Synthesis and luminescence studies of lanthanide complexes (Gd, Tb, Dy) with phenyl- and 2-pyridylthiolates supported by a bulky β-diketiminate ligand. Impact of the ligand environment on terbium(iii) emission
Mironova, Olga A.; Ryadun, Aleksey A.; Sukhikh, Taisiya S.; Konchenko, Sergey N.; Pushkarevsky, Nikolay A.; New Journal of Chemistry 44 (2020) 19769–19779; doi:10.1039/D0NJ04201C

data_7060078
_publ_section_title
;
 Synthesis and luminescence studies of lanthanide complexes (Gd, Tb, Dy)
 with phenyl- and 2-pyridylthiolates supported by a bulky \b-diketiminate
 ligand. Impact of the ligand environment on terbium(iii) emission
;
_journal_issue                   45
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              19769
_journal_page_last               19779
_journal_paper_doi               10.1039/D0NJ04201C
_journal_volume                  44
_journal_year                    2020
_chemical_formula_moiety         '1(C37 H57 I2 N2 O2 Tb)'
_chemical_formula_sum            'C37 H57 I2 N2 O2 Tb'
_chemical_formula_weight         974.56
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2020-10-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-10-01 deposited with the CCDC.	2020-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                94.1500(10)
_cell_angle_beta                 79.6990(10)
_cell_angle_gamma                107.4440(10)
_cell_formula_units_Z            4
_cell_length_a                   12.7128(5)
_cell_length_b                   19.5799(6)
_cell_length_c                   16.8372(5)
_cell_measurement_reflns_used    9896
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      26.25
_cell_measurement_theta_min      2.27
_cell_volume                     3933.1(2)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'Bruker APEXII CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0258
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            35394
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.448
_diffrn_reflns_theta_min         1.627
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    3.399
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6620
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0542 before and 0.0431 after correction. The Ratio of minimum to maximum transmission is 0.8881. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.646
_exptl_crystal_description       block
_exptl_crystal_F_000             1920
_exptl_crystal_preparation       Luminescent
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_refine_diff_density_max         2.025
_refine_diff_density_min         -2.169
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     860
_refine_ls_number_reflns         16094
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0365P)^2^+11.9913P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0879
_refine_ls_wR_factor_ref         0.0957
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12844
_reflns_number_total             16094
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nj04201c2.cif
_cod_data_source_block           moa50_red
_cod_depositor_comments
'Adding full bibliography for 7060074--7060081.cif.'
_cod_database_code               7060078
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.484
_shelx_estimated_absorpt_t_min   0.382
_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
 C237-C235
 2.35 with sigma of 0.04
 C234-C236
 2.35 with sigma of 0.04
 O22B-C236
 2.35 with sigma of 0.04
 O22B-C235
 2.35 with sigma of 0.04
 C237-C234
 2.35 with sigma of 0.04
 O21A-C1 \\sim O21A-C233 \\sim O21A-C4 \\sim O21A-C230
 with sigma of 0.02
 C233-C232 \\sim C1-C2 \\sim C4-C3 \\sim C230-C231
 with sigma of 0.02
 C2-C3 \\sim C232-C231
 with sigma of 0.02
 Tb1-O21B \\sim Tb21-O21A
 with sigma of 0.02
 O22A-C5 \\sim O22B-C237 \\sim O22B-C234 \\sim O22A-C6
 with sigma of 0.02
 C8-C5 \\sim C236-C237 \\sim C8-C7 \\sim C236-C235 \\sim C7-C6 \\sim C235-C234
 with sigma of 0.02
 Tb1-O22B \\sim Tb21-O22A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uiso(C233) = Uiso(C232) = Uiso(C231) = Uiso(C230)
Uiso(O22B) = Uiso(C237) = Uiso(C234) = Uiso(C235) = Uiso(C236)
4. Rigid body (RIGU) restrains
 O21A, C1, C2, C3, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O21A, C230, C231, C232, C233
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O22B, C234, C235, C236, C237
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Tb1)=Sof(I22B)=Sof(O21B)=Sof(O22B)=Sof(C230)=Sof(H23A)=Sof(H23B)=
 Sof(C231)=Sof(H23C)=Sof(H23D)=Sof(C232)=Sof(H23E)=Sof(H23F)=Sof(C233)=
 Sof(H23G)=Sof(H23H)=Sof(C234)=Sof(H23I)=Sof(H23J)=Sof(C235)=Sof(H23K)=
 Sof(H23L)=Sof(C236)=Sof(H23M)=Sof(H23N)=Sof(C237)=Sof(H23O)=Sof(H23P)=1-FVAR(1)
 Sof(Tb21)=Sof(I22A)=Sof(O21A)=Sof(O22A)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C112(H112), C115(H115), C124(H124), C127(H127), C212(H212), C215(H215),
 C224(H224), C227(H227)
6.b Secondary CH2 refined with riding coordinates:
 C130(H13A,H13B), C131(H13C,H13D), C132(H13E,H13F), C133(H13G,H13H), C134(H13I,
 H13J), C135(H13K,H13L), C136(H13M,H13N), C137(H13O,H13P), C1(H1A,H1B), C2(H2A,
 H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,
 H8B), C230(H23A,H23B), C231(H23C,H23D), C232(H23E,H23F), C233(H23G,H23H),
 C234(H23I,H23J), C235(H23K,H23L), C236(H23M,H23N), C237(H23O,H23P)
6.c Aromatic/amide H refined with riding coordinates:
 C102(H102), C108(H108), C109(H109), C110(H110), C120(H120), C121(H121),
 C122(H122), C202(H202), C208(H208), C209(H209), C210(H210), C220(H220),
 C221(H221), C222(H222)
6.d Idealised Me refined as rotating group:
 C104(H10A,H10B,H10C), C105(H10D,H10E,H10F), C113(H11A,H11B,H11C), C114(H11D,
 H11E,H11F), C116(H11G,H11H,H11I), C117(H11J,H11K,H11L), C125(H12A,H12B,H12C),
 C126(H12D,H12E,H12F), C128(H12G,H12H,H12I), C129(H12J,H12K,H12L), C204(H20A,
 H20B,H20C), C205(H20D,H20E,H20F), C213(H21A,H21B,H21C), C214(H21D,H21E,H21F),
 C216(H21G,H21H,H21I), C217(H21J,H21K,H21L), C225(H22A,H22B,H22C), C226(H22D,
 H22E,H22F), C228(H22G,H22H,H22I), C229(H22J,H22K,H22L)
;
_shelx_res_checksum              73648
_olex2_submission_special_instructions 'No special instructions were received'