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_4131833
_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'
_audit_creation_date             2016-03-16
_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                   19.5041(13)
_cell_length_b                   19.5041(13)
_cell_length_c                   32.072(3)
_cell_measurement_reflns_used    3037
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      25.1460
_cell_measurement_theta_min      1.9360
_cell_volume                     12200.5(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      295(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1592
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.701
_diffrn_measured_fraction_theta_max 0.701
_diffrn_measurement_details
;
  1 omega    4.00   60.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870    0.0000  150.0000 56

  2 omega   -5.00   40.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870  -53.0000   17.0000 45

  3 omega  -49.00  -16.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870  134.0000  123.0000 33

  4 omega  -30.00    5.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870   39.0000  -12.0000 35

  5 omega  -25.00   10.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870   13.0000   -3.0000 35

  6 omega   10.00   66.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4874  -97.0000 -143.0000 56

  7 omega  -57.00   -4.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500   53.0000  -17.0000 53

  8 omega    1.00   15.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -81.0000   29.0000 14

  9 omega   13.00   26.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -97.0000   35.0000 13

 10 omega  -20.00   13.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -53.0000   17.0000 33

 11 omega   -5.00   27.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -97.0000 -143.0000 32

 12 omega  -20.00    8.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870   81.0000  151.0000 28

 13 omega   -7.00   51.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870  -37.0000 -180.0000 58

 14 omega   29.00   70.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4870 -114.0000   44.0000 41

 15 omega  -52.00    0.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500   39.0000  167.0000 52

 16 omega  -25.00   29.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -39.0000   12.0000 54

 17 omega  -28.00   19.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500  -39.0000 -167.0000 47

 18 omega   27.00   37.00   1.0000   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -28.0500 -114.0000   44.0000 10
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0016513000
_diffrn_orient_matrix_UB_12      0.0317447000
_diffrn_orient_matrix_UB_13      0.0106255000
_diffrn_orient_matrix_UB_21      -0.0350492000
_diffrn_orient_matrix_UB_22      -0.0060058000
_diffrn_orient_matrix_UB_23      0.0047563000
_diffrn_orient_matrix_UB_31      0.0097543000
_diffrn_orient_matrix_UB_32      -0.0164986000
_diffrn_orient_matrix_UB_33      0.0188394000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2276
_diffrn_reflns_av_unetI/netI     0.2924
_diffrn_reflns_Laue_measured_fraction_full 0.701
_diffrn_reflns_Laue_measured_fraction_max 0.701
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            3862
_diffrn_reflns_point_group_measured_fraction_full 0.701
_diffrn_reflns_point_group_measured_fraction_max 0.701
_diffrn_reflns_theta_full        17.220
_diffrn_reflns_theta_max         17.220
_diffrn_reflns_theta_min         2.088
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.833
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.08486
_exptl_absorpt_correction_type   multi-scan
_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)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.541
_exptl_crystal_F_000             5668
_exptl_crystal_size_max          0.1152
_exptl_crystal_size_mid          0.0844
_exptl_crystal_size_min          0.0508
_refine_diff_density_max         1.327
_refine_diff_density_min         -0.975
_refine_diff_density_rms         0.190
_refine_ls_extinction_coef       0.0005(3)
_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   1.062
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     73
_refine_ls_number_reflns         1340
_refine_ls_number_restraints     113
_refine_ls_restrained_S_all      6.633
_refine_ls_R_factor_all          0.2378
_refine_ls_R_factor_gt           0.1388
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.001
_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          0.3201
_refine_ls_wR_factor_ref         0.3972
_reflns_Friedel_coverage         0.000
_reflns_number_gt                631
_reflns_number_total             1340
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            HfMOF_All.cif
_cod_data_source_block           hfmof_3.55kbar
_cod_original_cell_volume        12201(2)
_cod_database_code               4131833
_chemical_oxdiff_formula         'C88 H72 Hf6 O32'
_chemical_oxdiff_usercomment
'HfMOF1 in DAC, 4:1MeOH/EtOH, 3.6 kbar 28-10-2015'
_reflns_odcompleteness_completeness 69.29
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     17.19
_olex2_refinement_description
;
1. 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
2. Restrained angles
 C7-C6-C12
 fixed at 120 with sigma of 0.02
 C5-C6-C12
 fixed at 120 with sigma of 0.02
 C7-C6-C12
 fixed at 120 with sigma of 0.02
 C5-C6-C12
 fixed at 120 with sigma of 0.02
 C6-C12-C5
 fixed at 120 with sigma of 0.02
 C7-C6-C12
 fixed at 120 with sigma of 0.02
 C12-C6-C7
 fixed at 120 with sigma of 0.02
 C5-C6-C12
 fixed at 120 with sigma of 0.02
 C6-C12-O13
 fixed at 120 with sigma of 0.02
 O13-C12-C6
 fixed at 120 with sigma of 0.02
 C9-C3-C4
 fixed at 120 with sigma of 0.02
 C3-C9-C4
 fixed at 120 with sigma of 0.02
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)
 Fixed Uiso: C15D(0.05) C9D(0.05)
8.a Fitted hexagon refined as free rotating group:
 C9(C16,C15,C15D,C9D,C10)
;
_shelx_res_checksum              60732
_shelx_hkl_checksum              12209
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'