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_1572269
_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 I N2 Sc, 2(C7 H8)'
_chemical_formula_sum            'C86 H116 I N2 Sc'
_chemical_formula_weight         1349.66
_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                89.686(2)
_cell_angle_beta                 70.204(2)
_cell_angle_gamma                87.286(2)
_cell_formula_units_Z            2
_cell_length_a                   13.7201(3)
_cell_length_b                   15.2477(4)
_cell_length_c                   19.1530(4)
_cell_measurement_reflns_used    14385
_cell_measurement_temperature    100.01(13)
_cell_measurement_theta_max      75.2480
_cell_measurement_theta_min      2.8590
_cell_volume                     3765.56(16)
_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(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.954
_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    -62.00 -37.00   0.50    1.00    --  -44.09  57.00  90.00   50
  2  \w    -76.00  13.00   0.50    1.00    --  -44.09  57.00-120.00  178
  3  \w    -35.00  25.00   0.50    1.00    --  -44.09  57.00  90.00  120
  4  \w    -61.00  20.00   0.50    1.00    --  -44.09  76.00   0.00  162
  5  \w    -61.00  25.00   0.50    1.00    --  -44.09  57.00 150.00  172
  6  \w    -84.00  14.00   0.50    1.00    --  -46.31  76.00 -60.00  196
  7  \w   -180.00 -47.00   0.50    2.00    -- -107.20   0.00  90.00  266
  8  \w   -129.00 -79.00   0.50    2.00    -- -107.20  76.00  90.00  100
  9  \w    -68.00 -18.00   0.50    2.00    -- -107.20  76.00   0.00  100
 10  \w   -172.00-112.00   0.50    2.00    -- -107.20 -38.00 150.00  120
 11  \w   -100.00 -23.00   0.50    2.00    -- -107.20  76.00 -30.00  154
 12  \w   -147.00 -22.00   0.50    2.00    -- -107.20  38.00   0.00  250
 13  \w   -109.00 -83.00   0.50    2.00    -- -107.20  76.00 -60.00   52
 14  \w    -49.00 -23.00   0.50    2.00    -- -107.20  76.00 -60.00   52
 15  \w   -122.00 -42.00   0.50    2.00    -- -107.20  76.00-120.00  160
 16  \w   -148.00 -19.00   0.50    2.00    -- -107.20  76.00-150.00  258
 17  \w   -148.00 -40.00   0.50    2.00    -- -107.20  76.00  30.00  216
 18  \w    -74.00 -43.00   0.50    2.00    -- -107.20  76.00 150.00   62
 19  \w   -150.00 -85.00   0.50    2.00    -- -107.20 -38.00  30.00  130
 20  \w   -139.00 -93.00   0.50    2.00    -- -107.20  76.00 150.00   92
 21  \w   -139.00 -27.00   0.50    2.00    -- -107.20  76.00-180.00  224
 22  \w    -97.00 -72.00   0.50    2.00    -- -107.20 -38.00 150.00   50
 23  \w   -147.00 -74.00   0.50    2.00    -- -107.20  76.00   0.00  146
 24  \w   -181.00 -32.00   0.50    2.00    -- -107.20 -19.00  30.00  298
;
_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      0.0876149000
_diffrn_orient_matrix_UB_12      0.0333583000
_diffrn_orient_matrix_UB_13      0.0245974000
_diffrn_orient_matrix_UB_21      -0.0313725000
_diffrn_orient_matrix_UB_22      0.0952090000
_diffrn_orient_matrix_UB_23      -0.0135682000
_diffrn_orient_matrix_UB_31      -0.0748559000
_diffrn_orient_matrix_UB_32      0.0068426000
_diffrn_orient_matrix_UB_33      0.0807294000
_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  0.0225
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            42340
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.086
_diffrn_reflns_theta_min         2.902
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    4.374
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73786
_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 yellowish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.190
_exptl_crystal_description       block
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.194
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.119
_refine_diff_density_max         0.524
_refine_diff_density_min         -1.405
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.143
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     894
_refine_ls_number_reflns         15011
_refine_ls_number_restraints     319
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.0328
_refine_ls_R_factor_gt           0.0319
_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^)+(0.0500P)^2^+1.5581P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0883
_refine_ls_wR_factor_ref         0.0889
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14405
_reflns_number_total             15011
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           rcapg37
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_database_code               1572269
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         Sc(NHC6H3(C6H2(C3H7)3)2)2I(C7H8)2
_shelx_estimated_absorpt_t_max   0.624
_shelx_estimated_absorpt_t_min   0.484
_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
 C86A-C80A
 1.54 with sigma of 0.02
 C85A-C80A \\sim C80A-C81A
 with sigma of 0.02
 N2-H2 \\sim N1-H1
 with sigma of 0.02
3. Restrained planarity
 C80A, C81A, C82A, C83A, C84A, C85A, C86A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C80A
\\sim C81A \\sim C82A \\sim C83A \\sim C84A \\sim C85A \\sim C86A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C80, C81, C82, C83, C84, C85, C86, C80A, C81A, C82A, C83A, C84A, C85A, C86A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C80A)=Sof(H80D)=Sof(H80E)=Sof(H80F)=Sof(C81A)=Sof(H81A)=Sof(C82A)=
 Sof(H82A)=Sof(C83A)=Sof(H83A)=Sof(C84A)=Sof(H84A)=Sof(C85A)=Sof(H85A)=
 Sof(C86A)=1-FVAR(1)
 Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(C81)=Sof(C82)=Sof(H82)=Sof(C83)=
 Sof(H83)=Sof(C84)=Sof(H84)=Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C19(H19), C28(H28), C31(H31), C34(H34), C49(H49),
 C52(H52), C55(H55), C64(H64), C67(H67), C70(H70)
7.b Me refined with riding coordinates:
 C80(H80A,H80B,H80C), C80A(H80D,H80E,H80F)
7.c 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), C75(H75), C76(H76),
  C77(H77), C78(H78), C79(H79), C82(H82), C83(H83), C84(H84), C85(H85),
 C86(H86), C81A(H81A), C82A(H82A), C83A(H83A), C84A(H84A), C85A(H85A)
7.d Fitted hexagon refined as free rotating group:
 C81A(C82A,C83A,C84A,C85A,C86A)
7.e 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), C73(H73A,H73B,H73C)
;
_shelx_res_checksum              64168
_shelx_hkl_checksum              84160
_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 1.589
_oxdiff_exptl_absorpt_empirical_full_min 0.726