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_4343290
_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         'C78 H156 Cu6 N6 O48 P6 Tb6, 2(C3 H9 N)'
_chemical_formula_sum            'C84 H174 Cu6 N8 O48 P6 Tb6'
_chemical_formula_weight         3584.88
_space_group_crystal_system      orthorhombic
_space_group_IT_number           70
_space_group_name_Hall           '-F 2uv 2vw'
_space_group_name_H-M_alt        'F d d d'
_symmetry_space_group_name_Hall  '-F 2uv 2vw'
_symmetry_space_group_name_H-M   'F d d d :2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_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                90
_cell_formula_units_Z            16
_cell_length_a                   35.8531(5)
_cell_length_b                   39.1902(4)
_cell_length_c                   45.8138(5)
_cell_measurement_reflns_used    26997
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.3890
_cell_measurement_theta_min      2.9650
_cell_volume                     64372.5(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3705
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -59.00   34.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       11.6555  -57.0000  -90.0000 186

  2 omega  -16.00   74.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       11.6555   77.0000 -180.0000 180

  3 omega  -17.00   81.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       11.6555   57.0000   60.0000 196
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0053193000
_diffrn_orient_matrix_UB_12      0.0158493000
_diffrn_orient_matrix_UB_13      0.0061891000
_diffrn_orient_matrix_UB_21      -0.0190464000
_diffrn_orient_matrix_UB_22      0.0046914000
_diffrn_orient_matrix_UB_23      0.0013021000
_diffrn_orient_matrix_UB_31      -0.0005941000
_diffrn_orient_matrix_UB_32      -0.0073818000
_diffrn_orient_matrix_UB_33      0.0141276000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1010
_diffrn_reflns_av_unetI/netI     0.0696
_diffrn_reflns_laue_measured_fraction_full 0.998
_diffrn_reflns_laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       48
_diffrn_reflns_limit_k_min       -48
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -57
_diffrn_reflns_number            112524
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.697
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.498
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34799
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear blue'
_exptl_crystal_density_diffrn    1.480
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             28352
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.588
_refine_diff_density_min         -1.575
_refine_diff_density_rms         0.160
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     765
_refine_ls_number_reflns         16453
_refine_ls_number_restraints     424
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0881
_refine_ls_R_factor_gt           0.0551
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0703P)^2^+587.9560P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1355
_refine_ls_wR_factor_ref         0.1585
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11338
_reflns_number_total             16453
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b00649_si_006.cif
_cod_data_source_block           Cu6Tb6P6
_cod_database_code               4343290
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C5-C2 = C2-C3
 1.52 with sigma of 0.02
 C3-C2 = C2-C4
 1.52 with sigma of 0.02
 C4-C2 = C2-C5
 1.52 with sigma of 0.02
 C5-C2 = C2-C1
 1.52 with sigma of 0.02
 C13A-C12 = C12-C15A
 1.52 with sigma of 0.02
 C15A-C12 = C12-C14A
 1.52 with sigma of 0.02
 C14A-C12 = C12-C13A
 1.52 with sigma of 0.02
 C30A-C27 = C27-C28A
 1.52 with sigma of 0.02
 C28A-C27 = C27-C29A
 1.52 with sigma of 0.02
 C29A-C27 = C27-C30A
 1.52 with sigma of 0.02
 C18A-C17 = C17-C20A
 1.52 with sigma of 0.02
 C20A-C17 = C17-C19A
 1.52 with sigma of 0.02
 C19A-C17 = C17-C18A
 1.52 with sigma of 0.02
 C4A-C2 = C2-C5A
 1.52 with sigma of 0.02
 C5A-C2 = C2-C3A
 1.52 with sigma of 0.02
 C3A-C2 = C2-C4A
 1.52 with sigma of 0.02
 C23A-C22 = C22-C24A
 1.52 with sigma of 0.02
 C24A-C22 = C22-C25A
 1.52 with sigma of 0.02
 C25A-C22 = C22-C23A
 1.52 with sigma of 0.02
 C21-C22 = C22-C23A
 1.52 with sigma of 0.02
 C8-C7 = C7-C9
 1.52 with sigma of 0.02
 C10-C7 = C7-C9
 1.52 with sigma of 0.02
 C8-C7 = C7-C10
 1.52 with sigma of 0.02
 C8A-C7A = C7A-C9A
 1.52 with sigma of 0.02
 C9A-C7A = C7A-C10A
 1.52 with sigma of 0.02
 C10A-C7A = C7A-C8A
 1.52 with sigma of 0.02
 C30-C27
 1.52 with sigma of 0.02
 C5-C3
 2.483 with sigma of 0.04
 C3-C4
 2.483 with sigma of 0.04
 C4-C5
 2.483 with sigma of 0.04
 C5-C1
 2.483 with sigma of 0.04
 C13A-C15A
 2.483 with sigma of 0.04
 C15A-C14A
 2.483 with sigma of 0.04
 C14A-C13A
 2.483 with sigma of 0.04
 C30A-C28A
 2.483 with sigma of 0.04
 C28A-C29A
 2.483 with sigma of 0.04
 C29A-C30A
 2.483 with sigma of 0.04
 C18A-C20A
 2.483 with sigma of 0.04
 C20A-C19A
 2.483 with sigma of 0.04
 C19A-C18A
 2.483 with sigma of 0.04
 C4A-C5A
 2.483 with sigma of 0.04
 C5A-C3A
 2.483 with sigma of 0.04
 C3A-C4A
 2.483 with sigma of 0.04
 C23A-C24A
 2.483 with sigma of 0.04
 C24A-C25A
 2.483 with sigma of 0.04
 C25A-C23A
 2.483 with sigma of 0.04
 C21-C23A
 2.483 with sigma of 0.04
 C8-C9
 2.483 with sigma of 0.04
 C10-C9
 2.483 with sigma of 0.04
 C8-C10
 2.483 with sigma of 0.04
 C8A-C9A
 2.483 with sigma of 0.04
 C9A-C10A
 2.483 with sigma of 0.04
 C10A-C8A
 2.483 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C5) = Uanis(C4) = Uanis(C3)
Uanis(C13) = Uanis(C13A)
Uanis(C15) = Uanis(C15A)
Uanis(C14) = Uanis(C14A)
Uanis(C30) = Uanis(C30A)
Uanis(C29) = Uanis(C29A)
Uanis(C28) = Uanis(C28A)
Uanis(C20) = Uanis(C19) = Uanis(C18)
Uanis(C20) = Uanis(C20A)
Uanis(C19) = Uanis(C19A)
Uanis(C18) = Uanis(C18A)
Uanis(C3) = Uanis(C3A)
Uanis(C4) = Uanis(C4A)
Uanis(C5) = Uanis(C5A)
Uanis(C24) = Uanis(C24A)
Uanis(C25) = Uanis(C25A)
Uanis(C23) = Uanis(C23A)
Uanis(C7A) = Uanis(C7)
Uanis(C8A) = Uanis(C8)
Uanis(C9) = Uanis(C9A)
Uanis(C10) = Uanis(C10A)
4. Rigid body (RIGU) restrains
 C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C2, C3, C4, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C12, C13, C14, C15, C13A, C14A, C15A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C27, C28, C29, C30, C28A, C29A, C30A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C17, C18, C19, C20, C18A, C19A, C20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C2, C3, C4, C5, C3A, C4A, C5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C22, C23, C24, C25, C23A, C24A, C25A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6, C7, C8, C9, C10, C7A, C8A, C9A, C10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C18A)=Sof(H18E)=Sof(H18F)=Sof(H18D)=Sof(C19A)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=Sof(C20A)=Sof(H20E)=Sof(H20D)=Sof(H20F)=1-FVAR(1)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19C)=Sof(H19A)=Sof(H19B)=
 Sof(C20)=Sof(H20B)=Sof(H20C)=Sof(H20A)=FVAR(1)
 Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(2)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(2)
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=
 Sof(H29F)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(3)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(3)
 Sof(C7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=
 Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(4)
 Sof(C7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(4)
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=1-FVAR(5)
 Sof(C3)=Sof(H3C)=Sof(H3D)=Sof(H3E)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(5)
 Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=
 Sof(H24F)=Sof(C25A)=Sof(H25F)=Sof(H25D)=Sof(H25E)=1-FVAR(6)
 Sof(C23)=Sof(H23B)=Sof(H23A)=Sof(H23C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C25)=Sof(H25B)=Sof(H25A)=Sof(H25C)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C31(H31)
6.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B), N3(H3A,H3B)
6.c Me refined with riding coordinates:
 C3(H3C,H3D,H3E), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), 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(H19C,H19A,H19B), C20(H20B,H20C,
 H20A), C23(H23B,H23A,H23C), C24(H24A,H24B,H24C), C25(H25B,H25A,H25C), C28(H28A,
 H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C3A(H3AA,H3AB,H3AC),
 C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,H5AC), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,
 H9AC), C10A(H10D,H10E,H10F), C13A(H13D,H13E,H13F), C14A(H14D,H14E,H14F),
 C15A(H15D,H15E,H15F), C18A(H18E,H18F,H18D), C19A(H19D,H19E,H19F), C20A(H20E,
 H20D,H20F), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F), C25A(H25F,H25D,H25E),
 C28A(H28D,H28E,H28F), C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F)
6.d Idealised Me refined as rotating group:
 C2P(H2PA,H2PB,H2PC), C3P(H3PA,H3PB,H3PC), C5P(H5PA,H5PB,H5PC), C6P(H6PA,H6PB,
 H6PC), C8P(H8PA,H8PB,H8PC), C9P(H9PA,H9PB,H9PC), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C)
;
_shelx_fab_checksum              62513
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2013-10-25
_olex2_submission_special_instructions 'No special instructions were received'