δ-Bonding modulates the electronic structure of formally divalent nd<sup>1</sup> rare earth arene complexes.
MacKenzie, Ross E.; Hajdu, Tomáš; Seed, John A.; Whitehead, George F. S.; Adams, Ralph W.; Chilton, Nicholas F.; Collison, David; McInnes, Eric J. L.; Goodwin, Conrad A. P.; Chemical science 15 (2024) 15160–15169; doi:10.1039/d4sc03005b

data_1572262
_publ_section_title
;
 &#x3b4;-Bonding modulates the electronic structure of formally divalent
 nd<sup>1</sup> rare earth arene complexes.
;
_journal_issue                   37
_journal_name_full               'Chemical science'
_journal_page_first              15160
_journal_page_last               15169
_journal_paper_doi               10.1039/d4sc03005b
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C36 H50 Eu0.5 N), 1.5(C4 H10 O)'
_chemical_formula_sum            'C78 H115 Eu N2 O1.5'
_chemical_formula_weight         1256.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-06
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-09-15 deposited with the CCDC.	2024-07-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.3783(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.4535(3)
_cell_length_b                   16.0659(2)
_cell_length_c                   20.2346(2)
_cell_measurement_reflns_used    14063
_cell_measurement_temperature    99.97(10)
_cell_measurement_theta_max      74.5030
_cell_measurement_theta_min      3.3760
_cell_volume                     7003.14(15)
_computing_cell_refinement       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.980
_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    -21.00  20.00   0.50    1.50    --   43.40  50.00 120.00   82
  2  \w     28.00 119.00   0.50    1.50    --   43.40  50.00 120.00  182
  3  \w    -16.00 131.00   0.50    1.50    --   46.00  60.00  60.00  294
  4  \w     56.00  82.00   0.50    3.00    --  108.20  40.00 -30.00   52
  5  \w     87.00 121.00   0.50    3.00    --  108.20  30.00 120.00   68
  6  \w    162.00 188.00   0.50    3.00    --  108.20  30.00 120.00   52
  7  \w     38.00  64.00   0.50    3.00    --  108.20  30.00 120.00   52
  8  \w     99.00 198.00   0.50    3.00    --  108.20  50.00  30.00  198
  9  \w     19.00 191.00   0.50    3.00    --  108.20  50.00-120.00  344
 10  \w    144.00 198.00   0.50    3.00    --  108.20  40.00-120.00  108
 11  \w    109.00 135.00   0.50    3.00    --  108.20  30.00  60.00   52
 12  \w    145.00 177.00   0.50    3.00    --  108.20  30.00  60.00   64
 13  \w     20.00 172.00   0.50    3.00    --  108.20  20.00 -60.00  304
 14  \w     75.00 101.00   0.50    3.00    --  108.20  40.00   0.00   52
 15  \w    159.00 198.00   0.50    3.00    --  108.20  40.00   0.00   78
 16  \w     19.00  76.00   0.50    3.00    --  108.20  50.00  30.00  114
 17  \w     95.00 161.00   0.50    3.00    --  108.20  50.00  90.00  132
 18  \w    173.00 198.00   0.50    3.00    --  108.20  50.00  90.00   50
 19  \w    144.00 169.00   0.50    3.00    --  108.20  40.00 -30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0035652000
_diffrn_orient_matrix_UB_12      0.0406098000
_diffrn_orient_matrix_UB_13      -0.0677448000
_diffrn_orient_matrix_UB_21      0.0412779000
_diffrn_orient_matrix_UB_22      -0.0720162000
_diffrn_orient_matrix_UB_23      -0.0114808000
_diffrn_orient_matrix_UB_31      -0.0582728000
_diffrn_orient_matrix_UB_32      -0.0486014000
_diffrn_orient_matrix_UB_33      -0.0396801000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0318
_diffrn_reflns_av_unetI/netI     0.0462
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            26464
_diffrn_reflns_point_group_measured_fraction_full 0.827
_diffrn_reflns_point_group_measured_fraction_max 0.791
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.964
_diffrn_reflns_theta_min         3.432
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    6.733
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45625
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.192
_exptl_crystal_description       block
_exptl_crystal_F_000             2688
_exptl_crystal_size_max          0.101
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.066
_refine_diff_density_max         1.497
_refine_diff_density_min         -1.198
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 3678 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.037(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     843
_refine_ls_number_reflns         11576
_refine_ls_number_restraints     184
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0399
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0565P)^2^+10.4540P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1034
_refine_ls_wR_factor_ref         0.1046
_reflns_Friedel_coverage         0.556
_reflns_Friedel_fraction_full    0.643
_reflns_Friedel_fraction_max     0.587
_reflns_number_gt                10965
_reflns_number_total             11576
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           lcapg36
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_original_cell_volume        7003.18(17)
_cod_original_formula_sum        'C78 H115 Eu N2 O1.50'
_cod_database_code               1572262
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         Eu(NHC6H3(C6H2(C3H7)3)2)2
_shelx_estimated_absorpt_t_max   0.665
_shelx_estimated_absorpt_t_min   0.550
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1 = N1A-H1A
 0.85 with sigma of 0.02
 O3-C47 \\sim O3-C46 \\sim O1-C39 \\sim O1-C38
 with sigma of 0.02
 O2-C42 \\sim O2-C43 \\sim O1-C38 \\sim O1-C39
 with sigma of 0.02
 O2-C41 \\sim O2-C44 \\sim O1-C37 \\sim O1-C40
 with sigma of 0.02
 C38-C37 \\sim C40-C39 \\sim C44-C43 \\sim C42-C41
 with sigma of 0.02
 C42-C43 \\sim C38-C39
 with sigma of 0.02
 C46-C45 \\sim C48-C47 \\sim C40-C39 \\sim C38-C37
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C38 \\sim O1 \\sim C39 \\sim C40 \\sim C37 \\sim C44 \\sim C41 \\sim C42 \\sim
O2 \\sim C43: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C47 \\sim C45 \\sim C46 \\sim O3 \\sim C48: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C38, O1, C39, C40, C37, C44, C41, C42, O2, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(O2)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=1-FVAR(1)
 Sof(O1)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=FVAR(1)
 Fixed Sof: C45(0.5) H45A(0.5) H45B(0.5) H45C(0.5) C46(0.5) H46A(0.5)
 H46B(0.5) O3(0.5) C47(0.5) H47A(0.5) H47B(0.5) C48(0.5) H48A(0.5) H48B(0.5)
 H48C(0.5)
6.a Ternary CH refined with riding coordinates:
 C13(H13), C19(H19), C16(H16), C34(H34), C28(H28), C31(H31), C34A(H34A),
 C28A(H28A), C31A(H31A), C13A(H13A), C19A(H19A), C16A(H16A)
6.b Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C38(H38A,H38B), C43(H43A,H43B), C42(H42A,H42B), C46(H46A,
 H46B), C47(H47A,H47B)
6.c Me refined with riding coordinates:
 C37(H37A,H37B,H37C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C44(H44A,H44B,
 H44C), C45(H45A,H45B,H45C), C48(H48A,H48B,H48C)
6.d Aromatic/amide H refined with riding coordinates:
 C26(H26), C24(H24), C5(H5), C4(H4), C3(H3), C9(H9), C11(H11), C9A(H9A),
 C11A(H11A), C3A(H3A), C4A(H4A), C5A(H5A), C26A(H26A), C24A(H24A)
6.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C36(H36A,H36B,H36C), C35(H35A,
 H35B,H35C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C33(H33A,H33B,H33C),
 C32(H32A,H32B,H32C), C35A(H35D,H35E,H35F), C36A(H36D,H36E,H36F), C29A(H29D,
 H29E,H29F), C30A(H30D,H30E,H30F), C32A(H32D,H32E,H32F), C33A(H33D,H33E,H33F),
 C15A(H15D,H15E,H15F), C14A(H14D,H14E,H14F), C20A(H20D,H20E,H20F), C21A(H21D,
 H21E,H21F), C18A(H18D,H18E,H18F), C17A(H17D,H17E,H17F)
;
_shelx_res_checksum              61357
_shelx_hkl_checksum              519
_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 2.893
_oxdiff_exptl_absorpt_empirical_full_min 0.682