Exploring the luminescent and thermometric potentials of samarium(III) diketonate complexes with extended fluoroalkyl chains.
Metlina, Daria A.; Metlin, Mikhail T.; Korshunov, Vladislav M.; Gontcharenko, Victoria E.; Avetisov, Roman I.; Kiskin, Mikhail A.; Belousov, Yuriy A.; Taydakov, Ilya V.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 3812–3826; doi:10.1039/d4dt03262d

data_7717871
_publ_section_title
;
 Exploring the luminescent and thermometric potentials of samarium(III)
 diketonate complexes with extended fluoroalkyl chains.
;
_journal_issue                   9
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3812
_journal_page_last               3826
_journal_paper_doi               10.1039/d4dt03262d
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C54 H20 F45 N2 O6 S3 Sm'
_chemical_formula_sum            'C54 H20 F45 N2 O6 S3 Sm'
_chemical_formula_weight         1894.25
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-11-05
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-05 deposited with the CCDC.	2025-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.520(3)
_cell_length_b                   18.988(3)
_cell_length_c                   32.676(4)
_cell_measurement_reflns_used    9508
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      29.91
_cell_measurement_theta_min      2.23
_cell_volume                     12732(3)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1022
_diffrn_reflns_av_unetI/netI     0.0918
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            10589
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        24.713
_diffrn_reflns_theta_max         24.713
_diffrn_reflns_theta_min         1.921
_exptl_absorpt_coefficient_mu    1.205
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.976
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             7368
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.728
_refine_diff_density_min         -2.178
_refine_diff_density_rms         0.221
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.143
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1064
_refine_ls_number_reflns         10589
_refine_ls_number_restraints     951
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.1519
_refine_ls_R_factor_gt           0.1238
_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^)+(0.0739P)^2^+474.3499P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2609
_refine_ls_wR_factor_ref         0.2774
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8143
_reflns_number_total             10589
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03262d2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7717869--7717871.cif.'
_cod_database_code               7717871
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.910
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9870(12)
 0.0130(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 C38-C39 = C39-C40 = C40-C41 = C41-C42
 1.5 with sigma of 0.01
 C38-F17 = C38-F17A = C39-F18 = C39-F18A = C41-F20A = C41-F20 = C42-F21A = C42-
 F21B = C42-F21
 1.29171 with sigma of 0.004
 C4-S1 = C4-S1'
 1.7 with sigma of 0.005
 C4-C5 = C4-C5' = C5-C6 = C6-C7 = C5'-C7
 1.47 with sigma of 0.004
 C32-S3' = C32-S3
 1.7 with sigma of 0.005
 C32-C33' = C32-C33 = C33'-C35 = C35-C34 = C33-C34
 1.47 with sigma of 0.004
 C18-S2' = C18-S2
 1.7 with sigma of 0.005
 C18-C19' = C18-C19 = C19'-C21 = C21-C20 = C19-C20
 1.47 with sigma of 0.004
 C37-C36
 1.52 with sigma of 0.02
 C38-C37 = C36-C37
 1.52 with sigma of 0.02
 F17A-C37
 2.7 with sigma of 0.02
 F17A-C38 = F17-C38
 1.34 with sigma of 0.02
 F17A-F17
 2.1 with sigma of 0.02
 F16A-C37 = F16-C37
 1.34 with sigma of 0.02
 C36-C37 = C38-C37 = C39-C38 = C40-C39 = C41-C40 = C42-C41
 1.51 with sigma of 0.02
 F16A-C37 = F16-C37 = F17A-C38 = F17-C38 = F18-C39 = F18A-C39 = F19-C40 = F19A-
 C40 = F20-C41 = F20A-C41 = F21A-C42 = F21-C42 = F21B-C42
 1.34 with sigma of 0.02
 F18A-C40
 2.4 with sigma of 0.02
 C37'-C36 = C38'-C37' = C38'-C39' = C40'-C39' = C40'-C41' = C42'-C41'
 1.52 with sigma of 0.02
 F16A'-C37' = F16'-C37' = F17'-C38' = F17A'-C38' = F18'-C39' = F18A'-C39' = F19'-
 C40' = F19A'-C40' = F20'-C41' = F20A'-C41' = F21'-C42' = F21A'-C42' = F21B'-C42'
 1.34 with sigma of 0.02
 F18A'-C40'
 2.4 with sigma of 0.02
 F19'-F19A'
 2.1 with sigma of 0.02
 F20A'-F20'
 2.1 with sigma of 0.02
 F21'-F21A'
 2.1 with sigma of 0.02
 F21B'-F21A'
 2.1 with sigma of 0.02
 F21'-F21B'
 2.1 with sigma of 0.02
 F18'-F18A'
 2.1 with sigma of 0.02
 F17'-F17A'
 2.1 with sigma of 0.02
 F16A'-F16'
 2.1 with sigma of 0.02
 F14-C28 = F14B-C28 = F14A-C28
 1.34 with sigma of 0.02
 C28-C27
 1.52 with sigma of 0.02
 F14-F14B
 2.1 with sigma of 0.02
 F14B-F14A
 2.1 with sigma of 0.02
 C28'-C27 = C28-C27
 1.52 with sigma of 0.02
 F14B-C28 = F14-C28 = F14A-C28
 1.34 with sigma of 0.02
 F14A-F14
 2.1 with sigma of 0.02
 F14A-F14B
 2.1 with sigma of 0.02
 F14B-F14
 2.1 with sigma of 0.02
 C17-C22 \\sim C22-C23 \\sim C23-C24 \\sim C24-C25 \\sim C25-C26 \\sim C26-C27
 with sigma of 0.02
 C17-C23 \\sim C22-C24 \\sim C23-C25 \\sim C24-C26 \\sim C25-C27
 with sigma of 0.02
 F15-F15A \\sim F16A-F16 \\sim F17-F17A \\sim F18A-F18 \\sim F20A-F20 \\sim
F21A-F21B
 with sigma of 0.02
 C22-F8 \\sim C22-F8A \\sim C23-F9A \\sim C23-F9 \\sim C24-F10 \\sim C24-F10A
\\sim C25-F11 \\sim C25-F11A
 \\sim C26-F12 \\sim C26-F12A \\sim C27-F13 \\sim C27-F13A
 with sigma of 0.02
 F1-F1A \\sim F2-F2A \\sim F3A-F3 \\sim F4A-F4 \\sim F5A-F5 \\sim F6A-F6 \\sim
F7A-F7 \\sim F7A-F7B \\sim F7B-F7
 with sigma of 0.02
 C8-C9 \\sim C9-C10 \\sim C10-C11 \\sim C11-C12 \\sim C12-C13 \\sim C13-C14
 with sigma of 0.02
 C3-C9 \\sim C8-C10 \\sim C9-C11 \\sim C10-C12 \\sim C11-C13 \\sim C12-C14
\\sim C39-C41 \\sim C40-C42
 with sigma of 0.02
 F8-F8A \\sim F9A-F9 \\sim F10-F10A \\sim F11-F11A \\sim F12-F12A \\sim F13-F13A
 with sigma of 0.02
 C27-C28 \\sim C27-C28'
 with sigma of 0.02
 F14B-C28 \\sim F1J-C28'
 with sigma of 0.02
 F14A-C28 \\sim F14B'-C28'
 with sigma of 0.02
 F14-C28 \\sim F14'-C28'
 with sigma of 0.02
 C27-F14B \\sim C27-F1J
 with sigma of 0.04
 C27-F14A \\sim C27-F14B'
 with sigma of 0.04
 C27-F14 \\sim C27-F14'
 with sigma of 0.04
 F14B-F14A \\sim F1J-F14B'
 with sigma of 0.04
 F14B-F14 \\sim F1J-F14'
 with sigma of 0.04
 F14A-F14 \\sim F14B'-F14'
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C37 \\sim C36: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C38' \\sim C40' \\sim C39': within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C25 \\sim C27 \\sim C26 \\sim C28 \\sim C28': within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
F16' \\sim F16A' \\sim F20' \\sim F20A' \\sim F19' \\sim F19A' \\sim F18' \\sim F18A'
\\sim F17A' \\sim F17' \\sim F21' \\sim F21B' \\sim F21A': within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
Uanis(N1) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C5) \\sim
Ueq, Uanis(C6) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C35) \\sim Ueq,
Uanis(C34) \\sim Ueq, Uanis(S3') \\sim Ueq, Uanis(S3) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C45) \\sim Ueq,
Uanis(S2') \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(F16)
\\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(F19A) \\sim Ueq, Uanis(F7) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F7B) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F18A) \\sim Ueq, Uanis(F20A)
\\sim Ueq, Uanis(F21A) \\sim Ueq, Uanis(F21) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C40) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C53)
\\sim Ueq, Uanis(C46) \\sim Ueq: with sigma of 0.002 and sigma for terminal
atoms of 0.004
Uanis(O1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C5') \\sim Ueq, Uanis(S1')
\\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C1) \\sim Ueq,
Uanis(C47) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(F7A) \\sim Ueq, Uanis(O3) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C33') \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C48)
\\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C19') \\sim Ueq, Uanis(C38) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C10) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(F16A) \\sim Ueq, Uanis(F18A') \\sim Ueq, Uanis(C39') \\sim Ueq, Uanis(F19)
\\sim Ueq, Uanis(C42') \\sim Ueq, Uanis(F21B) \\sim Ueq, Uanis(F20A') \\sim Ueq,
Uanis(F16) \\sim Ueq, Uanis(F21B') \\sim Ueq, Uanis(F18A) \\sim Ueq, Uanis(C40')
\\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(F16A') \\sim Ueq, Uanis(F21A) \\sim Ueq,
Uanis(F19A') \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(F17') \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(C37') \\sim Ueq, Uanis(F17A) \\sim Ueq, Uanis(C38') \\sim Ueq,
Uanis(F20) \\sim Ueq, Uanis(C41') \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(F16')
\\sim Ueq, Uanis(F20A) \\sim Ueq, Uanis(F20') \\sim Ueq, Uanis(F17) \\sim Ueq,
Uanis(F19') \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F18') \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(F17A') \\sim Ueq, Uanis(F19A) \\sim Ueq, Uanis(F21') \\sim Ueq,
Uanis(C42) \\sim Ueq, Uanis(F21A') \\sim Ueq, Uanis(F18) \\sim Ueq: with sigma of
0.003 and sigma for terminal atoms of 0.006
Uanis(C17) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F14A) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F14B') \\sim Ueq, Uanis(F14B)
\\sim Ueq, Uanis(F1J) \\sim Ueq, Uanis(F14') \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(F17) = Uanis(F17A)
Uanis(F18) = Uanis(F18A)
Uanis(C5) = Uanis(C5')
Uanis(S3') = Uanis(S3)
Uanis(C33') = Uanis(C33)
Uanis(F20A) = Uanis(F20)
Uanis(S2') = Uanis(S2)
Uanis(C19') = Uanis(C19)
Uanis(C24) = Uanis(C25) = Uanis(C23)
Uanis(S1) = Uanis(S1')
Uanis(C5') = Uanis(C5) = Uanis(C6) = Uanis(C7)
Uanis(C9) = Uanis(C10) = Uanis(C8)
Uanis(C37') = Uanis(C38') = Uanis(C36)
Uanis(F14B) = Uanis(F14) = Uanis(F14A)
Uanis(C42') = Uanis(C41') = Uanis(C40') = Uanis(C39') = Uanis(C38') =
Uanis(C37')
Uanis(F21A') = Uanis(F21') = Uanis(F21B') = Uanis(F19A') = Uanis(F19') = Uanis(F20A') =
Uanis(F20') = Uanis(F18A') = Uanis(F18') = Uanis(F17') = Uanis(F17A')
5. Rigid body (RIGU) restrains
 C27, C40
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 0.016
 C38, C38, F17A, F17
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 0.016
 F16A, F16
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 0.016
 C18, C21, C19', C19'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C46, C53, C53, C54
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 0.016
 O5, C29, C29, C29, C32, C30
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 0.016
 C41, C42
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 0.016
 F7A, F7, F7B, C14, C14, C14
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 0.016
 N2, N2, C52, C49, C48, C48
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C38, C38, C39, C39, C40
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.006
 C41, C41, F21B, F20A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C37, C36
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: S1(0.6) C5(0.6) H5(0.6) S2'(0.5) S1'(0.4) C5'(0.4) H5'(0.4)
 F16A(0.5) F16(0.5) H6A(0.6) H6(0.4) H35A(0.5) H35(0.5) H7A(0.6) H7(0.4)
 H21A(0.5) H21(0.5) H34A(0.5) H34(0.5) H20A(0.5) H20(0.5) S3'(0.5) C33'(0.5)
 H33'(0.5) S3(0.5) C33(0.5) H33(0.5) C38(0.5) C39(0.5) F17A(0.5) C40(0.5)
 F17(0.5) C41(0.5) C42(0.5) F18(0.5) F18A(0.5) F20(0.5) F21B(0.5) F20A(0.5)
 F21A(0.5) F21(0.5) C19'(0.5) H19'(0.5) S2(0.5) C19(0.5) H19(0.5) F19(0.5)
 F19A(0.5) C37(0.5) C37'(0.5) C42'(0.5) C38'(0.5) C40'(0.5) C41'(0.5) C39'(0.5)
 F16'(0.5) F16A'(0.5) F20'(0.5) F20A'(0.5) F19'(0.5) F19A'(0.5) F18'(0.5) F18A'(0.5)
 F17A'(0.5) F17'(0.5) F21'(0.5) F21B'(0.5) F21A'(0.5) F14B(0.5) F14A(0.5) F14(0.5)
 C28(0.5) F14B'(0.5) F1J(0.5) F14'(0.5) C28'(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C5'(H5'), C53(H53), C2(H2), C45(H45), C6(H6A), C6(H6), C16(H16),
 C30(H30), C50(H50), C54(H54), C35(H35A), C35(H35), C7(H7A), C7(H7), C21(H21A),
 C21(H21), C49(H49), C48(H48), C44(H44), C43(H43), C34(H34A), C34(H34),
 C20(H20A), C20(H20), C33'(H33'), C33(H33), C19'(H19'), C19(H19)
;
_shelx_res_checksum              88734
_olex2_submission_special_instructions 'No special instructions were received'