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_1572268
_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 Sc'
_chemical_formula_sum            'C72 H100 N2 Sc'
_chemical_formula_weight         1038.49
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_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                75.703(2)
_cell_angle_beta                 89.2794(16)
_cell_angle_gamma                62.710(2)
_cell_formula_units_Z            2
_cell_length_a                   12.8855(3)
_cell_length_b                   13.5895(4)
_cell_length_c                   20.8228(4)
_cell_measurement_reflns_used    9512
_cell_measurement_temperature    100.01(12)
_cell_measurement_theta_max      75.5400
_cell_measurement_theta_min      3.7840
_cell_volume                     3118.51(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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(12)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.978
_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    -82.00 -12.00   0.50    2.00    --  -44.40  76.00-180.00  140
  2  \w    -77.00  44.00   0.50    2.00    --  -44.40  57.00 120.00  242
  3  \w   -134.00  45.00   0.50    2.00    --  -44.40 -19.00-150.00  358
  4  \w    -77.00  24.00   0.50    2.00    --  -44.40  57.00  30.00  202
  5  \w    -13.00  13.00   0.50    2.00    --  -46.40  76.00-120.00   52
  6  \w    -57.00 -21.00   0.50    2.00    --  -46.40  76.00-120.00   72
  7  \w   -120.00 -93.00   0.50    7.00    -- -107.20  59.00 179.50   54
  8  \w    -82.00 -35.00   0.50    7.00    -- -107.20  74.00-152.95   94
  9  \w   -126.00 -97.00   0.50    7.00    -- -107.20  71.00 166.85   58
 10  \w   -123.00 -97.00   0.50    7.00    -- -107.20  69.00  91.72   52
 11  \w    -67.00 -40.00   0.50    7.00    -- -107.20  69.00  91.72   54
 12  \w   -143.00-117.00   0.50    7.00    -- -107.20  27.00 117.90   52
 13  \w   -108.00 -82.00   0.50    7.00    -- -107.20  27.00 117.90   52
 14  \w   -138.00-100.00   0.50    7.00    -- -107.20 -21.00  44.83   76
 15  \w    -71.00 -45.00   0.50    7.00    -- -107.20  70.00 -49.28   52
 16  \w   -145.00 -92.00   0.50    7.00    -- -107.20  74.00-152.95  106
 17  \w   -174.00-126.00   0.50    7.00    -- -107.20 -76.00-150.00   96
 18  \w   -169.00-141.00   0.50    7.00    -- -107.20  23.00  25.63   56
 19  \w   -147.00-102.00   0.50    7.00    -- -107.20  76.00   0.00   90
 20  \w    -96.00 -70.00   0.50    7.00    -- -107.20  76.00   0.00   52
 21  \w    -48.00 -22.00   0.50    7.00    -- -107.20  76.00   0.00   52
 22  \w    -75.00 -34.00   0.50    7.00    -- -107.20  38.00-180.00   82
 23  \w   -113.00 -84.00   0.50    7.00    -- -107.20  76.00 -30.00   58
 24  \w    -51.00 -26.00   0.50    7.00    -- -107.20  76.00 -30.00   50
 25  \w   -106.00 -79.00   0.50    7.00    -- -107.20  76.00-180.00   54
 26  \w   -117.00 -18.00   0.50    7.00    -- -107.20  57.00  30.00  198
 27  \w   -179.00 -89.00   0.50    7.00    -- -107.20 -48.00 136.14  180
 28  \w   -181.00-155.00   0.50    7.00    -- -107.20 -21.00  44.83   52
 29  \w   -140.00-112.00   0.50    7.00    -- -107.20  57.00  60.00   56
 30  \w   -142.00-117.00   0.50    7.00    -- -107.20  76.00  60.00   50
 31  \w   -127.00 -80.00   0.50    7.00    -- -107.20  70.00 -49.28   94
 32  \w   -180.00-105.00   0.50    7.00    -- -107.20 -38.00  30.00  150
 33  \w   -147.00 -22.00   0.50    7.00    -- -107.20  76.00-120.00  250
 34  \w   -148.00 -41.00   0.50    7.00    -- -107.20  76.00  30.00  214
 35  \w   -100.00 -69.00   0.50    7.00    -- -107.20 -38.00  30.00   62
 36  \w   -116.00 -76.00   0.50    7.00    -- -107.20  76.00 150.00   80
 37  \w   -178.00 -98.00   0.50    7.00    -- -107.20 -41.00 145.81  160
 38  \w    -97.00 -72.00   0.50    7.00    -- -107.20 -76.00-150.00   50
 39  \w   -171.00-139.00   0.50    7.00    -- -107.20 -57.00 -60.00   64
 40  \w   -109.00 -84.00   0.50    7.00    -- -107.20  76.00 -90.00   50
 41  \w    -76.00 -51.00   0.50    7.00    -- -107.20  76.00 -90.00   50
 42  \w   -129.00 -93.00   0.50    7.00    -- -107.20 -75.00   5.14   72
 43  \w   -145.00 -97.00   0.50    7.00    -- -107.20  73.00  41.04   96
 44  \w    -80.00 -55.00   0.50    7.00    -- -107.20  73.00  41.04   50
 45  \w    -96.00 -18.00   0.50    7.00    -- -107.20  50.00-100.93  156
 46  \w    -78.00 -49.00   0.50    7.00    -- -107.20  57.00 150.00   58
 47  \w   -179.00 -74.00   0.50    7.00    -- -107.20 -38.00  90.00  210
 48  \w   -159.00-134.00   0.50    7.00    -- -107.20 -17.00 106.38   50
 49  \w    -92.00 -29.00   0.50    7.00    -- -107.20 -17.00 106.38  126
 50  \w   -179.00-153.00   0.50    7.00    -- -107.20 -13.00-116.99   52
 51  \w   -147.00-122.00   0.50    7.00    -- -107.20 -13.00-116.99   50
 52  \w    -94.00 -68.00   0.50    7.00    -- -107.20 -13.00-116.99   52
 53  \w   -146.00-121.00   0.50    7.00    -- -107.20 -38.00   0.00   50
 54  \w    -80.00 -23.00   0.50    7.00    -- -107.20  56.00-156.10  114
 55  \w   -177.00-151.00   0.50    7.00    -- -107.20 -38.00   0.00   52
 56  \w   -125.00-100.00   0.50    7.00    -- -107.20  71.00-106.22   50
 57  \w    -76.00 -51.00   0.50    7.00    -- -107.20  71.00-106.22   50
 58  \w   -124.00 -99.00   0.50    7.00    -- -107.20  76.00 -60.00   50
 59  \w   -104.00 -22.00   0.50    7.00    -- -107.20  76.00  60.00  164
 60  \w   -140.00-114.00   0.50    7.00    -- -107.20  56.00  79.04   52
 61  \w    -67.00 -28.00   0.50    7.00    -- -107.20  56.00  79.04   78
 62  \w   -147.00-121.00   0.50    7.00    -- -107.20 -73.00  16.58   52
 63  \w   -118.00 -87.00   0.50    7.00    -- -107.20  40.00 -30.18   62
 64  \w   -110.00 -84.00   0.50    7.00    -- -107.20  75.00 101.98   52
 65  \w   -128.00-103.00   0.50    7.00    -- -107.20  76.00  90.00   50
 66  \w   -125.00-100.00   0.50    7.00    -- -107.20  76.00 120.00   50
 67  \w   -112.00 -86.00   0.50    7.00    -- -107.20 -76.00-162.99   52
 68  \w   -102.00 -68.00   0.50    7.00    -- -107.20  36.00 -11.17   68
 69  \w    -63.00 -18.00   0.50    7.00    -- -107.20  36.00 -11.17   90
 70  \w    -70.00 -42.00   0.50    7.00    -- -107.20  73.00 -77.85   56
 71  \w   -122.00 -97.00   0.50    7.00    -- -107.20  73.00 -77.85   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1010147000
_diffrn_orient_matrix_UB_12      0.0949594000
_diffrn_orient_matrix_UB_13      0.0240660000
_diffrn_orient_matrix_UB_21      -0.0627245000
_diffrn_orient_matrix_UB_22      0.0569496000
_diffrn_orient_matrix_UB_23      -0.0718094000
_diffrn_orient_matrix_UB_31      -0.0648931000
_diffrn_orient_matrix_UB_32      -0.0728384000
_diffrn_orient_matrix_UB_33      0.0131938000
_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  0.0360
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            67098
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.109
_diffrn_reflns_theta_min         2.205
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    1.307
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88329
_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    1.106
_exptl_crystal_description       block
_exptl_crystal_F_000             1134
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.042
_refine_diff_density_max         0.312
_refine_diff_density_min         -0.501
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.00130(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     843
_refine_ls_number_reflns         12749
_refine_ls_number_restraints     872
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0514P)^2^+0.8684P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1046
_refine_ls_wR_factor_ref         0.1063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11638
_reflns_number_total             12749
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           rcapg43
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_original_cell_volume        3118.52(14)
_cod_database_code               1572268
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         Sc(NHC6H3(C6H2(C3H7)3)2)2
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.880
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-H2 \\sim N1-H1
 with sigma of 0.02
 C58-C42 \\sim C58A-C42
 with sigma of 0.02
 C61A-C60A \\sim C61-C60 \\sim C60-C59 \\sim C60A-C59A \\sim C59-C58 \\sim
C59A-C58A \\sim C63-C58 ~
 C63A-C58A \\sim C63A-C62A \\sim C63-C62 \\sim C62-C61 \\sim C62A-C61A
 with sigma of 0.02
 C67A-C60A \\sim C64A-C60A \\sim C64A-C58A \\sim C70A-C58A \\sim C70A-C62A
\\sim C67A-C62A \\sim C67-
 C62 \\sim C67-C60 \\sim C64-C60 \\sim C64-C58 \\sim C70-C58 \\sim C70-C62
 with sigma of 0.04
 C72-C63 \\sim C72A-C63A \\sim C71A-C63A \\sim C71-C63 \\sim C69-C61 \\sim
C68A-C61A \\sim C69A-C61A ~
 C68-C61 \\sim C65A-C59A \\sim C65-C59 \\sim C66-C59 \\sim C66A-C59A
 with sigma of 0.04
 C64-C59 \\sim C64A-C59A \\sim C70-C63 \\sim C70A-C63A \\sim C67-C61 \\sim
C67A-C61A
 with sigma of 0.02
 C68-C67 \\sim C69A-C67A \\sim C68A-C67A \\sim C69-C67 \\sim C66-C64 \\sim
C66A-C64A \\sim C65A-C64A ~
 C65-C64 \\sim C71A-C70A \\sim C71-C70 \\sim C72A-C70A \\sim C72-C70
 with sigma of 0.02
 C72A-C71A \\sim C72-C71 \\sim C69A-C68A \\sim C69-C68 \\sim C66-C65 \\sim
C66A-C65A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C59 \\sim C68A \\sim C63A \\sim C60 \\sim C59A \\sim C61 \\sim C67A \\sim C62
\\sim C65A \\sim C63 \\sim C61A \\sim C64 \\sim C71A \\sim C65 \\sim C69A \\sim
C66 \\sim C64A \\sim C67 \\sim C66A \\sim C68 \\sim C60A \\sim C69 \\sim C62A
\\sim C70 \\sim C70A \\sim C71 \\sim C72A \\sim C72: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C58A) = Uanis(C58)
4. Rigid body (RIGU) restrains
 C59, C68A, C63A, C60, C59A, C61, C67A, C62, C65A, C63, C61A, C64, C71A, C65,
 C69A, C66, C64A, C67, C66A, C68, C60A, C69, C62A, C70, C70A, C71, C72A, C72
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C67A)=Sof(H67A)=Sof(C69A)=Sof(H69D)=Sof(H69E)=Sof(H69F)=Sof(C68A)=
 Sof(H68D)=Sof(H68E)=Sof(H68F)=Sof(C64A)=Sof(H64A)=Sof(C65A)=Sof(H65D)=
 Sof(H65E)=Sof(H65F)=Sof(C66A)=Sof(H66D)=Sof(H66E)=Sof(H66F)=Sof(C59A)=
 Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(C62A)=Sof(H62A)=Sof(C63A)=Sof(C70A)=
 Sof(H70A)=Sof(C71A)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C72A)=Sof(H72D)=
 Sof(H72E)=Sof(H72F)=Sof(C58A)=1-FVAR(1)
 Sof(C58)=Sof(C59)=Sof(C60)=Sof(H60)=Sof(C61)=Sof(C62)=Sof(H62)=Sof(C63)=
 Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C66)=Sof(H66A)=
 Sof(H66B)=Sof(H66C)=Sof(C67)=Sof(H67)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=
 Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70)=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:
 C9(H9), C11(H11), C13(H13), C16(H16), C19(H19), C28(H28), C31(H31), C34(H34),
 C49(H49), C52(H52), C55(H55), C64(H64), C67(H67), C70(H70), C67A(H67A),
 C64A(H64A), C70A(H70A)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C24(H24), C26(H26), C39(H39), C40(H40), C41(H41),
 C45(H45), C47(H47), C60(H60), C62(H62), C60A(H60A), C62A(H62A)
6.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C32(H32A,H32B,H32C), 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), C69A(H69D,H69E,H69F), C68A(H68D,H68E,
 H68F), C65A(H65D,H65E,H65F), C66A(H66D,H66E,H66F), C71A(H71D,H71E,H71F),
 C72A(H72D,H72E,H72F)
;
_shelx_res_checksum              83866
_shelx_hkl_checksum              75855
_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 1.218
_oxdiff_exptl_absorpt_empirical_full_min 0.782