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_1572263
_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_formula_moiety         'C72 H100 N2 Sm, C4 H10 O'
_chemical_formula_sum            'C76 H110 N2 O Sm'
_chemical_formula_weight         1218.00
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 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                 96.7280(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.35080(10)
_cell_length_b                   24.2551(2)
_cell_length_c                   21.4353(2)
_cell_measurement_reflns_used    27122
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.5610
_cell_measurement_theta_min      2.7550
_cell_volume                     6893.48(10)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.968
_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   -114.00 -45.00   0.50    1.05    --  -49.61 -30.00 -74.00  138
  2  \w    -34.00   0.00   0.50    1.05    --  -49.61  30.00  85.00   68
  3  \w     58.00  83.00   0.50    1.05    --   49.61  30.00  85.00   50
  4  \w    -18.00  34.00   0.50    1.05    --   49.61 -30.00 -74.00  104
  5  \w   -116.00 -82.00   0.50    4.19    --  -90.00 -30.00 -74.00   68
  6  \w    105.00 178.00   0.50    4.19    --  111.50  30.00  85.00  146
  7  \w    -25.00  20.00   0.50    1.05    --  -49.61  19.00 120.00   90
  8  \w   -121.00 -96.00   0.50    1.05    --  -49.61-125.00  30.00   50
  9  \w    -20.00  24.00   0.50    1.05    --   49.61 -19.00  90.00   88
 10  \w    -23.00  25.00   0.50    1.05    --   49.61 -19.00 150.00   96
 11  \w    -64.00 -32.00   0.50    4.19    --  -90.00  61.00  30.00   64
 12  \w    -44.00 -19.00   0.50    4.19    --  -90.00  45.00-120.00   50
 13  \w    -44.00 -18.00   0.50    4.19    --  -90.00  61.00 -30.00   52
 14  \w    -51.00 -26.00   0.50    4.19    --  -90.00  45.00  90.00   50
 15  \w    -48.00 -23.00   0.50    4.19    --  -90.00  45.00 -90.00   50
 16  \w     54.00  81.00   0.50    4.19    --  111.50 -77.00-120.00   54
 17  \w     44.00  71.00   0.50    4.19    --  111.50 -61.00-120.00   54
 18  \w     41.00  71.00   0.50    4.19    --  111.50 -61.00 120.00   60
 19  \w     41.00  66.00   0.50    4.19    --  111.50 -61.00   0.00   50
 20  \w     43.00  70.00   0.50    4.19    --  111.50 -61.00-180.00   54
 21  \w     42.00  70.00   0.50    4.19    --  111.50 -61.00 -60.00   56
 22  \w    135.00 160.00   0.50    4.19    --  111.50   0.00-120.00   50
 23  \w     49.00 110.00   0.50    4.19    --  111.50   0.00-120.00  122
 24  \w     48.00 106.00   0.50    4.19    --  111.50 -77.00-180.00  116
 25  \w     43.00  69.00   0.50    4.19    --  111.50 -61.00  60.00   52
 26  \w     71.00 104.00   0.50    4.19    --  111.50 -94.00  90.00   66
 27  \w    102.00 178.00   0.50    4.19    --  111.50  45.00-180.00  152
 28  \w     43.00  69.00   0.50    4.19    --  111.50 -61.00 -90.00   52
 29  \w     41.00  68.00   0.50    4.19    --  111.50 -61.00  30.00   54
 30  \w     47.00 103.00   0.50    4.19    --  111.50 -94.00 150.00  112
 31  \w     55.00  94.00   0.50    4.19    --  111.50 -94.00-180.00   78
 32  \w     48.00  92.00   0.50    4.19    --  111.50 -77.00  30.00   88
 33  \w     42.00  68.00   0.50    4.19    --  111.50 -61.00 -30.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0725965000
_diffrn_orient_matrix_UB_12      -0.0244129000
_diffrn_orient_matrix_UB_13      0.0435726000
_diffrn_orient_matrix_UB_21      0.0867167000
_diffrn_orient_matrix_UB_22      -0.0023726000
_diffrn_orient_matrix_UB_23      0.0541094000
_diffrn_orient_matrix_UB_31      -0.0267177000
_diffrn_orient_matrix_UB_32      0.0585697000
_diffrn_orient_matrix_UB_33      0.0203066000
_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  0.0402
_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            58015
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.009
_diffrn_reflns_theta_min         2.762
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.705
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74120
_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 brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.174
_exptl_crystal_description       block
_exptl_crystal_F_000             2600
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.169
_exptl_crystal_size_min          0.092
_refine_diff_density_max         0.478
_refine_diff_density_min         -0.930
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     772
_refine_ls_number_reflns         14568
_refine_ls_number_restraints     63
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0454
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0375P)^2^+8.4596P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0920
_refine_ls_wR_factor_ref         0.0954
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12617
_reflns_number_total             14568
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           ccapg119
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_database_code               1572263
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_usercomment     hs
_shelx_estimated_absorpt_t_max   0.577
_shelx_estimated_absorpt_t_min   0.255
_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
 O1-C76 \\sim O1-C73
 with sigma of 0.02
 O1-C74 \\sim O1-C75
 with sigma of 0.02
 C76-C75 \\sim C74-C73
 with sigma of 0.02
 C72-C70 \\sim C72A-C70 \\sim C71A-C70 \\sim C71-C70
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C72 \\sim C72A \\sim C70 \\sim C71A \\sim C71: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C72A, C72, C70, C71A, C71
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H70A)=Sof(C72A)=Sof(H72D)=Sof(H72E)=Sof(H72F)=Sof(C71A)=Sof(H71D)=
 Sof(H71E)=Sof(H71F)=1-FVAR(1)
 Sof(H70)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(H72A)=Sof(H72B)=
 Sof(H72C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C28(H28), C31(H31), C13(H13), C16(H16), C19(H19), C34(H34), C49(H49),
 C52(H52), C55(H55), C64(H64), C67(H67), C70(H70A), C70(H70)
6.b Secondary CH2 refined with riding coordinates:
 C74(H74A,H74B), C75(H75A,H75B)
6.c Me refined with riding coordinates:
 C73(H73A,H73B,H73C), C76(H76A,H76B,H76C)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C11(H11), C24(H24), C26(H26), C39(H39),
 C40(H40), C41(H41), C45(H45), C47(H47), C60(H60), C62(H62)
6.e Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,
 H20B,H20C), C21(H21A,H21B,H21C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C),
 C36(H36A,H36B,H36C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,
 H53C), C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C65(H65A,
 H65B,H65C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C),
 C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C72A(H72D,H72E,H72F), C71A(H71D,H71E,
 H71F)
;
_shelx_res_checksum              36313
_shelx_hkl_checksum              9740
_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 1.499
_oxdiff_exptl_absorpt_empirical_full_min 0.561