Highly Stable Zr(IV)-Based Metal-Organic Frameworks with Chiral Phosphoric Acids for Catalytic Asymmetric Tandem Reactions.
Gong, Wei; Chen, Xu; Jiang, Hong; Chu, Dandan; Cui, Yong; Liu, Yan; Journal of the American Chemical Society 141 (2019) 7498–7508; doi:10.1021/jacs.9b02294

data_4128684
_publ_section_title
;
 Highly Stable Zr(IV)-Based Metal-Organic Frameworks with Chiral
 Phosphoric Acids for Catalytic Asymmetric Tandem Reactions.
;
_journal_issue                   18
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7498
_journal_page_last               7508
_journal_paper_doi               10.1021/jacs.9b02294
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C183 H102 O60 P3 Zr9'
_chemical_formula_sum            'C182.67 H102 O60 P3 Zr9'
_chemical_formula_weight         4170.53
_space_group_crystal_system      trigonal
_space_group_IT_number           154
_space_group_name_Hall           'P 32 2"'
_space_group_name_H-M_alt        'P 32 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-08-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   45.122(6)
_cell_length_b                   45.122(6)
_cell_length_c                   49.238(10)
_cell_measurement_reflns_used    635370
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      25.349
_cell_measurement_theta_min      0.903
_cell_volume                     86818(2)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0266
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       54
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       0
_diffrn_reflns_limit_k_min       -46
_diffrn_reflns_limit_l_max       59
_diffrn_reflns_limit_l_min       -59
_diffrn_reflns_number            105991
_diffrn_reflns_point_group_measured_fraction_full 0.520
_diffrn_reflns_point_group_measured_fraction_max 0.520
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         0.903
_exptl_absorpt_coefficient_mu    0.191
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    0.479
_exptl_crystal_description       block
_exptl_crystal_F_000             12498
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.932
_refine_diff_density_min         -1.023
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
No quotients, so Flack parameter determined by classical intensity fit
;
_refine_ls_abs_structure_Flack   -0.06(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.964
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1901
_refine_ls_number_reflns         55181
_refine_ls_number_restraints     5333
_refine_ls_restrained_S_all      0.957
_refine_ls_R_factor_all          0.1213
_refine_ls_R_factor_gt           0.0872
_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^)+(0.1887P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2634
_refine_ls_wR_factor_ref         0.2897
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    0.000
_reflns_Friedel_fraction_max     0.000
_reflns_number_gt                26891
_reflns_number_total             55181
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02294_si_003.cif
_cod_data_source_block           a
_cod_original_cell_volume        86818(30)
_cod_database_code               4128684
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C172-O28
 1.25 with sigma of 0.01
 O52-C164
 1.27 with sigma of 0.005
 C176-O11
 1.25 with sigma of 0.01
 C176-O12
 1.25 with sigma of 0.01
 C165-O54
 1.25 with sigma of 0.01
 C165-O55
 1.25 with sigma of 0.01
 C158-C145
 1.52 with sigma of 0.01
 C157-O58
 1.27 with sigma of 0.01
 C157-O59
 1.27 with sigma of 0.01
 C176-C40
 1.5 with sigma of 0.01
 O8-C174
 1.27 with sigma of 0.01
 C174-O7
 1.27 with sigma of 0.01
 C63-C61
 1.5 with sigma of 0.01
 C97-C81
 1.5 with sigma of 0.01
 C157-C154
 1.48 with sigma of 0.01
 C76-C172
 1.48 with sigma of 0.005
 C165-C102
 1.5 with sigma of 0.01
 C145-C158
 1.48 with sigma of 0.005
 C174-C9
 1.5 with sigma of 0.01
 C177-C31
 1.48 with sigma of 0.01
 C177-O2
 1.27 with sigma of 0.01
 C177-O1
 1.27 with sigma of 0.01
 C50-C175
 1.5 with sigma of 0.01
 C158-O57
 1.27 with sigma of 0.01
 C164-O53
 1.27 with sigma of 0.005
 C164-C112
 1.48 with sigma of 0.01
 C93-C183
 1.5 with sigma of 0.02
 C180-C179
 1.55 with sigma of 0.01
 C170-C171
 1.55 with sigma of 0.02
 C169-C170
 1.55 with sigma of 0.02
 C22-C178
 1.52 with sigma of 0.02
 C131-C161
 1.52 with sigma of 0.02
 C169-C168
 1.55 with sigma of 0.01
 C19-C35
 1.5 with sigma of 0.02
 O1-O2
 2.36 with sigma of 0.01
 O52-O53
 2.36 with sigma of 0.01
 O53-O52
 2.36 with sigma of 0.01
 O56-O57
 2.36 with sigma of 0.01
 C39-C176 \\sim C176-C41
 with sigma of 0.02
 O7-C174 \\sim C174-O8
 with sigma of 0.02
 C101-C165 \\sim C165-C103
 with sigma of 0.02
 O55-C165 \\sim C165-O54
 with sigma of 0.02
 C146-C158 \\sim C158-C144
 with sigma of 0.01
 O58-C157 \\sim C157-O59
 with sigma of 0.02
 C174-C8 \\sim C8-C10
 with sigma of 0.01
 C32-C177 \\sim C177-C30
 with sigma of 0.01
 O56-C158 \\sim C158-O57
 with sigma of 0.02
 O2_$1-O57 \\sim O57-O52_$2
 with sigma of 0.01
3. Restrained planarity
 C103, C102, C101, O54, C165, O55
 with sigma of 0.1
 C153, C154, C155, O59, O58, C157
 with sigma of 0.1
 C30, C31, C32, C177, O1, O2
 with sigma of 0.05
 C158, O57, C145, C146, C144
 with sigma of 0.1
4. Rigid bond restraints
 O56, O57, C158
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.04
 O33, O34, C183
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.04
5. Uiso/Uaniso restraints and constraints
C180 \\sim C178 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68
\\sim C146 \\sim C145 \\sim C144 \\sim C143 \\sim C142 \\sim C141 \\sim C140
\\sim C139 \\sim C138 \\sim C137 \\sim C163 \\sim C80 \\sim C81 \\sim C82 \\sim
C83 \\sim C84 \\sim C79 \\sim C183 \\sim C170 \\sim C69 \\sim C70 \\sim C71
\\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C26
\\sim C25 \\sim C24 \\sim C23 \\sim C28 \\sim C27 \\sim C32 \\sim C31 \\sim C30
\\sim C29 \\sim C133 \\sim C132 \\sim C131 \\sim C136 \\sim C135 \\sim C134
\\sim C4 \\sim C3 \\sim C2 \\sim C1 \\sim C6 \\sim C5 \\sim C10 \\sim C9 \\sim
C8 \\sim C7 \\sim C175 \\sim C153 \\sim C154 \\sim C155 \\sim C156 \\sim C151
\\sim C152 \\sim C147 \\sim C148 \\sim C149 \\sim C150 \\sim C88 \\sim C87
\\sim C86 \\sim C85 \\sim C90 \\sim C89 \\sim C94 \\sim C93 \\sim C92 \\sim C91
\\sim C168 \\sim C161 \\sim C171 \\sim C56 \\sim C55 \\sim C54 \\sim C53 \\sim
C58 \\sim C57 \\sim C62 \\sim C61 \\sim C60 \\sim C59 \\sim C181 \\sim C46
\\sim C45 \\sim C44 \\sim C43 \\sim C48 \\sim C47 \\sim C52 \\sim C51 \\sim C50
\\sim C49 \\sim C16 \\sim C15 \\sim C14 \\sim C13 \\sim C12 \\sim C11 \\sim
C169 \\sim C17 \\sim C22 \\sim C21 \\sim C20 \\sim C19 \\sim C18 \\sim C167
\\sim C98 \\sim C97 \\sim C96 \\sim C95 \\sim C100 \\sim C99 \\sim C104 \\sim
C103 \\sim C102 \\sim C101 \\sim C179 \\sim C162 \\sim C174 \\sim C117 \\sim
C116 \\sim C115 \\sim C120 \\sim C119 \\sim C118 \\sim C165 \\sim C108 \\sim
C107 \\sim C106 \\sim C105 \\sim C110 \\sim C109 \\sim C114 \\sim C113 \\sim
C112 \\sim C111 \\sim C157 \\sim C173 \\sim C160 \\sim C182 \\sim C159 \\sim
C164 \\sim C166 \\sim C172 \\sim C130 \\sim C129 \\sim C128 \\sim C127 \\sim
C126 \\sim C125 \\sim C124 \\sim C123 \\sim C122 \\sim C121 \\sim C176 \\sim
C158 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39
\\sim C40 \\sim C41 \\sim C42 \\sim C177: within 3.8A with sigma of 0.01 and
sigma for terminal atoms of 0.02
O33 \\sim O34 \\sim C183: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O56 \\sim O57 \\sim C158: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C176) = Uanis(C158)
Uanis(O11) = Uanis(O12)
Uanis(O53) = Uanis(O52)
Uanis(O39) = Uanis(O40) = Uanis(O41) = Uanis(O42)
6.a Secondary CH2 refined with riding coordinates:
 C178(H17A,H17B), C163(H16A,H16B), C170(H17C,H17D), C168(H16C,H16D), C171(H17E,
 H17F), C181(H18A,H18B), C167(H16E,H16F), C179(H17G,H17H), C162(H16G,H16H),
 C160(H16I,H16J), C182(H18C,H18D), C159(H15A,H15B)
6.b Aromatic/amide H refined with riding coordinates:
 C68(H68), C146(H146), C144(H144), C143(H143), C140(H140), C139(H139),
 C137(H137), C82(H82), C69(H69), C70(H70), C72(H72), C75(H75), C77(H77),
 C78(H78), C26(H26), C25(H25), C23(H23), C32(H32), C30(H30), C29(H29),
 C134(H134), C4(H4), C3(H3), C1(H1), C10(H10), C8(H8), C7(H7), C153(H153),
 C155(H155), C156(H156), C147(H147), C148(H148), C150(H150), C88(H88), C87(H87),
  C85(H85), C94(H94), C92(H92), C91(H91), C56(H56), C55(H55), C53(H53),
 C62(H62), C60(H60), C59(H59), C46(H46), C44(H44), C43(H43), C52(H52), C51(H51),
  C49(H49), C12(H12), C20(H20), C98(H98), C96(H96), C95(H95), C104(H104),
 C103(H103), C101(H101), C120(H120), C108(H108), C106(H106), C105(H105),
 C114(H114), C113(H113), C111(H111), C130(H130), C129(H129), C127(H127),
 C124(H124), C122(H122), C121(H121), C33(H33), C34(H34), C36(H36), C39(H39),
 C41(H41), C42(H42)
6.c Fitted hexagon refined as free rotating group:
 C63(C64,C65,C66,C67,C68), C80(C81,C82,C83,C84,C79), C133(C132,C131,C136,C135,
 C134), C16(C15,C14,C13,C12,C11), C17(C22,C21,C20,C19,C18), C117(C116,C115,C120,
 C119,C118)
6.d Naphthalene refined as free rotating group:
 C146(C145,C144,C143,C142,C141,C140,C139,C138,C137), C69(C70,C71,C72,C73,C74,
 C75,C76,C77,C78), C26(C25,C24,C23,C28,C27,C32,C31,C30,C29), C4(C3,C2,C1,C6,C5,
 C10,C9,C8,C7), C153(C154,C155,C156,C151,C152,C147,C148,C149,C150), C88(C87,C86,
 C85,C90,C89,C94,C93,C92,C91), C56(C55,C54,C53,C58,C57,C62,C61,C60,C59),
 C46(C45,C44,C43,C48,C47,C52,C51,C50,C49), C98(C97,C96,C95,C100,C99,C104,C103,
 C102,C101), C108(C107,C106,C105,C110,C109,C114,C113,C112,C111), C130(C129,C128,
 C127,C126,C125,C124,C123,C122,C121), C33(C34,C35,C36,C37,C38,C39,C40,C41,C42)
;
_shelx_res_checksum              30093
_shelx_hkl_checksum              88081
_olex2_submission_special_instructions 'No special instructions were received'