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_7716635
_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         'C90 H114 N6 Sm3, 5(C3 H3)'
_chemical_formula_sum            'C105 H129 N6 Sm3'
_chemical_formula_weight         1926.18
_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   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                 93.570(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.9712(5)
_cell_length_b                   17.2882(3)
_cell_length_c                   17.9740(3)
_cell_measurement_reflns_used    76242
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      36.1270
_cell_measurement_theta_min      1.8050
_cell_volume                     9295.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 42.94a 64-bit (release 21-06-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000HE'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.973
_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    -71.00 -17.00   0.50   15.00    --  -20.84 135.00  74.00  108
  2  \w    -71.00 -17.00   0.50   15.00    --  -20.84 135.00-105.00  108
  3  \w     23.00  74.00   0.50   15.00    --   23.65-135.00   8.00  102
  4  \w     23.00  74.00   0.50   15.00    --   23.65-135.00-170.00  102
  5  \w    -17.00  54.00   0.50   15.00    --  -20.84  38.00 -30.00  142
  6  \w    -56.00  -9.00   0.50   15.00    --  -20.84 -57.00  30.00   94
  7  \w    -17.00  54.00   0.50   15.00    --  -20.84  38.00  30.00  142
  8  \w    -56.00  -9.00   0.50   15.00    --  -20.84 -57.00-150.00   94
  9  \w    -56.00  -9.00   0.50   15.00    --  -20.84 -57.00-180.00   94
 10  \w     21.00  57.00   0.50   15.00    --  -20.84  19.00-180.00   72
 11  \w    -30.00  -4.00   0.50   15.00    --  -20.84 -70.00-171.47   52
 12  \w    -54.00 -17.00   0.50   15.00    --   23.65 -19.00-120.00   74
 13  \w    -54.00 -17.00   0.50   15.00    --   23.65 -19.00 150.00   74
 14  \w    -54.00 -17.00   0.50   15.00    --   23.65 -19.00 120.00   74
 15  \w      7.00  36.00   0.50   15.00    --   23.65  70.00-174.00   58
 16  \w      6.00  34.00   0.50   15.00    --   23.65  72.00  12.60   56
 17  \w      6.00  34.00   0.50   15.00    --   23.65  72.00-124.45   56
 18  \w    -54.00 -17.00   0.50   15.00    --   23.65 -19.00  90.00   74
 19  \w      8.00  39.00   0.50   15.00    --   23.65  69.00  77.54   62
 20  \w      8.00  41.00   0.50   15.00    --   23.65  68.00  70.45   66
 21  \w    -54.00 -17.00   0.50   15.00    --   23.65 -19.00-150.00   74
 22  \w    -72.00 -18.00   0.50   15.00    --  -20.84 136.00 125.00  108
 23  \w    -40.00  24.00   0.50   15.00    --  -20.84  77.00-180.00  128
 24  \w    -35.00  -5.00   0.50   15.00    --  -20.84 -68.00  62.76   60
 25  \w    -40.00  24.00   0.50   15.00    --  -20.84  77.00-150.00  128
 26  \w    -56.00  -9.00   0.50   15.00    --  -20.84 -57.00-120.00   94
 27  \w    -40.00  24.00   0.50   15.00    --  -20.84  77.00  60.00  128
 28  \w    -73.00 -19.00   0.50   15.00    --  -20.84 138.00 -34.21  108
 29  \w    -48.00  11.00   0.50   15.00    --  -20.84  92.00-112.62  118
 30  \w    -74.00 -20.00   0.50   15.00    --  -20.84 139.00 145.72  108
 31  \w    -56.00  -9.00   0.50   15.00    --  -20.84 -57.00 150.00   94
 32  \w    -48.00  11.00   0.50   15.00    --  -20.84  92.00  33.71  118
 33  \w    -56.00  -9.00   0.50   15.00    --  -20.84 -57.00 -30.00   94
 34  \w    -72.00 -18.00   0.50   15.00    --  -20.84 136.00 -64.38  108
 35  \w    -99.00 -17.00   0.50   15.00    --  -20.84 -19.00-150.00  164
 36  \w      8.00  41.00   0.50   15.00    --   23.65  68.00 136.74   66
 37  \w     21.00 102.00   0.50   15.00    --   23.65  19.00-180.00  162
 38  \w     18.00  99.00   0.50   15.00    --   23.65  38.00   0.00  162
 39  \w    -74.00 -20.00   0.50   15.00    --  -20.84 139.00-167.89  108
 40  \w    -74.00 -20.00   0.50   15.00    --  -20.84 139.00  34.96  108
 41  \w    -74.00 -20.00   0.50   15.00    --  -20.84 139.00  80.76  108
 42  \w    -72.00 -18.00   0.50   15.00    --  -20.84 136.00 -85.40  108
 43  \w    -72.00 -18.00   0.50   15.00    --  -20.84 136.00-121.09  108
 44  \w    -56.00  -9.00   0.50   15.00    --  -20.84 -57.00 120.00   94
 45  \w    -74.00 -41.00   0.50   15.00    --  -20.84 139.00  -6.24   66
 46  \w     18.00  99.00   0.50   15.00    --   23.65  38.00 150.00  162
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, UG2 \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ diffractometer with Arc)Sec VHF Varimax confocal mirrors, a UG2 goniometer and HyPix 6000HE detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       49
_diffrn_reflns_limit_h_min       -49
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            105765
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         36.157
_diffrn_reflns_theta_min         1.745
_exptl_absorpt_coefficient_mu    1.920
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.688
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.119a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.376
_exptl_crystal_description       block
_exptl_crystal_F_000             3948
_exptl_crystal_recrystallization_method 'The material was used as supplied'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.052
_exptl_crystal_size_min          0.04
_refine_diff_density_max         8.779
_refine_diff_density_min         -2.804
_refine_diff_density_rms         0.210
_refine_ls_abs_structure_details
;
 Flack x determined using 19454 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.131(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1062
_refine_ls_number_reflns         105765
_refine_ls_number_restraints     1452
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0686
_refine_ls_R_factor_gt           0.0661
_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^)+(0.0670P)^2^+147.7366P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1640
_refine_ls_wR_factor_ref         0.1666
_reflns_Friedel_coverage         0.924
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.948
_reflns_number_gt                102831
_reflns_number_total             105765
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 60.0250\% 
around [-0.10 -0.00 1.00] (reciprocal) or [0.00 -0.00 1.00] (direct)
;
_cod_data_source_file            d4dt01835d2.cif
_cod_data_source_block           2sm_2_5c6h6
_cod_depositor_comments
'Adding full bibliography for 7716633--7716636.cif.'
_cod_database_code               7716635
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.635
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.4919(9)
 0.5081(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C98-C97 = C98-C102 = C101-C102 = C100-C101 = C100-C99 = C99-C97 = C96-C91 =
 C96-C95 = C94-C95 = C94-C93 = C93-C92 = C91-C92 = C105-C104 = C104-C103
 1.4 with sigma of 0.01
 C100-C101 \\sim C101-C102 \\sim C98-C102 \\sim C98-C97 \\sim C99-C97 \\sim
C100-C99
 with sigma of 0.02
4. Rigid body (RIGU) restrains
 C61, Sm3, N6, N5, C52, C41, C42, C45, C55, C43, C51, C54, C53, C44, C65, C84,
 C66, C68, C57, C46, C47, C50, C60, C48, C56, C59, C58, C49, C64, C83, C86, C67,
  C70, H57A, H57B, H57C, H46A, H46B, H46C, H47A, H47B, H47C, H50A, H50B, H50C,
 H60A, H60B, H60C, H48A, H48B, H48C, H56A, H56B, H56C, H59A, H59B, H59C, H58A,
 H58B, H58C, H49A, H49B, H49C, N1, C63, C85, H86, C87, C62, N4, C69, H70, C72,
 Sm1, N2, H85, C88, C89, N3, Sm2, H69, C71, C74, C3, C12, C14, C11, C2, C5, C1,
 C4, C15, C13, C76, C90, H89A, H89B, H89C, C75, C34, C25, C32, C23, C35, C21,
 C22, C33, C24, C31, C73, H74A, H74B, H74C, C8, C19, C16, C7, C10, C6, C9, C20,
 C18, C77, H90A, H90B, H90C, C79, C39, C30, C37, C28, C40, C26, C27, C38, C29,
 C36, H73A, H73B, H73C, H8A, H8B, H8C, H19A, H19B, H19C, H16A, H16B, H16C, H7A,
 H7B, H7C, H10A, H10B, H10C, H6A, H6B, H6C, H9A, H9B, H9C, H20A, H20B, H20C,
 H18A, H18B, H18C, H77, C78, H79, C80, H39A, H39B, H39C, H30A, H30B, H30C, H37A,
  H37B, H37C, H28A, H28B, H28C, H40A, H40B, H40C, H26A, H26B, H26C, H27A, H27B,
 H27C, H38A, H38B, H38C, H29A, H29B, H29C, H36A, H36B, H36C, C82, C81, H82A,
 H82B, H82C, H81A, H81B, H81C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C64, Sm3, N6, N5, C41, C52, C42, C45, C55, C51, C43, C53, C54, C44, C65, C84,
 C66, C68, C46, C57, C47, C50, C60, C56, C48, C58, C59, C49, C83, C86, C61, C67,
  C70, N1, C63, C85, C87, C62, N4, C69, C72, Sm1, N2, C88, C89, N3, Sm2, C71,
 C74, C14, C12, C3, C11, C13, C1, C2, C4, C15, C5, C76, C90, C75, C34, C25, C35,
  C32, C21, C22, C23, C33, C31, C24, C73, C19, C17, C8, C16, C18, C6, C7, C9,
 C20, C10, C77, C79, C39, C30, C40, C37, C26, C27, C28, C38, C36, C29, C78, C80,
  C82, C81
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Me refined with riding coordinates:
 C18(H18A,H18B,H18C), C9(H9A,H9B,H9C)
5.b Aromatic/amide H refined with riding coordinates:
 C85(H85), C70(H70), C79(H79), C69(H69), C77(H77), C86(H86), C103(H103),
 C92(H92), C91(H91), C95(H95), C96(H96), C102(H102), C104(H104), C101(H101),
 C93(H93), C105(H105), C97(H97), C94(H94), C99(H99), C100(H100), C98(H98)
5.c Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C58(H58A,H58B,H58C), C29(H29A,H29B,H29C), C37(H37A,H37B,
 H37C), C48(H48A,H48B,H48C), C39(H39A,H39B,H39C), C57(H57A,H57B,H57C), C10(H10A,
 H10B,H10C), C30(H30A,H30B,H30C), C46(H46A,H46B,H46C), C26(H26A,H26B,H26C),
 C6(H6A,H6B,H6C), C28(H28A,H28B,H28C), C36(H36A,H36B,H36C), C81(H81A,H81B,H81C),
  C50(H50A,H50B,H50C), C56(H56A,H56B,H56C), C19(H19A,H19B,H19C), C74(H74A,H74B,
 H74C), C16(H16A,H16B,H16C), C59(H59A,H59B,H59C), C47(H47A,H47B,H47C), C82(H82A,
 H82B,H82C), C60(H60A,H60B,H60C), C73(H73A,H73B,H73C), C27(H27A,H27B,H27C),
 C20(H20A,H20B,H20C), C7(H7A,H7B,H7C), C49(H49A,H49B,H49C), C8(H8A,H8B,H8C),
 C89(H89A,H89B,H89C), C40(H40A,H40B,H40C), C90(H90A,H90B,H90C), C17(H17A,H17B,
 H17C)
;
_shelx_res_checksum              9721
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_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
;