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_4343294
_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 Gd6 N6 O48 P6, 2(C3 H9 N)'
_chemical_formula_sum            'C84 H174 Cu6 Gd6 N8 O48 P6'
_chemical_formula_weight         3574.86
_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     direct
_audit_creation_date             2015-03-11
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
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_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   35.8449(3)
_cell_length_b                   39.1793(4)
_cell_length_c                   45.6982(4)
_cell_measurement_reflns_used    78922
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      28.8460
_cell_measurement_theta_min      1.6550
_cell_volume                     64177.6(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega    2.20  182.01   0.2997    9.9860
omega____ theta____ kappa____ phi______ frames
    -       28.0000   73.8962  -25.8019 600

  2 omega    2.20  182.01   0.2997    9.9860
omega____ theta____ kappa____ phi______ frames
    -       28.0000   73.8962   94.1981 600

  3 omega    2.20  182.01   0.2997    9.9860
omega____ theta____ kappa____ phi______ frames
    -       28.0000   73.8962 -145.8038 600
;
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0173252000
_diffrn_orient_matrix_UB_12      -0.0019783000
_diffrn_orient_matrix_UB_13      0.0073037000
_diffrn_orient_matrix_UB_21      -0.0054181000
_diffrn_orient_matrix_UB_22      -0.0124869000
_diffrn_orient_matrix_UB_23      -0.0104025000
_diffrn_orient_matrix_UB_31      0.0078846000
_diffrn_orient_matrix_UB_32      -0.0129675000
_diffrn_orient_matrix_UB_33      0.0088977000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0546
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_laue_measured_fraction_full 0.999
_diffrn_reflns_laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       48
_diffrn_reflns_limit_k_min       -48
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -57
_diffrn_reflns_number            126015
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.373
_diffrn_reflns_theta_min         2.654
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.344
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81188
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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    1.480
_exptl_crystal_description       block
_exptl_crystal_F_000             28256
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.913
_refine_diff_density_min         -1.389
_refine_diff_density_rms         0.162
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.120
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     770
_refine_ls_number_reflns         16412
_refine_ls_number_restraints     384
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.0670
_refine_ls_R_factor_gt           0.0580
_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^)+(0.0505P)^2^+2558.5537P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1357
_refine_ls_wR_factor_ref         0.1403
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14370
_reflns_number_total             16412
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b00649_si_005.cif
_cod_data_source_block           Cu6Gd6P6
_cod_original_cell_volume        64177.5(10)
_cod_database_code               4343294
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 C5A-C2 = C2-C3A
 1.52 with sigma of 0.02
 C3A-C2 = C2-C4A
 1.52 with sigma of 0.02
 C4A-C2 = C2-C5A
 1.52 with sigma of 0.02
 C5-C2 = C2-C4
 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
 C13A-C12 = C12-C15A
 1.52 with sigma of 0.02
 C19A-C17 = C17-C18A
 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
 C25A-C22 = C22-C21
 1.52 with sigma of 0.02
 C23A-C22 = C22-C21
 1.52 with sigma of 0.02
 C24A-C22 = C22-C21
 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-C22 = C22-C25A
 1.52 with sigma of 0.02
 C23-C22 = C22-C24
 1.52 with sigma of 0.02
 C24-C22 = C22-C25
 1.52 with sigma of 0.02
 C25-C22 = C22-C23
 1.52 with sigma of 0.02
 C8-C7 = C7-C10
 1.52 with sigma of 0.02
 C8A-C7A = C7A-C10A
 1.52 with sigma of 0.02
 C10A-C7A = C7A-C6
 1.52 with sigma of 0.02
 C10A-C7A = C7A-C9A
 1.52 with sigma of 0.02
 C8A-C7A = C7A-C9A
 1.52 with sigma of 0.02
 C9-C7 = C7-C10
 1.52 with sigma of 0.02
 C8-C7 = C7-C9
 1.52 with sigma of 0.02
 C5A-C3A
 2.483 with sigma of 0.04
 C3A-C4A
 2.483 with sigma of 0.04
 C4A-C5A
 2.483 with sigma of 0.04
 C5-C4
 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
 C13A-C15A
 2.483 with sigma of 0.04
 C19A-C18A
 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
 C25A-C21
 2.483 with sigma of 0.04
 C23A-C21
 2.483 with sigma of 0.04
 C24A-C21
 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
 C23A-C25A
 2.483 with sigma of 0.04
 C23-C24
 2.483 with sigma of 0.04
 C24-C25
 2.483 with sigma of 0.04
 C25-C23
 2.483 with sigma of 0.04
 C8-C10
 2.483 with sigma of 0.04
 C8A-C10A
 2.483 with sigma of 0.04
 C10A-C6
 2.483 with sigma of 0.04
 C10A-C9A
 2.483 with sigma of 0.04
 C8A-C9A
 2.483 with sigma of 0.04
 C9-C10
 2.483 with sigma of 0.04
 C8-C9
 2.483 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C18) \\sim Ueq, Uanis(C20) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C15) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) = Uanis(C7A)
Uanis(C17) = Uanis(C27)
Uanis(C4) = Uanis(C5)
Uanis(C5) = Uanis(C5A)
Uanis(C3) = Uanis(C3A)
Uanis(C4) = Uanis(C4A)
Uanis(C13) = Uanis(C13A)
Uanis(C15) = Uanis(C15A)
Uanis(C14) = Uanis(C14A)
Uanis(C18) = Uanis(C18A)
Uanis(C20) = Uanis(C20A)
Uanis(C19) = Uanis(C19A)
Uanis(C23) = Uanis(C23A)
Uanis(C24) = Uanis(C24A)
Uanis(C25) = Uanis(C25A)
Uanis(C8) = Uanis(C8A)
Uanis(C10) = Uanis(C10A)
Uanis(C9) = Uanis(C9A)
4. Rigid body (RIGU) restrains
 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
 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
 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
 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(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(1)
 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(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(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(3)
 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(3)
 Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(4)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(4)
 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(5)
 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(5)
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), C3A(H3AA,H3AB,H3AC), C4(H4A,H4B,H4C), C4A(H4AA,H4AB,H4AC),
 C5(H5A,H5B,H5C), C5A(H5AA,H5AB,H5AC), C8(H8A,H8B,H8C), C8A(H8AA,H8AB,H8AC),
 C9(H9A,H9B,H9C), C9A(H9AA,H9AB,H9AC), C10(H10A,H10B,H10C), C10A(H10D,H10E,
 H10F), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F), C14(H14A,H14B,H14C),
 C14A(H14D,H14E,H14F), C15(H15A,H15B,H15C), C15A(H15D,H15E,H15F), C18(H18A,H18B,
 H18C), C18A(H18D,H18E,H18F), C19(H19A,H19B,H19C), C19A(H19D,H19E,H19F),
 C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F), C23(H23A,H23B,H23C), C23A(H23D,H23E,
 H23F), C24(H24A,H24B,H24C), C24A(H24D,H24E,H24F), C25(H25A,H25B,H25C),
 C25A(H25D,H25E,H25F)
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), C28(H28A,H28B,H28C), C29(H29A,
 H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
;
_shelx_fab_checksum              64681
_olex2_submission_special_instructions 'No special instructions were received'