Reduction of hexaazatrinaphthylenes by divalent lanthanocenes leads to ligand-based multiconfigurational properties.
Temple, Siobhan R.; Tang, Jinkui; Tizzard, Graham J.; Mansikkamäki, Akseli; Layfield, Richard A.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 12460–12464; doi:10.1039/d4dt01835d

data_7716634
_publ_section_title
;
 Reduction of hexaazatrinaphthylenes by divalent lanthanocenes leads to
 ligand-based multiconfigurational properties.
;
_journal_issue                   30
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              12460
_journal_page_last               12464
_journal_paper_doi               10.1039/d4dt01835d
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C84 H102 N6 Sm3, C7 H8'
_chemical_formula_sum            'C91 H110 N6 Sm3'
_chemical_formula_weight         1738.89
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-05-01
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-05-01 deposited with the CCDC.	2024-07-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9992(2)
_cell_length_b                   23.8500(2)
_cell_length_c                   18.1211(2)
_cell_measurement_reflns_used    19334
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      66.6300
_cell_measurement_theta_min      3.4540
_cell_volume                     7779.04(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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    -81.00 -54.00   1.00    1.50    --    0.00  52.00 -49.00   27
  2  \w   -116.00 -85.00   1.00    6.00    --  -87.00  52.00 -49.00   31
  3  \w   -154.00-127.00   1.00    6.00    --  -87.00  52.00 -49.00   27
  4  \w    -44.00  16.00   1.00    1.50    --    0.00   0.00-180.00   60
  5  \w    -19.00   6.00   1.00    6.00    --    5.00  52.00 -49.00   25
  6  \w    -95.00 -41.00   1.00    6.00    --  -87.00  30.00  60.00   54
  7  \w    -68.00   1.00   1.00    6.00    --  -87.00  59.00  45.95   69
  8  \w   -117.00 -90.00   1.00    6.00    --  -87.00  30.00 -90.00   27
  9  \w    -77.00 -18.00   1.00    6.00    --  -87.00  30.00 -90.00   59
 10  \w   -175.00   1.00   1.00    6.00    --  -87.00  56.00 113.10  176
 11  \w   -172.00-100.00   1.00    6.00    --  -87.00  59.00  45.95   72
 12  \w   -170.00 -83.00   1.00    6.00    --  -87.00  40.00 -60.00   87
 13  \w    -26.00   1.00   1.00    6.00    --  -87.00  40.00 -60.00   27
 14  \w    -65.00 -25.00   1.00    6.00    --  -87.00  40.00-120.00   40
 15  \w   -164.00-116.00   1.00    6.00    --  -87.00  30.00  60.00   48
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0584
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            48843
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.162
_diffrn_reflns_theta_max         67.162
_diffrn_reflns_theta_min         3.461
_exptl_absorpt_coefficient_mu    17.138
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30648
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.485
_exptl_crystal_description       block
_exptl_crystal_F_000             3536
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.864
_refine_diff_density_min         -1.076
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     496
_refine_ls_number_reflns         7082
_refine_ls_number_restraints     217
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0546
_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^)+(0.1054P)^2^+7.4330P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1501
_refine_ls_wR_factor_ref         0.1569
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6337
_reflns_number_total             7082
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01835d2.cif
_cod_data_source_block           1sm_c7h8
_cod_depositor_comments
'Adding full bibliography for 7716633--7716636.cif.'
_cod_database_code               7716634
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.726
_shelx_estimated_absorpt_t_min   0.627
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1A-C1B \\sim C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1A
 with sigma of 0.02
 C1A-C1C \\sim C1B-C1D \\sim C1C-C1E \\sim C1E-C1B \\sim C1A-C1D
 with sigma of 0.04
 C1A-C1J \\sim C1B-C1I \\sim C1C-C1H \\sim C1D-C1G \\sim C1E-C1F
 with sigma of 0.02
 C1J-C1B \\sim C1J-C1E \\sim C1I-C1A \\sim C1I-C1C \\sim C1H-C1B \\sim C1H-C1D
\\sim C1G-C1C \\sim C1G-C1E
 \\sim C1F-C1D \\sim C1F-C1A
 with sigma of 0.04
3. Restrained planarity
 C1A, C1B, C1C, C1D, C1E, C1F, C1G, C1H, C1I, C1J
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F \\sim C1G \\sim C1H \\sim
C1I \\sim C1J: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
5. Rigid body (RIGU) restrains
 C1A, C1B, C1C, C1D, C1E, C1F, C1G, C1H, C1I, C1J
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Fixed Sof: H26A(0.5) H26B(0.5) H26C(0.5) H52A(0.5) H52B(0.5) H52C(0.5)
 C1A(0.5) C1B(0.5) C1C(0.5) C1D(0.5) C1E(0.5) C1F(0.5) H1FA(0.5) H1FB(0.5)
 H1FC(0.5) C1G(0.5) H1GA(0.5) H1GB(0.5) H1GC(0.5) C1H(0.5) H1HA(0.5) H1HB(0.5)
 H1HC(0.5) C1I(0.5) H1IA(0.5) H1IB(0.5) H1IC(0.5) C1J(0.5) H1JA(0.5) H1JB(0.5)
 H1JC(0.5)
7.a Free rotating group:
 C1A(C1B,C1C,C1D,C1E,C1F,C1G,C1H,C1I,C1J)
7.b Me refined with everything fixed:
 C26(H26A,H26B,H26C), C52(H52A,H52B,H52C)
7.c Me refined with riding coordinates:
 C1I(H1IA,H1IB,H1IC), C1J(H1JA,H1JB,H1JC)
7.d Aromatic/amide H refined with riding coordinates:
 C47(H47), C44(H44), C46(H46), C37(H37), C45(H45), C36(H36), C50(H50),
 C48(H48), C49(H49)
7.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C24(H24A,H24B,H24C), C20(H20A,H20B,H20C), C7(H7A,H7B,
 H7C), C19(H19A,H19B,H19C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C17(H17A,H17B,
 H17C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C18(H18A,H18B,H18C), C16(H16A,H16B,
 H16C), C1F(H1FA,H1FB,H1FC), C1G(H1GA,H1GB,H1GC), C1H(H1HA,H1HB,H1HC)
;
_shelx_res_checksum              23770
_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
;