A Hafnium-Based Metal-Organic Framework as a Nature-Inspired Tandem Reaction Catalyst.
Beyzavi, M. Hassan; Vermeulen, Nicolaas A.; Howarth, Ashlee J.; Tussupbayev, Samat; League, Aaron B.; Schweitzer, Neil M.; Gallagher, James R.; Platero-Prats, Ana E; Hafezi, Nema; Sarjeant, Amy A.; Miller, Jeffrey T.; Chapman, Karena W.; Stoddart, J. Fraser; Cramer, Christopher J.; Hupp, Joseph T.; Farha, Omar K.; Journal of the American Chemical Society 137 (2015) 13624–13631; doi:10.1021/jacs.5b08440

data_4129574
_publ_section_title
;
 A Hafnium-Based Metal-Organic Framework as a Nature-Inspired Tandem
 Reaction Catalyst.
;
_journal_issue                   42
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13624
_journal_page_last               13631
_journal_paper_doi               10.1021/jacs.5b08440
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         '(C96 H56 Cl2 Fe2 Hf6 N8 O32), 2(Fe)'
_chemical_formula_sum            'C96 H56 Cl2 Fe4 Hf6 N8 O32'
_chemical_formula_weight         3198.72
_space_group_crystal_system      hexagonal
_space_group_IT_number           191
_space_group_name_Hall           '-P 6 2'
_space_group_name_H-M_alt        'P 6/m m m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-20
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   42.7645(13)
_cell_length_b                   42.7645(13)
_cell_length_c                   16.7556(5)
_cell_measurement_reflns_used    4053
_cell_measurement_temperature    250(2)
_cell_measurement_theta_max      52.852
_cell_measurement_theta_min      2.637
_cell_volume                     26537.3(14)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      249.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.665
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1282
_diffrn_reflns_av_unetI/netI     0.0673
_diffrn_reflns_Laue_measured_fraction_full 0.665
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            58687
_diffrn_reflns_point_group_measured_fraction_full 0.665
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         53.437
_diffrn_reflns_theta_min         1.193
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    4.751
_exptl_absorpt_correction_T_max  0.7505
_exptl_absorpt_correction_T_min  0.6401
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1106 before and 0.0687 after correction.
The Ratio of minimum to maximum transmission is 0.8529.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    0.600
_exptl_crystal_description       needle
_exptl_crystal_F_000             4542
_exptl_crystal_size_max          0.112
_exptl_crystal_size_mid          0.017
_exptl_crystal_size_min          0.017
_refine_diff_density_max         1.371
_refine_diff_density_min         -0.942
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.962
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     195
_refine_ls_number_reflns         5902
_refine_ls_number_restraints     204
_refine_ls_restrained_S_all      0.963
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0433
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0778P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1228
_refine_ls_wR_factor_ref         0.1280
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4223
_reflns_number_total             5902
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b08440_si_002.cif
_cod_data_source_block           cx0273
_cod_original_cell_volume        26537.3(18)
_cod_database_code               4129574
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.618
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(Fe2) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(Cl1A) = Uanis(Cl1)
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(Cl1A)=0.25*(1-FVAR(2))
 Sof(Cl1)=0.25*FVAR(2)
 Fixed Sof: Fe2(0.125) Fe3(0.125)
5.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C10(H10)
;
_smtbx_masks_special_details
;
The solvent masking procedure as implemented in Olex2 was used to remove the
electronic contribution of solvent molecules from the refinement.  As the exact
solvent content is not known, only the atoms used in the refinement model are
reported in the formula here.  Evidence exists that suggests additional Cl atoms
are present in the void space to balance charges of the additional Fe atoms. 

While we were able to locate the Fe atoms surrounding the Hf core, we did not
observe localized electron density corresponding to partially occupied Cl atoms.
It is likely they they have been removed via solvent masking.

Total solvent accessible volume / cell = 20041.7 Ang^3^ [75.5%]
Total electron count / cell = 7718.1
;
_shelx_res_checksum              82420
_shelx_hkl_checksum              95743
_olex2_date_sample_data_collection 2015-02-12
_olex2_date_sample_submission    2015-02-11
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in oil'
_olex2_submission_original_sample_id 218
_olex2_submission_special_instructions 'No special instructions were received'