Controlling the crystallization of porous organic cages: molecular analogs of isoreticular frameworks using shape-specific directing solvents.
Hasell, Tom; Culshaw, Jamie L.; Chong, Samantha Y.; Schmidtmann, Marc; Little, Marc A.; Jelfs, Kim E.; Pyzer-Knapp, Edward O; Shepherd, Hilary; Adams, Dave J.; Day, Graeme M.; Cooper, Andrew I.; Journal of the American Chemical Society 136 (2014) 1438–1448; doi:10.1021/ja409594s

data_4120480
_publ_section_title
;
 Controlling the crystallization of porous organic cages: molecular
 analogs of isoreticular frameworks using shape-specific directing
 solvents.
;
_journal_issue                   4
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1438
_journal_page_last               1448
_journal_paper_doi               10.1021/ja409594s
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C60 H72 N12, 3.67 (C H2 Cl2)'
_chemical_formula_sum            'C63.67 H79.33 Cl7.33 N12'
_chemical_formula_weight         1269.33
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      trigonal
_space_group_IT_number           143
_space_group_name_Hall           'P 3'
_space_group_name_H-M_alt        'P 3'
_symmetry_space_group_name_Hall  'P 3'
_symmetry_space_group_name_H-M   'P 3'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-11-19
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2013.11.15 svn.r2834 for OlexSys, GUI svn.r4713)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_formula_units_Z            3
_cell_length_a                   24.075(2)
_cell_length_b                   24.075(2)
_cell_length_c                   10.7146(12)
_cell_measurement_reflns_used    5455
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      18.11
_cell_measurement_theta_min      2.54
_cell_volume                     5378.2(9)
_computing_cell_refinement       'Bruker AXS SAINT V7.68A'
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0503
_diffrn_reflns_av_unetI/netI     0.0425
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            46401
_diffrn_reflns_theta_full        20.81
_diffrn_reflns_theta_max         20.81
_diffrn_reflns_theta_min         1.69
_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
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.334
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7130
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2008/1 (Sheldrick, 2008)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.176
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2010
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.139
_refine_diff_density_min         -0.113
_refine_diff_density_rms         0.027
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.946
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     685
_refine_ls_number_reflns         7451
_refine_ls_number_restraints     204
_refine_ls_restrained_S_all      0.972
_refine_ls_R_factor_all          0.0859
_refine_ls_R_factor_gt           0.0598
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1252P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1688
_refine_ls_wR_factor_ref         0.1882
_reflns_number_gt                4675
_reflns_number_total             7451
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            CC13.3.67(CH2Cl2)_Alpha_Phase_JACS_PUBL.cif
_cod_data_source_block           CC13_3.67(CH2Cl2)
_cod_original_cell_volume        5378.3(9)
_cod_database_code               4120480
_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) groups
2. Restrained distances
 C5-C4
 1.54 with sigma of 0.02
 N1-C4
 1.43 with sigma of 0.02
 C7A-C4
 1.54 with sigma of 0.02
 N8-C37
 1.43 with sigma of 0.02
 C18-C16
 1.54 with sigma of 0.02
 C23-C22
 1.47 with sigma of 0.02
 C27B-C25
 1.54 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Others
 Fixed Sof: H4A(0.5) H4B(0.5) H5A(0.5) H5B(0.5) C6A(0.5) H6AA(0.5) H6AB(0.5)
 H6AC(0.5) C6B(0.5) H6BA(0.5) H6BB(0.5) H6BC(0.5) C7A(0.5) H7AA(0.5) H7AB(0.5)
 H7AC(0.5) C7B(0.5) H7BA(0.5) H7BB(0.5) H7BC(0.5) H24A(0.5) H24B(0.5) H25A(0.5)
 H25B(0.5) C26A(0.5) H26A(0.5) H26B(0.5) H26C(0.5) C26B(0.5) H26D(0.5)
 H26E(0.5) H26F(0.5) C27A(0.5) H27A(0.5) H27B(0.5) H27C(0.5) C27B(0.5)
 H27D(0.5) H27E(0.5) H27F(0.5) H44A(0.5) H44B(0.5) H45A(0.5) H45B(0.5)
 C46A(0.5) H46A(0.5) H46B(0.5) H46C(0.5) C46B(0.5) H46D(0.5) H46E(0.5)
 H46F(0.5) C47A(0.5) H47A(0.5) H47B(0.5) H47C(0.5) C47B(0.5) H47D(0.5)
 H47E(0.5) H47F(0.5) H56A(0.75) H56B(0.75) H57A(0.25) H57B(0.25) C58A(0.75)
 H58A(0.75) H58B(0.75) H58C(0.75) C58B(0.25) H58D(0.25) H58E(0.25) H58F(0.25)
 C59A(0.75) H59A(0.75) H59B(0.75) H59C(0.75) C59B(0.25) H59D(0.25) H59E(0.25)
 H59F(0.25)
5.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C17(H17A,H17B), C24(H24A,H24B), C25(H25A,H25B),
 C37(H37A,H37B), C44(H44A,H44B), C45(H45A,H45B), C56(H56A,H56B), C57(H57A,H57B)
5.b Me refined with riding coordinates:
 C6A(H6AA,H6AB,H6AC), C6B(H6BA,H6BB,H6BC), C7A(H7AA,H7AB,H7AC), C7B(H7BA,H7BB,
 H7BC), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C26A(H26A,H26B,H26C),
 C26B(H26D,H26E,H26F), C27A(H27A,H27B,H27C), C27B(H27D,H27E,H27F), C38(H38A,
 H38B,H38C), C39(H39A,H39B,H39C), C46A(H46A,H46B,H46C), C46B(H46D,H46E,H46F),
 C47A(H47A,H47B,H47C), C47B(H47D,H47E,H47F), C58A(H58A,H58B,H58C), C58B(H58D,
 H58E,H58F), C59A(H59A,H59B,H59C), C59B(H59D,H59E,H59F)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C8(H8), C14(H14), C12(H12), C10(H10), C15(H15), C20(H20),
 C21(H21), C23(H23), C28(H28), C32(H32), C34(H34), C30(H30), C35(H35), C40(H40),
  C41(H41), C43(H43), C48(H48), C54(H54), C52(H52), C50(H50), C55(H55), C60(H60)
5.d Fitted hexagon refined as free rotating group:
 C9(C14,C13,C12,C11,C10), C31(C32,C33,C34,C29,C30), C49(C54,C53,C52,C51,C50)
;
_chemw03_alert_2_a
;
Problem: The ratio of given/expected molecular weight as
            calculated from the _atom_site* data lies outside
            the range 0.90 <> 1.10
Response: Solvent was too diffuse to model and therefore a solvent masking
routine was performed during refinement. This routine removed a
total of 458 electrons. The only solvent present in the crystallisation
of this sample was CH2Cl2. Therefore the
residual electron was assigned as being 11 CH2Cl2 solvent molecules, these
have been included in the formula unit.
;
_thetm01_alert_3_a
;
Problem: The value of sine(theta_max)/wavelength is less than 0.550
            Calculated sin(theta_max)/wavelength =    0.4999   
Response: Crystals of this material were wealky diffracting. A resolution
limit of 1 angstroms was applied during refinement.
;
_plat043_alert_1_a
;
Problem: Calculated and Reported Mol. Weight Differ by ..     934.18 Check
Response: Solvent was too diffuse to model and therefore a solvent masking
routine was performed during refinement. This routine removed a
total of 458 electrons. The only solvent present in the crystallisation
of this sample was CH2Cl2. Therefore the
residual electron was assigned as being 11 CH2Cl2 solvent molecules, these
have been included in the formula unit.
;
_plat051_alert_1_a
;
Problem: Mu(calc) and Mu(CIF) Ratio Differs from 1.0 by .      83.80 % 
Response: Solvent was too diffuse to model and therefore a solvent masking
routine was performed during refinement. This routine removed a
total of 458 electrons. The only solvent present in the crystallisation
of this sample was CH2Cl2. Therefore the
residual electron was assigned as being 11 CH2Cl2 solvent molecules, these
have been included in the formula unit.
;
_plat413_alert_2_a
;
Problem: Short Inter XH3 .. XHn     H10    ..  H27E    ..       1.81 Ang. 
Response: Hydrogen atoms were placed in geometrically estimated positions
using the riding model. The exact position should therefore be regarded as 
being tentatively assigned and the close contact between H10 and H27E 
is likely the result of wrongly positioned protons.   
;
_plat602_alert_2_a
;
Problem: VERY LARGE Solvent Accessible VOID(S) in Structure        ! Info 
Response: Lattice solvent was very diffuse and could not be accurately 
modelled. A solvent masking routine was performed during refinement. The
result of which would indicate the presence of 11 CH2Cl2 solvent 
molecules in these voids.
;