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_7044169
_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         '2(C66 H90 Cl3 Dy N6 O6 Zn3), 3(O)'
_chemical_formula_sum            'C132 H186 Cl6 Dy2 N12 O15 Zn6'
_chemical_formula_weight         3110.84
_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     heavy
_audit_creation_date             2017-05-27
_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                74.390(2)
_cell_angle_beta                 82.638(2)
_cell_angle_gamma                80.894(2)
_cell_formula_units_Z            1
_cell_length_a                   12.4388(3)
_cell_length_b                   16.1852(4)
_cell_length_c                   19.6324(5)
_cell_measurement_reflns_used    17258
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      28.9530
_cell_measurement_theta_min      3.6150
_cell_volume                     3743.48(17)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2137
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.837
_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    -27.00  89.00   1.00   10.00    --    9.97  19.00  90.00  116
  2  \w    -12.00  14.00   1.00   10.00    --  -11.85 -99.00  60.00   26
  3  \w    -17.00  29.00   1.00   10.00    --  -11.85 -99.00 -30.00   46
  4  \w     45.00  97.00   1.00   10.00    --    9.97-178.00 -60.00   52
  5  \w    -13.00  56.00   1.00   10.00    --    9.97  38.00-180.00   69
  6  \w    -80.00  -2.00   1.00   10.00    --  -11.85 -38.00-120.00   78
;
_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      -0.0444994000
_diffrn_orient_matrix_UB_12      0.0336227000
_diffrn_orient_matrix_UB_13      -0.0017900000
_diffrn_orient_matrix_UB_21      -0.0214149000
_diffrn_orient_matrix_UB_22      -0.0145360000
_diffrn_orient_matrix_UB_23      -0.0258715000
_diffrn_orient_matrix_UB_31      -0.0303909000
_diffrn_orient_matrix_UB_32      -0.0276417000
_diffrn_orient_matrix_UB_33      0.0273158000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0289
_diffrn_reflns_av_unetI/netI     0.0529
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.837
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            40293
_diffrn_reflns_point_group_measured_fraction_full 0.758
_diffrn_reflns_point_group_measured_fraction_max 0.598
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.626
_diffrn_reflns_theta_min         3.245
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.094
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74404
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.380
_exptl_crystal_description       block
_exptl_crystal_F_000             1596
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.339
_refine_diff_density_min         -0.757
_refine_diff_density_rms         0.109
_refine_ls_abs_structure_details
;
 Flack x determined using 6405 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.024(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1602
_refine_ls_number_reflns         25259
_refine_ls_number_restraints     157
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0513
_refine_ls_R_factor_gt           0.0430
_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^)+(0.0580P)^2^+4.5260P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1033
_refine_ls_wR_factor_ref         0.1100
_reflns_Friedel_coverage         0.429
_reflns_Friedel_fraction_full    0.518
_reflns_Friedel_fraction_max     0.359
_reflns_number_gt                22718
_reflns_number_total             25259
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt02409f3.cif
_cod_data_source_block           1-delta
_cod_original_cell_volume        3743.46(17)
_cod_database_code               7044169
_chemical_oxdiff_formula         CHNODyZnCl
_reflns_odcompleteness_completeness 99.75
_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
 N3-C123 = N4-C10
 1.501 with sigma of 0.005
 C123-C10
 1.421 with sigma of 0.005
3. Rigid bond restraints
 N4, C10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
N4 \\sim C10: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C120) \\sim Ueq, Uanis(C122) \\sim Ueq, Uanis(C0AA) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C27) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C116) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C15) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C11) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N4) \\sim Ueq, Uanis(O1W) \\sim Ueq, Uanis(O2W) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C124) \\sim Ueq, Uanis(C128) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C123) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O3W) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O4W) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C28) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Others
 Fixed Sof: O3W(0.5) O4W(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C12(H12A,H12B), C30(H30A,H30B), C32(H32A,H32B), C33(H33A,
 H33B), C35(H35A,H35B), C52(H52A,H52B), C54(H54A,H54B), C55(H55A,H55B),
 C57(H57A,H57B), C65(H65A,H65B), C123(H12C,H12D), C75(H75A,H75B), C77(H77A,
 H77B), C78(H78A,H78B), C80(H80A,H80B), C97(H97A,H97B), C99(H99A,H99B),
 C100(H10C,H10D), C102(H10H,H10I), C119(H11J,H11K), C121(H12H,H12I), C122(H12J,
 H12K), C124(H12L,H12M)
6.b Me refined with riding coordinates:
 C9(H9A,H9B,H9C)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C14(H14), C19(H19), C23(H23), C28(H28), C37(H37), C42(H42),
 C45(H45), C50(H50), C59(H59), C63(H63), 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.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C11(H11A,H11B,H11C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C31(H31A,H31B,
 H31C), C34(H34A,H34B,H34C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C47(H47A,
 H47B,H47C), C49(H49A,H49B,H49C), C53(H53A,H53B,H53C), C56(H56A,H56B,H56C),
 C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C0AA(H0AA,H0AB,H0AC), 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(H10E,H10F,H10G), C106(H10J,H10K,H10L), C108(H10M,
 H10N,H10O), C114(H11D,H11E,H11F), C116(H11G,H11H,H11I), C120(H12E,H12F,H12G),
 C128(H12N,H12O,H12P), C130(H13A,H13B,H13C)
;
_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 1.439
_oxdiff_exptl_absorpt_empirical_full_min 0.625