Ultrahigh Surface Area Zirconium MOFs and Insights into the Applicability of the BET Theory.
Wang, Timothy C.; Bury, Wojciech; Gómez-Gualdrón, Diego A; Vermeulen, Nicolaas A.; Mondloch, Joseph E.; Deria, Pravas; Zhang, Kainan; Moghadam, Peyman Z.; Sarjeant, Amy A.; Snurr, Randall Q.; Stoddart, J. Fraser; Hupp, Joseph T.; Farha, Omar K.; Journal of the American Chemical Society 137 (2015) 3585–3591; doi:10.1021/ja512973b

data_4123497
_publ_section_title
;
 Ultrahigh Surface Area Zirconium MOFs and Insights into the Applicability
 of the BET Theory.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3585
_journal_page_last               3591
_journal_paper_doi               10.1021/ja512973b
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C228 H114 O32 Zr6'
_chemical_formula_sum            'C228 H114 O32 Zr6'
_chemical_formula_weight         3912.51
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      cubic
_space_group_IT_number           221
_space_group_name_Hall           '-P 4 2 3'
_space_group_name_H-M_alt        'P m -3 m'
_symmetry_space_group_name_Hall  '-P 4 2 3'
_symmetry_space_group_name_H-M   'P m -3 m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2013-10-23
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   27.9293(5)
_cell_length_b                   27.9293(5)
_cell_length_c                   27.9293(5)
_cell_measurement_reflns_used    9113
_cell_measurement_temperature    225(2)
_cell_measurement_theta_max      67.606
_cell_measurement_theta_min      2.740
_cell_volume                     21786.1(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
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      225.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_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  0.0614
_diffrn_reflns_av_unetI/netI     0.0172
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            103147
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.29
_diffrn_reflns_theta_min         1.58
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    0.698
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.6922
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 
0.0810 before and 0.0624 after correction. The Ratio of minimum to maximum 
transmission is 0.9193. The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.298
_exptl_crystal_description       cube
_exptl_crystal_F_000             1978
_exptl_crystal_size_max          0.099
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.084
_refine_diff_density_max         2.467
_refine_diff_density_min         -1.185
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.653
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         3871
_refine_ls_number_restraints     3763
_refine_ls_restrained_S_all      1.544
_refine_ls_R_factor_all          0.1143
_refine_ls_R_factor_gt           0.1071
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3332
_refine_ls_wR_factor_ref         0.3502
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3266
_reflns_number_total             3871
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja512973b_si_004.cif
_cod_data_source_block           n3147b_a
_cod_depositor_comments
'Adding full bibliography for 4123497--4123500.cif.'
_cod_original_cell_volume        21786.1(12)
_cod_database_code               4123497
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.934
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C18-H18 = C49-H49
 0.94 with sigma of 0.001
 C1-C2 \\sim C16-C17 \\sim C31-C32 \\sim C46-C47 \\sim C8-C5 \\sim C23-C20
\\sim C38-C35 \\sim C53-C50 -
 C10-C9 \\sim C25-C24 \\sim C40-C39 \\sim C54-C55 \\sim C13-C61 \\sim C28-C66
\\sim C43-C68 \\sim C58-C73
 with sigma of 0.02
 C9-C8 \\sim C24-C23 \\sim C39-C38 \\sim C54-C53
 with sigma of 0.02
 C61-C74 \\sim C61-C62 \\sim C63-C62 \\sim C64-C63 \\sim C65-C64 \\sim C65-C66
\\sim C67-C66 \\sim C68-C67
 \\sim C69-C68 \\sim C70-C69 \\sim C71-C70 \\sim C72-C71 \\sim C72-C73 \\sim
C74-C73 \\sim C62-C75 \\sim C65-
 C76 \\sim C76-C69 \\sim C76-C75 \\sim C72-C75
 with sigma of 0.02
 C61-C73 \\sim C74-C72 \\sim C71-C69 \\sim C70-C76 \\sim C68-C66 \\sim C67-C65
\\sim C64-C62 \\sim C63-C75
 with sigma of 0.02
 C61-C72 \\sim C62-C73 \\sim C75-C74 \\sim C76-C67 \\sim C66-C69 \\sim C68-C65
\\sim C65-C62 \\sim C63-C76
 \\sim C64-C75 \\sim C69-C72 \\sim C70-C75 \\sim C71-C76
 with sigma of 0.02
 C58-C74 \\sim C13-C62 \\sim C28-C67 \\sim C43-C69 \\sim C58-C72 \\sim C13-C74
\\sim C28-C65 \\sim C43-C67
 with sigma of 0.02
 C57-C73 \\sim C12-C61 \\sim C27-C66 \\sim C42-C68 \\sim C49-C53 \\sim C4-C8
\\sim C19-C23 \\sim C34-C38 -
 C59-C73 \\sim C14-C61 \\sim C29-C66 \\sim C44-C68 \\sim C51-C53 \\sim C6-C8
\\sim C21-C23 \\sim C36-C38
 with sigma of 0.02
 C45-C39 \\sim C60-C54 \\sim C15-C9 \\sim C30-C24 \\sim C41-C39 \\sim C56-C54
\\sim C11-C9 \\sim C26-C24
 with sigma of 0.02
 C39-C34 \\sim C38-C41 \\sim C54-C49 \\sim C53-C56 \\sim C9-C4 \\sim C8-C11
\\sim C24-C19 \\sim C23-C26 -
 C39-C36 \\sim C38-C45 \\sim C54-C51 \\sim C53-C60 \\sim C9-C6 \\sim C8-C15
\\sim C24-C21 \\sim C23-C30
 with sigma of 0.02
 C15-C10 \\sim C11-C10 \\sim C12-C11 \\sim C13-C12 \\sim C14-C13 \\sim C15-C14
\\sim C7-C2 \\sim C7-C6 -
 C6-C5 \\sim C5-C4 \\sim C4-C3 \\sim C3-C2 \\sim C33-C32 \\sim C34-C33 \\sim
C35-C34 \\sim C36-C35 \\sim C37-
 C36 \\sim C37-C32 \\sim C56-C55 \\sim C57-C56 \\sim C58-C57 \\sim C59-C58
\\sim C60-C59 \\sim C60-C55 -
 C41-C40 \\sim C42-C41 \\sim C43-C42 \\sim C44-C43 \\sim C45-C44 \\sim C45-C40
\\sim C30-C25 \\sim C30-C29
 \\sim C29-C28 \\sim C28-C27 \\sim C27-C26 \\sim C26-C25 \\sim C48-C47 \\sim
C49-C48 \\sim C50-C49 \\sim C51-
 C50 \\sim C52-C51 \\sim C52-C47 \\sim C18-C17 \\sim C19-C18 \\sim C20-C19
\\sim C21-C20 \\sim C22-C21 -
 C22-C17
 with sigma of 0.02
 C10-C13 \\sim C11-C14 \\sim C12-C15 \\sim C25-C28 \\sim C26-C29 \\sim C27-C30
\\sim C40-C43 \\sim C41-C44
 \\sim C42-C45 \\sim C55-C58 \\sim C56-C59 \\sim C57-C60 \\sim C32-C35 \\sim
C33-C36 \\sim C34-C37 \\sim C17-
 C20 \\sim C18-C21 \\sim C19-C22 \\sim C47-C50 \\sim C48-C51 \\sim C49-C52
\\sim C2-C5 \\sim C7-C4 \\sim C6-C3
 with sigma of 0.02
 C10-C12 \\sim C11-C13 \\sim C12-C14 \\sim C13-C15 \\sim C14-C10 \\sim C15-C11
\\sim C25-C27 \\sim C26-C28
 \\sim C27-C29 \\sim C28-C30 \\sim C29-C25 \\sim C30-C26 \\sim C40-C42 \\sim
C41-C43 \\sim C42-C44 \\sim C43-
 C45 \\sim C44-C40 \\sim C45-C41 \\sim C55-C57 \\sim C56-C58 \\sim C57-C59
\\sim C58-C60 \\sim C59-C55 -
 C60-C56 \\sim C47-C49 \\sim C48-C50 \\sim C49-C51 \\sim C50-C52 \\sim C51-C47
\\sim C52-C48 \\sim C32-C34
 \\sim C33-C35 \\sim C34-C36 \\sim C35-C37 \\sim C36-C32 \\sim C37-C33 \\sim
C17-C19 \\sim C18-C20 \\sim C19-
 C21 \\sim C20-C22 \\sim C21-C17 \\sim C22-C18 \\sim C2-C6 \\sim C7-C5 \\sim
C6-C4 \\sim C5-C3 \\sim C4-C2 \\sim C3-
 C7
 with sigma of 0.02
 C31-C33 \\sim C31-C37
 with sigma of 0.02
 O1-C1 \\sim O1_$1-C1 \\sim C31-O1_$2 \\sim C31-O1_$3 \\sim O1_$4-C46 \\sim
O1_$5-C46 \\sim O1_$6-C16
 \\sim C16-O1_$7
 with sigma of 0.02
 C1-C3 \\sim C1-C7
 with sigma of 0.02
 C16-C18 \\sim C16-C22
 with sigma of 0.02
 C46-C48 \\sim C46-C52
 with sigma of 0.02
 C15-H14 \\sim C13-H14
 with sigma of 0.02
 C10-C5 \\sim C55-C50 \\sim C40-C35 \\sim C25-C20
 with sigma of 0.01
 C17-H18 \\sim C19-H18
 with sigma of 0.02
3. Restrained planarity
 C17, C18, C19, C20, C21, C22
 with sigma of 0.1
 C66, C67, C68, C69, C76, C65, C70, C71, C72, C75, C62, C63, C64, C73, C74, C61
 with sigma of 0.1
 C10, C11, C12, C13, C14, C15
 with sigma of 0.1
 C25, C26, C27, C28, C29, C30, C24, C66
 with sigma of 0.1
 C40, C41, C42, C43, C44, C45, C39, C68, H44
 with sigma of 0.01
 C55, C56, C57, C58, C59, C60, C54, C73
 with sigma of 0.1
 C47, C48, C49, C50, C51, C52, H49
 with sigma of 0.1
 C32, C33, C34, C35, C36, C37, C31
 with sigma of 0.1
 C2, C7, C6, C5, C4, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C69)
\\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C70) \\sim Ueq,
Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C62)
\\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C73) \\sim Ueq,
Uanis(C74) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C22) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34)
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq,
Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C2) \\sim Ueq,
Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim
Ueq, Uanis(C7) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq,
Uanis(C16) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C31)
\\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56) \\sim Ueq,
Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C60)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C40)
\\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq,
Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq,
Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C66) = Uanis(C67) = Uanis(C68) = Uanis(C69) = Uanis(C76) = Uanis(C65) =
Uanis(C70) = Uanis(C71) = Uanis(C72) = Uanis(C75) = Uanis(C62) = Uanis(C63) =
Uanis(C64) = Uanis(C73) = Uanis(C74) = Uanis(C61) = Uanis(C17) = Uanis(C18) =
Uanis(C19) = Uanis(C20) = Uanis(C21) = Uanis(C22) = Uanis(C32) = Uanis(C33) =
Uanis(C34) = Uanis(C35) = Uanis(C36) = Uanis(C37) = Uanis(C47) = Uanis(C48) =
Uanis(C49) = Uanis(C50) = Uanis(C51) = Uanis(C52) = Uanis(C2) = Uanis(C3) =
Uanis(C4) = Uanis(C5) = Uanis(C6) = Uanis(C7) = Uanis(C38) = Uanis(C39) =
Uanis(C8) = Uanis(C9) = Uanis(C23) = Uanis(C24) = Uanis(C16) = Uanis(C53) =
Uanis(C46) = Uanis(C31) = Uanis(C1) = Uanis(C55) = Uanis(C56) = Uanis(C57) =
Uanis(C58) = Uanis(C59) = Uanis(C60) = Uanis(C25) = Uanis(C26) = Uanis(C27) =
Uanis(C28) = Uanis(C29) = Uanis(C30) = Uanis(C40) = Uanis(C41) = Uanis(C42) =
Uanis(C43) = Uanis(C44) = Uanis(C45) = Uanis(C54) = Uanis(C10) = Uanis(C11) =
Uanis(C12) = Uanis(C13) = Uanis(C14) = Uanis(C15)
5. Others
 Fixed Sof: C1(0.0625) C2(0.0625) C3(0.0625) H3(0.0625) C4(0.0625) H4(0.0625)
 C5(0.0625) C6(0.0625) H6(0.0625) C7(0.0625) H7(0.0625) C8(0.0625) C9(0.0625)
 C10(0.0625) C11(0.0625) H11(0.0625) C12(0.0625) H12(0.0625) C13(0.0625)
 C14(0.0625) H14(0.0625) C15(0.0625) H15(0.0625) C16(0.0625) C17(0.0625)
 C18(0.0625) H18(0.0625) C19(0.0625) H19(0.0625) C20(0.0625) C21(0.0625)
 H21(0.0625) C22(0.0625) H22(0.0625) C23(0.0625) C24(0.0625) C25(0.0625)
 C26(0.0625) H26(0.0625) C27(0.0625) H27(0.0625) C28(0.0625) C29(0.0625)
 H29(0.0625) C30(0.0625) H30(0.0625) C31(0.0625) C32(0.0625) C33(0.0625)
 H33(0.0625) C34(0.0625) H34(0.0625) C35(0.0625) C36(0.0625) H36(0.0625)
 C37(0.0625) H37(0.0625) C38(0.0625) C39(0.0625) C40(0.0625) C41(0.0625)
 H41(0.0625) C42(0.0625) H42(0.0625) C43(0.0625) C44(0.0625) H44(0.0625)
 C45(0.0625) H45(0.0625) C46(0.0625) C47(0.0625) C48(0.0625) H48(0.0625)
 C49(0.0625) H49(0.0625) C50(0.0625) C51(0.0625) H51(0.0625) C52(0.0625)
 H52(0.0625) C53(0.0625) C54(0.0625) C55(0.0625) C56(0.0625) H56(0.0625)
 C57(0.0625) H57(0.0625) C58(0.0625) C59(0.0625) H59(0.0625) C60(0.0625)
 H60(0.0625) C61(0.0625) C62(0.0625) C63(0.0625) H63(0.0625) C64(0.0625)
 H64(0.0625) C65(0.0625) C66(0.0625) C67(0.0625) H67(0.0625) C68(0.0625)
 C69(0.0625) C70(0.0625) H70(0.0625) C71(0.0625) H71(0.0625) C72(0.0625)
 C73(0.0625) C74(0.0625) H74(0.0625) C75(0.0625) C76(0.0625)
 Fixed X: C1(0.5) C2(0.5) C5(0.5) C8(0.5) C9(0.5) C10(0.5) C13(0.5) C16(0.5)
 C17(0.5) C18(0.5) H18(0.5) C19(0.5) C20(0.5) C21(0.5) C22(0.5) C23(0.5)
 C24(0.5) C25(0.5) C28(0.5) C31(0.5) C32(0.5) C35(0.5) C38(0.5) C39(0.5)
 C40(0.5) C43(0.5) C46(0.5) C47(0.5) C50(0.5) C53(0.5) C54(0.5) C55(0.5)
 C58(0.5) C61(0.5) C62(0.5) C63(0.5) C64(0.5) C65(0.5) C66(0.5) C67(0.5)
 C68(0.5) C69(0.5) C70(0.5) C71(0.5) C72(0.5) C73(0.5) C74(0.5) C75(0.5)
 C76(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C11(H11), C12(H12), C14(H14), C15(H15),
 C19(H19), C21(H21), C22(H22), C26(H26), C27(H27), C29(H29), C30(H30), C33(H33),
  C34(H34), C36(H36), C37(H37), C41(H41), C42(H42), C44(H44), C45(H45),
 C48(H48), C49(H49), C51(H51), C52(H52), C56(H56), C57(H57), C59(H59), C60(H60),
  C63(H63), C64(H64), C67(H67), C70(H70), C71(H71), C74(H74)
;
_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.

Total solvent accessible volume / cell = 16316.2 Ang^3^ [74.9%]
Total electron count / cell = 3879.2
;
_shelx_res_checksum              30190
_shelx_hkl_checksum              97765