Efficient circularly polarized luminescence from zero-dimensional terbium- and europium-based hybrid metal halides.
Zhang, Yan; Wei, Yi; Li, Chen; Wang, Yuxuan; Liu, Yulian; He, Meiying; Luo, Zhishan; Chang, Xiaoyong; Kuang, Xiaojun; Quan, Zewei; Chemical communications (Cambridge, England) 61 (2024) 85–88; doi:10.1039/d4cc05206d

data_7134025
_publ_section_title
;
 Efficient circularly polarized luminescence from zero-dimensional
 terbium- and europium-based hybrid metal halides.
;
_journal_issue                   1
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              85
_journal_page_last               88
_journal_paper_doi               10.1039/d4cc05206d
_journal_volume                  61
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(Cl6 Eu), 6(C5 H12 N O)'
_chemical_formula_sum            'C30 H72 Cl12 Eu2 N6 O6'
_chemical_formula_weight         1342.25
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-09-18
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-20 deposited with the CCDC.	2024-11-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.753(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.3233(6)
_cell_length_b                   11.9727(6)
_cell_length_c                   16.8005(8)
_cell_measurement_reflns_used    9744
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      27.46
_cell_measurement_theta_min      3
_cell_volume                     2655.4(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT 2014'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker PHOTON III area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0679
_diffrn_reflns_av_unetI/netI     0.0575
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            63859
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.511
_diffrn_reflns_theta_min         1.835
_diffrn_source                   'microfocus Metaljet'
_diffrn_source_type              'Incoatec Metaljet'
_exptl_absorpt_coefficient_mu    2.985
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5721
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1464 before and 0.0826 after correction.
The Ratio of minimum to maximum transmission is 0.7673.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.679
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.22
_refine_diff_density_max         1.116
_refine_diff_density_min         -1.229
_refine_diff_density_rms         0.144
_refine_ls_abs_structure_details
;
 Flack x determined using 3725 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.015(8)
_refine_ls_extinction_coef       0.00052(8)
_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   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     603
_refine_ls_number_reflns         12198
_refine_ls_number_restraints     415
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0734
_refine_ls_R_factor_gt           0.0474
_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^)+14.9363P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0783
_refine_ls_wR_factor_ref         0.0881
_reflns_Friedel_coverage         0.907
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                9480
_reflns_number_total             12198
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc05206d2.cif
_cod_data_source_block           mo_seu_0m
_cod_depositor_comments
'Adding full bibliography for 7134023--7134026.cif.'
_cod_database_code               7134025
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N5-C25 \\sim N5A-C25A
 with sigma of 0.02
 N5-C22 \\sim N5A-C22A
 with sigma of 0.02
 C25-C24 \\sim C25A-C24A
 with sigma of 0.02
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 O5-C23 \\sim O5A-C23A
 with sigma of 0.02
 O5-C24 \\sim O5A-C24A
 with sigma of 0.02
 C22-C23 \\sim C22A-C23A
 with sigma of 0.02
 N5-C21 \\sim N5A-C21A
 with sigma of 0.04
 N5-C23 \\sim N5A-C23A
 with sigma of 0.04
 N5-C24 \\sim N5A-C24A
 with sigma of 0.04
 C25-O5 \\sim C25A-O5A
 with sigma of 0.04
 C25-C22 \\sim C25A-C22A
 with sigma of 0.04
 C21-C23 \\sim C21A-C23A
 with sigma of 0.04
 O5-C22 \\sim O5A-C22A
 with sigma of 0.04
 C23-C24 \\sim C23A-C24A
 with sigma of 0.04
3. Rigid bond restraints
 N2, O2, C9, C8, C10, C7, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C25 \\sim N5 \\sim C22 \\sim C24 \\sim C23 \\sim C21 \\sim O5 \\sim C25A \\sim
C21A \\sim C22A \\sim N5A \\sim C23A \\sim O5A \\sim C24A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
N2 \\sim O2 \\sim C9 \\sim C8 \\sim C10 \\sim C7 \\sim C6: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C21) \\sim Ueq, Uanis(N5) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(O5) \\sim Ueq,
Uanis(C21A) \\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(N5A) \\sim Ueq, Uanis(C23A)
\\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(O5A) \\sim Ueq, Uanis(C24A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N2) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim
Ueq, Uanis(C10) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(N1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Cl5) = Uanis(Cl5A)
Uanis(Eu1) = Uanis(Eu1A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(Cl8) = Uanis(Cl8A)
Uanis(Cl7) = Uanis(Cl7A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(Cl11) = Uanis(Cl9)
Uanis(Cl6) = Uanis(Cl6A)
Uanis(Cl4) = Uanis(Cl4A)
Uanis(Cl9A) = Uanis(Cl12)
Uanis(Cl13) = Uanis(Cl15)
Uanis(Cl10) = Uanis(Cl14)
Uanis(N5) = Uanis(N5A)
Uanis(C21A) = Uanis(C21)
5. Others
 Sof(Cl5A)=Sof(Cl2A)=Sof(Cl1A)=Sof(Cl6A)=Sof(Cl4A)=Sof(Eu1A)=1-FVAR(1)
 Sof(Eu1)=Sof(Cl6)=Sof(Cl1)=Sof(Cl4)=Sof(Cl2)=Sof(Cl5)=FVAR(1)
 Sof(Cl11)=Sof(Cl12)=Sof(Cl14)=Sof(Cl15)=Sof(Cl8A)=Sof(Cl7A)=1-FVAR(2)
 Sof(Cl13)=Sof(Cl8)=Sof(Cl7)=Sof(Cl9A)=Sof(Cl10)=Sof(Cl9)=FVAR(2)
 Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(N5A)=Sof(H5AA)=Sof(H5AB)=
 Sof(C25A)=Sof(H25C)=Sof(H25D)=Sof(C22A)=Sof(H22A)=Sof(C24A)=Sof(H24C)=
 Sof(H24D)=Sof(C23A)=Sof(H23C)=Sof(H23D)=Sof(O5A)=1-FVAR(3)
 Sof(N5)=Sof(H5A)=Sof(H5B)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C21)=Sof(H21A)=
 Sof(H21B)=Sof(H21C)=Sof(O5)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23A)=Sof(H23B)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C27(H27), C17(H17), C12(H12), C2(H2), C22(H22), C7(H7), C22A(H22A)
6.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), N4(H4A,H4B), C13(H13A,H13B), N5(H5A,H5B), C25(H25A,H25B),
 C20(H20A,H20B), N3(H3C,H3D), C18(H18A,H18B), C28(H28A,H28B), C10(H10A,H10B),
 N2(H2A,H2B), C31(H31A,H31B), C3(H3A,H3B), C9(H9A,H9B), C19(H19A,H19B),
 C14(H14A,H14B), C4(H4C,H4D), C30(H30A,H30B), C8(H8A,H8B), C23(H23A,H23B),
 N6(H6A,H6B), C15(H15A,H15B), C24(H24A,H24B), C29(H29A,H29B), N5A(H5AA,H5AB),
 C25A(H25C,H25D), C24A(H24C,H24D), C23A(H23C,H23D)
6.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C11(H11A,H11B,H11C), C6(H6C,H6D,H6E), C1(H1C,H1D,H1E),
 C16(H16A,H16B,H16C), C26(H26A,H26B,H26C), C21A(H21D,H21E,H21F)
;
_shelx_res_checksum              96972
_shelx_hkl_checksum              5851
_olex2_submission_special_instructions 'No special instructions were received'