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_4123499
_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 H162 O32 Zr6'
_chemical_formula_sum            'C228 H162 O32 Zr6'
_chemical_formula_weight         3960.89
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-02-04
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   24.3050(9)
_cell_length_b                   24.3050(9)
_cell_length_c                   24.3050(9)
_cell_measurement_reflns_used    9876
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      67.467
_cell_measurement_theta_min      2.571
_cell_volume                     14357.8(9)
_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    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.997
_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  0.0382
_diffrn_reflns_av_unetI/netI     0.0094
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            93713
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.121
_diffrn_reflns_theta_min         1.818
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.060
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.6924
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0669 before and 0.0481 after correction.
The Ratio of minimum to maximum transmission is 0.9195.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.458
_exptl_crystal_description       block
_exptl_crystal_F_000             2026
_exptl_crystal_size_max          0.114
_exptl_crystal_size_mid          0.111
_exptl_crystal_size_min          0.066
_refine_diff_density_max         2.689
_refine_diff_density_min         -1.889
_refine_diff_density_rms         0.196
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     186
_refine_ls_number_reflns         2599
_refine_ls_number_restraints     3708
_refine_ls_restrained_S_all      1.803
_refine_ls_R_factor_all          0.1249
_refine_ls_R_factor_gt           0.1183
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.002
_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          0.3845
_refine_ls_wR_factor_ref         0.4034
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2373
_reflns_number_total             2599
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja512973b_si_002.cif
_cod_data_source_block           n3287
_cod_depositor_comments
'Adding full bibliography for 4123497--4123500.cif.'
_cod_original_cell_volume        14357.8(16)
_cod_database_code               4123499
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.889
_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
 C3-C2 \\sim C7-C2 \\sim C7-C6 \\sim C6-C5 \\sim C5-C4 \\sim C4-C3 \\sim C8-C13
\\sim C13-C12 \\sim C12-C11 -
 C11-C10 \\sim C9-C10 \\sim C9-C8 \\sim C48-C47 \\sim C52-C47 \\sim C52-C51
\\sim C51-C50 \\sim C50-C49 -
 C49-C48 \\sim C58-C53 \\sim C58-C57 \\sim C57-C56 \\sim C56-C55 \\sim C55-C54
\\sim C54-C53 \\sim C33-C32
 \\sim C37-C32 \\sim C37-C36 \\sim C36-C35 \\sim C35-C34 \\sim C34-C33 \\sim
C39-C38 \\sim C40-C39 \\sim C41-
 C40 \\sim C42-C41 \\sim C43-C42 \\sim C43-C38 \\sim C18-C17 \\sim C19-C18
\\sim C20-C19 \\sim C21-C20 -
 C22-C21 \\sim C22-C17 \\sim C28-C23 \\sim C28-C27 \\sim C27-C26 \\sim C26-C25
\\sim C25-C24 \\sim C24-C23
 \\sim C74-C61 \\sim C74-C73 \\sim C73-C72 \\sim C72-C71 \\sim C71-C70 \\sim
C70-C69 \\sim C69-C68 \\sim C68-
 C67 \\sim C67-C66 \\sim C66-C65 \\sim C65-C64 \\sim C64-C63 \\sim C63-C62
\\sim C62-C61 \\sim C75-C62 -
 C75-C72 \\sim C76-C75 \\sim C76-C69 \\sim C76-C65
 with sigma of 0.02
 C2-C1 \\sim C8-C5 \\sim C61-C11 \\sim C53-C50 \\sim C73-C56 \\sim C38-C35
\\sim C68-C41 \\sim C23-C20 -
 C66-C26
 with sigma of 0.02
 C9-C14 \\sim C15-C12 \\sim C60-C58 \\sim C59-C55 \\sim C45-C43 \\sim C44-C40
\\sim C29-C25 \\sim C30-C28
 with sigma of 0.02
 C2-C5 \\sim C7-C4 \\sim C3-C6 \\sim C8-C11 \\sim C13-C10 \\sim C12-C9 \\sim
C47-C50 \\sim C52-C49 \\sim C51-
 C48 \\sim C53-C56 \\sim C58-C55 \\sim C57-C54 \\sim C32-C35 \\sim C37-C34
\\sim C36-C33 \\sim C38-C41 -
 C39-C42 \\sim C40-C43 \\sim C17-C20 \\sim C18-C21 \\sim C19-C22 \\sim C23-C26
\\sim C28-C25 \\sim C27-C24
 with sigma of 0.02
 C8-C12 \\sim C13-C11 \\sim C12-C10 \\sim C11-C9 \\sim C10-C8 \\sim C9-C13
 with sigma of 0.02
 C8-C14 \\sim C10-C14 \\sim C11-C15 \\sim C13-C15 \\sim C24-C29 \\sim C26-C29
\\sim C27-C30 \\sim C23-C30
 \\sim C38-C45 \\sim C42-C45 \\sim C41-C44 \\sim C39-C44 \\sim C53-C60 \\sim
C57-C60 \\sim C56-C59 \\sim C54-C59
 with sigma of 0.02
 O1_$1-C1 \\sim O1-C1
 with sigma of 0.02
 C67-C69 \\sim C68-C66 \\sim C65-C63 \\sim C64-C62 \\sim C61-C73 \\sim C74-C72
\\sim C75-C71 \\sim C70-C76
 with sigma of 0.02
 C67-C76 \\sim C68-C65 \\sim C69-C66 \\sim C75-C74 \\sim C73-C62 \\sim C72-C61
\\sim C72-C69 \\sim C71-C76
 \\sim C75-C70 \\sim C62-C65 \\sim C75-C64 \\sim C63-C76
 with sigma of 0.02
 C1-C3 \\sim C1-C7 \\sim C4-C8 \\sim C6-C8 \\sim C10-C61 \\sim C12-C61 \\sim
C29-C24 \\sim C20-C28 \\sim C25-
 C66 \\sim C27-C66 \\sim C34-C38 \\sim C36-C38 \\sim C40-C68 \\sim C42-C68
\\sim C49-C53 \\sim C51-C53 -
 C55-C73 \\sim C57-C73
 with sigma of 0.02
 C11-C62 \\sim C11-C74 \\sim C26-C65 \\sim C26-C67 \\sim C41-C67 \\sim C41-C69
\\sim C56-C72 \\sim C56-C74
 with sigma of 0.02
3. Restrained planarity
 C8, C13, C12, C11, C10, C9, C14, C15
 with sigma of 0.1
 C53, C58, C57, C56, C55, C54, C59, C60
 with sigma of 0.1
 C23, C28, C27, C26, C25, C24, C29, C30
 with sigma of 0.1
 C38, C39, C40, C41, C42, C43, C44, C45
 with sigma of 0.1
 C35, C38, C41, C68
 with sigma of 0.1
 C20, C23, C26, C66
 with sigma of 0.1
 C17, C18, C19, C20, C21, C22
 with sigma of 0.1
 C47, C48, C49, C50, C51, C52
 with sigma of 0.1
 C47, C48, C49, C50, C51, C52
 with sigma of 0.1
 C23, C24, C25, C26, C27, C28, C29, C30, C20
 with sigma of 0.1
 C47, C48, C49, C50, C51, C52, C53
 with sigma of 0.1
 C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C66
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C62)
\\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C63) \\sim Ueq,
Uanis(C64) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C69)
\\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C66) \\sim Ueq,
Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C57) \\sim Ueq,
Uanis(C58) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq,
Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C40) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C43)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C35) \\sim Ueq,
Uanis(C34) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C47) \\sim Ueq,
Uanis(C52) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C3)
\\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C6) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C4) \\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(C1) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C59)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C29) \\sim Ueq,
Uanis(C30) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq: with sigma of
0.05 and sigma for terminal atoms of 0.1
Uanis(C73) = Uanis(C74) = Uanis(C61) = Uanis(C62) = Uanis(C75) = Uanis(C72) =
Uanis(C63) = Uanis(C64) = Uanis(C65) = Uanis(C76) = Uanis(C69) = Uanis(C70) =
Uanis(C71) = Uanis(C66) = Uanis(C67) = Uanis(C68) = Uanis(C56) = Uanis(C11) =
Uanis(C26) = Uanis(C41) = Uanis(C57) = Uanis(C58) = Uanis(C53) = Uanis(C54) =
Uanis(C55) = Uanis(C10) = Uanis(C9) = Uanis(C8) = Uanis(C13) = Uanis(C12) =
Uanis(C25) = Uanis(C24) = Uanis(C23) = Uanis(C28) = Uanis(C27) = Uanis(C40) =
Uanis(C39) = Uanis(C38) = Uanis(C43) = Uanis(C42) = Uanis(C36) = Uanis(C35) =
Uanis(C34) = Uanis(C33) = Uanis(C32) = Uanis(C37) = Uanis(C49) = Uanis(C48) =
Uanis(C47) = Uanis(C52) = Uanis(C51) = Uanis(C50) = Uanis(C3) = Uanis(C2) =
Uanis(C7) = Uanis(C6) = Uanis(C5) = Uanis(C4) = Uanis(C17) = Uanis(C18) =
Uanis(C19) = Uanis(C20) = Uanis(C21) = Uanis(C22) = Uanis(C1) = Uanis(C60) =
Uanis(C59) = Uanis(C14) = Uanis(C15) = Uanis(C29) = Uanis(C30) = Uanis(C44) =
Uanis(C45)
5. Others
 Fixed Sof: 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)
 H10(0.0625) C11(0.0625) C12(0.0625) C13(0.0625) H13(0.0625) C14(0.0625)
 H14A(0.0625) H14B(0.0625) H14C(0.0625) C15(0.0625) H15A(0.0625) H15B(0.0625)
 H15C(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) H24(0.0625) C25(0.0625) C26(0.0625) C27(0.0625) H27(0.0625)
 C28(0.0625) C29(0.0625) H29A(0.0625) H29B(0.0625) H29C(0.0625) C30(0.0625)
 H30A(0.0625) H30B(0.0625) H30C(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) H39(0.0625) C40(0.0625) C41(0.0625)
 C42(0.0625) H42(0.0625) C43(0.0625) C44(0.0625) H44A(0.0625) H44B(0.0625)
 H44C(0.0625) C45(0.0625) H45A(0.0625) H45B(0.0625) H45C(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) H54(0.0625)
 C55(0.0625) C56(0.0625) C57(0.0625) H57(0.0625) C58(0.0625) C59(0.0625)
 H59A(0.0625) H59B(0.0625) H59C(0.0625) C60(0.0625) H60A(0.0625) H60B(0.0625)
 H60C(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 Y: C2(0.5) C3(0.5) C4(0.5) C5(0.5) C6(0.5) C7(0.5) C8(0.5) C11(0.5)
 C26(0.5) C32(0.5) C33(0.5) C34(0.5) C35(0.5) C36(0.5) C37(0.5) C38(0.5)
 C41(0.5) C47(0.5) C48(0.5) C49(0.5) C50(0.5) C51(0.5) C52(0.5) C53(0.5)
 C54(0.5) C55(0.5) C56(0.5) C57(0.5) C58(0.5) C59(0.5) C60(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 Me refined with riding coordinates:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C59(H59A,H59B,H59C), C60(H60A,
 H60B,H60C)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C10(H10), C13(H13), C18(H18), C19(H19),
 C21(H21), C22(H22), C24(H24), C27(H27), C33(H33), C34(H34), C36(H36), C37(H37),
  C39(H39), C42(H42), C48(H48), C49(H49), C51(H51), C52(H52), C54(H54),
 C57(H57), 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 = 8027.3 Ang^3^ [55.9%]
Total electron count / cell = 1553.0
;
_shelx_res_checksum              87597
_shelx_hkl_checksum              87767