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_7715331
_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 H150 La2 N36 O3 Zn, 8(C F3 O3 S), 7.25(C2 H3 N)'
_chemical_formula_sum            'C187.75 H171.75 F24 La2 N43.25 O27 S8 Zn'
_chemical_formula_weight         4521.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-08-26
_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                90
_cell_angle_beta                 104.6438(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   27.68761(13)
_cell_length_b                   50.6972(3)
_cell_length_c                   30.80194(17)
_cell_measurement_reflns_used    112671
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      72.7390
_cell_measurement_theta_min      2.5880
_cell_volume                     41831.7(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      99.99(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 0.998
_diffrn_measured_fraction_theta_max 0.985
_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   -102.00 -75.00   0.50    2.00    --  -57.32 -15.00-180.00   54
  2  \w    -97.00 -21.00   0.50    2.00    --  -57.32   0.00 -90.00  152
  3  \w    -79.00 -35.00   0.50    2.00    --  -57.32 125.00  90.00   88
  4  \w    -63.00 -37.00   0.50    2.00    --  -57.32   0.00-150.00   52
  5  \w    -66.00 -39.00   0.50    2.00    --  -57.32 -15.00-180.00   54
  6  \w     21.00  71.00   0.50    2.00    --   60.51 -94.00-150.00  100
  7  \w     30.00  67.00   0.50    2.00    --   60.51 -94.00 -30.00   74
  8  \w     46.00  71.00   0.50    2.00    --   60.51 -94.00  60.00   50
  9  \w     23.00  55.00   0.50    2.00    --   60.51 -94.00  30.00   64
 10  \w     59.00  85.00   0.50    2.00    --   75.05 -94.00   0.00   52
 11  \w     36.00  71.00   0.50    2.00    --   75.05 -94.00-120.00   70
 12  \w     61.00  92.00   0.50    2.00    --   77.03  15.00 -60.00   62
 13  \w     60.00  86.00   0.50    2.00    --   77.03-125.00-120.00   52
 14  \w     37.00  76.00   0.50    2.00    --   77.03-125.00 150.00   78
 15  \w     65.00 104.00   0.50    2.00    --   77.03-125.00 -60.00   78
 16  \w     59.00  85.00   0.50    2.00    --   77.03 -94.00  90.00   52
 17  \w     55.00 101.00   0.50    2.00    --   77.03-125.00   0.00   92
 18  \w     44.00  69.00   0.50    2.00    --   77.03 -94.00 -60.00   50
 19  \w     81.00 107.00   0.50    2.00    --   77.03-125.00-180.00   52
 20  \w     40.00  76.00   0.50    2.00    --   77.03 -94.00  30.00   72
 21  \w     36.00  63.00   0.50    2.00    --   77.03-125.00-180.00   54
 22  \w     83.00 108.00   0.50    2.00    --   77.03-125.00  90.00   50
 23  \w     44.00  96.00   0.50    2.00    --   77.03  15.00 -90.00  104
 24  \w     44.00  70.00   0.50    2.00    --   77.03-125.00  90.00   52
 25  \w     53.00 110.00   0.50    2.00    --   77.03  15.00  30.00  114
 26  \w     66.00 108.00   0.50    2.00    --   77.03-125.00-150.00   84
 27  \w     83.00 108.00   0.50    2.00    --   77.03-125.00 150.00   50
 28  \w     53.00  82.00   0.50    2.00    --   77.03 -94.00  60.00   58
 29  \w     39.00 112.00   0.50    2.00    --   77.03   0.00   0.00  146
;
_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      -0.0322297000
_diffrn_orient_matrix_UB_12      -0.0212590000
_diffrn_orient_matrix_UB_13      -0.0294711000
_diffrn_orient_matrix_UB_21      0.0101997000
_diffrn_orient_matrix_UB_22      -0.0189597000
_diffrn_orient_matrix_UB_23      0.0403972000
_diffrn_orient_matrix_UB_31      -0.0465301000
_diffrn_orient_matrix_UB_32      0.0105762000
_diffrn_orient_matrix_UB_33      0.0131152000
_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  0.0253
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       62
_diffrn_reflns_limit_k_min       -62
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            185218
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.743
_diffrn_reflns_theta_min         2.592
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.806
_exptl_absorpt_correction_T_max  0.575
_exptl_absorpt_correction_T_min  0.444
_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    1.436
_exptl_crystal_description       prism
_exptl_crystal_F_000             18440
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_refine_diff_density_max         2.779
_refine_diff_density_min         -0.999
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2715
_refine_ls_number_reflns         41060
_refine_ls_number_restraints     189
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0722
_refine_ls_R_factor_gt           0.0669
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1411P)^2^+138.6754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1996
_refine_ls_wR_factor_ref         0.2058
_reflns_Friedel_coverage         0.000
_reflns_number_gt                36868
_reflns_number_total             41060
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00610k2.cif
_cod_data_source_block           L4La2Zn
_cod_depositor_comments
'Adding full bibliography for 7715330--7715332.cif.'
_cod_database_code               7715331
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C185 H162 Cl F24 La2 N43 O26 S8 Zn'
_shelx_estimated_absorpt_t_max   0.533
_shelx_estimated_absorpt_t_min   0.392
_reflns_odcompleteness_completeness 99.16
_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
 C4T-S4T
 1.77 with sigma of 0.02
 S9T-C9T
 1.82 with sigma of 0.02
 C9T-F19T
 1.32 with sigma of 0.02
 S9T-O25T
 1.41 with sigma of 0.02
 S9T-O27T
 1.41 with sigma of 0.02
 S9T-O26T
 1.41 with sigma of 0.02
 C9T-F9T
 1.32 with sigma of 0.02
 C9T-F26T
 1.32 with sigma of 0.02
 C6T-F6 = C6T-F4 = C6T-F5
 1.33 with sigma of 0.02
 C6T-S6T
 1.82 with sigma of 0.02
 S6T-O7 = S6T-O8 = S6T-O9
 1.44 with sigma of 0.02
 C7T-S7T
 1.82 with sigma of 0.02
 C7T-F20T = C7T-F21T = C7T-F22T
 1.33 with sigma of 0.02
 C10T-F28T = C10T-F30T = C10T-F29T
 1.33 with sigma of 0.02
 C10T-S10T
 1.82 with sigma of 0.02
 S10T-O28T = S10T-O29T = S10T-O30T
 1.44 with sigma of 0.02
 C59-C60
 1.5 with sigma of 0.02
 C63-C58
 1.5 with sigma of 0.02
 C60-N21
 1.14 with sigma of 0.02
 S3-O66 = S3-O68 = S3-O67
 1.4 with sigma of 0.02
 S3-C66
 1.81 with sigma of 0.02
 F68-C66 = F66-C66 = F67-C66
 1.34 with sigma of 0.02
 C69-C68
 1.5 with sigma of 0.02
 C6T-O8
 2.56 with sigma of 0.04
 C6T-O7
 2.58 with sigma of 0.04
 C6T-O9
 2.57 with sigma of 0.04
 C7T-O19T
 2.56 with sigma of 0.04
 C7T-O20T
 2.58 with sigma of 0.04
 C7T-O21T
 2.57 with sigma of 0.04
 C10T-O30T
 2.57 with sigma of 0.04
 C10T-O29T
 2.56 with sigma of 0.04
 C10T-O28T
 2.58 with sigma of 0.04
 C59-N21
 2.6 with sigma of 0.04
 N68-C68
 2.55 with sigma of 0.04
 S6T-F6 \\sim S6T-F4 \\sim S6T-F5
 with sigma of 0.04
 C6T-O7 \\sim C6T-O8 \\sim C6T-O9
 with sigma of 0.04
 O7-O8 \\sim O8-O9 \\sim O7-O9
 with sigma of 0.04
 S6T-O7 \\sim S6T-O8 \\sim S6T-O9
 with sigma of 0.02
 F6-F4 \\sim F4-F5 \\sim F5-F6
 with sigma of 0.04
 C6T-F6 \\sim C6T-F4 \\sim C6T-F5
 with sigma of 0.02
 C7T-F20T \\sim C7T-F21T \\sim C7T-F22T
 with sigma of 0.02
 S10T-O28T \\sim S10T-O29T \\sim S10T-O30T
 with sigma of 0.02
 O28T-O29T \\sim O29T-O30T \\sim O28T-O30T
 with sigma of 0.04
 C10T-F28T \\sim C10T-F30T \\sim C10T-F29T
 with sigma of 0.02
 F28T-F30T \\sim F30T-F29T \\sim F29T-F28T
 with sigma of 0.04
 C10T-O28T \\sim C10T-O29T \\sim C10T-O30T
 with sigma of 0.04
 S10T-F28T \\sim S10T-F30T \\sim S10T-F29T
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C6T \\sim F6 \\sim F4 \\sim F5 \\sim S6T \\sim O7 \\sim O8 \\sim O9: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C10T \\sim F28T \\sim F30T \\sim F29T \\sim S10T \\sim O28T \\sim O29T \\sim
O30T: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
2A
: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C9T) = Uanis(S9T)
Uanis(C7T) = Uanis(F22T)
Uanis(C7T) = Uanis(F21T)
Uanis(C7T) = Uanis(F20T)
Uiso(C63) = Uiso(C59)
Uiso(O27T) = Uiso(O25T)
Uiso(F29T) = Uiso(F28T) = Uiso(F30T)
Uiso(S3) = Uiso(C66)
Uiso(C59) = Uiso(N21)
Uiso(O25T) = Uiso(F26T)
Uiso(O68) = Uiso(O66) = Uiso(O67)
Uiso(F67) = Uiso(F66) = Uiso(F68)
4. Rigid body (RIGU) restrains
 C6T, F6, F4, F5, S6T, O7, O8, O9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10T, F28T, F30T, F29T, S10T, O28T, O29T, O30T
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O24T(0.5) C13S(0.5) C14S(0.5) H14A(0.5) H14B(0.5) H14C(0.5)
 S7T(0.5) F20T(0.5) F21T(0.5) O19T(0.5) O20T(0.5) O21T(0.5) S9T(0.5) O26T(0.5)
 O27T(0.5) O25T(0.5) C9T(0.5) F9T(0.5) F26T(0.5) F19T(0.5) C56(0.5) N13(0.5)
 C57(0.5) H57A(0.5) H57B(0.5) H57C(0.5) O2(0.5) F22T(0.5) C7T(0.5) N16(0.5)
 C62(0.5) H62A(0.5) H62B(0.5) H62C(0.5) C61(0.5) C6T(0.5) F6(0.5) F4(0.5)
 F5(0.5) S6T(0.5) O7(0.5) O8(0.5) O9(0.5) N21(0.5) C60(0.5) C59(0.5) H59A(0.5)
 H59B(0.5) H59C(0.5) C58(0.5) C63(0.5) H63A(0.5) H63B(0.5) H63C(0.5) S10T(0.25)
 O28T(0.25) O29T(0.25) O30T(0.25) C10T(0.25) F28T(0.25) F29T(0.25) F30T(0.25)
 N15(0.5) C64(0.5) C65(0.5) H65A(0.5) H65B(0.5) H65C(0.5) S3(0.25) O66(0.25)
 O67(0.25) O68(0.25) C66(0.25) F66(0.25) F67(0.25) F68(0.25) C68(0.25)
 H68A(0.25) H68B(0.25) H68C(0.25) N68(0.25)
6.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C13B(H13C,H13D), C13C(H13E,H13F), C33(H33A,H33B), C33C(H33C,
 H33D), C33B(H33E,H33F), C47(H47A,H47B), C47C(H47C,H47D), C47B(H47E,H47F),
 C49B(H49A,H49B), C49C(H49C,H49D), C49(H49E,H49F)
6.b Me refined with everything fixed:
 C59(H59A,H59B,H59C), C63(H63A,H63B,H63C), C68(H68A,H68B,H68C)
6.c Aromatic/amide H refined with riding coordinates:
 C1C(H1C), C1B(H1B), C1(H1), C3(H3), C3B(H3B), C3C(H3C), C4(H4), C4B(H4B),
 C4C(H4C), C8(H8), C8C(H8C), C8B(H8B), C9(H9), C9B(H9B), C9C(H9C), C11(H11),
 C11C(H11C), C11B(H11B), C15B(H15B), C15(H15), C15C(H15C), C19B(H19B), C19(H19),
  C19C(H19C), C20B(H20B), C20C(H20C), C20(H20), C22(H22), C22C(H22C),
 C22B(H22B), C23B(H23B), C23(H23), C23C(H23C), C24(H24), C24C(H24C), C24B(H24B),
  C28C(H28C), C28(H28), C28B(H28B), C30C(H30C), C30(H30), C30B(H30B),
 C31C(H31C), C31B(H31B), C31(H31), C35B(H35B), C35(H35), C35C(H35C), C39C(H39C),
  C39B(H39B), C39(H39), C40B(H40B), C40C(H40C), C40(H40), C42C(H42C), C42(H42),
 C42B(H42B), C43(H43), C43C(H43C), C43B(H43B), C44B(H44B), C44C(H44C), C44(H44)
6.d Idealised Me refined as rotating group:
 C48B(H48A,H48B,H48C), C48(H48D,H48E,H48F), C48C(H48G,H48H,H48I), C50(H50A,
 H50B,H50C), C50B(H50D,H50E,H50F), C50C(H50G,H50H,H50I), C51B(H51A,H51B,H51C),
 C51C(H51D,H51E,H51F), C51(H51G,H51H,H51I), C52B(H52A,H52B,H52C), C52(H52D,H52E,
 H52F), C52C(H52G,H52H,H52I), C53C(H53A,H53B,H53C), C53B(H53D,H53E,H53F),
 C53(H53G,H53H,H53I), C54C(H54A,H54B,H54C), C54(H54D,H54E,H54F), C54B(H54G,H54H,
 H54I), C55C(H55A,H55B,H55C), C55(H55D,H55E,H55F), C55B(H55G,H55H,H55I),
 C12S(H12A,H12B,H12C), C14S(H14A,H14B,H14C), C3S(H3SA,H3SB,H3SC), C6S(H6SA,H6SB,
 H6SC), C9S(H9SA,H9SB,H9SC), C57(H57A,H57B,H57C), C62(H62A,H62B,H62C), C65(H65A,
 H65B,H65C)
;
_shelx_res_checksum              21640
_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 1.315
_oxdiff_exptl_absorpt_empirical_full_min 0.760