Excitation modulation of Eu:BPEPC based complexes as low-energy reference standards for circularly polarised luminescence (CPL).
starck, matthieu; MacKenzie, Lewis Edward; Batsanov, Andrei Stepanovich; Parker, David; Pal, Robert; Chemical Communications  (2019) –; doi:10.1039/C9CC07290J

data_7124419
_publ_section_title
;
 Excitation modulation of Eu:BPEPC based complexes as low-energy reference
 standards for circularly polarised luminescence (CPL).
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC07290J
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C96 H87 Eu N9 O9 3+, C5 H12 O, 3(C H4 O), H2 O, 3(Cl 1-)'
_chemical_formula_sum            'C104 H113 Cl3 Eu N9 O14'
_chemical_formula_weight         1971.34
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-09-10
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.08.16 svn.r3652 for OlexSys, GUI svn.r5895)
;
_audit_update_record
;
2019-09-10 deposited with the CCDC.	2019-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.685(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.884(8)
_cell_length_b                   23.010(10)
_cell_length_c                   23.107(11)
_cell_measurement_reflns_used    8415
_cell_measurement_temperature    120
_cell_measurement_theta_max      30.14
_cell_measurement_theta_min      2.28
_cell_volume                     10353(8)
_computing_cell_refinement       'SAINT v8.38A (Bruker, 2017)'
_computing_data_collection       'APEX3 v.2016.1-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.38A (Bruker, 2017)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 multi-CPU (Sheldrick, 2015a)'
_computing_structure_solution    'ShelXT 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_temperature      120
_diffrn_detector                 'Bruker PHOTON 100 CMOS'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS sensor'
_diffrn_measured_fraction_theta_full 0.955
_diffrn_measured_fraction_theta_max 0.932
_diffrn_measurement_device       '3-circle area detector diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'focusing mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0986
_diffrn_reflns_av_unetI/netI     0.0927
_diffrn_reflns_Laue_measured_fraction_full 0.955
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            241190
_diffrn_reflns_point_group_measured_fraction_full 0.955
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_min         2.006
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\mS microsource'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.747
_exptl_absorpt_correction_T_max  0.9527
_exptl_absorpt_correction_T_min  0.7718
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
 SADABS-2016/2 (Krause et al., 2015) was used for absorption correction. 
  wR2(int) was 0.1709 before and 0.1024 after correction. The Ratio of 
  minimum to maximum transmission is 0.8101. The \l/2 correction factor is 
  Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.265
_exptl_crystal_description       prism
_exptl_crystal_F_000             4104
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: MeOH, MeOBu-t'
_exptl_crystal_size_max          0.431
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.083
_refine_diff_density_max         1.870
_refine_diff_density_min         -0.769
_refine_diff_density_rms         0.093
_refine_ls_abs_structure_details
;
 Flack x determined using 13729 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons et al., 2013).
  x = 0.002(7) by classical fit to all intensities. 
 Hooft parameter y = 0.017(3).
;
_refine_ls_abs_structure_Flack   0.006(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2493
_refine_ls_number_reflns         44258
_refine_ls_number_restraints     2191
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0763
_refine_ls_R_factor_gt           0.0501
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0592P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1053
_refine_ls_wR_factor_ref         0.1135
_reflns_Friedel_coverage         0.948
_reflns_Friedel_fraction_full    0.954
_reflns_Friedel_fraction_max     0.929
_reflns_number_gt                35028
_reflns_number_total             44258
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07290j2.cif
_cod_data_source_block           Eu(SS-L)3Cl3_19s002
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               7124419
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.941
_shelx_estimated_absorpt_t_min   0.739
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups, All O(H) groups, All O(H,H)
  groups
2. Restrained distances
 C14S-C14T = C14T-O6T = O6S-C14S
 1.4 with sigma of 0.01
 C89B-C88B \\sim C89-C88
 with sigma of 0.02
 C95-C90 \\sim C91-C90
 with sigma of 0.02
 C92-C91 \\sim C95-C94
 with sigma of 0.02
 C93-C92 \\sim C94-C93
 with sigma of 0.02
 O5T-C13S \\sim O5S-C13S
 with sigma of 0.02
 O5S-C13S \\sim O5T-C13S
 with sigma of 0.02
 C18-C16 \\sim C18B-C16
 with sigma of 0.02
 C19-C18 \\sim C23-C18
 with sigma of 0.02
 C23-C22 \\sim C20-C19
 with sigma of 0.02
 C22-C21 \\sim C21-C20
 with sigma of 0.02
 C81B-C80 \\sim C81-C80
 with sigma of 0.02
 C56-C58B \\sim C58-C56
 with sigma of 0.02
 C18'-C16' \\sim C18D-C16'
 with sigma of 0.01
 C9S-C7S \\sim C8S-C7S \\sim C7S-C10S
 with sigma of 0.02
 O11S-C16S \\sim O8S-C16S
 with sigma of 0.02
 C90D-C88' \\sim C90'-C88'
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C93 \\sim C93B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C94 \\sim C94B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C90 \\sim C90B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C91 \\sim C91B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C92 \\sim C92B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C88 \\sim C88B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
O5S \\sim O5T: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C22' \\sim C21D: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C89 \\sim C89B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C18' \\sim C18D: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C18 \\sim C18B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C63 \\sim C63B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C62 \\sim C62B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C91' \\sim C91D: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C92' \\sim C92D: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C90' \\sim C90D: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C14T \\sim C14S: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(Cl3B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C58) = Uanis(C58B)
Uanis(C95) = Uanis(C95B)
Uanis(C18) = Uanis(C18B)
Uiso(C88B) = Uiso(C88)
Uiso(C89) = Uiso(C89B)
Uiso(C90B) = Uiso(C90)
4. Rigid body (RIGU) restrains
 C4, C8, C9, C10
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Fixed Sof: H9B(0.4) H9A(0.6) H16(0.7) H16A(0.3) H56(0.75) H56A(0.25)
 H80A(0.55) H80(0.45) C18(0.7) C19(0.7) H19(0.7) C20(0.7) H20(0.7) C21(0.7)
 H21(0.7) C22(0.7) H22(0.7) C23(0.7) H23(0.7) C58(0.75) C59(0.75) H59(0.75)
 C60(0.75) H60(0.75) C61(0.75) H61(0.75) C62(0.75) H62(0.75) C63(0.75)
 H63(0.75) C81B(0.45) H81A(0.45) H81B(0.45) H81C(0.45) C88(0.6) H88(0.6)
 C89(0.6) H89A(0.6) H89B(0.6) H89C(0.6) C90(0.6) C95(0.6) H95(0.6) C94(0.6)
 H94(0.6) C93(0.6) H93(0.6) C92(0.6) H92(0.6) C91(0.6) H91(0.6) C18B(0.3)
 C23B(0.3) H23B(0.3) C22B(0.3) H22B(0.3) C21B(0.3) H21B(0.3) C20B(0.3)
 H20B(0.3) C19B(0.3) H19B(0.3) C58B(0.25) C59B(0.25) H59B(0.25) C60B(0.25)
 H60B(0.25) C61B(0.25) H61B(0.25) C62B(0.25) H62B(0.25) C63B(0.25) H63B(0.25)
 C81(0.55) H81D(0.55) H81E(0.55) H81F(0.55) C88B(0.4) H88B(0.4) C89B(0.4)
 H89D(0.4) H89E(0.4) H89F(0.4) C90B(0.4) C95B(0.4) H95B(0.4) C94B(0.4)
 H94B(0.4) C93B(0.4) H93B(0.4) C92B(0.4) H92B(0.4) C91B(0.4) H91B(0.4)
 C18'(0.5) C19'(0.5) H19'(0.5) C20'(0.5) H20'(0.5) C21'(0.5) H21'(0.5)
 C22'(0.5) H22'(0.5) C23'(0.5) H23'(0.5) C90'(0.4) C91'(0.4) H91'(0.4)
 C92'(0.4) H92'(0.4) C93'(0.4) H93'(0.4) C94'(0.4) H94'(0.4) C95'(0.4)
 H95'(0.4) C18D(0.5) C23D(0.5) H23D(0.5) C22D(0.5) H22D(0.5) C21D(0.5)
 H21D(0.5) C20D(0.5) H20D(0.5) C19D(0.5) H19D(0.5) C90D(0.6) C95D(0.6)
 H95D(0.6) C94D(0.6) H94D(0.6) C93D(0.6) H93D(0.6) C92D(0.6) H92D(0.6)
 C91D(0.6) H91D(0.6) H13A(0.7) H13B(0.7) H13C(0.7) H13D(0.3) H13E(0.3)
 H13F(0.3) O5S(0.7) H5S(0.7) O5T(0.3) H5T(0.3) O6T(0.4) H6T(0.4) C14T(0.4)
 H14A(0.4) H14B(0.4) H14C(0.4) O8S(0.5) H8S(0.5) C16S(0.5) H16B(0.5) H16C(0.5)
 H16D(0.5) O7S(0.4) H7S(0.4) C15S(0.4) H15A(0.4) H15B(0.4) H15C(0.4) O8T(0.5)
 H8T(0.5) C16T(0.5) H16E(0.5) H16F(0.5) H16G(0.5) O7T(0.6) H7T(0.6) C15T(0.6)
 H15D(0.6) H15E(0.6) H15F(0.6) O6S(0.6) H6S(0.6) C14S(0.6) H14D(0.6) H14E(0.6)
 H14F(0.6) O9S(0.6) H9SD(0.6) H9SE(0.6) O10T(0.4) H10D(0.4) H10E(0.4) O11S(0.5)
 H11D(0.5) H11E(0.5) O10S(0.3) H10F(0.3) H10G(0.3) O9T(0.2) H9TA(0.2) H9TB(0.2)
 Cl3A(0.35) Cl6B(0.55) Cl3B(0.4) Cl6A(0.7)
6.a Riding coordinates:
 C81B(H81A,H81B,H81C), C88(H88), C89(H89A,H89B,H89C), C81(H81D,H81E,H81F),
 C6S(H6SA,H6SB,H6SC), C13S(H13A,H13B,H13C), C13S(H13D,H13E,H13F), O5S(H5S),
 O5T(H5T), O6T(H6T), C14T(H14A,H14B,H14C), O8S(H8S), C16S(H16B,H16C,H16D),
 O4S(H4S), O7S(H7S), C15S(H15A,H15B,H15C), O8T(H8T), C16T(H16E,H16F,H16G),
 O3S(H3S), O7T(H7T), C15T(H15D,H15E,H15F), O6S(H6S), C14S(H14D,H14E,H14F),
 O9S(H9SD,H9SE), O10T(H10D,H10E), O11S(H11D,H11E), O10S(H10F,H10G), O9T(H9TA,
 H9TB)
6.b Rotating group:
 C25(H25A,H25B,H25C), C57(H57A,H57B,H57C), C64(H64A,H64B,H64C), C96'(H96D,H96E,
 H96F)
6.c Ternary CH refined with riding coordinates:
 C16(H16), C16(H16A), C24(H24), C48(H48), C56(H56), C56(H56A), C80(H80A),
 C80(H80), C88B(H88B), C16'(H16'), C24'(H24'), C48'(H48'), C56'(H56'),
 C80'(H80'), C88'(H88')
6.d Me refined with riding coordinates:
 C89B(H89D,H89E,H89F), C8S(H8SA,H8SB,H8SC), C9S(H9SA,H9SB,H9SC), C10S(H10A,
 H10B,H10C)
6.e Aromatic/amide H refined with riding coordinates:
 N4(H4), N5(H5), N6(H6), N7(H7), N8(H8), N9(H9B), N9(H9A), C3(H3), C5(H5A),
 C11(H11), C12(H12), C14(H14), C15(H15), C27(H27), C28(H28), C29(H29), C30(H30),
  C31(H31), C35(H35), C37(H37), C51(H51), C52(H52), C53(H53), C54(H54),
 C55(H55), C67(H67), C69(H69), C75(H75), C76(H76), C78(H78), C79(H79), C83(H83),
  C84(H84), C85(H85), C86(H86), C87(H87), C19(H19), C20(H20), C21(H21),
 C22(H22), C23(H23), C43(H43), C44(H44), C46(H46), C47(H47), C59(H59), C60(H60),
  C61(H61), C62(H62), C63(H63), C95(H95), C94(H94), C93(H93), C92(H92),
 C91(H91), C23B(H23B), C22B(H22B), C21B(H21B), C20B(H20B), C19B(H19B),
 C59B(H59B), C60B(H60B), C61B(H61B), C62B(H62B), C63B(H63B), C95B(H95B),
 C94B(H94B), C93B(H93B), C92B(H92B), C91B(H91B), N4'(H4'), N5'(H5'), N6'(H6'),
 N7'(H7'), N8'(H8'), N9'(H9'), C3'(H3'), C5'(H5'A), C11'(H11'), C12'(H12'),
 C14'(H14'), C15'(H15'), C27'(H27'), C28'(H28'), C29'(H29'), C30'(H30'),
 C31'(H31'), C35'(H35'), C37'(H37'), C43'(H43'), C44'(H44'), C46'(H46'),
 C47'(H47'), C51'(H51'), C52'(H52'), C53'(H53'), C54'(H54'), C55'(H55'),
 C59'(H59'), C60'(H60'), C61'(H61'), C62'(H62'), C63'(H63'), C67'(H67'),
 C69'(H69'), C75'(H75'), C76'(H76'), C78'(H78'), C79'(H79'), C83'(H83'),
 C84'(H84'), C85'(H85'), C86'(H86'), C87'(H87'), C19'(H19'), C20'(H20'),
 C21'(H21'), C22'(H22'), C23'(H23'), C91'(H91'), C92'(H92'), C93'(H93'),
 C94'(H94'), C95'(H95'), C23D(H23D), C22D(H22D), C21D(H21D), C20D(H20D),
 C19D(H19D), C95D(H95D), C94D(H94D), C93D(H93D), C92D(H92D), C91D(H91D)
6.f Fitted hexagon refined as free rotating group:
 C90(C95,C94,C93,C92,C91), C18B(C23B,C22B,C21B,C20B,C19B), C58B(C59B,C60B,C61B,
 C62B,C63B), C90B(C95B,C94B,C93B,C92B,C91B), C18D(C23D,C22D,C21D,C20D,C19D),
 C90D(C95D,C94D,C93D,C92D,C91D)
6.g Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C32(H32A,H32B,H32C), C49(H49A,H49B,H49C), C96(H96A,H96B,
 H96C), C17'(H17D,H17E,H17F), C25'(H25D,H25E,H25F), C32'(H32D,H32E,H32F),
 C49'(H49D,H49E,H49F), C57'(H57D,H57E,H57F), C64'(H64D,H64E,H64F), C81'(H81G,
 H81H,H81I), C89'(H89G,H89H,H89I), C1S(H1SA,H1SB,H1SC), C3S(H3SA,H3SB,H3SC),
 C4S(H4SA,H4SB,H4SC), C5S(H5SA,H5SB,H5SC), C12S(H12A,H12B,H12C), C11S(H11A,H11B,
 H11C)
;
_shelx_res_checksum              70251
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'