Nanocapsules of unprecedented internal volume seamed by calcium ions.
Sikligar, Kanishka; Kelley, Steven P.; Wagle, Durgesh V.; Ishtaweera, Piyuni; Baker, Gary A.; Atwood, Jerry L.; Chemical science 14 (2023) 9063–9067; doi:10.1039/d3sc01629c

data_1569408
_publ_section_title
;
 Nanocapsules of unprecedented internal volume seamed by calcium ions.
;
_journal_issue                   34
_journal_name_full               'Chemical science'
_journal_page_first              9063
_journal_page_last               9067
_journal_paper_doi               10.1039/d3sc01629c
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C432 H334 Ca24 Cl6 O200'
_chemical_formula_sum            'C432 H334 Ca24 Cl6 O186'
_chemical_formula_weight         9675.59
_chemical_properties_physical    Air-sensitive,Efflorescent
_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
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-05-02
_audit_creation_method
; 
Olex2 1.2 
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506) 
;
_audit_update_record
;
2021-05-02 deposited with the CCDC.	2023-06-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.733(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   31.196(3)
_cell_length_b                   31.607(3)
_cell_length_c                   44.006(4)
_cell_measurement_reflns_used    9245
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      18.82
_cell_measurement_theta_min      2.18
_cell_volume                     43371(7)
_computing_cell_refinement       'Bruker Apex3 V.2016.9-0/SAINT V8.37A'
_computing_data_collection       'Bruker Apex3 V.2016.9-0'
_computing_data_reduction        'Bruker Apex3 V.2016.9-0/SAINT V8.37A'
_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      100.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX II area detector'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.7749
_diffrn_reflns_av_R_equivalents  0.0784
_diffrn_reflns_av_unetI/netI     0.0326
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            269848
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        18.838
_diffrn_reflns_theta_max         18.838
_diffrn_reflns_theta_min         1.230
_diffrn_source                   'Sealed Source Mo with TRIUMPH optics'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.267
_exptl_absorpt_correction_T_max  0.7443
_exptl_absorpt_correction_T_min  0.6749
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
; 
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.0843 before and 0.0679 after correction. 
The Ratio of minimum to maximum transmission is 0.9068. 
The \l/2 correction factor is Not present. 
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    0.741
_exptl_crystal_description       prism
_exptl_crystal_F_000             9992
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.302
_refine_diff_density_min         -0.516
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.606
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2629
_refine_ls_number_reflns         26222
_refine_ls_number_restraints     4409
_refine_ls_restrained_S_all      2.486
_refine_ls_R_factor_all          0.1893
_refine_ls_R_factor_gt           0.1663
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4734
_refine_ls_wR_factor_ref         0.5175
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20121
_reflns_number_total             26222
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01629c2.cif
_cod_data_source_block           ks291_1_a_sq
_cod_depositor_comments
'Adding full bibliography for 1569408--1569409.cif.'
_cod_database_code               1569408
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.964
_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 
2. Restrained distances 
 C43-C44 = C71-C70 = C62-C61 = C52-C53 = C54-C53 = C72-C71 = C45-C44 = C107- 
 C106 = C108-C107 = C99-C98 = C98-C97 = C80-C79 = C89-C88 = C90-C89 = C215-C214 
 = C216-C215 = C188-C187 = C197-C196 = C197-C198 = C207-C206 = C205-C206 = C134- 
 C133 = C135-C134 = C125-C124 = C126-C125 = C171-C170 = C170-C169 = C179-C178 = 
 C180-C179 = C26-C25 = C27-C26 = C35-C34 = C36-C35 = C17-C16 = C9-C8 = C7-C8 = 
 C63-C62 = C116-C115 = C144-C143 = C143-C142 
 1.54 with sigma of 0.01 
 Ca7-O89 = Ca7-O90 = Ca8-O92 = Ca8-O91 = Ca5-O84 = Ca5-O83 = Ca9-O94 = Ca9-O93 
 = Ca10-O96 = Ca10-O95 = Ca3-O80 = Ca3-O79 
 2.36 with sigma of 0.02 
 Ca1-O75 = Ca1-O74 = Ca1-O73 = Ca4-O82 = Ca4-O81 = Ca2-O77 = Ca2-O78 = Ca2-O76 
 = Ca6-O87 = Ca6-O88 = Ca6-O86 = Ca11-O97 = Ca11-O99 = Ca12-O100 = Ca12-O101 
 2.4 with sigma of 0.02 
 O87-O88 
 2.8 with sigma of 0.02 
 O88-O87 
 2.8 with sigma of 0.02 
 Ca11-O98 = Ca11-O99 = Ca11-O97 
 2.4 with sigma of 0.02 
 Ca4-O82 = Ca4-O81 
 2.4 with sigma of 0.02 
 C153-C152 
 1.54 with sigma of 0.02 
 C89'-C188 = C189-C188 
 1.54 with sigma of 0.02 
 C72'-C71 
 1.54 with sigma of 0.02 
 C81-C80 
 1.54 with sigma of 0.02 
 C17'-C116 = C117-C116 
 1.54 with sigma of 0.02 
 C18-C17 = C18'-C17 
 1.54 with sigma of 0.02 
 Ca4-O5AA = Ca4-O82 
 2.4 with sigma of 0.02 
 Ca4-O81 
 2.4 with sigma of 0.02 
 Ca4-O81 = Ca4-O5AA = Ca4-O82 
 2.36 with sigma of 0.02 
 Ca11-O99 = Ca11-O98 = Ca11-O97 
 2.36 with sigma of 0.02 
 C166-C165 \\sim C164-C165 \\sim C173-C174 \\sim C175-C174 \\sim C146-C145 
\\sim C147-C146 \\sim C156- 
 C157 \\sim C156-C155 \\sim C128-C129 \\sim C130-C129 \\sim C119-C120 \\sim 
C120-C121 \\sim C111-C110 ~ 
 C109-C110 \\sim C139-C138 \\sim C138-C137 \\sim C202-C201 \\sim C201-C200 
\\sim C192-C191 \\sim C192- 
 C193 \\sim C181-C182 \\sim C183-C182 \\sim C211-C210 \\sim C210-C209 \\sim 
C102-C101 \\sim C103-C102 ~ 
 C74-C73 \\sim C75-C74 \\sim C83-C84 \\sim C84-C85 \\sim C92-C93 \\sim C94-C93 
\\sim C39-C38 \\sim C38-C37 
 \\sim C49-C48 \\sim C48-C47 \\sim C56-C57 \\sim C58-C57 \\sim C66-C65 \\sim 
C67-C66 \\sim C12-C13 \\sim C12- 
 C11 \\sim C20-C21 \\sim C21-C22 \\sim C30-C29 \\sim C30-C31 \\sim C1-C2 \\sim 
C3-C2 
 with sigma of 0.02 
 C49-C50 \\sim C47-C46 \\sim C39-C40 \\sim C42-C37 \\sim C68-C67 \\sim C64-C65 
\\sim C58-C59 \\sim C56-C55 
 \\sim C101-C100 \\sim C103-C104 \\sim C95-C94 \\sim C91-C92 \\sim C86-C85 
\\sim C83-C82 \\sim C75-C76 ~ 
 C73-C78 \\sim C191-C190 \\sim C194-C193 \\sim C199-C200 \\sim C202-C203 \\sim 
C209-C208 \\sim C212- 
 C211 \\sim C186-C181 \\sim C183-C184 \\sim C114-C109 \\sim C111-C112 \\sim 
C140-C139 \\sim C137-C136 ~ 
 C130-C131 \\sim C128-C127 \\sim C122-C121 \\sim C119-C118 \\sim C173-C172 
\\sim C175-C176 \\sim C166- 
 C167 \\sim C164-C163 \\sim C158-C157 \\sim C155-C154 \\sim C150-C145 \\sim 
C147-C148 \\sim C3-C4 \\sim C6- 
 C1 \\sim C31-C32 \\sim C28-C29 \\sim C23-C22 \\sim C19-C20 \\sim C13-C14 \\sim 
C11-C10 
 with sigma of 0.02 
 C91-C96 \\sim C95-C96 \\sim C105-C100 \\sim C105-C104 \\sim C77-C78 \\sim 
C77-C76 \\sim C82-C87 \\sim C86- 
 C87 \\sim C213-C208 \\sim C212-C213 \\sim C185-C184 \\sim C186-C185 \\sim 
C195-C190 \\sim C195-C194 ~ 
 C199-C204 \\sim C204-C203 \\sim C132-C131 \\sim C132-C127 \\sim C123-C122 
\\sim C123-C118 \\sim C112- 
 C113 \\sim C114-C113 \\sim C141-C140 \\sim C141-C136 \\sim C168-C167 \\sim 
C163-C168 \\sim C177-C172 ~ 
 C177-C176 \\sim C148-C149 \\sim C150-C149 \\sim C158-C159 \\sim C159-C154 
\\sim C28-C33 \\sim C33-C32 
 \\sim C6-C5 \\sim C5-C4 \\sim C15-C14 \\sim C15-C10 \\sim C24-C19 \\sim 
C24-C23 \\sim C41-C42 \\sim C41-C40 ~ 
 C51-C46 \\sim C51-C50 \\sim C60-C55 \\sim C60-C59 \\sim C69-C68 \\sim C64-C69 
 with sigma of 0.02 
 C160-C163 \\sim C169-C167 \\sim C150-C178 \\sim C151-C154 
 with sigma of 0.02 
 C178-C176 \\sim C169-C172 \\sim C158-C160 \\sim C151-C154 
 with sigma of 0.02 
 C28-C25 \\sim C34-C32 \\sim C7-C10 \\sim C16-C14 
 with sigma of 0.02 
 C19-C16 \\sim C25-C23 \\sim C7-C4 \\sim C6-C34 
 with sigma of 0.02 
 C112-C115 \\sim C124-C127 \\sim C133-C131 \\sim C114-C142 
 with sigma of 0.02 
 C115-C118 \\sim C140-C142 \\sim C133-C136 \\sim C124-C122 
 with sigma of 0.02 
 C186-C214 \\sim C205-C203 \\sim C187-C184 \\sim C199-C196 
 with sigma of 0.02 
 C212-C214 \\sim C205-C208 \\sim C187-C190 \\sim C196-C194 
 with sigma of 0.02 
 C97-C100 \\sim C106-C104 \\sim C79-C82 \\sim C86-C88 
 with sigma of 0.02 
 C106-C78 \\sim C79-C76 \\sim C97-C95 \\sim C91-C88 
 with sigma of 0.02 
 C59-C61 \\sim C52-C55 \\sim C43-C40 \\sim C42-C70 
 with sigma of 0.02 
 C64-C61 \\sim C52-C50 \\sim C43-C46 \\sim C68-C70 
 with sigma of 0.02 
3. Uiso/Uaniso restraints and constraints 
C165 \\sim C166 \\sim C167 \\sim C164 \\sim C163 \\sim C168 \\sim C158 \\sim 
C157 \\sim C156 \\sim C159 \\sim C154 \\sim C155 \\sim C149 \\sim C148 \\sim 
C147 \\sim C150 \\sim C145 \\sim C146 \\sim C176 \\sim C177 \\sim C172 \\sim 
C173 \\sim C174 \\sim C175: within 2A with sigma of 0.04 and sigma for terminal 
atoms of 0.08 
C165 \\sim C166 \\sim C164 \\sim C167 \\sim C163 \\sim C168 \\sim C157 \\sim 
C158 \\sim C156 \\sim C159 \\sim C154 \\sim C155 \\sim C176 \\sim C177 \\sim 
C172 \\sim C173 \\sim C174 \\sim C175 \\sim C149 \\sim C148 \\sim C147 \\sim 
C145 \\sim C146 \\sim C150 \\sim C129 \\sim C130 \\sim C131 \\sim C132 \\sim 
C127 \\sim C128 \\sim C122 \\sim C121 \\sim C120 \\sim C123 \\sim C118 \\sim 
C119 \\sim C113 \\sim C112 \\sim C111 \\sim C110 \\sim C109 \\sim C114 \\sim 
C139 \\sim C140 \\sim C138 \\sim C141 \\sim C137 \\sim C136 \\sim C31 \\sim C30 
\\sim C29 \\sim C28 \\sim C33 \\sim C32 \\sim C6 \\sim C1 \\sim C2 \\sim C3 
\\sim C4 \\sim C5 \\sim C10 \\sim C11 \\sim C12 \\sim C15 \\sim C14 \\sim C13 
\\sim C24 \\sim C23 \\sim C22 \\sim C21 \\sim C19 \\sim C20 \\sim C200 \\sim 
C199 \\sim C204 \\sim C203 \\sim C202 \\sim C201 \\sim C208 \\sim C213 \\sim 
C212 \\sim C211 \\sim C209 \\sim C210 \\sim C194 \\sim C193 \\sim C192 \\sim 
C191 \\sim C190 \\sim C195 \\sim C184 \\sim C185 \\sim C186 \\sim C181 \\sim 
C182 \\sim C183 \\sim C85 \\sim C86 \\sim C87 \\sim C82 \\sim C83 \\sim C84 
\\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C100 \\sim 
C105 \\sim C104 \\sim C103 \\sim C102 \\sim C77 \\sim C76 \\sim C75 \\sim C74 
\\sim C73 \\sim C78 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C37 
\\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C60 \\sim C55 
\\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C65 \\sim C64 \\sim C69 \\sim C68 
\\sim C67 \\sim C66: within 2A with sigma of 0.04 and sigma for terminal atoms 
of 0.08 
C205 \\sim C214 \\sim C196 \\sim C187 \\sim C160 \\sim C169 \\sim C178 \\sim 
C151 \\sim C25 \\sim C34 \\sim C7 \\sim C16 \\sim C52 \\sim C61 \\sim C70 \\sim 
C43 \\sim C106 \\sim C79 \\sim C88 \\sim C97 \\sim C124 \\sim C133 \\sim C142 
\\sim C115: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 
O8 \\sim O2 \\sim O26 \\sim O32 \\sim O14 \\sim O20 \\sim O38 \\sim O44 \\sim 
O56 \\sim O50 \\sim O62 \\sim O68: within 2A with sigma of 0.04 and sigma for 
terminal atoms of 0.08 
O61 \\sim O63 \\sim O67 \\sim O69 \\sim O55 \\sim O57 \\sim O51 \\sim O49 \\sim 
O43 \\sim O45 \\sim O39 \\sim O37 \\sim O27 \\sim O25 \\sim O33 \\sim O31 \\sim 
O1 \\sim O3 \\sim O9 \\sim O7 \\sim O13 \\sim O15 \\sim O21 \\sim O19: within 
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 
O52 \\sim O53 \\sim O54 \\sim O60 \\sim O58 \\sim O59 \\sim O41 \\sim O42 \\sim 
O40 \\sim O48 \\sim O47 \\sim O46 \\sim O11 \\sim O12 \\sim O10 \\sim O6 \\sim 
O5 \\sim O4 \\sim O22 \\sim O23 \\sim O24 \\sim O18 \\sim O17 \\sim O16 \\sim 
O72 \\sim O71 \\sim O70 \\sim O64 \\sim O65 \\sim O66 \\sim O36 \\sim O35 \\sim 
O34 \\sim O28 \\sim O29 \\sim O30: within 2A with sigma of 0.04 and sigma for 
terminal atoms of 0.08 
4. Others 
 Fixed Sof: H71C(0.5) H71D(0.5) H71A(0.5) H71B(0.5) H11C(0.5) H11D(0.5) 
 H11A(0.5) H11B(0.5) H18C(0.5) H18D(0.5) H18A(0.5) H18B(0.5) H17C(0.5) 
 H17D(0.5) H17E(0.5) H17F(0.5) O82(0.5) C72(0.5) H72A(0.5) H72B(0.5) H72C(0.5) 
 O99(0.5) O98(0.5) C117(0.5) H11E(0.5) H11F(0.5) H11G(0.5) C72'(0.5) H72D(0.5) 
 H72E(0.5) H72F(0.5) C189(0.5) H18H(0.5) H18I(0.5) H18J(0.5) C89'(0.5) 
 H89C(0.5) H89D(0.5) H89E(0.5) C17'(0.5) H17L(0.5) H17M(0.5) H17N(0.5) 
 O5AA(0.5) C18(0.5) H18K(0.5) H18L(0.5) H18M(0.5) C18'(0.5) H18N(0.5) H18O(0.5) 
 H18P(0.5) 
5.a Ternary CH refined with riding coordinates: 
 C61(H61), C70(H70), C43(H43), C196(H196), C187(H187), C133(H133), C34(H34), 
 C115(H115), C214(H214), C52(H52), C88(H88), C16(H16), C160(H160), C106(H106), 
 C25(H25), C142(H142), C169(H169), C97(H97), C79(H79), C205(H205), C7(H7), 
 C178(H178), C124(H124) 
5.b Secondary CH2 refined with riding coordinates: 
 C44(H44A,H44B), C71(H71C,H71D), C71(H71A,H71B), C206(H20A,H20B), C62(H62A, 
 H62B), C134(H13A,H13B), C116(H11C,H11D), C116(H11A,H11B), C188(H18C,H18D), 
 C188(H18A,H18B), C215(H21A,H21B), C143(H14A,H14B), C107(H10A,H10B), C26(H26A, 
 H26B), C161(H16A,H16B), C89(H89A,H89B), C170(H17A,H17B), C17(H17C,H17D), 
 C17(H17E,H17F), C98(H98A,H98B), C197(H19D,H19E), C125(H12A,H12B), C179(H17G, 
 H17H), C53(H53A,H53B), C35(H35A,H35B), C152(H15A,H15B), C80(H80A,H80B), C8(H8A, 
 H8B) 
5.c Me refined with riding coordinates: 
 C45(H45A,H45B,H45C), C198(H19A,H19B,H19C), C63(H63A,H63B,H63C), C54(H54A,H54B, 
 H54C), C126(H12C,H12D,H12E), C207(H20C,H20D,H20E), C108(H10C,H10D,H10E), 
 C135(H13C,H13D,H13E), C72(H72A,H72B,H72C), C144(H14C,H14D,H14E), C216(H21C, 
 H21D,H21E), C171(H17I,H17J,H17K), C99(H99A,H99B,H99C), C90(H90A,H90B,H90C), 
 C9(H9A,H9B,H9C), C180(H18E,H18F,H18G), C36(H36A,H36B,H36C), C27(H27A,H27B, 
 H27C), C153(H15C,H15D,H15E), C117(H11E,H11F,H11G), C72'(H72D,H72E,H72F), 
 C189(H18H,H18I,H18J), C81(H81A,H81B,H81C), C89'(H89C,H89D,H89E), C17'(H17L, 
 H17M,H17N), C162(H16C,H16D,H16E), C18(H18K,H18L,H18M), C18'(H18N,H18O,H18P) 
5.d Aromatic/amide H refined with riding coordinates: 
 C41(H41), C96(H96), C51(H51), C5(H5), C113(H113), C159(H159), C149(H149), 
 C168(H168), C24(H24), C60(H60), C177(H177), C213(H213), C105(H105), C69(H69), 
 C195(H195), C204(H204), C33(H33), C15(H15), C132(H132), C123(H123), C141(H141), 
  C87(H87), C185(H185), C77(H77) 
;
_shelx_res_checksum              11149
_shelx_hkl_checksum              37421
_shelx_fab_checksum              61846
_olex2_submission_special_instructions 'No special instructions were received'