Lanthanide Triangles Supported by Radical Bridging Ligands.
Dolinar, Brian S.; Alexandropoulos, Dimitris I.; Vignesh, Kuduva R.; James, Tia'Asia; Dunbar, Kim R.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b12495

data_4127011
_publ_section_title
;
 Lanthanide Triangles Supported by Radical Bridging Ligands.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b12495
_journal_year                    2017
_chemical_formula_moiety
'C66.06 H30.01 Dy3 F36.07 N18 O12.02, 1.01(C4 H10 O)'
_chemical_formula_sum            'C70.38 H40.58 Dy3 F36.19 N18 O13.12'
_chemical_formula_weight         2523.38
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-07-14
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                73.227(3)
_cell_angle_beta                 78.360(3)
_cell_angle_gamma                79.675(4)
_cell_formula_units_Z            2
_cell_length_a                   14.8664(8)
_cell_length_b                   16.6091(9)
_cell_length_c                   19.8643(10)
_cell_measurement_reflns_used    5293
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      20.375
_cell_measurement_theta_min      2.249
_cell_volume                     4561.1(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 Ver. 2014.1-1 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2008-2013)'
_computing_structure_solution    'SHELXS (Sheldrick, 2008-2013)'
_diffrn_ambient_temperature      110.0
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.5\ \w and 0.5\ \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.1014
_diffrn_reflns_av_unetI/netI     0.1310
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            51133
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.754
_diffrn_reflns_theta_min         1.084
_diffrn_source                   'sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.573
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6563
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0740 before and 0.0602 after correction. The Ratio of minimum to maximum transmission is 0.8651. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'orangish brown'
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.837
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2435
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.034
_refine_diff_density_min         -0.862
_refine_diff_density_rms         0.160
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1813
_refine_ls_number_reflns         17264
_refine_ls_number_restraints     3083
_refine_ls_restrained_S_all      0.980
_refine_ls_R_factor_all          0.1298
_refine_ls_R_factor_gt           0.0590
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0397P)^2^+4.7274P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0989
_refine_ls_wR_factor_ref         0.1245
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9946
_reflns_number_total             17264
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b12495_si_002.cif
_cod_data_source_block           Compound_2-Dy
_cod_database_code               4127011
_shelxl_version_number           2014/6
_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. Shared sites
{O9, O9A, O9B, O9C}
{O10, O10A, O10B, O10C}
3. Restrained distances
 F9-C6 \\sim F7A-C6 \\sim F7-C6 \\sim F8A-C6 \\sim F8-C6 \\sim F9A-C6
 with sigma of 0.01
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F7A-F8A \\sim F8A-F9A \\sim F9A-F7A
 with sigma of 0.01
 C30A-C29 \\sim C30-C29 \\sim C27-C26A \\sim C27-C26 \\sim C5A-C4 \\sim C5-C4
 with sigma of 0.01
 C20-C19 \\sim C20A-C19
 with sigma of 0.01
 F22A-C20A \\sim F22-C20 \\sim F23A-C20A \\sim F23-C20 \\sim F24A-C20A \\sim
F24-C20
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
O1S \\sim C1S \\sim C2S \\sim C3S \\sim C4S \\sim O1T \\sim C1T \\sim C2T \\sim
C3T \\sim C4T \\sim O1U \\sim C1U \\sim C2U \\sim C3U \\sim C4U: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
F4 \\sim F5 \\sim F6 \\sim C5 \\sim F4A \\sim F5A \\sim F6A \\sim C5A: within
1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
F7 \\sim F8 \\sim F8A \\sim F9A \\sim F7A \\sim F9 \\sim C6 \\sim C6A: within
1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
F34 \\sim F35 \\sim C30 \\sim F34A \\sim F35A \\sim F36A \\sim C30A \\sim F36:
within 1.7A with sigma of 0.005 and sigma for terminal atoms of 0.01
F31 \\sim F32 \\sim F33 \\sim C26 \\sim F31A \\sim F32A \\sim F33A \\sim C26A:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
F25 \\sim F26 \\sim F27 \\sim F28 \\sim F29 \\sim F30 \\sim O9 \\sim O10 \\sim
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim F25A \\sim F26A \\sim F27A
\\sim F28A \\sim F29A \\sim F30A \\sim O9A \\sim O10A \\sim C21A \\sim C22A
\\sim C23A \\sim C24A \\sim C25A \\sim F25B \\sim F26B \\sim F27B \\sim F28B
\\sim F29B \\sim F30B \\sim O9B \\sim O10B \\sim C21B \\sim C22B \\sim C23B
\\sim C24B \\sim C25B \\sim F25C \\sim F26C \\sim F27C \\sim F28C \\sim F29C
\\sim F30C \\sim O9C \\sim O10C \\sim C21C \\sim C22C \\sim C23C \\sim C24C
\\sim C25C: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
F22 \\sim F23 \\sim F24 \\sim C20 \\sim F22A \\sim F23A \\sim F24A \\sim C20A:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O9) = Uanis(O9A) = Uanis(O9B) = Uanis(O9C)
Uanis(O10) = Uanis(O10A) = Uanis(O10B) = Uanis(O10C)
5. Same fragment restrains
{F4A, F5A, F6A, C5A} sigma for 1-2: 0.01, 1-3: 0.02
{F7, F8, F9, C6} sigma for 1-2: 0.01, 1-3: 0.02
{F7A, F8A, F9A, C6A} sigma for 1-2: 0.01, 1-3: 0.02
{F31, F32, F33, C26} sigma for 1-2: 0.01, 1-3: 0.02
{F34, F35, F36, C30} sigma for 1-2: 0.01, 1-3: 0.02
{F31A, F32A, F33A, C26A} sigma for 1-2: 0.01, 1-3: 0.02
{F34A, F35A, F36A, C30A} sigma for 1-2: 0.01, 1-3: 0.02
as
{F4, F5, F6, C5}
{F25, F26, F27, F28, F29, F30, O9, O10, C21, C22, C23, C24, C25} sigma for 1-2:
0.01, 1-3: 0.02
{F25A, F26A, F27A, F28A, F29A, F30A, O9A, O10A, C21A, C22A, C23A, C24A, C25A}
sigma for 1-2: 0.01, 1-3: 0.02
{F25B, F26B, F27B, F28B, F29B, F30B, O9B, O10B, C21B, C22B, C23B, C24B, C25B}
sigma for 1-2: 0.01, 1-3: 0.02
{F25C, F26C, F27C, F28C, F29C, F30C, O9C, O10C, C21C, C22C, C23C, C24C, C25C}
sigma for 1-2: 0.01, 1-3: 0.02
as
{F13, F14, F15, F16, F17, F18, O5, O6, C11, C12, C13, C14, C15}
6. Others
 1*[Sof(F25)+Sof(F26)+Sof(F27)+Sof(F28)+Sof(F29)+Sof(F30)+Sof(O9)+Sof(O10)+
 Sof(C21)+Sof(C22)+Sof(C23)+Sof(H23)+Sof(C24)+Sof(C25)]+1*[Sof(F25A)+Sof(F26A)+
 Sof(F27A)+Sof(F28A)+Sof(F29A)+Sof(F30A)+Sof(O9A)+Sof(O10A)+Sof(C21A)+Sof(C22A)+
 Sof(C23A)+Sof(H23A)+Sof(C24A)+Sof(C25A)]+1*[Sof(F25B)+Sof(F26B)+Sof(F27B)+
 Sof(F28B)+Sof(F29B)+Sof(F30B)+Sof(O9B)+Sof(O10B)+Sof(C21B)+Sof(C22B)+Sof(C23B)+
 Sof(H23B)+Sof(C24B)+Sof(C25B)]+1*[Sof(F25C)+Sof(F26C)+Sof(F27C)+Sof(F28C)+
 Sof(F29C)+Sof(F30C)+Sof(O9C)+Sof(O10C)+Sof(C21C)+Sof(C22C)+Sof(C23C)+Sof(H23C)+
 Sof(C24C)+Sof(C25C)]=1 with esd of 0.01
 1*[Sof(O1S)+Sof(C1S)+Sof(H1SA)+Sof(H1SB)+Sof(H1SC)+Sof(C2S)+Sof(H2SA)+
 Sof(H2SB)+Sof(C3S)+Sof(H3SA)+Sof(H3SB)+Sof(C4S)+Sof(H4SA)+Sof(H4SB)+Sof(H4SC)]+
 1*[Sof(O1T)+Sof(C1T)+Sof(H1TA)+Sof(H1TB)+Sof(H1TC)+Sof(C2T)+Sof(H2TA)+
 Sof(H2TB)+Sof(C3T)+Sof(H3TA)+Sof(H3TB)+Sof(C4T)+Sof(H4TA)+Sof(H4TB)+Sof(H4TC)]+
 1*[Sof(O1U)+Sof(C1U)+Sof(H1UA)+Sof(H1UB)+Sof(H1UC)+Sof(C2U)+Sof(H2UA)+
 Sof(H2UB)+Sof(C3U)+Sof(H3UA)+Sof(H3UB)+Sof(C4U)+Sof(H4UA)+Sof(H4UB)+Sof(H4UC)]=
 1 with esd of 0.01
 Sof(F25)=Sof(F26)=Sof(F27)=Sof(F28)=Sof(F29)=Sof(F30)=Sof(O9)=Sof(O10)=
 Sof(C21)=Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(C25)=FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(C6A)=1-FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(C6)=FVAR(2)
 Sof(F31A)=Sof(F32A)=Sof(F33A)=Sof(C26A)=1-FVAR(3)
 Sof(F31)=Sof(F32)=Sof(F33)=Sof(C26)=FVAR(3)
 Sof(F34A)=Sof(F35A)=Sof(F36A)=Sof(C30A)=1-FVAR(4)
 Sof(F34)=Sof(F35)=Sof(F36)=Sof(C30)=FVAR(4)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(C5A)=1-FVAR(5)
 Sof(F4)=Sof(F5)=Sof(F6)=Sof(C5)=FVAR(5)
 Sof(F25A)=Sof(F26A)=Sof(F27A)=Sof(F28A)=Sof(F29A)=Sof(F30A)=Sof(O9A)=
 Sof(O10A)=Sof(C21A)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(C25A)=FVAR(6)
 Sof(O1S)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=
 Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(H4SC)=FVAR(7)
 Sof(O1T)=Sof(C1T)=Sof(H1TA)=Sof(H1TB)=Sof(H1TC)=Sof(C2T)=Sof(H2TA)=Sof(H2TB)=
 Sof(C3T)=Sof(H3TA)=Sof(H3TB)=Sof(C4T)=Sof(H4TA)=Sof(H4TB)=Sof(H4TC)=FVAR(8)
 Sof(O1U)=Sof(C1U)=Sof(H1UA)=Sof(H1UB)=Sof(H1UC)=Sof(C2U)=Sof(H2UA)=Sof(H2UB)=
 Sof(C3U)=Sof(H3UA)=Sof(H3UB)=Sof(C4U)=Sof(H4UA)=Sof(H4UB)=Sof(H4UC)=FVAR(9)
 Sof(F25B)=Sof(F26B)=Sof(F27B)=Sof(F28B)=Sof(F29B)=Sof(F30B)=Sof(O9B)=
 Sof(O10B)=Sof(C21B)=Sof(C22B)=Sof(C23B)=Sof(H23B)=Sof(C24B)=Sof(C25B)=FVAR(10)
 Sof(F25C)=Sof(F26C)=Sof(F27C)=Sof(F28C)=Sof(F29C)=Sof(F30C)=Sof(O9C)=
 Sof(O10C)=Sof(C21C)=Sof(C22C)=Sof(C23C)=Sof(H23C)=Sof(C24C)=Sof(C25C)=FVAR(11)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=Sof(C20A)=1-FVAR(12)
 Sof(F22)=Sof(F23)=Sof(F24)=Sof(C20)=FVAR(12)
7.a Free rotating group:
 O1S(C1S,C2S,C3S,C4S), O1T(C1T,C2T,C3T,C4T), O1U(C1U,C2U,C3U,C4U)
7.b Secondary CH2 refined with riding coordinates:
 C2S(H2SA,H2SB), C3S(H3SA,H3SB), C2T(H2TA,H2TB), C3T(H3TA,H3TB), C2U(H2UA,
 H2UB), C3U(H3UA,H3UB)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C18(H18), C28(H28), C31(H31), C32(H32), C33(H33), C34(H34),
 C39(H39), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46),
  C51(H51), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C57(H57),
 C58(H58), C63(H63), C64(H64), C65(H65), C66(H66), C13(H13), C23(H23),
 C23A(H23A), C23B(H23B), C23C(H23C)
7.d Idealised Me refined with riding coordinates:
 C1S(H1SA,H1SB,H1SC), C4S(H4SA,H4SB,H4SC), C1T(H1TA,H1TB,H1TC), C4T(H4TA,H4TB,
 H4TC), C1U(H1UA,H1UB,H1UC), C4U(H4UA,H4UB,H4UC)
;
_shelx_res_checksum              44158
_shelx_hkl_checksum              93078
_olex2_submission_special_instructions 'No special instructions were received'