Three-dimensional protonic conductivity in porous organic cage solids
Ming Liu; Linjiang Chen; Scott Lewis; Samantha Y. Chong; Marc A. Little; Tom Hasell; Iain M. Aldous; Craig M. Brown; Martin W. Smith; Carole A. Morrison; Laurence J. Hardwick; Andrew I. Cooper; Nature Communications 7 (2016) 12750–; doi:10.1038/ncomms12750

data_1547993
_publ_section_title
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 Three-dimensional protonic conductivity in porous organic cage solids
;
_journal_name_full               'Nature Communications'
_journal_page_first              12750
_journal_paper_doi               10.1038/ncomms12750
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety         '6(O4 S), 27.25(H2 O), C48 H84 N12'
_chemical_formula_sum            'C48 H138.5 N12 O51.25 S6'
_chemical_formula_weight         1896.56
_space_group_crystal_system      orthorhombic
_space_group_IT_number           43
_space_group_name_Hall           'F 2 -2d'
_space_group_name_H-M_alt        'F d d 2'
_symmetry_space_group_name_Hall  'F 2 -2d'
_symmetry_space_group_name_H-M   'F d d 2'
_atom_sites_solution_hydrogens   geom
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   32.757(2)
_cell_length_b                   34.249(2)
_cell_length_c                   31.088(2)
_cell_measurement_reflns_used    9058
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.505
_cell_measurement_theta_min      2.756
_cell_volume                     34877(4)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection
'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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(2)
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0600
_diffrn_reflns_av_unetI/netI     0.0449
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -46
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            117747
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.128
_diffrn_reflns_theta_min         1.999
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.263
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.4338
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1287 before and 0.0899 after correction.
The Ratio of minimum to maximum transmission is 0.5814.
The \l/2 correction factor is 0.0000.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.445
_exptl_crystal_description       block
_exptl_crystal_F_000             16264
_exptl_crystal_size_max          0.171
_exptl_crystal_size_mid          0.129
_exptl_crystal_size_min          0.124
_refine_diff_density_max         1.231
_refine_diff_density_min         -0.626
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Flack x determined using 10151 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.115(14)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1302
_refine_ls_number_reflns         23450
_refine_ls_number_restraints     131
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0684
_refine_ls_R_factor_gt           0.0660
_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^)+(0.1119P)^2^+109.4371P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1824
_refine_ls_wR_factor_ref         0.1854
_reflns_Friedel_coverage         0.965
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                22347
_reflns_number_total             23450
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ncomms12750-s3.cif
_cod_data_source_block           RCC1.6(SO4).27.25(H2O)_100K
_cod_original_formula_sum        'C48 H138.50 N12 O51.25 S6'
_cod_database_code               1547993
_olex2_refinement_description
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1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H,H)
  groups, All N(H,H,H,H) groups
2. Restrained distances
 S2-O6 = S2-O8B
 1.41 with sigma of 0.01
 S2-O6
 1.41 with sigma of 0.01
 S5-O20
 1.41 with sigma of 0.01
 S4-O14A
 1.41 with sigma of 0.01
 S4-O16A
 1.41 with sigma of 0.01
 S4-O13B
 1.41 with sigma of 0.01
3. Rigid bond restraints
 C48A, C48, C47, N10
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S6, O21, O22, O23, O24, S7, O25, O26, O27, O28
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O14A, S4, O13A, O15A, O16A, O16B, O14B, O13B, O15B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(O8B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O13B) \\sim Ueq, Uanis(O13A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 S4, O13A, O14A, O15A, O16A, O13B, O14B, O15B, O16B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H10C)=Sof(H10D)=Sof(H47C)=Sof(H47D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=1-FVAR(1)
 Sof(H10A)=Sof(H10B)=Sof(H47A)=Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=FVAR(1)
 Sof(O21W)=1-FVAR(2)
 Sof(O19W)=FVAR(2)
 Sof(O13B)=Sof(O14B)=Sof(O15B)=Sof(O16B)=1-FVAR(3)
 Sof(O13A)=Sof(O14A)=Sof(O15A)=Sof(O16A)=FVAR(3)
 Fixed Sof: O6(0.75) O8(0.75) O6B(0.25) O8B(0.25) O21(0.5) O22(0.5) O23(0.5)
 O25(0.5) O26(0.5) O27(0.5) O28(0.5) O20W(0.5) O43W(0.5) O31W(0.5) O35W(0.5)
 O44W(0.25) O29W(0.3) O33W(0.5) O3W(0.5) O37W(0.5) O41W(0.5) O5W(0.25) O6W(0.6)
 O7W(0.5) O8W(0.4) O25W(0.5) O10W(0.5) O30W(0.5) O11W(0.75) O32W(0.5) O12W(0.5)
 O13W(0.25) O36W(0.5) O14W(0.5) O38W(0.25) O15W(0.5) O40W(0.5) O42W(0.5)
 O17W(0.5) O18W(0.5) O28W(0.7)
7.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B), N3(H3A,H3B), N4(H4A,H4B), N5(H5A,H5B), N6(H6A,H6B),
 N7(H7A,H7B), N8(H8A,H8B), N9(H9A,H9B), N10(H10A,H10B), N10(H10C,H10D),
 N11(H11A,H11B), N12(H12A,H12B), C7(H7C,H7D), C8(H8C,H8D), C9(H9C,H9D),
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C25(H25A,H25B), C26(H26A,H26B),
  C27(H27A,H27B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,
 H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B),
 C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B),
  C47(H47A,H47B), C47(H47C,H47D), C48(H48A,H48B), C48A(H48C,H48D)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C11(H11), C13(H13), C15(H15), C20(H20), C22(H22),
 C24(H24), C29(H29), C31(H31), C33(H33)
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_plat043_alert_1_b
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Problem:  Calculated and Reported Mol. Weight Differ by .. 219.71 Check
Response: H2O molecules were refined without H-atoms, H-atoms for these 
molecules were included in the unit cell atom count  
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_plat306_alert_2_b
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Problem: Isolated Oxygen Atom (H-atoms Missing ?)
Response: It was not possible to accurately locate H-atoms for the H2O
molecules in the crystal structure.  
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_plat430_alert_2_b
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Problem: Short Inter D...A Contact  
Response: Hydrogen bonding interactions between H2O molecules and (SO4)2- 
anions resulted in close D...A distances. 
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_shelx_res_checksum              21365
_shelx_hkl_checksum              2677
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'