Air-stable chiral double-decker Dy(III) macrocycle with fluoride ion as sole axial ligand
Liu, Xiaodong; Zhao, Chen; Wu, Jinjiang; Zhu, Zhenhua; Tang, Jinkui; Dalton Transactions  (2022) –; doi:10.1039/D2DT02902B

data_7711491
_publ_section_title
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 Air-stable chiral double-decker Dy(III) macrocycle with fluoride ion as
 sole axial ligand
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_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02902B
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C84 H68 Dy2 F4 N12, 2(C24 H20 B), 4(C H2 Cl2)'
_chemical_formula_sum            'C136 H116 B2 Cl8 Dy2 F4 N12'
_chemical_formula_weight         2624.62
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-09-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
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_audit_update_record
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2022-10-01 deposited with the CCDC.	2022-10-14 downloaded from the CCDC.
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_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.2123(5)
_cell_length_b                   25.8184(6)
_cell_length_c                   27.5581(8)
_cell_measurement_reflns_used    9985
_cell_measurement_temperature    180.0
_cell_measurement_theta_max      24.971
_cell_measurement_theta_min      2.366
_cell_volume                     12246.7(6)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      180.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1061
_diffrn_reflns_av_unetI/netI     0.0887
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            91773
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.051
_diffrn_reflns_theta_max         25.051
_diffrn_reflns_theta_min         1.972
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.447
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6789
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0920 before and 0.0833 after correction.
The Ratio of minimum to maximum transmission is 0.9110.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.424
_exptl_crystal_description       block
_exptl_crystal_F_000             5320
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.355
_refine_diff_density_min         -1.144
_refine_diff_density_rms         0.116
_refine_ls_abs_structure_details
;
 Flack x determined using 5978 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(6)
_refine_ls_extinction_coef       0.00061(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1464
_refine_ls_number_reflns         21639
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0877
_refine_ls_R_factor_gt           0.0544
_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^)+(0.0525P)^2^+20.2933P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1173
_refine_ls_wR_factor_ref         0.1403
_reflns_Friedel_coverage         0.848
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                16468
_reflns_number_total             21639
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02902b2.cif
_cod_data_source_block           1
_cod_database_code               7711491
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.931
_olex2_refinement_description
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1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 Cl5-C67
 1.77 with sigma of 0.02
 Cl3-C67 = Cl5-C67
 1.771 with sigma of 0.01
 Cl3-C67
 1.78 with sigma of 0.02
 Cl3-Cl5
 2.916 with sigma of 0.03
 Cl6-C135
 1.78 with sigma of 0.02
 Cl6-C135 = Cl7-C135
 1.771 with sigma of 0.01
 Cl6-Cl7
 2.916 with sigma of 0.03
 Cl7-C135
 1.77 with sigma of 0.02
 Cl3-Cl5
 2.92 with sigma of 0.04
 Cl6-Cl7
 2.92 with sigma of 0.04
 Cl5-C67 \\sim Cl5A-C67
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl3 \\sim Cl5 \\sim C67: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl6 \\sim Cl7 \\sim C135: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C61) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C31) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C41) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C131) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C15) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 Cl3, Cl5, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl6, Cl7, C135
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H67C)=Sof(H67D)=Sof(Cl5A)=1-FVAR(1)
 Sof(Cl5)=Sof(H67A)=Sof(H67B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C6(H6), C16(H16), C28(H28), C36(H36), C38(H38), C44(H44), C56(H56)
6.b Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C133(H13A,H13B), C67(H67A,H67B), C67(H67C,H67D), C135(H13C,
 H13D)
6.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C20(H20), C24(H24), C26(H26), C30(H30), C32(H32), C40(H40),
 C42(H42), C46(H46), C48(H48), C52(H52), C54(H54), C62(H62), C68(H68), C74(H74),
  C76(H76), C78(H78), C80(H80), C82(H82), C84(H84), C86(H86), C88(H88),
 C90(H90), C92(H92), C94(H94), C96(H96), C100(H100), C102(H102), C104(H104),
 C106(H106), C110(H110), C112(H112), C114(H114), C116(H116), C118(H118),
 C120(H120), C124(H124), C126(H126), C130(H130), C132(H132), C134(H134),
 C136(H136), C17(H17), C69(H69), C35(H35), C71(H71), C9(H9), C73(H73), C37(H37),
  C75(H75), C19(H19), C77(H77), C39(H39), C79(H79), C5(H5), C81(H81), C41(H41),
 C83(H83), C21(H21), C85(H85), C87(H87), C11(H11), C89(H89), C91(H91), C23(H23),
  C93(H93), C47(H47), C3(H3), C97(H97), C49(H49), C99(H99), C25(H25),
 C101(H101), C51(H51), C103(H103), C13(H13), C105(H105), C53(H53), C107(H107),
 C109(H109), C111(H111), C7(H7), C113(H113), C57(H57), C115(H115), C29(H29),
 C117(H117), C59(H59), C119(H119), C15(H15), C121(H121), C61(H61), C123(H123),
 C31(H31), C125(H125), C63(H63), C2(H2), C129(H129), C65(H65), C131(H131)
6.d Fitted hexagon refined as free rotating group:
 C41(C83,C21,C85,C43,C87), C31(C125,C63,C127,C2,C129)
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_smtbx_masks_special_details
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A solvent mask was calculated and 132 electrons were 
found in a volume of 676\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
2[H2O] per Asymmetric Unit 
which account for 80 electrons 
per unit cell.
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_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              23757
_shelx_fab_checksum              47654
_olex2_submission_special_instructions 'No special instructions were received'