Site-Specific Metal Chelation Facilitates the Unveiling of Hidden Coordination Sites in an Fe<sup>II</sup>/Fe<sup>III</sup>-Seamed Pyrogallol[4]arene Nanocapsule.
Rathnayake, Asanka S.; Fraser, Hector W. L.; Brechin, Euan K.; Dalgarno, Scott J.; Baumeister, Jakob E.; White, Joshua; Rungthanaphatsophon, Pokpong; Walensky, Justin R.; Kelley, Steven P.; Barnes, Charles L.; Atwood, Jerry L.; Journal of the American Chemical Society 140 (2018) 15611–15615; doi:10.1021/jacs.8b10186

data_4133453
_publ_section_title
;
 Site-Specific Metal Chelation Facilitates the Unveiling of Hidden
 Coordination Sites in an Fe<sup>II</sup>/Fe<sup>III</sup>-Seamed
 Pyrogallol[4]arene Nanocapsule.
;
_journal_issue                   46
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15611
_journal_page_last               15615
_journal_paper_doi               10.1021/jacs.8b10186
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C348 H431 Cl20 Fe32 N12 O100'
_chemical_formula_sum            'C348 H476 Cl20 Fe32 N12 O100'
_chemical_formula_weight         8923.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-10-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.96(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   29.594(6)
_cell_length_b                   27.812(6)
_cell_length_c                   30.175(6)
_cell_measurement_reflns_used    9937
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      60.84
_cell_measurement_theta_min      2.17
_cell_volume                     24702(9)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.2054
_diffrn_reflns_av_unetI/netI     0.1285
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            540647
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        65.319
_diffrn_reflns_theta_max         65.319
_diffrn_reflns_theta_min         1.990
_diffrn_source                   'Sealed Source Mo with TRIUMPH optics'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.784
_exptl_absorpt_correction_T_max  0.2989
_exptl_absorpt_correction_T_min  0.1230
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Bruker AXScale'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.200
_exptl_crystal_description       Prism
_exptl_crystal_F_000             9240
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_refine_diff_density_max         2.024
_refine_diff_density_min         -1.163
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1901
_refine_ls_number_reflns         41656
_refine_ls_number_restraints     176
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1860
_refine_ls_R_factor_gt           0.1166
_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^)+(0.1172P)^2^+335.6307P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2550
_refine_ls_wR_factor_ref         0.2997
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24846
_reflns_number_total             41656
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b10186_si_002.cif
_cod_data_source_block           ar8083_0m_a_sq
_cod_database_code               4133453
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.217
_shelx_estimated_absorpt_t_min   0.097
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C83-C84
 1.54 with sigma of 0.01
 C153-C154
 1.54 with sigma of 0.01
 C154-C155
 1.54 with sigma of 0.01
 C155-C156
 1.54 with sigma of 0.01
 C43-C44
 1.54 with sigma of 0.01
 C44-C45
 1.54 with sigma of 0.01
 C45-C46
 1.54 with sigma of 0.01
 C89-C90
 1.54 with sigma of 0.01
 C90-C91
 1.54 with sigma of 0.01
 C91-C92
 1.54 with sigma of 0.01
 C95-C96
 1.54 with sigma of 0.01
 C96-C97
 1.54 with sigma of 0.01
 C97-C98
 1.54 with sigma of 0.01
 C101-C102
 1.54 with sigma of 0.01
 C102-C103
 1.54 with sigma of 0.01
 C103-C104
 1.54 with sigma of 0.01
 C153-C152 = C154-C153 = C155-C154 = C156-C155
 1.54 with sigma of 0.02
 C85-C84
 1.54 with sigma of 0.02
 C85-C86
 1.54 with sigma of 0.02
 C153-C155
 2.54 with sigma of 0.01
 C154-C156
 2.54 with sigma of 0.01
 C43-C45
 2.54 with sigma of 0.01
 C44-C46
 2.54 with sigma of 0.01
 C89-C91
 2.54 with sigma of 0.01
 C90-C92
 2.54 with sigma of 0.01
 C95-C97
 2.54 with sigma of 0.01
 C96-C98
 2.54 with sigma of 0.01
 C101-C103
 2.54 with sigma of 0.01
 C102-C104
 2.54 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C125) = Uanis(C118)
Uanis(C57) = Uanis(C24)
Uanis(C56) = Uanis(C25)
Uanis(C55) = Uanis(C26)
Uanis(C58) = Uanis(C23)
Uanis(C53) = Uanis(C22)
Uanis(C54) = Uanis(C27)
Uanis(O18) = Uanis(O7)
Uanis(O17) = Uanis(O8)
Uanis(O16) = Uanis(O9)
Uanis(O19) = Uanis(O6)
Uanis(O20) = Uanis(O5)
Uanis(O21) = Uanis(O4)
Uanis(O22) = Uanis(O3)
Uanis(O23) = Uanis(O2)
Uanis(O24) = Uanis(O1)
Uanis(O34) = Uanis(O30)
Uanis(O13) = Uanis(O12)
Uanis(O14) = Uanis(O11)
Uanis(O15) = Uanis(O10)
Uanis(O35) = Uanis(O29)
Uanis(O36) = Uanis(O28)
Uanis(O33) = Uanis(O31)
Uanis(O25) = Uanis(O27)
Uanis(C123) = Uanis(C121)
Uanis(C124) = Uanis(C120)
Uanis(C127) = Uanis(C117)
Uanis(C128) = Uanis(C116)
Uanis(C129) = Uanis(C115)
Uanis(C130) = Uanis(C114)
Uanis(C131) = Uanis(C113)
Uanis(C126) = Uanis(C112)
Uanis(C106) = Uanis(C110)
Uanis(C107) = Uanis(C109)
Uanis(C62) = Uanis(C19)
Uanis(C63) = Uanis(C18)
Uanis(C64) = Uanis(C17)
Uanis(C16) = Uanis(C65)
Uanis(C15) = Uanis(C60)
Uanis(C61) = Uanis(C20)
Uanis(C21) = Uanis(C59)
Uanis(C11) = Uanis(C70)
Uanis(C10) = Uanis(C71)
Uanis(C9) = Uanis(C72)
Uanis(C67) = Uanis(C8)
Uanis(C13) = Uanis(C68)
Uanis(C69) = Uanis(C12)
Uanis(C3) = Uanis(C78)
Uanis(C78) = Uanis(C3)
Uanis(C4) = Uanis(C77)
Uanis(C76) = Uanis(C5)
Uanis(C75) = Uanis(C6)
Uanis(C74) = Uanis(C1)
Uanis(C2) = Uanis(C79)
4. Rigid body (RIGU) restrains
 C13N, C110, C105, C106, C107, C108, C109, C130, C129, C128, C127, C126, C131,
 C113, C114, C115, C116, C117, C112, C119, C124, C123, C122, C121, C120
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl3I(0.5) H42A(0.5) H42B(0.5) H42C(0.5) H42D(0.5) C43(0.5)
 H43A(0.5) H43B(0.5) H44A(0.5) H44B(0.5) H44C(0.5) H44D(0.5) H111(0.5)
 H15J(0.5) H15K(0.5) H15L(0.5) H15M(0.5) C155(0.5) H15N(0.5) H15O(0.5)
 H15P(0.5) H15Q(0.5) H15R(0.5) H15S(0.5) H15T(0.5) H15U(0.5) Cl1I(0.6)
 Cl4I(0.5) Cl2I(0.4) O0AA(0.5) O2I(0.6) C1AA(0.5) H1AA(0.5) H1AB(0.5) O9I(0.4)
 O10I(0.5) C15'(0.5) H15Y(0.5) H(0.5)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C14(H14), C21(H21), C28(H28), C59(H59), C66(H66), C73(H73), C80(H80),
 C111(H111), C118(H118), C125(H125), C132(H132)
6.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,
 H33B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B),
 C39(H39A,H39B), C41(H41A,H41B), C42(H42A,H42B), C42(H42C,H42D), C43(H43A,H43B),
  C44(H44A,H44B), C44(H44C,H44D), C45(H45A,H45B), C47(H47A,H47B), C48(H48A,
 H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C81(H81A,H81B),
 C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B), C87(H87A,H87B), C88(H88A,H88B),
  C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B), C93(H93A,H93B), C94(H94A,
 H94B), C95(H95A,H95B), C96(H96A,H96B), C97(H97A,H97B), C99(H99A,H99B),
 C100(H10A,H10B), C101(H10C,H10D), C102(H10E,H10F), C103(H10G,H10H), C133(H13A,
 H13B), C134(H13C,H13D), C135(H13E,H13F), C136(H13G,H13H), C137(H13I,H13J),
 C139(H13N,H13O), C140(H14A,H14B), C141(H14C,H14D), C142(H14E,H14F), C143(H14G,
 H14H), C145(H14L,H14M), C146(H14N,H14O), C147(H14P,H14Q), C148(H14R,H14S),
 C149(H14T,H14U), C151(H15D,H15E), C152(H15F,H15G), C153(H15H,H15I), C154(H15J,
 H15K), C154(H15L,H15M), C155(H15N,H15O), C1AA(H1AA,H1AB), C85(H85A,H85B),
 C15'(H15Y,H)
6.c Me refined with riding coordinates:
 C34(H34A,H34B,H34C), C40(H40A,H40B,H40C), C46(H46A,H46B,H46C), C52(H52A,H52B,
 H52C), C92(H92A,H92B,H92C), C98(H98A,H98B,H98C), C104(H10I,H10J,H10K),
 C138(H13K,H13L,H13M), C144(H14I,H14J,H14K), C150(H15A,H15B,H15C), C156(H15P,
 H15Q,H15R), C156(H15S,H15T,H15U), C2N(H2NA,H2NB,H2NC), C3N(H3NA,H3NB,H3NC),
 C5N(H5NA,H5NB,H5NC), C6N(H6NA,H6NB,H6NC), C8N(H8NA,H8NB,H8NC), C9N(H9NA,H9NB,
 H9NC), C11N(H11A,H11B,H11C), C12N(H12A,H12B,H12C), C14N(H14V,H14W,H14X),
 C15N(H15V,H15W,H15X), C17N(H17A,H17B,H17C), C18N(H18A,H18B,H18C), C86(H86A,
 H86B,H86C)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C8(H8), C15(H15), C22(H22), C53(H53), C60(H60), C67(H67), C74(H74),
 C105(H105), C112(H112), C119(H119), C126(H126)
;
_shelx_res_checksum              59010
_shelx_hkl_checksum              61126
_shelx_fab_checksum              51806
_olex2_submission_special_instructions 'No special instructions were received'