Chiral six-coordinate Dy(III) and Tb(III) complexes of an achiral ligand: Structure, fluorescence, and magnetism
Liu, Mei-Jiao; Yuan, Juan; Zhang, Yiquan; Sun, Hao-Ling; Liu, Cai-Ming; Kou, Hui-Zhong; Dalton Trans.  (2017) –; doi:10.1039/C7DT02409F

data_7044168
_publ_section_title
;
 Chiral six-coordinate Dy(III) and Tb(III) complexes of an achiral ligand:
 Structure, fluorescence, and magnetism
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT02409F
_journal_year                    2017
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C66 H90 Cl3 Dy N6 O6 Zn3, 0.5(O), C O'
_chemical_formula_sum            'C67 H95 Cl3 Dy N6 O7.5 Zn3'
_chemical_formula_weight         1569.44
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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     direct
_audit_creation_date             2017-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-07-03 deposited with the CCDC.
2017-09-11 downloaded from the CCDC.
;
_cell_angle_alpha                74.601(3)
_cell_angle_beta                 82.797(2)
_cell_angle_gamma                81.024(2)
_cell_formula_units_Z            2
_cell_length_a                   12.4023(4)
_cell_length_b                   16.1328(5)
_cell_length_c                   19.4673(6)
_cell_measurement_reflns_used    16704
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      29.1370
_cell_measurement_theta_min      3.7670
_cell_volume                     3694.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2137
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.847
_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     -4.00  33.00   1.00   19.19    --    9.97 -38.00   0.00   37
  2  \w    -14.00  41.00   1.00   19.19    --    9.97 -99.00  60.00   55
  3  \w     -8.00  28.00   1.00   19.19    --  -11.85 -99.00 120.00   36
  4  \w    -59.00 -17.00   1.00   19.19    --    9.97 -38.00 -30.00   42
  5  \w     25.00  80.00   1.00   19.19    --    9.97  38.00-120.00   55
  6  \w    -13.00  51.00   1.00   19.19    --    9.97  38.00-180.00   64
  7  \w     -6.00  27.00   1.00   19.19    --  -11.85 -99.00-150.00   33
  8  \w     43.00  99.00   1.00   19.19    --    9.97 178.00  30.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0268122000
_diffrn_orient_matrix_UB_12      0.0187402000
_diffrn_orient_matrix_UB_13      -0.0336724000
_diffrn_orient_matrix_UB_21      0.0434542000
_diffrn_orient_matrix_UB_22      -0.0346341000
_diffrn_orient_matrix_UB_23      0.0057475000
_diffrn_orient_matrix_UB_31      -0.0277765000
_diffrn_orient_matrix_UB_32      -0.0237455000
_diffrn_orient_matrix_UB_33      -0.0165123000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0358
_diffrn_reflns_av_unetI/netI     0.0613
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.847
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            38086
_diffrn_reflns_point_group_measured_fraction_full 0.730
_diffrn_reflns_point_group_measured_fraction_max 0.580
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.511
_diffrn_reflns_theta_min         3.287
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.122
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63608
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.411
_exptl_crystal_description       plate
_exptl_crystal_F_000             1612
_refine_diff_density_max         2.462
_refine_diff_density_min         -1.652
_refine_diff_density_rms         0.148
_refine_ls_abs_structure_details
;
 Flack x determined using 5564 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1621
_refine_ls_number_reflns         23902
_refine_ls_number_restraints     225
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0575
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0855P)^2^+0.4706P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1247
_refine_ls_wR_factor_ref         0.1305
_reflns_Friedel_coverage         0.369
_reflns_Friedel_fraction_full    0.462
_reflns_Friedel_fraction_max     0.312
_reflns_number_gt                21416
_reflns_number_total             23902
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt02409f3.cif
_cod_data_source_block           1-lambda
_cod_original_formula_sum        'C67 H95 Cl3 Dy N6 O7.50 Zn3'
_cod_database_code               7044168
_chemical_oxdiff_formula         CHNOClZnDy
_chemical_oxdiff_usercomment     '0.1x0.1x0.3, colorless prism'
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 C11-C12 = C77-C78
 1.465 with sigma of 0.005
3. Rigid bond restraints
 C77, C78
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C11, C12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C17, C19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C19, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C79) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(N9) \\sim Ueq,
Uanis(N10) \\sim Ueq, Uanis(N8) \\sim Ueq, Uanis(C106) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C4) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C102)
\\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C76) \\sim Ueq,
Uanis(C108) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C72)
\\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C44) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(O132) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
Uanis(O1W) \\sim Ueq, Uanis(O2W) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C77) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C99) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C101) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3) \\sim Ueq, Uanis(C39) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Others
 Fixed Sof: O1W(0.5) O2W(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C9(H9a,H9b), C11(H11a,H11b), C12(H12a,H12b), C14(H14a,H14b), C31(H31a,H31b),
 C33(H33a,H33b), C34(H34a,H34b), C36(H36a,H36b), C53(H53a,H53b), C55(H55a,H55b),
  C56(H56a,H56b), C58(H58a,H58b), C75(H75a,H75b), C77(H77a,H77b), C78(H78a,
 H78b), C80(H80a,H80b), C97(H97a,H97b), C99(H99a,H99b), C100(H10d,H10e),
 C102(H10i,H10j), C119(H11i,H11j), C121(H12f,H12g), C122(H12h,H12i), C124(H12m,
 H12n)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C16(H16), C21(H21), C23(H23), C28(H28), C37(H37), C41(H41),
 C46(H46), C51(H51), C60(H60), C65(H65), C68(H68), C73(H73), C82(H82), C87(H87),
  C90(H90), C95(H95), C104(H104), C109(H109), C112(H112), C117(H117),
 C126(H126), C131(H131)
6.c Idealised Me refined as rotating group:
 C3(H3a,H3b,H3c), C5(H5a,H5b,H5c), C10(H10a,H10b,H10c), C13(H13a,H13b,H13c),
 C18(H18a,H18b,H18c), C20(H20a,H20b,H20c), C25(H25a,H25b,H25c), C27(H27a,H27b,
 H27c), C32(H32a,H32b,H32c), C35(H35a,H35b,H35c), C39(H39a,H39b,H39c), C44(H44a,
 H44b,H44c), C48(H48a,H48b,H48c), C50(H50a,H50b,H50c), C54(H54a,H54b,H54c),
 C57(H57a,H57b,H57c), C62(H62a,H62b,H62c), C64(H64a,H64b,H64c), C70(H70a,H70b,
 H70c), C72(H72a,H72b,H72c), C76(H76a,H76b,H76c), C79(H79a,H79b,H79c), C84(H84a,
 H84b,H84c), C86(H86a,H86b,H86c), C92(H92a,H92b,H92c), C94(H94a,H94b,H94c),
 C98(H98a,H98b,H98c), C101(H10f,H10g,H10h), C106(H10k,H10l,H10m), C108(H10n,
 H10o,H10p), C114(H11c,H11d,H11e), C116(H11f,H11g,H11h), C120(H12c,H12d,H12e),
 C123(H12j,H12k,H12l), C128(H12o,H12p,H12q), C130(H13d,H13e,H13f)
;
_shelx_shelxl_version_number     2014/7
_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 1.770
_oxdiff_exptl_absorpt_empirical_full_min 0.604