Dynamic Topochemical Reaction Tuned by Guest Molecules in the Nanospace of a Metal-Organic Framework.
Kusaka, Shinpei; Kiyose, Atsushi; Sato, Hiroshi; Hijikata, Yuh; Hori, Akihiro; Ma, Yunsheng; Matsuda, Ryotaro; Journal of the American Chemical Society 141 (2019) 15742–15746; doi:10.1021/jacs.9b07682

data_4128316
_publ_section_title
;
 Dynamic Topochemical Reaction Tuned by Guest Molecules in the Nanospace
 of a Metal-Organic Framework.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15742
_journal_page_last               15746
_journal_paper_doi               10.1021/jacs.9b07682
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C26.19 H18.31 N0.94 O4 Zn, C4 H9 N O'
_chemical_formula_sum            'C29 H33 N2 O5 Zn'
_chemical_formula_weight         554.94
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                76.954(2)
_cell_angle_beta                 78.816(3)
_cell_angle_gamma                83.430(2)
_cell_formula_units_Z            2
_cell_length_a                   8.5379(3)
_cell_length_b                   11.6565(3)
_cell_length_c                   14.3665(5)
_cell_measurement_reflns_used    8189
_cell_measurement_temperature    93
_cell_measurement_theta_max      28.48
_cell_measurement_theta_min      2.92
_cell_volume                     1362.69(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.9b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT Version 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      93.15
_diffrn_detector_area_resol_mean 5.811
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.859
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       \w
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0561
_diffrn_reflns_av_unetI/netI     0.0511
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.859
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            23309
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.859
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.398
_diffrn_reflns_theta_min         2.438
_exptl_absorpt_coefficient_mu    0.942
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.723
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            nONE
_exptl_crystal_density_diffrn    1.352
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       nONE
_exptl_crystal_F_000             582
_refine_diff_density_max         1.164
_refine_diff_density_min         -1.225
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     663
_refine_ls_number_reflns         6439
_refine_ls_number_restraints     512
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.0720
_refine_ls_R_factor_gt           0.0621
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1079P)^2^+1.9562P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1621
_refine_ls_wR_factor_ref         0.1688
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5571
_reflns_number_total             6439
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07682_si_007.cif
_cod_data_source_block           xcalibur
_cod_database_code               4128316
_shelx_shelxl_version_number     2014/7
_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
 O5-C51
 1.3 with sigma of 0.02
 N5-O6 = O6-C56
 2.55 with sigma of 0.02
 C55-C57 = C55-C58
 2.42 with sigma of 0.01
 C55-H57B
 2.7 with sigma of 0.001
 C55-O6 = O5-C51
 1.1 with sigma of 0.02
 C51-N4 = C55-N5
 1.3 with sigma of 0.02
 C52-C51 = C55-C56
 1.5 with sigma of 0.02
 C40-C41 = C41-C42 = C42-C43 = C43-C44 = C44-C45 = C45-C40
 1.39 with sigma of 0.02
 C40-C42 = C41-C43 = C42-C44 = C43-C45 = C44-C40
 2.41 with sigma of 0.02
 C38-C59 = C59-C60 = C60-C61
 1.39 with sigma of 0.02
 C61-C62 = C62-C63 = C63-C38
 1.39 with sigma of 0.02
 C38-C60 = C59-C61 = C60-C62
 2.41 with sigma of 0.02
 C61-C63 = C62-C38 = C63-C59
 2.41 with sigma of 0.02
 C31-C32 = C36-C37
 1.32 with sigma of 0.02
 C21-C22 = C22-C23 = C23-C24 = C24-C25
 1.39 with sigma of 0.02
 C21-C23 = C22-C24 = C23-C25
 2.41 with sigma of 0.02
 C24-C31 = C22-C31
 2.41 with sigma of 0.02
 N2-C25 = N2-C21
 1.37 with sigma of 0.02
 N2-C24 = N2-C22
 2.36 with sigma of 0.02
 C26-C27 = C27-C28 = C28-C29 = C29-C30
 1.39 with sigma of 0.02
 C26-C28 = C27-C29 = C28-C30
 2.41 with sigma of 0.02
 C36-C27 = C36-C29
 2.41 with sigma of 0.02
 N3-C26 = N3-C30
 1.37 with sigma of 0.02
 N3-C29 = N3-C27
 2.36 with sigma of 0.02
 C23-C31 = C28-C36
 1.48 with sigma of 0.02
 C50-C49 = C49-C48 = C48-C47
 1.39 with sigma of 0.02
 C50-C48 = C49-C47
 2.41 with sigma of 0.02
 N1-C16 = N1-C20
 1.37 with sigma of 0.02
 N1-C17 = N1-C19
 2.36 with sigma of 0.02
 C16-C17 = C17-C18 = C18-C19 = C19-C20
 1.39 with sigma of 0.02
 C16-C18 = C17-C19 = C18-C20
 2.41 with sigma of 0.02
 C39-C46
 1.58 with sigma of 0.02
 C46-C35
 2.07 with sigma of 0.02
 C50-C39 = C47-C46
 1.48 with sigma of 0.02
 C39-C49 = C39-C47 = C46-C50 = C46-C48
 2.45 with sigma of 0.02
 C50-C35
 2.1 with sigma of 0.02
 C37-C38 = C35-C39
 1.48 with sigma of 0.02
 C34-C19 = C34-C17
 2.41 with sigma of 0.02
 C18-C34
 1.51 with sigma of 0.001
 C35-C34
 1.58 with sigma of 0.02
 C34-C36
 1.51 with sigma of 0.02
 C34-C39
 2.35 with sigma of 0.02
 C34-C46
 1.58 with sigma of 0.02
 C32-C23 = C35-C18 = C37-C28
 2.4 with sigma of 0.02
 C39-C35
 1.58 with sigma of 0.02
 C35-C39
 1.58 with sigma of 0.02
 C39-C35 = C35-C39
 1.58 with sigma of 0.02
 C35-C39 = C39-C35
 1.58 with sigma of 0.01
 C35-C39_$1
 1.58 with sigma of 0.01
 C52-C53
 2.42 with sigma of 0.001
 H53B-N4
 1.85 with sigma of 0.0001
 C51-H53C
 2.758 with sigma of 0.001
 C53-C51
 2.15 with sigma of 0.02
 N4-C53 = N4-C54 = N5-C57 = N5-C58
 1.32 with sigma of 0.02
 H53C-H4_$2
 -2 with sigma of 0.02
 H53B-H4_$2
 -2 with sigma of 0.02
3. Restrained atomic chiral volume
 C55, C56, N5
 fixed at 0.05 with sigma of 0.1
 N4, C54, C53, C51
 fixed at 0.05 with sigma of 0.1
4. Restrained planarity
 C45, C44, C42, C41, C43, C40
 with sigma of 0.1
 C38, C59, C60, C63, C62, C62
 with sigma of 0.1
 C22, C23, C24, C21, N2, C25, C31, C32
 with sigma of 0.1
 C28, C27, C26, N3, C29, C30, C36, C37
 with sigma of 0.1
 C14, C15, C9, C13, C10, C64
 with sigma of 0.1
 C50, C49, C47, C48
 with sigma of 0.1
 N1, C16, C17, C20, C19, C18
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
O5 \\sim N4: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C57 \\sim C56 \\sim C55 \\sim N5 \\sim C58 \\sim O6: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
O5 \\sim O6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C54 \\sim C58: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C51 \\sim C55: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C51 \\sim N4 \\sim N5: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C56 \\sim C52: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C31 \\sim C32: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C45 \\sim C44 \\sim C42 \\sim C41 \\sim C43 \\sim C40: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C36 \\sim C37: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C38 \\sim C59 \\sim C60 \\sim C63 \\sim C61 \\sim C62: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C30 \\sim C29 \\sim C28 \\sim C27 \\sim C26: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C9 \\sim C10 \\sim C64 \\sim C13 \\sim C14 \\sim C15: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C50 \\sim C48: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
N1 \\sim N2 \\sim N3: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02
N1 \\sim C16 \\sim C17 \\sim C20 \\sim C19 \\sim C18: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002
C35 \\sim C39: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C39 \\sim C50 \\sim C48 \\sim C46 \\sim C49 \\sim C47: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C35 \\sim C46 \\sim C34 \\sim C39: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C53 \\sim O5 \\sim C54 \\sim C52 \\sim C51 \\sim N4: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
C53 \\sim C57: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C34) = Uanis(C39)
6. Others
 Sof(N1)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C20)=Sof(H20)=Sof(C19)=
 Sof(H19)=Sof(C18)=Sof(C35)=Sof(H35)=Sof(C39)=Sof(C50)=Sof(H50)=Sof(C49)=
 Sof(H49)=Sof(C47)=Sof(H47)=Sof(C48)=Sof(H48)=Sof(C34)=Sof(H34)=Sof(C46)=
 Sof(H46)=FVAR(1)
 Sof(C22)=Sof(H22)=Sof(C23)=Sof(C24)=Sof(H24)=Sof(C21)=Sof(H21)=Sof(N2)=
 Sof(C25)=Sof(H25)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C45)=Sof(H45)=
 Sof(C44)=Sof(H44)=Sof(C42)=Sof(H42)=Sof(C41)=Sof(H41)=Sof(C43)=Sof(H43)=
 Sof(C40)=FVAR(2)
 Sof(C28)=Sof(C27)=Sof(H27)=Sof(C26)=Sof(H26)=Sof(N3)=Sof(C29)=Sof(H29)=
 Sof(C30)=Sof(H30)=Sof(C36)=Sof(H36)=Sof(C37)=Sof(H37)=Sof(C59)=Sof(H59)=
 Sof(C60)=Sof(H60)=Sof(C63)=Sof(H63)=Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62)=FVAR(3)
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=
 Sof(C55)=Sof(N5)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(O6)=1-FVAR(4)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(O5)=Sof(C54)=Sof(H54A)=Sof(H54B)=
 Sof(H54C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C51)=Sof(N4)=FVAR(4)
7.a Ternary CH refined with riding coordinates:
 C35(H35), C34(H34), C46(H46)
7.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C4(H4), C3(H3), C6(H6), C7(H7), C16(H16), C10(H10),
 C17(H17), C20(H20), C22(H22), C19(H19), C24(H24), C21(H21), C25(H25), C27(H27),
  C26(H26), C29(H29), C30(H30), C36(H36), C31(H31), C37(H37), C32(H32),
 C45(H45), C44(H44), C42(H42), C41(H41), C43(H43), C50(H50), C49(H49), C47(H47),
  C48(H48), C59(H59), C60(H60), C63(H63), C61(H61), C62(H62), C64(H64)
7.c Idealised Me refined as rotating group:
 C53(H53A,H53B,H53C), C57(H57A,H57B,H57C), C54(H54A,H54B,H54C), C56(H56A,H56B,
 H56C), C52(H52A,H52B,H52C), C58(H58A,H58B,H58C)
;
_shelx_res_checksum              90944
_shelx_hkl_checksum              99654
_olex2_submission_special_instructions 'No special instructions were received'