Structural and spectroscopic investigations of redox active seven coordinate luminescent lanthanide complexes
Molloy, Jennifer K.; Fedele, Lionel; Jarjayes, Olivier; Philouze, Christian; Imbert, Daniel; Thomas, Fabrice; Inorganica Chimica Acta 483 (2018) 609–617; doi:10.1016/j.ica.2018.08.054

data_1563925
_publ_section_title
;
 Structural and spectroscopic investigations of redox active seven
 coordinate luminescent lanthanide complexes
;
_journal_name_full               'Inorganica Chimica Acta'
_journal_page_first              609
_journal_page_last               617
_journal_paper_doi               10.1016/j.ica.2018.08.054
_journal_volume                  483
_journal_year                    2018
_chemical_formula_moiety         '2(C51 H75 Gd N4 O3), 2(C2 H3 N)'
_chemical_formula_sum            'C106 H156 Gd2 N10 O6'
_chemical_formula_weight         1980.90
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_cell_angle_alpha                92.94(3)
_cell_angle_beta                 109.29(3)
_cell_angle_gamma                112.25(3)
_cell_formula_units_Z            2
_cell_length_a                   16.392(3)
_cell_length_b                   17.851(4)
_cell_length_c                   20.793(4)
_cell_measurement_reflns_used    135841
_cell_measurement_temperature    200
_cell_measurement_theta_max      30.0
_cell_measurement_theta_min      1.258
_cell_volume                     5206(3)
_computing_cell_refinement       EvalCCD
_computing_data_collection       Collect
_computing_data_reduction        EvalCCD
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      200
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'APEX II'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker-AXS-enraf-nonius KappaAPEXII'
_diffrn_measurement_method       'Phi and omega scans'
_diffrn_radiation_collimation    'Montel optic'
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0514
_diffrn_reflns_av_unetI/netI     0.0342
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            135841
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.000
_diffrn_reflns_theta_min         1.258
_diffrn_source                   'Incoatec ISG250'
_diffrn_source_target            Mo
_diffrn_source_type              'Microfocus sealed tube'
_exptl_absorpt_coefficient_mu    1.318
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.633225
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2004/1 (Bruker,2004) was used for absorption correction.
R(int) was 0.1092 before and 0.0603 after correction.
The Ratio of minimum to maximum transmission is 0.6332.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.264
_exptl_crystal_description       block
_exptl_crystal_F_000             2076
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.11
_refine_diff_density_max         2.010
_refine_diff_density_min         -1.948
_refine_diff_density_rms         0.098
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.212
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1194
_refine_ls_number_reflns         30053
_refine_ls_number_restraints     118
_refine_ls_restrained_S_all      1.217
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0334
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0221P)^2^+7.1523P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0769
_refine_ls_wR_factor_ref         0.0923
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                24875
_reflns_number_total             30053
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ICA-2018-483-609.cif
_cod_data_source_block           Gd
_cod_original_cell_volume        5205(2)
_cod_database_code               1563925
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N6-C54'
 1.12 with sigma of 0.02
 N6-C54"
 1.12 with sigma of 0.02
 C54"-C55"
 1.44 with sigma of 0.02
 C54'-C55'
 1.44 with sigma of 0.02
 C55"-N6
 2.56 with sigma of 0.02
 C55'-N6
 2.56 with sigma of 0.02
 C37A-C36A
 1.55 with sigma of 0.02
 C38A-C36A
 1.55 with sigma of 0.02
 C36A-C39A
 1.55 with sigma of 0.02
 C30A-C28A
 1.55 with sigma of 0.02
 C28A-C29A
 1.55 with sigma of 0.02
 C31A-C28A
 1.55 with sigma of 0.02
 C47C-C44B
 1.5 with sigma of 0.02
 C31A-C30A
 2.45 with sigma of 0.02
 C47C-C45C
 2.45 with sigma of 0.02
 C47C-C46C
 2.45 with sigma of 0.02
3. Rigid bond restraints
 C47B, C46C, C46B, C45C, C45B, C47C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N6, C54", C54', C55", C55'
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N4A, C25A, C23A, C27A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C47C \\sim C46C \\sim C47B \\sim C45B \\sim C45C \\sim C46B: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C54" \\sim N6 \\sim C54' \\sim C55" \\sim C55': within 1.7A with sigma of 0.04
and sigma for terminal atoms of 0.08
N4A \\sim C25A \\sim C23A \\sim C27A: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C54") = Uanis(C54')
Uanis(C46B) = Uanis(C47C)
5. Others
 Sof(C45C)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C46C)=Sof(H46D)=Sof(H46E)=
 Sof(H46F)=Sof(C47C)=Sof(H47D)=Sof(H47E)=Sof(H47F)=1-FVAR(1)
 Sof(C46B)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C45B)=Sof(H45A)=Sof(H45B)=
 Sof(H45C)=Sof(C47B)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(1)
 Sof(C54")=Sof(C55")=Sof(H55A)=Sof(H55B)=Sof(H55C)=1-FVAR(2)
 Sof(C55')=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(C54')=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C25B(H25A,H25B), C23A(H23C,H23D), C24B(H24A,H24B), C27A(H27C,H27D), C26A(H26C,
 H26D), C22A(H22C,H22D), C22B(H22A,H22B), C23B(H23A,H23B), C26B(H26A,H26B),
 C27B(H27A,H27B), C25A(H25C,H25D), C24A(H24C,H24D)
6.b Aromatic/amide H refined with riding coordinates:
 C12B(H12B), C5A(H5A), C7A(H7A), C14B(H14B), C7B(H7B), C21A(H21A), C19A(H19A),
 C3B(H3B), C10B(H10B), C3A(H3A), C12A(H12A), C10A(H10A), C19B(H19B), C14A(H14A),
  C21B(H21B), C5B(H5B), C17A(H17A), C17B(H17B)
6.c Idealised Me refined as rotating group:
 C37B(H37A,H37B,H37C), C51A(H51D,H51E,H51F), C42A(H42D,H42E,H42F), C41B(H41A,
 H41B,H41C), C50B(H50A,H50B,H50C), C35A(H35A,H35B,H35C), C32B(H32A,H32B,H32C),
 C41A(H41D,H41E,H41F), C49B(H49A,H49B,H49C), C43A(H43D,H43E,H43F), C43B(H43A,
 H43B,H43C), C34B(H34A,H34B,H34C), C53(H53A,H53B,H53C), C33B(H33A,H33B,H33C),
 C51B(H51A,H51B,H51C), C33A(H33D,H33E,H33F), C45A(H45G,H45H,H45I), C39A(H39A,
 H39B,H39C), C36B(H36A,H36B,H36C), C29B(H29A,H29B,H29C), C49A(H49D,H49E,H49F),
 C42B(H42A,H42B,H42C), C50A(H50D,H50E,H50F), C34A(H34D,H34E,H34F), C46A(H46G,
 H46H,H46I), C31A(H31D,H31E,H31F), C38B(H38A,H38B,H38C), C31B(H31A,H31B,H31C),
 C30A(H30D,H30E,H30F), C46B(H46A,H46B,H46C), C30B(H30A,H30B,H30C), C45B(H45A,
 H45B,H45C), C47B(H47A,H47B,H47C), C55"(H55A,H55B,H55C), C45C(H45D,H45E,H45F),
 C46C(H46D,H46E,H46F), C47C(H47D,H47E,H47F), C55'(H55D,H55E,H55F), C38A(H38D,
 H38E,H38F), C37A(H37D,H37E,H37F), C29A(H29D,H29E,H29F), C47A(H47G,H47H,H47I)
;
_shelx_res_checksum              28230