Copper Lanthanide Phosphonate Cages: Highly Symmetric {Cu3Ln9P6} and {Cu6Ln6P6} Clusters with C3v and D3h Symmetry.
Moreno Pineda, Eufemio; Heesing, Christian; Tuna, Floriana; Zheng, Yan-Zhen; McInnes, Eric J. L.; Schnack, Jürgen; Winpenny, Richard E. P.; Inorganic chemistry  (2015) 150610150327001–; doi:10.1021/acs.inorgchem.5b00649

data_4343292
_publ_section_title
;
 Copper Lanthanide Phosphonate Cages: Highly Symmetric {Cu3Ln9P6} and
 {Cu6Ln6P6} Clusters with C3v and D3h Symmetry.
;
_journal_name_full               'Inorganic chemistry'
_journal_page_first              150610150327001
_journal_paper_doi               10.1021/acs.inorgchem.5b00649
_journal_year                    2015
_chemical_formula_moiety         'C99 H189 Cu3 O55 P6 Tb9, C8 H12 Cu1 N4'
_chemical_formula_sum            'C107 H201 Cu4 N4 O55 P6 Tb9'
_chemical_formula_weight         4293.96
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3'
_symmetry_space_group_name_Hall  'R 3'
_symmetry_space_group_name_H-M   'R 3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-11
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   20.5015(5)
_cell_length_b                   20.5015(5)
_cell_length_c                   32.8593(14)
_cell_measurement_reflns_used    7203
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      28.7600
_cell_measurement_theta_min      1.9160
_cell_volume                     11960.8(7)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega  -60.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000    0.0000    0.0000 175

  2 omega  -60.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -50.0000    0.0000 120

  3 omega  -60.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -50.0000  120.0000 120

  4 omega  -60.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -50.0000  240.0000 120
;
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0025312000
_diffrn_orient_matrix_UB_12      0.0232752000
_diffrn_orient_matrix_UB_13      -0.0142300000
_diffrn_orient_matrix_UB_21      -0.0380341000
_diffrn_orient_matrix_UB_22      -0.0249829000
_diffrn_orient_matrix_UB_23      -0.0020059000
_diffrn_orient_matrix_UB_31      -0.0073954000
_diffrn_orient_matrix_UB_32      0.0184252000
_diffrn_orient_matrix_UB_33      0.0152682000
_diffrn_radiation_monochromator  synchrotron
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.1039
_diffrn_reflns_av_unetI/netI     0.0971
_diffrn_reflns_laue_measured_fraction_full 1.000
_diffrn_reflns_laue_measured_fraction_max 1.000
_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       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            33868
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.415
_diffrn_reflns_theta_max         24.513
_diffrn_reflns_theta_min         1.802
_diffrn_source                   synchrotron
_exptl_absorpt_coefficient_mu    4.590
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76985
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'clear blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.788
_exptl_crystal_description       block
_exptl_crystal_F_000             6306
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.622
_refine_diff_density_min         -0.891
_refine_diff_density_rms         0.146
_refine_ls_abs_structure_details
;
 Flack x determined using 3659 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.569(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     590
_refine_ls_number_reflns         9741
_refine_ls_number_restraints     64
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0589
_refine_ls_R_factor_gt           0.0499
_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^)+(0.0269P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1029
_refine_ls_wR_factor_ref         0.1099
_reflns_Friedel_coverage         0.996
_reflns_friedel_fraction_full    0.995
_reflns_friedel_fraction_max     0.995
_reflns_number_gt                8604
_reflns_number_total             9741
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b00649_si_007.cif
_cod_data_source_block           Cu3Tb9P6
_cod_original_cell_volume        11960.8(8)
_cod_database_code               4343292
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         Cu4Tb9O32P6C100H150
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.50
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C23A-C22 = C22-C25A
 1.52 with sigma of 0.02
 C25A-C22 = C22-C24A
 1.52 with sigma of 0.02
 C24A-C22 = C22-C23A
 1.52 with sigma of 0.02
 C23A-C25A
 2.483 with sigma of 0.04
 C25A-C24A
 2.483 with sigma of 0.04
 C24A-C23A
 2.483 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(O2OH) \\sim Ueq, Uanis(O1OH) \\sim Ueq, Uanis(O1P) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.01
Uanis(C23) = Uanis(C23A)
Uanis(C25) = Uanis(C25A)
Uanis(C24) = Uanis(C24A)
Uanis(N2) = Uanis(N1)
4. Rigid body (RIGU) restrains
 C22, C23, C24, C25, C23A, C25A, C24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=
 Sof(H24F)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(1)
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(1)
 Fixed Sof: H4NA(0.33333) H4NB(0.33333) H4NC(0.33333)
6.a Idealised Me refined as rotating group:
 C2P(H2PA,H2PB,H2PC), C3(H3A,H3B,H3C), C3P(H3PA,H3PB,H3PC), C4(H4A,H4B,H4C),
 C4P(H4PA,H4PB,H4PC), C5(H5A,H5B,H5C), C6P(H6PA,H6PB,H6PC), C7P(H7PA,H7PB,H7PC),
  C8(H8A,H8B,H8C), C8P(H8PA,H8PB,H8PC), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C23(H23A,H23B,H23C),
 C23A(H23D,H23E,H23F), C24(H24A,H24B,H24C), C24A(H24D,H24E,H24F), C25(H25A,H25B,
 H25C), C25A(H25D,H25E,H25F), C2N(H2NA,H2NB,H2NC), C4N(H4NA,H4NB,H4NC)
;
_olex2_submission_special_instructions 'No special instructions were received'