Further investigations into tetrahedral M4L6 cage complexes containing guest anions: new structures and NMR spectroscopic studies
Tidmarsh, Ian S.; Taylor, Brian F.; Hardie, Michaele J.; Russo, Luca; Clegg, William; Ward, Michael D.; New Journal of Chemistry 33 (2009) 366–; doi:10.1039/b816864d

data_7051641
_publ_section_title
;
 Further investigations into tetrahedral M4L6 cage complexes containing
 guest anions: new structures and NMR spectroscopic studies
;
_journal_issue                   2
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              366
_journal_paper_doi               10.1039/b816864d
_journal_volume                  33
_journal_year                    2009
_chemical_formula_sum            'C173 H158 B8 Cd4 F32 N36 O8'
_chemical_formula_weight         4013.43
_chemical_name_systematic
;
?
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 92.863(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   22.0402(7)
_cell_length_b                   19.5943(6)
_cell_length_c                   43.0372(13)
_cell_measurement_reflns_used    9687
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      24.97
_cell_measurement_theta_min      2.19
_cell_volume                     18562.9(10)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0899
_diffrn_reflns_av_sigmaI/netI    0.0648
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            286472
_diffrn_reflns_theta_full        24.71
_diffrn_reflns_theta_max         24.71
_diffrn_reflns_theta_min         0.93
_exptl_absorpt_coefficient_mu    0.549
_exptl_absorpt_correction_T_max  0.8981
_exptl_absorpt_correction_T_min  0.6679
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             8128
_exptl_crystal_size_max          0.80
_exptl_crystal_size_mid          0.40
_exptl_crystal_size_min          0.20
_platon_squeeze_details
;

The lattice contains five MeOH solvent molecules. All solvent MeOH
molecules except for O41S C42S have had their occupancies set to 10.5 to
bring their thermal parameters in line with those of the main residue.
Geometric and displacement restrains were employed to improve the
appearance of solvent molecules. The water molecule O1 is disordered over
two sites (60:40) and has been modelled as such. The water molecules O3S
and O4S have had their occupancies set to 10.5 for the same reasons as
outlined above. All solvent molecules have been left isotropic due to
their inherently fluxional nature.

Alcohol and water protons could not be found from the data and were
therefore omitted from the refinement. This results in a discrepancy of
44 protons from the UNIT instruction (when Z = 4, 20 protons from the
solvent alcohol molecules and 24 from the water molecules).

The final R1 value is higher than would normally be acceptable at ca 0.11.
Attempts to obtain a better data were hampered by the weakly diffracting
nature of the crystals at higher resolutions, presumably due to the large
number of voids present in the structure and lattice and the high disorder
arising from a combination of fluxional solvent molecules and counter-ions.
The high concentration of solvent molecules resulted in a rapid loss of
crystallinity when the crystals were removed from the mother liquor adding
further complication. Given these factors we feel that the R1 value
obtained for this structure is reasonable. A lower R1 value could be
obtained by allowing a 'SQUEEZE' function to remove all electron density
associated with the found solvent molecules (0.09). This did not form the
final refinement as doing such was felt to portray a misleading view of
the overall packing within the lattice.

Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;
_refine_diff_density_max         1.599
_refine_diff_density_min         -1.409
_refine_diff_density_rms         0.179
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.138
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2217
_refine_ls_number_reflns         31653
_refine_ls_number_restraints     228
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.1426
_refine_ls_R_factor_gt           0.1148
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0902P)^2^+307.1890P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2724
_refine_ls_wR_factor_ref         0.2849
_reflns_number_gt                23404
_reflns_number_total             31653
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            b816864d.txt
_cod_data_source_block           imw1247p21c
_cod_depositor_comments
;
The following automatic conversions were performed:
'_symmetry_cell_setting' value 'Monoclinic' changed to 'monoclinic'
according to '/home/saulius/struct/CIF-dictionaries/cif_core.dic'
dictionary named 'cif_core.dic' version 2.4.1 from
2010-06-29.

'_exptl_absorpt_correction_type' value 'Multi-scan' changed
to 'multi-scan' according to
'/home/saulius/struct/CIF-dictionaries/cif_core.dic' dictionary named
'cif_core.dic' version 2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_enum 1527 2010-12-29 10:47:43Z saulius 
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_cod_original_sg_symbol_H-M      'P2(1)/c '
_cod_database_code               7051641