Principles of Designing Extra-Large Pore Openings and Cages in Zeolitic Imidazolate Frameworks.
Yang, Jingjing; Zhang, Yue-Biao; Liu, Qi; Trickett, Christopher A.; Gutiérrez-Puebla, Enrique; Monge, M Ángeles; Cong, Hengjiang; Aldossary, Abdulrahman; Deng, Hexiang; Yaghi, Omar M.; Journal of the American Chemical Society 139 (2017) 6448–6455; doi:10.1021/jacs.7b02272

data_4126001
_publ_section_title
;
 Principles of Designing Extra-Large Pore Openings and Cages in Zeolitic
 Imidazolate Frameworks.
;
_journal_issue                   18
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6448
_journal_page_last               6455
_journal_paper_doi               10.1021/jacs.7b02272
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C195 H74 Br13 N52 Zn13'
_chemical_formula_sum            'C195 H77 Br13 N52 Zn13'
_chemical_formula_weight         5036.72
_chemical_name_common            ZIF-516
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_symmetry_space_group_name_Hall  'P 4nw 2abw'
_symmetry_space_group_name_H-M   'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     'intrinsic phasing'
_atom_sites_solution_secondary   'rigid body and difmap'
_audit_creation_date             2016-10-18
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   29.157(3)
_cell_length_b                   29.157(3)
_cell_length_c                   69.955(9)
_cell_measurement_reflns_used    9894
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      16.863
_cell_measurement_theta_min      2.222
_cell_volume                     59471(12)
_computing_cell_refinement       'SAINT V8.34A Bruker-AXS, Madison WI'
_computing_data_collection       'Bruker APEX2 Bruker-AXS, Madison WI'
_computing_data_reduction        'SAINT V8.34A Bruker-AXS, Madison WI'
_computing_molecular_graphics
;
Bruker SHELXTL Bruker-AXS, Madison WI
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.
and local programs
;
_computing_publication_material  'Bruker SHELXTL Bruker-AXS, Madison WI'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/4 Bruker-AXS, Madison WI'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.42
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker D8 with PHOTON 100 detector'
_diffrn_measurement_method       '\f and \w shutterless scans'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.7749
_diffrn_reflns_av_R_equivalents  0.1308
_diffrn_reflns_av_unetI/netI     0.0730
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       52
_diffrn_reflns_limit_l_min       -52
_diffrn_reflns_number            94423
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        16.950
_diffrn_reflns_theta_max         16.950
_diffrn_reflns_theta_min         1.951
_diffrn_source
;
Advanced Light Source, station 11.3.1
;
_exptl_absorpt_coefficient_mu    3.529
_exptl_absorpt_correction_T_max  0.7441
_exptl_absorpt_correction_T_min  0.3970
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1263 before and 0.0879 after correction.
The Ratio of minimum to maximum transmission is 0.5335.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.125
_exptl_crystal_description       Block
_exptl_crystal_F_000             19648
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.610
_refine_diff_density_min         -0.646
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 3971 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.498(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     609
_refine_ls_number_reflns         13193
_refine_ls_number_restraints     271
_refine_ls_restrained_S_all      7.871
_refine_ls_R_factor_all          0.1191
_refine_ls_R_factor_gt           0.0972
_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^)+(0.1586P)^2^+344.1839P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2523
_refine_ls_wR_factor_ref         0.2730
_reflns_Friedel_coverage         0.776
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                10439
_reflns_number_total             13193
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b02272_si_013.cif
_cod_data_source_block           ZIF-516
_cod_depositor_comments
'Adding full bibliography for 4125998--4126004.cif.'
_cod_original_cell_volume        59470(15)
_cod_database_code               4126001
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.872
_shelx_estimated_absorpt_t_min   0.766
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C78-C337
 2 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C161 \\sim C160 \\sim C165 \\sim C164 \\sim C163 \\sim C162 \\sim C318 \\sim
Br1E \\sim Br1F \\sim C319: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Br1J \\sim Br1I \\sim C328 \\sim C329 \\sim C237 \\sim C236 \\sim C235 \\sim
C230 \\sim C234 \\sim C238 \\sim N232 \\sim C233 \\sim N231: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
N128 \\sim C129 \\sim N127 \\sim C131 \\sim C130 \\sim C135 \\sim C134 \\sim
C133 \\sim C132 \\sim C298 \\sim Br16 \\sim C299 \\sim Br17: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C82 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C84 \\sim C343 \\sim Br1P
\\sim C291 \\sim Br80: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C106 \\sim C105 \\sim C287 \\sim Br12 \\sim Br9 \\sim C286 \\sim C104: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C196 \\sim C197 \\sim C199 \\sim C198 \\sim C200 \\sim C201 \\sim C325 \\sim
Br1H \\sim C324 \\sim Br1G: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C251 \\sim C256 \\sim C255 \\sim C254 \\sim C253 \\sim C252 \\sim C262 \\sim
Br26 \\sim C261 \\sim Br5: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C144 \\sim C268 \\sim Br14 \\sim Br25 \\sim C267 \\sim C142: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Br15 \\sim C295 \\sim C97 \\sim C96 \\sim C294 \\sim Br29 \\sim C94 \\sim C95:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Br1C \\sim C311 \\sim C44 \\sim C43 \\sim C310 \\sim Br1B: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
Br19 \\sim C306 \\sim C178 \\sim C183 \\sim C307 \\sim Br1A \\sim C182 \\sim
C179: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Br3 \\sim C279 \\sim C152 \\sim C153 \\sim C280 \\sim Br2 \\sim C154 \\sim
C151: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Br41 \\sim C265 \\sim C211 \\sim C217 \\sim C266 \\sim Br21: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Br8 \\sim C278 \\sim C4 \\sim C5 \\sim C277 \\sim Br1: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
Br13 \\sim C290 \\sim C42 \\sim C38 \\sim C288 \\sim Br34: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
Br1K \\sim C333 \\sim C31 \\sim C30 \\sim Br33 \\sim C332 \\sim C29 \\sim C32:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Br1R \\sim C347 \\sim C227 \\sim C226 \\sim Br1Q \\sim C346 \\sim C225 \\sim
C229: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Br32 \\sim C321 \\sim Br45 \\sim C451 \\sim C56 \\sim C57 \\sim C58 \\sim C55
\\sim C60 \\sim C59: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
Br27 \\sim C272 \\sim C192 \\sim C191 \\sim C271 \\sim Br6: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Br18 \\sim C303 \\sim C247 \\sim C244 \\sim C302 \\sim Br30: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Br28 \\sim C281 \\sim C124 \\sim C125 \\sim C282 \\sim Br11: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Br31 \\sim C67 \\sim C68 \\sim C315 \\sim Br1D \\sim C66 \\sim C69: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C314 \\sim Br31 \\sim C67 \\sim C68 \\sim C315 \\sim Br1D: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C174 \\sim C173 \\sim C172 \\sim C171 \\sim Br36 \\sim C264 \\sim Br4 \\sim
C263 \\sim C170 \\sim C169: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C202 \\sim N203 \\sim Br1M \\sim C336 \\sim C207 \\sim C206 \\sim C337 \\sim
C210 \\sim N204 \\sim C208 \\sim C205: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Br1L \\sim C336 \\sim Br1M \\sim C337 \\sim C209 \\sim C208 \\sim C207 \\sim
C210: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Br1M \\sim C337 \\sim Br1L \\sim C336 \\sim C209 \\sim C208 \\sim C207 \\sim
C205 \\sim C202 \\sim C210: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Br1N \\sim C340 \\sim C76 \\sim C77 \\sim C341 \\sim Br1O: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C73 \\sim C74 \\sim C78: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Br1O \\sim C341 \\sim C77 \\sim C78 \\sim C74 \\sim C73 \\sim C75 \\sim C76
\\sim C340 \\sim Br1N \\sim N70 \\sim C72 \\sim N71: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
Br7 \\sim C275 \\sim C110 \\sim C111 \\sim C274 \\sim Br10 \\sim C112 \\sim
C113 \\sim C114 \\sim C115 \\sim N107 \\sim N109 \\sim C116: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uiso(C275) = Uiso(Br7) = Uiso(Br10) = Uiso(C274)
4. Rigid body (RIGU) restrains
 Zn15, N53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Zn13, N117, N250
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Zn16, N195
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Zn23, N221
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Zn22, N157
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Zn19, N119
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N33, Zn16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Zn15, N193
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N136, Zn12, N166
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Br31(0.25) Br1D(0.25) C314(0.25) C315(0.25) Br1(0.25) Br8(0.25)
 C277(0.25) C278(0.25) Br6(0.25) Br27(0.25) C271(0.25) C272(0.25) Br33(0.25)
 Br1K(0.25) C332(0.25) C333(0.25) Br30(0.25) Br18(0.25) C302(0.25) C303(0.25)
 Br32(0.25) C321(0.25) Br45(0.25) C451(0.25) Br1A(0.25) Br19(0.25) C306(0.25)
 C307(0.25) Br1B(0.25) Br1C(0.25) C310(0.25) C311(0.25) Br1Q(0.25) Br1R(0.25)
 C346(0.25) C347(0.25) Br1E(0.25) Br1F(0.25) C318(0.25) C319(0.25) Br1G(0.25)
 Br1H(0.25) C324(0.25) C325(0.25) Br1I(0.25) Br1J(0.25) C328(0.25) C329(0.25)
 Br1L(0.25) Br1M(0.25) C336(0.25) C337(0.25) Br2(0.25) Br3(0.25) C279(0.25)
 C280(0.25) Br7(0.25) Br10(0.25) C274(0.25) C275(0.25) Br21(0.25) Br41(0.25)
 C265(0.25) C266(0.25) Br13(0.25) Br34(0.25) C288(0.25) C290(0.25) Br1P(0.25)
 Br80(0.25) C291(0.25) C343(0.25) Br15(0.25) Br29(0.25) C294(0.25) C295(0.25)
 Br9(0.25) Br12(0.25) C286(0.25) C287(0.25) Br11(0.25) Br28(0.25) C281(0.25)
 C282(0.25) Br14(0.25) Br25(0.25) C267(0.25) C268(0.25) Br4(0.25) Br36(0.25)
 C263(0.25) C264(0.25) Br1N(0.25) Br1O(0.25) C340(0.25) C341(0.25) Br16(0.25)
 C298(0.25) Br17(0.25) C299(0.25) Br5(0.25) Br26(0.25) C261(0.25) C262(0.25)
6.a Free rotating group:
 C61(C62,N63,C64,N65,C66,C67,C68,C69,Br31,Br1D,C314,C315), Br1(Br8,N2,N3,C4,C5,
 C6,C7,C8,C9,C10,C277,C278), N184(N185,C186,C187,C188,C189,C190,C191,C192,Br6,
 Br27,C271,C272), N24(N25,C26,C27,C28,C29,C30,C31,C32,Br33,Br1K,C332,C333),
 C239(N240,N241,C242,C243,C244,C245,C246,C247,Br30,Br18,C302,C303), N52(N53,C54,
 C55,C56,C57,C58,C59,C60,Br32,C321,Br45,C451), Br1A(Br19,N175,N176,C177,C178,
 C179,C180,C181,C182,C183,C306,C307), Br1B(Br1C,N49,N51,C43,C44,C45,C46,C47,C48,
 C50,C310,C311), N221(N222,C223,C224,C225,C226,C227,C228,C229,Br1Q,Br1R,C346,
 C347), Br1E(Br1F,N157,N158,C159,C160,C161,C162,C163,C164,C165,C318,C319),
 Br1G(Br1H,N193,N195,C194,C196,C197,C198,C199,C200,C201,C324,C325), Br1I(Br1J,
 N231,N232,C230,C233,C234,C235,C236,C237,C238,C328,C329), C202(N203,N204,C205,
 C206,C207,C208,C209,C210,Br1L,Br1M,C336,C337), Br2(Br3,N146,N149,C150,C151,
 C152,C153,C154,C155,C156,C279,C280), Br7(Br10,N107,N109,C110,C111,C112,C113,
 C114,C115,C116,C274,C275), Br21(Br41,N213,N214,C211,C215,C216,C217,C218,C219,
 C220,C265,C266), N33(Br13,Br34,N35,C36,C37,C38,C39,C40,C41,C42,C288,C290),
 N79(Br1P,Br80,N81,C82,C83,C84,C85,C86,C87,C88,C291,C343), N89(Br15,Br29,N90,
 C91,C92,C93,C94,C95,C96,C97,C294,C295), N98(Br9,Br12,N99,C100,C101,C102,C103,
 C104,C105,C106,C286,C287), N117(Br11,Br28,N119,C120,C121,C122,C123,C124,C125,
 C126,C281,C282), N137(Br14,Br25,N136,C138,C139,C140,C141,C142,C143,C144,C267,
 C268), N167(Br4,Br36,N166,C168,C169,C170,C171,C172,C173,C174,C263,C264),
 C76(Br1N,Br1O,N70,N71,C72,C73,C74,C75,C77,C78,C340,C341), Br16(C131,C132,C133,
 C134,C298,Br17,C130,C135,C299,N127,N128,C129), C248(Br5,Br26,N249,N250,C251,
 C252,C253,C254,C255,C256,C261,C262)
6.b Aromatic/amide H refined with riding coordinates:
 C64(H64), C66(H66), C69(H69), C6(H6), C9(H9), C10(H10), C186(H186),
 C187(H187), C190(H190), C27(H27), C29(H29), C32(H32), C243(H243), C245(H245),
 C246(H246), C54(H54), C58(H58), C177(H177), C179(H179), C182(H182), C45(H45),
 C46(H46), C50(H50), C223(H223), C225(H225), C229(H229), C159(H159), C162(H162),
  C165(H165), C194(H194), C199(H199), C201(H201), C233(H233), C235(H235),
 C238(H238), C150(H150), C151(H151), C154(H154), C112(H112), C115(H115),
 C116(H116), C215(H215), C218(H218), C220(H220), C36(H36), C37(H37), C40(H40),
 C83(H83), C84(H84), C86(H86), C93(H93), C94(H94), C95(H95), C102(H102),
 C103(H103), C106(H106), C121(H121), C123(H123), C126(H126), C138(H138),
 C141(H141), C143(H143), C168(H168), C171(H171), C174(H174), C72(H72), C75(H75),
  C78(H78), C132(H132), C135(H135), C129(H129), C248(H248), C253(H253),
 C256(H256)
;
_shelx_fab_checksum              73653
_olex2_submission_special_instructions 'No special instructions were received'