Vapor-Phase Metalation by Atomic Layer Deposition in a Metal-Organic Framework
Joseph E. Mondloch; Wojciech Bury; David Fairen-Jimenez; Stephanie Kwon; Erica J. DeMarco; Mitchell H. Weston; Amy A. Sarjeant; SonBinh T. Nguyen; Peter C. Stair; Randall Q. Snurr; Omar K. Farha; Joseph T. Hupp; Journal of the American Chemical Society 135 (2013) 10294–10297; doi:10.1021/ja4050828

data_4120127
_publ_section_title
;
 Vapor-Phase Metalation by Atomic Layer Deposition in a Metal-Organic
 Framework
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10294
_journal_page_last               10297
_journal_paper_doi               10.1021/ja4050828
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C88 H44 O32 Zr6'
_chemical_formula_sum            'C88 H44 O32 Zr6'
_chemical_formula_weight         2160.55
_chemical_name_systematic
;
 ?
;
_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'
_symmetry_space_group_name_Hall  '-P 6 2'
_symmetry_space_group_name_H-M   'P 6/m m m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2013-03-29
_audit_creation_method
;
  Olex2 1.2
  (compiled Mar 21 2013 11:17:50, GUI svn.r4446)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   39.3875(7)
_cell_length_b                   39.3875(7)
_cell_length_c                   16.4829(3)
_cell_measurement_reflns_used    9848
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      65.19
_cell_measurement_theta_min      2.59
_cell_volume                     22145.3(7)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXD, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      99.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.946
_diffrn_measured_fraction_theta_max 0.996
_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  0.0814
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 0.946
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            93168
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         65.23
_diffrn_reflns_theta_min         1.29
_diffrn_source                   microsource
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.889
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6291
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1040 before and 0.0771 after correction.
The Ratio of minimum to maximum transmission is 0.8359.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.486
_exptl_crystal_description       block
_exptl_crystal_F_000             3204
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.043
_refine_diff_density_max         5.371
_refine_diff_density_min         -5.536
_refine_diff_density_rms         0.225
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.737
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     152
_refine_ls_number_reflns         7057
_refine_ls_number_restraints     133
_refine_ls_restrained_S_all      1.734
_refine_ls_R_factor_all          0.1317
_refine_ls_R_factor_gt           0.1216
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_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          0.3707
_refine_ls_wR_factor_ref         0.3858
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5862
_reflns_number_total             7057
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja4050828_si_002.cif
_cod_data_source_block           n2414
_cod_original_cell_volume        22145.3(9)
_cod_database_code               4120127
_cod_database_fobs_code          4120127
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Rigid bond restraints
 O5A, O5
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
O5A \\sim O5: within 3A with sigma of 0.005 and sigma for terminal atoms of 0.01
Uiso(O5A) = Uiso(O5)
4. others
 Fixed Sof: O5(0.25) O5A(0.25)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C11(H11), C12(H12)
;
_smtbx_masks_special_details
;

The solvent masking procedure as implemented in Olex2 was used to remove the
electronic contribution of disordered solvent molecules as well as a partially
occupied framework that was disordered about the 6-fold axis running through
the channels of this MOF.  While the residual electron density clearly showed
evidence of a disordered node and ligands, attempts to refine these species
led to unstable refinements, despite a liberal use of restraints and 
constraints.  We elected to report here, only the structure of the
main framework.

Total solvent accessible volume / cell = 17697.6 Ang^3^ [79.9%]
Total electron count / cell = 2707.7

;
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.805
_shelxl_version_number           2012-9