0000 33

  4 omega  -30.00    4.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870   39.0000  -12.0000 34

  5 omega  -25.00   12.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870   13.0000   -3.0000 37

  6 omega    8.00   65.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4874  -97.0000 -143.0000 57

  7 omega  -28.00  -20.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870   97.0000  -35.0000 8

  8 omega  -57.00   -2.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500   53.0000  -17.0000 55

  9 omega   -4.00   15.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -81.0000   29.0000 19

 10 omega   11.00   26.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -97.0000   35.0000 15

 11 omega  -21.00   13.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -53.0000   17.0000 34

 12 omega   -6.00   27.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -97.0000 -143.0000 33

 13 omega  -20.00    4.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870   81.0000  151.0000 24

 14 omega   -7.00   51.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870  -37.0000 -180.0000 58

 15 omega  -29.00  -19.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870   97.0000  -35.0000 10

 16 omega   21.00   70.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870 -114.0000   44.0000 49

 17 omega  -52.00    5.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500   39.0000  167.0000 57

 18 omega  -25.00   29.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -39.0000   12.0000 54

 19 omega  -28.00   24.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -39.0000 -167.0000 52

 20 omega   23.00   27.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500 -114.0000   44.0000 4
;
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.3884
_diffrn_reflns_av_unetI/netI     0.4289
_diffrn_reflns_Laue_measured_fraction_full 0.586
_diffrn_reflns_Laue_measured_fraction_max 0.586
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            17634
_diffrn_reflns_point_group_measured_fraction_full 0.586
_diffrn_reflns_point_group_measured_fraction_max 0.586
_diffrn_reflns_theta_full        25.955
_diffrn_reflns_theta_max         25.955
_diffrn_reflns_theta_min         1.954
_exptl_absorpt_coefficient_mu    2.619
_exptl_absorpt_correction_T_max  0.028
_exptl_absorpt_correction_T_min  0.003
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    0.751
_exptl_crystal_F_000             2568
_exptl_crystal_size_max          0.1224
_exptl_crystal_size_mid          0.0976
_exptl_crystal_size_min          0.0524
_refine_diff_density_max         2.204
_refine_diff_density_min         -3.667
_refine_diff_density_rms         0.260
_refine_ls_extinction_coef       0.00015(12)
_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   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     75
_refine_ls_number_reflns         3513
_refine_ls_number_restraints     113
_refine_ls_restrained_S_all      4.391
_refine_ls_R_factor_all          0.3713
_refine_ls_R_factor_gt           0.1800
_refine_ls_shift/su_max          0.097
_refine_ls_shift/su_mean         0.036
_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          0.3851
_refine_ls_wR_factor_ref         0.4902
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1003
_reflns_number_total             3513
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            HfMOF_All.cif
_cod_data_source_block           hfmof_17.9kbar
_cod_original_cell_volume        11980.0(19)
_cod_database_code               4131840
_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              21388
_shelx_hkl_checksum              71520
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-11-10
_olex2_submission_special_instructions 'No special instructions were received'