Lanthanide Speciation in Potential SANEX and GANEX Actinide/Lanthanide Separations Using Tetra-N-Donor Extractants
Daniel M. Whittaker; Tamara L. Griffiths; Madeleine Helliwell; Adam N. Swinburne; Louise S. Natrajan; Frank W. Lewis; Laurence M. Harwood; Stephen A. Parry; Clint A. Sharrad; Inorganic Chemistry 52 (2013) 3429–3444; doi:10.1021/ic301599y

data_4334264
_publ_contact_author_address
;
Centre for Radiochemistry Research
School of Chemistry
University of Manchester
Oxford Road
Manchester
M13 9PL
;
_publ_contact_author_email       daniel.whittaker@postgrad.manchester.ac.uk
_publ_contact_author_name        'Daniel Whittaker'
_publ_contact_author_phone       +441612751405
_publ_section_title
;
 Lanthanide Speciation in Potential SANEX and GANEX Actinide/Lanthanide
 Separations Using Tetra-N-Donor Extractants
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              3429
_journal_page_last               3444
_journal_paper_doi               10.1021/ic301599y
_journal_volume                  52
_journal_year                    2013
_chemical_formula_moiety         'C64 H76 N16 O Tb, 3(N O3), 4(C2 H6 O)'
_chemical_formula_sum            'C72 H100 N19 O14 Tb'
_chemical_formula_weight         1614.63
_chemical_name_systematic        '[Tb(CyMe4-BTBP)2(H2O)](NO3)3.4EtOH'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-11-15
_audit_creation_method
;
  Olex2 1.2
  (compiled Nov  5 2012 18:22:26, GUI svn.r4372)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 129.4280(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   30.5621(7)
_cell_length_b                   14.8217(4)
_cell_length_c                   23.9083(6)
_cell_measurement_reflns_used    9917
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      66.633
_cell_measurement_theta_min      3.521
_cell_volume                     8365.4(4)
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0658
_diffrn_reflns_av_unetI/netI     0.0617
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            25718
_diffrn_reflns_theta_full        66.72
_diffrn_reflns_theta_max         66.72
_diffrn_reflns_theta_min         3.52
_diffrn_source                   'micro-focus sealed tube'
_diffrn_source_current           0.65
_diffrn_source_power             0.02925
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.723
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.3405
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1495 before and 0.0830 after correction.
The Ratio of minimum to maximum transmission is 0.4523.
The \l/2 correction factor is 0.0000.
;
_exptl_crystal_colour            'clear ? yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       plate
_exptl_crystal_F_000             3368
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.03
_platon_squeeze_details
;
SQUEEZE was performed to remove residual unmodellable ethanol molecules
and water
;
_refine_diff_density_max         1.956
_refine_diff_density_min         -1.849
_refine_diff_density_rms         0.164
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.145
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         7271
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.0944
_refine_ls_R_factor_gt           0.0915
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0853P)^2^+217.9753P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2363
_refine_ls_wR_factor_ref         0.2381
_reflns_number_gt                6866
_reflns_number_total             7271
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic301599y_si_002_10.cif
_cod_data_source_block           complex10
_cod_database_code               4334264
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  {H27C,H27D} of C27B, {H26A,H26B} of C26A, H18 of C18, H19 of C19, {H1A,H1B}
  of C1, {H2A,H2B} of C2, H13 of C13, H14 of C14, H15 of C15, {H35A,H35B} of
  C35, {H33A,H33B} of C33, {H26C,H26D} of C26B, H20 of C20, {H27A,H27B} of C27A
 At 1.5 times of:
  {H9A,H9B,H9C} of C9, {H36A,H36B,H36C} of C36, {H31A,H31B,H31C} of C31,
  {H10A,H10B,H10C} of C10, {H30A,H30B,H30C} of C30, {H7A,H7B,H7C} of C7, {H8A,
  H8B,H8C} of C8, {H34A,H34B,H34C} of C34, {H32A,H32B,H32C} of C32, {H29A,H29B,
  H29C} of C29
2. Uiso/Uaniso restraints and constraints
Uanis(O2) = Uanis(O3) = Uanis(N9)
Uanis(C29) = Uanis(C30) = Uanis(C32) = Uanis(C31)
Uanis(C34) = Uanis(C33) = Uanis(O7) = Uanis(C36) = Uanis(C35) = Uanis(O8)
3. others
 Sof(O4A)=1-Sof(O4B)=Sof(O5A)=1-Sof(O4B)=Sof(O6A)=1-Sof(O4B)
 Sof(C26A)=Sof(H26A)=Sof(H26B)=1-Sof(H26A)=1-Sof(H26A)=1-Sof(H26A)=Sof(C27A)=
 Sof(H27A)=Sof(H27B)=1-Sof(H26A)=1-Sof(H26A)=1-Sof(H26A)
4.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C26A(H26A,H26B), C26B(H26C,H26D), C27A(H27A,H27B),
 C27B(H27C,H27D), C33(H33A,H33B), C35(H35A,H35B)
4.b Me refined with riding coordinates:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C)
4.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C18(H18), C19(H19), C20(H20)
;