Programming heterometallic 4f-4f' helicates under thermodynamic control: the circle is complete.
Egger, Charlotte; Guénée, Laure; Deorukhkar, Neel; Piguet, Claude; Dalton transactions (Cambridge, England : 2003) 53 (2024) 6050–6062; doi:10.1039/d4dt00610k

data_7715332
_publ_section_title
;
 Programming heterometallic 4f-4f' helicates under thermodynamic control:
 the circle is complete.
;
_journal_issue                   13
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6050
_journal_page_last               6062
_journal_paper_doi               10.1039/d4dt00610k
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety
'C165 H148 Eu2 N36 O3 Zn, C3 H8 O, 7(C F3 O3 S), 1[CF3SO3], 12[C3H8O]'
_chemical_formula_sum            'C175 H155 Eu2 F21 N36 O25 S7 Zn'
_chemical_formula_weight         4155.05
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-08-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-12-20 deposited with the CCDC.	2024-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                92.6755(14)
_cell_angle_beta                 95.8386(14)
_cell_angle_gamma                118.0562(18)
_cell_formula_units_Z            2
_cell_length_a                   16.5519(3)
_cell_length_b                   17.2409(3)
_cell_length_c                   48.1977(9)
_cell_measurement_reflns_used    29275
_cell_measurement_temperature    119.99(10)
_cell_measurement_theta_max      66.8910
_cell_measurement_theta_min      2.7720
_cell_volume                     12004.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      119.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.864
_diffrn_measured_fraction_theta_max 0.848
_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    -96.00 -63.00   0.50   15.00    --  -57.30   0.00   0.00   66
  2  \w    -46.00 -18.00   0.50   15.00    --  -57.30   0.00   0.00   56
  3  \w    -91.00 -25.00   0.50   15.00    --  -57.30 -15.00  60.00  132
  4  \w    -70.00 -32.00   0.50   15.00    --  -57.30 -15.00   0.00   76
  5  \w   -102.00 -25.00   0.50   15.00    --  -57.30 -15.00 -60.00  154
  6  \w     36.00  61.00   0.50   15.00    --   60.27-125.00 150.00   50
  7  \w     21.00  70.00   0.50   15.00    --   60.27 -94.00  60.00   98
  8  \w     26.00  56.00   0.50   15.00    --   60.27 -94.00-120.00   60
  9  \w     22.00  62.00   0.50   15.00    --   60.27 -94.00-180.00   80
 10  \w     24.00  53.00   0.50   15.00    --   60.27 -94.00 -90.00   58
 11  \w     21.00  61.00   0.50   15.00    --   60.27 -94.00 -30.00   80
 12  \w     35.00  85.00   0.50   15.00    --   74.70 -94.00  60.00  100
 13  \w     44.00  84.00   0.50   15.00    --   74.70 -94.00-180.00   80
 14  \w     43.00 105.00   0.50   15.00    --   74.70-125.00  30.00  124
 15  \w     36.00  78.00   0.50   15.00    --   74.70 -94.00 120.00   84
 16  \w     70.00 121.00   0.50   15.00    --   74.70  15.00-120.00  102
 17  \w     66.00 111.00   0.50   15.00    --   77.04   0.00  30.00   90
 18  \w     43.00  81.00   0.50   15.00    --   77.04 -94.00 -30.00   76
 19  \w     39.00  64.00   0.50   15.00    --   77.04 -94.00 -60.00   50
 20  \w     41.00  69.00   0.50   15.00    --   77.04 -94.00-150.00   56
 21  \w     51.00 123.00   0.50   15.00    --   77.04  15.00 120.00  144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0068932000
_diffrn_orient_matrix_UB_12      0.0163509000
_diffrn_orient_matrix_UB_13      -0.0310937000
_diffrn_orient_matrix_UB_21      0.0452512000
_diffrn_orient_matrix_UB_22      -0.0577646000
_diffrn_orient_matrix_UB_23      -0.0065617000
_diffrn_orient_matrix_UB_31      -0.0961863000
_diffrn_orient_matrix_UB_32      -0.0822705000
_diffrn_orient_matrix_UB_33      -0.0058803000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0536
_diffrn_reflns_av_unetI/netI     0.0663
_diffrn_reflns_Laue_measured_fraction_full 0.864
_diffrn_reflns_Laue_measured_fraction_max 0.848
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       58
_diffrn_reflns_limit_l_min       -58
_diffrn_reflns_number            85991
_diffrn_reflns_point_group_measured_fraction_full 0.864
_diffrn_reflns_point_group_measured_fraction_max 0.848
_diffrn_reflns_theta_full        72.000
_diffrn_reflns_theta_max         73.236
_diffrn_reflns_theta_min         2.781
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.018
_exptl_absorpt_correction_T_max  0.812
_exptl_absorpt_correction_T_min  0.452
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.89a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.149
_exptl_crystal_description       plate
_exptl_crystal_F_000             4228
_exptl_crystal_size_max          0.251
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.041
_refine_diff_density_max         1.732
_refine_diff_density_min         -1.328
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.167
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2244
_refine_ls_number_reflns         40878
_refine_ls_number_restraints     114
_refine_ls_restrained_S_all      1.174
_refine_ls_R_factor_all          0.1352
_refine_ls_R_factor_gt           0.1086
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3049
_refine_ls_wR_factor_ref         0.3255
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27649
_reflns_number_total             40878
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00610k2.cif
_cod_data_source_block           L4Eu2Zn
_cod_depositor_comments
'Adding full bibliography for 7715330--7715332.cif.'
_cod_database_code               7715332
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C212 H251 Eu2 F24 N36 O41 S8 Zn'
_shelx_estimated_absorpt_t_max   0.821
_shelx_estimated_absorpt_t_min   0.366
_reflns_odcompleteness_completeness 86.27
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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
 C1A-F3 = C1A-F4 = C1A-F5
 1.33 with sigma of 0.02
 C1A-S9
 1.82 with sigma of 0.02
 S9-O7 = S9-O8 = S9-O9
 1.44 with sigma of 0.02
 C1TA-F1TA = C1TA-F2TA = C1TA-F3TA
 1.33 with sigma of 0.02
 C1TA-S1A
 1.82 with sigma of 0.02
 S1A-O1TA = S1A-O2TA = S1A-O3TA
 1.44 with sigma of 0.02
 C4T-F10T = C4T-F11T = C4T-F12T
 1.33 with sigma of 0.02
 C4T-S4
 1.82 with sigma of 0.02
 S4-O10T = S4-O11T = S4-O12T
 1.44 with sigma of 0.02
 C6T-F16T = C6T-F17T = C6T-F18T
 1.33 with sigma of 0.02
 C6T-S6
 1.82 with sigma of 0.02
 S6-O16T = S6-O17T = S6-O18T
 1.44 with sigma of 0.02
 C7T-F19T = C7T-F20T = C7T-F21T
 1.33 with sigma of 0.02
 C7T-S7
 1.72 with sigma of 0.02
 S7-O19T = S7-O20T = S7-O21T
 1.44 with sigma of 0.02
 C8T-S8
 1.82 with sigma of 0.02
 C6T-F18T
 1.33 with sigma of 0.02
 C6T-F16T
 1.33 with sigma of 0.02
 C6T-F17T
 1.33 with sigma of 0.02
 S5-C5T
 1.8 with sigma of 0.02
 C8T-F24T
 1.33 with sigma of 0.02
 C8T-F22T
 1.33 with sigma of 0.02
 C8T-F23T
 1.33 with sigma of 0.02
 C1A-O8
 2.56 with sigma of 0.04
 C1A-O9
 2.57 with sigma of 0.04
 C1A-O7
 2.58 with sigma of 0.04
 C1TA-O2TA
 2.56 with sigma of 0.04
 C1TA-O3TA
 2.57 with sigma of 0.04
 C1TA-O1TA
 2.58 with sigma of 0.04
 C4T-O11T
 2.56 with sigma of 0.04
 C4T-O12T
 2.57 with sigma of 0.04
 C4T-O10T
 2.58 with sigma of 0.04
 C6T-O17T
 2.56 with sigma of 0.04
 C6T-O18T
 2.57 with sigma of 0.04
 C6T-O16T
 2.58 with sigma of 0.04
 C7T-O20T
 2.56 with sigma of 0.04
 C7T-O21T
 2.57 with sigma of 0.04
 C7T-O19T
 2.58 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uiso(C2T) = Uiso(C1A)
Uiso(F4) = Uiso(F5T) = Uiso(F3) = Uiso(F6T) = Uiso(F5) = Uiso(F4T)
Uiso(O9) = Uiso(O5T) = Uiso(O7) = Uiso(O6T) = Uiso(O8) = Uiso(O4T)
Uiso(S2) = Uiso(S9)
Uiso(F2TA) = Uiso(F2TB) = Uiso(F1TB) = Uiso(F1TA) = Uiso(F3TA) = Uiso(F3TB)
Uiso(O1TB) = Uiso(O1TA) = Uiso(O2TA) = Uiso(O2TB) = Uiso(O3TA) = Uiso(O3TB)
Uiso(C1TA) = Uiso(C1TB)
Uiso(S1A) = Uiso(S1B)
4. Rigid body (RIGU) restrains
 C4S, C2S, C3S, O1S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C1TB, F1TB, F2TB, F3TB, S1B, O1TB, O2TB, O3TB} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1TA, F1TA, F2TA, F3TA, S1A, O1TA, O2TA, O3TA}
{C1A, F3, F4, F5, S9, O7, O8, O9} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C2T, F4T, F5T, F6T, S2, O4T, O5T, O6T}
6. Others
 Sof(C1A)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(S9)=Sof(O7)=Sof(O8)=Sof(O9)=1-FVAR(1)
 Sof(C2T)=Sof(F4T)=Sof(F5T)=Sof(F6T)=Sof(S2)=Sof(O4T)=Sof(O5T)=Sof(O6T)=FVAR(1)
 Sof(C1TB)=Sof(F1TB)=Sof(F2TB)=Sof(F3TB)=Sof(S1B)=Sof(O1TB)=Sof(O2TB)=
 Sof(O3TB)=1-FVAR(2)
 Sof(C1TA)=Sof(F1TA)=Sof(F2TA)=Sof(F3TA)=Sof(S1A)=Sof(O1TA)=Sof(O2TA)=
 Sof(O3TA)=FVAR(2)
 Fixed Sof: S8(0.5) F22T(0.5) F23T(0.5) F24T(0.5) O23T(0.5) O24T(0.5)
 O26T(0.5) C8T(0.5) C7T(0.5) F19T(0.5) F20T(0.5) F21T(0.5) S7(0.5) O19T(0.5)
 O20T(0.5) O21T(0.5)
7.a Riding coordinates:
 C3S(H3SA,H3SB,H3SC), C4S(H4SA,H4SB,H4SC)
7.b Ternary CH refined with riding coordinates:
 C2S(H2S)
7.c Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C13B(H13C,H13D), C13C(H13E,H13F), C33C(H33A,H33C), C33(H33D,
 H33E), C47C(H47A,H47B), C47B(H47C,H47D), C49(H49A,H49B), C49C(H49C,H49D),
 C49B(H49E,H49F)
7.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C1B(H1B), C1C(H1C), C3C(H3C), C3B(H3B), C3(H3), C4C(H4C), C4(H4),
 C4B(H4B), C8B(H8B), C8(H8), C8C(H8C), C10B(H10B), C10(H10), C10C(H10C),
 C11(H11), C11C(H11C), C11B(H11B), C15B(H15B), C15C(H15C), C15(H15), C19C(H19C),
  C19B(H19B), C19(H19), C20B(H20B), C20C(H20C), C20(H20), C22B(H22B),
 C22C(H22C), C22(H22), C23C(H23C), C23(H23), C23B(H23B), C24B(H24B), C24(H24),
 C24C(H24C), C28B(H28B), C28C(H28C), C28(H28), C30(H30), C30B(H30B), C30C(H30C),
  C31C(H31C), C31(H31), C31B(H31B), C33B(H33B), C35(H35), C35C(H35C),
 C35B(H35B), C39(H39), C39C(H39C), C39B(H39B), C40(H40), C40C(H40C), C40B(H40B),
  C42C(H42C), C42B(H42B), C42(H42), C43(H43), C43B(H43B), C43C(H43C),
 C44C(H44C), C44(H44), C44B(H44B), C47(H47)
7.e Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C48B(H48D,H48E,H48F), C48C(H48G,H48H,H48I), C50B(H50A,
 H50B,H50C), C50C(H50D,H50E,H50F), C50(H50G,H50H,H50I), C51(H51A,H51B,H51C),
 C51B(H51D,H51E,H51F), C51C(H51G,H51H,H51I), C52C(H52A,H52B,H52C), C52(H52D,
 H52E,H52F), C52B(H52G,H52H,H52I), C53B(H53A,H53B,H53C), C53C(H53D,H53E,H53F),
 C53(H53G,H53H,H53I), C54B(H54A,H54B,H54C), C54(H54D,H54E,H54F), C54C(H54G,H54H,
 H54I), C55(H55A,H55B,H55C), C55C(H55D,H55E,H55F), C55B(H55G,H55H,H55I)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 1007 electrons were 
found in a volume of 3947\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
1[CF3SO3], 12[C3H8O] per Formula Unit 
which account for 962 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              86179
_shelx_fab_checksum              70266
_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 1.587
_oxdiff_exptl_absorpt_empirical_full_min 0.612