Trends in benzene inverse sandwich complexes of the alkaline-earth metals Mg, Ca, Sr and Ba.
Jędrzkiewicz, Dawid; Morasch, Michael; Townrow, Oliver P. E.; Rösch, Bastian; Langer, Jens; Mathe, Zachary; Harder, Sjoerd; Chemical science 16 (2025) 17793–17802; doi:10.1039/d5sc05373k

data_1575572
_publ_section_title
;
 Trends in benzene inverse sandwich complexes of the alkaline-earth metals
 Mg, Ca, Sr and Ba.
;
_journal_issue                   38
_journal_name_full               'Chemical science'
_journal_page_first              17793
_journal_page_last               17802
_journal_paper_doi               10.1039/d5sc05373k
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C86 H116 Ba2 N4, 3(C6 H6)'
_chemical_formula_sum            'C104 H134 Ba2 N4'
_chemical_formula_weight         1714.82
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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     dual
_audit_creation_date             2025-03-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-03-28 deposited with the CCDC.	2025-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                78.9461(10)
_cell_angle_beta                 85.4731(10)
_cell_angle_gamma                79.5197(11)
_cell_formula_units_Z            3
_cell_length_a                   9.64881(13)
_cell_length_b                   26.2579(3)
_cell_length_c                   27.1109(3)
_cell_measurement_reflns_used    52269
_cell_measurement_temperature    99.97(13)
_cell_measurement_theta_max      29.0880
_cell_measurement_theta_min      1.9450
_cell_volume                     6621.94(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -42.00  21.00   0.75   23.00    --  -14.06 -77.00 120.00   84
  2  \w    -42.00  21.00   0.75   23.00    --  -14.06 -77.00 -30.00   84
  3  \w    -16.00  95.00   0.75   23.00    --   15.31  38.00-180.00  148
  4  \w    -42.00  51.00   0.75   23.00    --   15.31 -77.00 -60.00  124
  5  \w    -42.00  99.00   0.75   23.00    --   15.31  19.00 -60.00  188
  6  \w    -16.00  95.00   0.75   23.00    --   15.31  38.00 -30.00  148
  7  \w     39.00 108.00   0.75   23.00    --   15.31 178.00 120.00   92
  8  \w    -17.00  18.25   0.75   23.00    --   15.31  57.00  60.00   47
  9  \w    -15.00  57.00   0.75   23.00    --   15.31 -99.00-150.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0395735000
_diffrn_orient_matrix_UB_12      -0.0204514000
_diffrn_orient_matrix_UB_13      0.0089577000
_diffrn_orient_matrix_UB_21      -0.0449568000
_diffrn_orient_matrix_UB_22      0.0165334000
_diffrn_orient_matrix_UB_23      0.0145799000
_diffrn_orient_matrix_UB_31      -0.0448706000
_diffrn_orient_matrix_UB_32      0.0094124000
_diffrn_orient_matrix_UB_33      -0.0204766000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0443
_diffrn_reflns_av_unetI/netI     0.0428
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            108756
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         1.532
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.936
_exptl_absorpt_correction_T_max  0.933
_exptl_absorpt_correction_T_min  0.785
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear bluish black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       plate
_exptl_crystal_F_000             2694
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.248
_exptl_crystal_size_min          0.093
_refine_diff_density_max         1.724
_refine_diff_density_min         -0.694
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1677
_refine_ls_number_reflns         26072
_refine_ls_number_restraints     210
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0477
_refine_ls_R_factor_gt           0.0358
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0261P)^2^+4.6196P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0721
_refine_ls_wR_factor_ref         0.0770
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22066
_reflns_number_total             26072
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05373k2.cif
_cod_data_source_block           hasj240412b
_cod_depositor_comments
'Adding full bibliography for 1575569--1575577.cif.'
_cod_original_cell_volume        6621.95(14)
_cod_database_code               1575572
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C104 H134 Ba2 N4'
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.773
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.97
_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. Uiso/Uaniso restraints and constraints
C151 \\sim C152 \\sim C153 \\sim C154 \\sim C155 \\sim C156 \\sim C157 \\sim
C158 \\sim C159 \\sim C160 \\sim C161 \\sim C162: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 2A
C70 \\sim C70A \\sim C71A \\sim C71: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
C69 \\sim C69A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
3. Same fragment restrains
{C151, C152, C153, C154, C155, C156} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C157, C158, C159, C160, C161, C162}
4. Others
 Sof(C69A)=Sof(H69A)=Sof(C70A)=Sof(H70D)=Sof(H70E)=Sof(H70F)=Sof(C71A)=
 Sof(H71D)=Sof(H71E)=Sof(H71F)=1-FVAR(1)
 Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C71)=Sof(H71A)=
 Sof(H71B)=Sof(H71C)=FVAR(1)
 Sof(C157)=Sof(H157)=Sof(C158)=Sof(H158)=Sof(C159)=Sof(H159)=Sof(C160)=
 Sof(H160)=Sof(C161)=Sof(H161)=Sof(C162)=Sof(H162)=1-FVAR(2)
 Sof(C151)=Sof(H151)=Sof(C152)=Sof(H152)=Sof(C153)=Sof(H153)=Sof(C154)=
 Sof(H154)=Sof(C155)=Sof(H155)=Sof(C156)=Sof(H156)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C34(H34), C37(H37), C46(H46), C49(H49), C69(H69), C69A(H69A), C72(H72),
 C81(H81), C84(H84), C87(H87), C112(H112), C115(H115), C124(H124), C127(H127)
5.b Aromatic/amide H refined with riding coordinates:
 C30(H30), C31(H31), C32(H32), C42(H42), C43(H43), C44(H44), C65(H65),
 C66(H66), C67(H67), C77(H77), C78(H78), C79(H79), C92(H92), C108(H108),
 C109(H109), C110(H110), C120(H120), C121(H121), C122(H122), C130(H130),
 C131(H131), C132(H132), C139(H139), C140(H140), C141(H141), C142(H142),
 C143(H143), C144(H144), C145(H145), C146(H146), C147(H147), C148(H148),
 C149(H149), C150(H150), C133(H133), C134(H134), C135(H135), C136(H136),
 C137(H137), C138(H138), C151(H151), C152(H152), C153(H153), C154(H154),
 C155(H155), C156(H156), C157(H157), C158(H158), C159(H159), C160(H160),
 C161(H161), C162(H162)
5.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C47(H47A,H47B,H47C),
 C48(H48A,H48B,H48C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C56(H56A,H56B,
 H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C60(H60A,H60B,H60C), C61(H61A,
 H61B,H61C), C62(H62A,H62B,H62C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C),
 C70A(H70D,H70E,H70F), C71A(H71D,H71E,H71F), C73(H73A,H73B,H73C), C74(H74A,H74B,
 H74C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C85(H85A,H85B,H85C), C86(H86A,
 H86B,H86C), C99(H99A,H99B,H99C), C100(H10A,H10B,H10C), C101(H10D,H10E,H10F),
 C103(H10G,H10H,H10I), C104(H10J,H10K,H10L), C105(H10M,H10N,H10O), C113(H11A,
 H11B,H11C), C114(H11D,H11E,H11F), C116(H11G,H11H,H11I), C117(H11J,H11K,H11L),
 C125(H12A,H12B,H12C), C126(H12D,H12E,H12F), C128(H12G,H12H,H12I), C129(H12J,
 H12K,H12L)
;
_shelx_res_checksum              55501
_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 1.477
_oxdiff_exptl_absorpt_empirical_full_min 0.664