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_4343289
_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 Gd9 O55 P6, C8 H12 Cu1 N4'
_chemical_formula_sum            'C107 H201 Cu4 Gd9 N4 O55 P6'
_chemical_formula_weight         4278.93
_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                   20.5695(3)
_cell_length_b                   20.5695(3)
_cell_length_c                   33.1977(5)
_cell_measurement_reflns_used    12158
_cell_measurement_temperature    150.1(1)
_cell_measurement_theta_max      28.9390
_cell_measurement_theta_min      3.2540
_cell_volume                     12164.3(3)
_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      150.1(1)
_diffrn_detector_area_resol_mean 10.3705
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -82.00   13.00   1.0000    4.2600
omega____ theta____ kappa____ phi______ frames
    -      -11.6555  -57.0000 -180.0000 95

  2 omega  -34.00   55.00   1.0000    4.2600
omega____ theta____ kappa____ phi______ frames
    -      -11.6555   57.0000  -30.0000 89

  3 omega  -20.00   54.00   1.0000    4.2600
omega____ theta____ kappa____ phi______ frames
    -       11.6555  -99.0000   90.0000 74
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0034363000
_diffrn_orient_matrix_UB_12      0.0158529000
_diffrn_orient_matrix_UB_13      0.0182998000
_diffrn_orient_matrix_UB_21      -0.0033663667
_diffrn_orient_matrix_UB_22      0.0277084667
_diffrn_orient_matrix_UB_23      -0.0110149333
_diffrn_orient_matrix_UB_31      -0.0395240333
_diffrn_orient_matrix_UB_32      -0.0238021667
_diffrn_orient_matrix_UB_33      -0.0006518667
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0425
_diffrn_reflns_av_unetI/netI     0.0610
_diffrn_reflns_laue_measured_fraction_full 0.998
_diffrn_reflns_laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            27448
_diffrn_reflns_point_group_measured_fraction_full 0.936
_diffrn_reflns_point_group_measured_fraction_max 0.925
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.367
_diffrn_reflns_theta_min         2.704
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.269
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68174
_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    1.752
_exptl_crystal_description       cube
_exptl_crystal_F_000             6279
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.226
_refine_diff_density_min         -1.117
_refine_diff_density_rms         0.128
_refine_ls_abs_structure_details
;
 Flack x determined using 3660 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.012(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     598
_refine_ls_number_reflns         10260
_refine_ls_number_restraints     155
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0383
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0393P)^2^+8.6311P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0779
_refine_ls_wR_factor_ref         0.0848
_reflns_Friedel_coverage         0.853
_reflns_friedel_fraction_full    0.874
_reflns_friedel_fraction_max     0.851
_reflns_number_gt                9052
_reflns_number_total             10260
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b00649_si_003.cif
_cod_data_source_block           Cu3Gd9P6
_cod_original_cell_volume        12164.3(4)
_cod_database_code               4343289
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         Cu3Gd10P6O32C100H150
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C36-N2
 1.3 with sigma of 0.02
 N1-C34
 1.3 with sigma of 0.02
 C35-C34
 1.4 with sigma of 0.02
 C37-C36
 1.4 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
 C5A-C2 = C2-C3A
 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
 C23-C22 = C22-C24
 1.52 with sigma of 0.02
 C23A-C22A = C22A-C25A
 1.52 with sigma of 0.02
 C25A-C22A = C22A-C24A
 1.52 with sigma of 0.02
 C24A-C22A = C22A-C23A
 1.52 with sigma of 0.02
 C3A-C4A
 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
 C24-C25
 2.483 with sigma of 0.04
 C25-C23
 2.483 with sigma of 0.04
 C23-C24
 2.483 with sigma of 0.04
 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(C18) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N1) = Uanis(N2)
Uanis(C34) = Uanis(C36)
Uanis(C37) = Uanis(C35)
Uanis(C22) = Uanis(C22A)
Uanis(C4) = Uanis(C4A)
Uanis(C5) = Uanis(C5A)
Uanis(C3) = Uanis(C3A)
Uanis(C24) = Uanis(C24A)
Uanis(C25) = Uanis(C25A)
Uanis(C23) = Uanis(C23A)
Uanis(Cu2A) = Uanis(Cu2B)
4. Rigid body (RIGU) restrains
 C3A, C4, C4A, C5, C3, C5A, C2, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22, C23, C24, C25, C24A, C25A, C23A, C22A, C21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Cu2B)=0.33333*(1-FVAR(2))
 Sof(Cu2A)=0.33333*FVAR(2)
 Sof(C22A)=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(2)
 Sof(C22)=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(2)
 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(3)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(3)
 Fixed Sof: H37A(0.33333) H37B(0.33333) H37C(0.33333)
6.a Me refined with riding coordinates:
 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.b Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C3A(H3AA,H3AB,H3AC), C4(H4A,H4B,H4C), C4A(H4AA,H4AB,H4AC),
 C5(H5A,H5B,H5C), C5A(H5AA,H5AB,H5AC), 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(H19A,H19B,H19C), C20(H20A,H20B,H20C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C37(H37A,H37B,
 H37C)
;
_olex2_date_sample_data_collection 2013-10-24
_olex2_submission_special_instructions 'No special instructions were received'