Modulation of Water Vapor Sorption by a Fourth-Generation Metal-Organic Material with a Rigid Framework and Self-Switching Pores.
Zhang, Shi-Yuan; Jensen, Stephanie; Tan, Kui; Wojtas, Lukasz; Roveto, Matthew; Cure, Jeremy; Thonhauser, Timo; Chabal, Yves J.; Zaworotko, Michael J.; Journal of the American Chemical Society 140 (2018) 12545–12552; doi:10.1021/jacs.8b07290

data_4132895
_publ_section_title
;
 Modulation of Water Vapor Sorption by a Fourth-Generation Metal-Organic
 Material with a Rigid Framework and Self-Switching Pores.
;
_journal_issue                   39
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12545
_journal_page_last               12552
_journal_paper_doi               10.1021/jacs.8b07290
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration rm
_chemical_formula_moiety
'C46 H35 Cl2 N6 O6 Zn2, 2(C F3 O3 S), 1(C7 H5 F3), C0.8 H3.2 O0.8'
_chemical_formula_sum            'C55.8 H43.2 Cl2 F9 N6 O12.8 S2 Zn2'
_chemical_formula_weight         1439.32
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-08-27
_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                90
_cell_formula_units_Z            4
_cell_length_a                   10.2985(4)
_cell_length_b                   22.9298(9)
_cell_length_c                   25.5072(9)
_cell_measurement_reflns_used    9366
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.42
_cell_measurement_theta_min      3.97
_cell_volume                     6023.3(4)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.29
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0666
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            78344
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.048
_diffrn_reflns_theta_min         2.591
_diffrn_source                   'INCOATEC Imus micro-focus source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.284
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6280
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1471 before and 0.1045 after correction. The Ratio of minimum to maximum transmission is 0.6280. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.587
_exptl_crystal_description       block
_exptl_crystal_F_000             2918
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.918
_refine_diff_density_min         -0.709
_refine_diff_density_rms         0.142
_refine_ls_abs_structure_details
;
 Flack x determined using 4945 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.168(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     963
_refine_ls_number_reflns         12497
_refine_ls_number_restraints     1024
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0681
_refine_ls_R_factor_gt           0.0657
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0945P)^2^+21.3519P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1934
_refine_ls_wR_factor_ref         0.1953
_reflns_Friedel_coverage         0.794
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.968
_reflns_number_gt                11896
_reflns_number_total             12497
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07290_si_005.cif
_cod_data_source_block           Zn23R
_cod_original_formula_sum        'C55.80 H43.20 Cl2 F9 N6 O12.80 S2 Zn2'
_cod_database_code               4132895
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.908
_shelx_estimated_absorpt_t_min   0.827
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H,H,H,H) groups, All O(H) groups
2. Restrained distances
 O4-H4 = O6-H6
 0.87 with sigma of 0.01
 F16-C64 = F17-C64 = F18-C64
 1.32 with sigma of 0.02
 F9-C55 = F7-C55 = F8-C55 = F13-C63 = F14-C63 = F15-C63
 1.32 with sigma of 0.02
 C60-C55 = C63-C49
 1.5 with sigma of 0.02
 H34A-H4 = H34-H4
 -2.2 with sigma of 0.02
 C16-O58
 -3.22 with sigma of 0.01
 S58-O10 = S58-O59 = S58-O58
 1.44 with sigma of 0.02
 C34-H4 = C25-H6
 1.92 with sigma of 0.02
 F16-F18 = F18-F17 = F17-F16
 2.1 with sigma of 0.04
 F8-F9 = F7-F9 = F8-F7 = F14-F13 = F13-F15 = F15-F14
 2.1 with sigma of 0.02
 F16-S58 = S58-F18 = S58-F17
 2.59 with sigma of 0.02
 O59-O10 = O10-O58 = O58-O59
 2.41 with sigma of 0.04
 O59-C64 = C64-O58
 2.55 with sigma of 0.01
 F14-C49 = F13-C49 = F15-C49
 2.35 with sigma of 0.04
 F7-C60 = F8-C60 = F9-C60
 2.35 with sigma of 0.04
 C55-C59 = C63-C54 = C55-C61 = C63-C50
 2.49 with sigma of 0.04
 C41B-C34 \\sim C41A-C34
 with sigma of 0.005
 Cl2B-C46B \\sim Cl2A-C46A
 with sigma of 0.005
3. Restrained planarity
 C50, C49, C54, C63
 with sigma of 0.1
 C50, C60, C59, C55
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C60 \\sim F7 \\sim C55 \\sim F8 \\sim F9 \\sim C59 \\sim C61 \\sim C58 \\sim
C62 \\sim C57 \\sim C49 \\sim C50 \\sim C54 \\sim C63 \\sim C51 \\sim C53 \\sim
F13 \\sim F14 \\sim F15 \\sim C52: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
F16 \\sim O12: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
O58 \\sim S58 \\sim O59 \\sim O10 \\sim C64 \\sim F17 \\sim F16 \\sim F18:
within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
O58 \\sim F4 \\sim F18 \\sim O11: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C41A \\sim C42A \\sim C47A \\sim C43A \\sim C46A \\sim C40A \\sim C41B \\sim
C42B \\sim C47B \\sim C43B \\sim C46B \\sim C40B \\sim Cl2A \\sim Cl2B: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Cl2A \\sim Cl2B: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C50 \\sim F7 \\sim C55 \\sim F8 \\sim F9 \\sim C60 \\sim F14 \\sim C59 \\sim
C61 \\sim C63 \\sim C58 \\sim C62 \\sim C49 \\sim F13 \\sim F15 \\sim C57 \\sim
C54 \\sim C51 \\sim C53 \\sim C52: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Cl2B \\sim C41B \\sim C42B \\sim C47B \\sim C43B \\sim C46B \\sim C40B \\sim
Cl2A \\sim C41A \\sim C42A \\sim C47A \\sim C43A \\sim C46A \\sim C40A \\sim
C34: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
S58 \\sim S2 \\sim O10 \\sim O11 \\sim O12 \\sim C48 \\sim F4 \\sim F5 \\sim F6
\\sim O59 \\sim O58 \\sim C64 \\sim F17 \\sim F16 \\sim F18: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C41A) = Uanis(C41B)
5. Rigid body (RIGU) restrains
 C41A, C42A, C47A, C43A, C46A, C40A, Cl2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C50, C49, C54, C63, C51, C53, F13, F14, F15, C52
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C61, F7, C55, F8, F9, C60, C59, C58, C62, C57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34, C41B, C42B, C47B, C43B, C46B, C40B, Cl2B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=Sof(C53)=
 Sof(H53)=Sof(C54)=Sof(H54)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(C63)=1-FVAR(1)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(C55)=Sof(C60)=Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62)=
 Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=FVAR(1)
 Sof(S58)=Sof(O59)=Sof(O58)=Sof(F17)=Sof(F16)=Sof(F18)=Sof(C64)=1-FVAR(2)
 Sof(S2)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(O11)=Sof(O12)=Sof(C48)=FVAR(2)
 Fixed Sof: Cl2B(0.2) H34A(0.2) H34(0.8) C41B(0.2) C42B(0.2) H42B(0.2)
 C47B(0.2) H47B(0.2) C43B(0.2) H43B(0.2) C46B(0.2) C40B(0.2) H40B(0.2)
 O56(0.45) H56(0.45) O57(0.35) H57A(0.35) Cl2A(0.8) C41A(0.8) C42A(0.8)
 H42A(0.8) C47A(0.8) H47A(0.8) C43A(0.8) H43A(0.8) C46A(0.8) C40A(0.8)
 H40A(0.8) C15(0.8) H15D(0.45) H15E(0.45) H15F(0.45) H15A(0.35) H15B(0.35)
 H15C(0.35)
7.a Ternary CH refined with riding coordinates:
 C25(H25), C34(H34A), C34(H34)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6A), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13),
  C14(H14), C0AA(H0AA), C16(H16), C17(H17), C19(H19), C21(H21), C22(H22),
 C24(H24), C26(H26), C28(H28), C31(H31), C32(H32), C35(H35), C36(H36), C37(H37),
  C38(H38), C39(H39), C42B(H42B), C47B(H47B), C43B(H43B), C40B(H40B), C44(H44),
 C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C61(H61), C62(H62), C57(H57),
  C58(H58), C59(H59), C42A(H42A), C47A(H47A), C43A(H43A), C40A(H40A)
7.c Fitted hexagon refined as free rotating group:
 C41B(C42B,C47B,C43B,C46B,C40B), C49(C50,C51,C52,C53,C54), C60(C61,C62,C57,C58,
 C59), C41A(C42A,C47A,C43A,C46A,C40A)
7.d Idealised Me refined as rotating group:
 C15(H15D,H15E,H15F), C15(H15A,H15B,H15C)
7.e Idealised tetrahedral OH refined as rotating group:
 O56(H56), O57(H57A)
;
_olex2_submission_special_instructions 'No special instructions were received'