Synthesis of a series of hetero-multi-spin Ln<sub>2</sub>Cu<sub>3</sub> complexes based on a methyl-pyrazole nitronyl nitroxide radical with slow magnetic relaxation behaviors.
Shi, Jian Yun; Chen, Peng Yun; Wu, Ming Ze; Tian, Li; Liu, Zhong Yi; Dalton transactions (Cambridge, England : 2003) 48 (2019) 9187–9193; doi:10.1039/c9dt00981g

data_7701672
_publ_section_title
;
 Synthesis of a series of hetero-multi-spin Ln<sub>2</sub>Cu<sub>3</sub>
 complexes based on a methyl-pyrazole nitronyl nitroxide radical with slow
 magnetic relaxation behaviors.
;
_journal_issue                   25
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9187
_journal_page_last               9193
_journal_paper_doi               10.1039/c9dt00981g
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         'C52 H40 Cu1.5 F36 N8 O16 Tb'
_chemical_formula_sum            'C52 H40 Cu1.5 F36 N8 O16 Tb'
_chemical_formula_weight         1971.15
_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_block_doi                 10.5517/ccdc.csd.cc21t7sx
_audit_creation_date             2018-11-28
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-05 deposited with the CCDC.	2019-05-31 downloaded from the CCDC.
;
_cell_angle_alpha                94.5361(15)
_cell_angle_beta                 92.4970(15)
_cell_angle_gamma                95.6302(15)
_cell_formula_units_Z            2
_cell_length_a                   11.9225(2)
_cell_length_b                   18.3300(3)
_cell_length_c                   20.3485(4)
_cell_measurement_reflns_used    18887
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.7450
_cell_measurement_theta_min      2.3900
_cell_volume                     4405.73(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2740
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -91.00 -48.00   1.00    1.27    --  -41.49 125.00  30.00   43
  2  \w    -63.00  32.00   1.00    1.27    --  -41.49  38.00-150.00   95
  3  \w    -30.00  -2.00   1.00    1.27    --  -41.49 125.00  30.00   28
  4  \w   -116.00 -17.00   1.00    1.27    --  -41.49 -38.00  30.00   99
  5  \w     25.00  52.00   1.00    1.27    --   41.49-125.00  30.00   27
  6  \w     21.00  69.00   1.00    1.27    --   41.49 -77.00-150.00   48
  7  \w     15.00 101.00   1.00    1.27    --   41.49  57.00 -30.00   86
  8  \w     42.00 107.00   1.00    5.10    --  107.08 -95.00-120.00   65
  9  \w     52.00 118.00   1.00    5.10    --  107.08-125.00-180.00   66
 10  \w     32.00 135.00   1.00    5.10    --  107.08 -30.00-180.00  103
 11  \w     70.00 117.00   1.00    5.10    --  107.08  15.00 120.00   47
 12  \w     83.00 118.00   1.00    5.10    --  107.08-125.00  30.00   35
 13  \w     50.00  76.00   1.00    5.10    --  107.08 -95.00 -60.00   26
 14  \w     82.00 153.00   1.00    5.10    --  107.08  30.00  30.00   71
 15  \w     37.00  63.00   1.00    5.10    --  107.08-125.00  30.00   26
 16  \w     54.00 137.00   1.00    5.10    --  107.08  15.00-180.00   83
 17  \w     40.00 132.00   1.00    5.10    --  107.08 -61.00 -60.00   92
 18  \w    126.00 152.00   1.00    5.10    --  107.08 125.00-120.00   26
 19  \w    105.00 178.00   1.00    5.10    --  107.08 125.00 -60.00   73
 20  \w    106.00 138.00   1.00    5.10    --  107.08 125.00 -30.00   32
 21  \w     96.00 140.00   1.00    5.10    --  107.08 -77.00 -30.00   44
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0595364000
_diffrn_orient_matrix_UB_12      -0.0600943000
_diffrn_orient_matrix_UB_13      -0.0503967000
_diffrn_orient_matrix_UB_21      -0.1100370000
_diffrn_orient_matrix_UB_22      0.0373110000
_diffrn_orient_matrix_UB_23      0.0043636000
_diffrn_orient_matrix_UB_31      0.0353738000
_diffrn_orient_matrix_UB_32      0.0466846000
_diffrn_orient_matrix_UB_33      -0.0567850000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0455
_diffrn_reflns_av_unetI/netI     0.0504
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            30960
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         2.181
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.528
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.09203
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.486
_exptl_crystal_description       block
_exptl_crystal_F_000             1937
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.2
_platon_squeeze_details
;
TITL A180918c  P -1         R = 0.08
CELL   11.9225   18.3300   20.3485     94.54     92.50     95.63
SPGR P-1
C101 0.598 0.555 0.124 !       3.53 eA-3
C102 0.623 0.492 0.115 !       3.37 eA-3
C103 0.503 0.484 0.003 !       3.21 eA-3
C104 0.536 0.030 0.478 !       3.17 eA-3
C105 0.514 0.027 0.427 !       3.15 eA-3
C106 0.580 0.091 0.388 !       2.87 eA-3
C107 0.531 0.460 0.064 !       2.82 eA-3
C108 0.046 1.000 0.109 !       2.49 eA-3
C109 0.590 0.556 0.050 !       2.45 eA-3
C110 0.953 0.019 0.114 !       2.27 eA-3
C111 0.142 0.037 0.131 !       2.04 eA-3
C112 0.844 0.974 0.103 !       1.77 eA-3
C113 0.563 0.114 0.325 !       1.63 eA-3
C114 0.735 0.007 0.099 !       1.61 eA-3
C115 0.251 0.018 0.135 !       1.45 eA-3
Q116 0.861 0.788 0.279 !       1.43 eA-3
Q117 0.574 0.207 0.160 !       1.43 eA-3
Q118 0.234 0.367 0.338 !       1.35 eA-3
Q119 0.671 0.755 0.089 !       1.28 eA-3
C120 0.170 0.092 0.116 !       1.20 eA-3
Q121 0.247 0.643 0.270 !       1.17 eA-3
Q122 0.737 0.822 0.111 !       1.12 eA-3
Q123 0.014 0.877 0.273 !       1.06 eA-3
Q124 0.999 0.792 0.205 !       1.05 eA-3
Q125 0.969 0.853 0.318 !       0.98 eA-3
Q126 0.532 0.122 0.116 !       0.96 eA-3
Q127 0.608 0.225 0.065 !       0.92 eA-3
Q128 0.282 0.650 0.361 !       0.91 eA-3
Q129 0.316 0.626 0.294 !       0.87 eA-3
Q130 0.231 0.428 0.427 !       0.79 eA-3
C131 0.392 0.974 0.097 !       0.75 eA-3
C132 0.547 0.968 0.097 !       0.72 eA-3
Q133 0.048 0.371 0.374 !       0.71 eA-3
Q134 0.595 0.258 0.093 !       0.70 eA-3
Q135 0.440 0.863 0.208 !       0.68 eA-3
Q136 0.250 0.211 0.127 !       0.68 eA-3
Q137 0.561 0.141 0.033 !       0.65 eA-3
Q138 0.861 0.318 0.239 !       0.63 eA-3
Q139 0.108 0.436 0.441 !       0.58 eA-3
Q140 0.606 0.878 0.271 !       0.58 eA-3
C141 0.470 0.978 0.110 !       0.58 eA-3
Q142 0.233 0.251 0.184 !       0.58 eA-3
Q143 0.447 0.894 0.270 !       0.57 eA-3
Q144 0.375 0.668 0.213 !       0.56 eA-3
Q145 0.684 0.811 0.406 !       0.55 eA-3
C146 0.624 0.011 0.498 !       0.53 eA-3
Q147 0.810 0.842 0.094 !       0.52 eA-3
Q148 0.919 0.578 0.421 !       0.50 eA-3
;
_refine_diff_density_max         1.112
_refine_diff_density_min         -1.457
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1079
_refine_ls_number_reflns         15726
_refine_ls_number_restraints     144
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0439
_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^)+(0.0634P)^2^+3.6248P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1123
_refine_ls_wR_factor_ref         0.1146
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14815
_reflns_number_total             15726
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt00981g2.cif
_cod_data_source_block           a180918c_sq
_cod_original_cell_volume        4405.71(14)
_cod_original_formula_sum        'C52 H40 Cu1.50 F36 N8 O16 Tb'
_cod_database_code               7701672
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.404
_shelx_estimated_absorpt_t_min   0.339
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F18-C37 = F18A-C37 = F17-C37 = F17A-C37 = F16-C37 = F16A-C37
 1.35 with sigma of 0.01
 F32-C48 = F33A-C48 = F33-C48 = F31A-C48 = F31-C48 = F32A-C48
 1.35 with sigma of 0.01
 F35-C52 = F35A-C52 = F36-C52 = F36A-C52 = F34-C52 = F34A-C52
 1.35 with sigma of 0.01
 F18-F16 \\sim F16-F17
 with sigma of 0.001
 F17-F18 \\sim F18-F16
 with sigma of 0.001
 F16-F17 \\sim F17-F18
 with sigma of 0.001
 F18A-F16A \\sim F16A-F17A
 with sigma of 0.001
 F17A-F18A \\sim F18A-F16A
 with sigma of 0.001
 F16A-F17A \\sim F17A-F18A
 with sigma of 0.001
 F32-F33 \\sim F33-F31
 with sigma of 0.001
 F31-F32 \\sim F32-F33
 with sigma of 0.001
 F33-F31 \\sim F31-F32
 with sigma of 0.001
 F32A-F33A \\sim F33A-F31A
 with sigma of 0.001
 F31A-F32A \\sim F32A-F33A
 with sigma of 0.001
 F33A-F31A \\sim F31A-F32A
 with sigma of 0.001
 F36-F34 \\sim F34-F35
 with sigma of 0.001
 F35-F36 \\sim F36-F34
 with sigma of 0.001
 F34-F35 \\sim F35-F36
 with sigma of 0.001
 F35A-F36A \\sim F36A-F34A
 with sigma of 0.001
 F34A-F35A \\sim F35A-F36A
 with sigma of 0.001
 F36A-F34A \\sim F34A-F35A
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(F34) \\sim Ueq, Uanis(F35) \\sim Ueq, Uanis(F36) \\sim Ueq, Uanis(F31)
\\sim Ueq, Uanis(F33) \\sim Ueq, Uanis(F32) \\sim Ueq, Uanis(F21) \\sim Ueq,
Uanis(F19) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F17)
\\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F9) \\sim Ueq,
Uanis(F20) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(F16) \\sim Ueq, Uanis(F32) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.005
Uanis(F16) \\sim Ueq, Uanis(F34) \\sim Ueq, Uanis(F16A) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.005
Uanis(F34) \\sim Ueq, Uanis(F32A) \\sim Ueq, Uanis(F31) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.005
Uanis(F31A) \\sim Ueq, Uanis(F33) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.005
Uanis(F18) = Uanis(F18A)
Uanis(F17) = Uanis(F17A)
Uanis(F16) = Uanis(F16A)
Uanis(F32) = Uanis(F32A)
Uanis(F33A) = Uanis(F33)
Uanis(F35) = Uanis(F35A)
Uanis(F36) = Uanis(F36A)
Uanis(F34) = Uanis(F34A)
4. Others
 Sof(F18A)=Sof(F17A)=Sof(F16A)=1-FVAR(1)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(1)
 Sof(F32A)=Sof(F33A)=Sof(F31A)=1-FVAR(2)
 Sof(F31)=Sof(F32)=Sof(F33)=FVAR(2)
 Sof(F34A)=Sof(F35A)=Sof(F36A)=1-FVAR(3)
 Sof(F34)=Sof(F35)=Sof(F36)=FVAR(3)
5.a Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C20(H20), C21(H21), C25(H25), C30(H30), C35(H35), C40(H40),
 C45(H45), C50(H50)
5.b Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C11(H11A,
 H11B,H11C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C22(H22A,H22B,H22C)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 7.712
_oxdiff_exptl_absorpt_empirical_full_min 0.582