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_1575571
_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         '2(C92 H144 Ca2 N4), C5 H12'
_chemical_formula_sum            'C189 H300 Ca4 N8'
_chemical_formula_weight         2844.67
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-05
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-03-28 deposited with the CCDC.	2025-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.930(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.4360(14)
_cell_length_b                   22.839(2)
_cell_length_c                   30.727(3)
_cell_measurement_reflns_used    15844
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.6180
_cell_measurement_theta_min      3.4520
_cell_volume                     8643.8(15)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.965
_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    -41.00  29.00   1.00    4.00    --  -41.73  38.00-150.00   70
  2  \w    -66.00 -19.00   1.00    4.00    --  -41.73 125.00-180.00   47
  3  \w    -83.00  19.00   1.00    4.00    --  -41.73  19.00 150.00  102
  4  \w    108.00 173.00   1.00   16.00    --  104.33  77.00  60.00   65
  5  \w    101.00 157.00   1.00   16.00    --  104.33 125.00  90.00   56
  6  \w     22.00 101.00   1.00   16.00    --  104.33 -94.00  90.00   79
  7  \w    103.00 144.00   1.00   16.00    --  104.33  77.00-150.00   41
  8  \w     75.00 177.00   1.00   16.00    --  104.33  61.00 150.00  102
  9  \w    103.00 145.00   1.00   16.00    --  104.33  77.00  90.00   42
;
_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      -0.1221797000
_diffrn_orient_matrix_UB_12      -0.0121377000
_diffrn_orient_matrix_UB_13      -0.0009795000
_diffrn_orient_matrix_UB_21      -0.0266008000
_diffrn_orient_matrix_UB_22      0.0509269000
_diffrn_orient_matrix_UB_23      -0.0326001000
_diffrn_orient_matrix_UB_31      0.0029559000
_diffrn_orient_matrix_UB_32      -0.0425034000
_diffrn_orient_matrix_UB_33      -0.0387306000
_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  0.0185
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            32013
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.682
_diffrn_reflns_theta_min         2.904
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.476
_exptl_absorpt_correction_T_max  0.894
_exptl_absorpt_correction_T_min  0.792
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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 brownish black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.093
_exptl_crystal_description       block
_exptl_crystal_F_000             3140
_exptl_crystal_size_max          0.218
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.464
_refine_diff_density_min         -0.216
_refine_diff_density_rms         0.036
_refine_ls_extinction_coef       0.000099(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     991
_refine_ls_number_reflns         16601
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0330
_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^)+(0.0381P)^2^+2.8979P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0796
_refine_ls_wR_factor_ref         0.0833
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14558
_reflns_number_total             16601
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05373k2.cif
_cod_data_source_block           hasj220622a
_cod_depositor_comments
'Adding full bibliography for 1575569--1575577.cif.'
_cod_database_code               1575571
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N Ca '
_shelx_estimated_absorpt_t_max   0.866
_shelx_estimated_absorpt_t_min   0.739
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: C93(0.5) H93A(0.5) H93B(0.5) H93C(0.5) C94(0.5) H94A(0.5)
 H94B(0.5) C95(0.5) H95A(0.5) H95B(0.5) C96(0.5) H96A(0.5) H96B(0.5) C97(0.5)
 H97A(0.5) H97B(0.5) H97C(0.5)
3.a Ternary CH refined with riding coordinates:
 C24(H24), C29(H29), C40(H40), C45(H45), C67(H67), C72(H72), C83(H83), C88(H88)
3.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C27(H27A,H27B), C30(H30A,H30B), C32(H32A,H32B), C41(H41A,
 H41B), C43(H43A,H43B), C46(H46A,H46B), C48(H48A,H48B), C68(H68A,H68B),
 C70(H70A,H70B), C73(H73A,H73B), C75(H75A,H75B), C84(H84A,H84B), C86(H86A,H86B),
  C89(H89A,H89B), C91(H91A,H91B), C94(H94A,H94B), C95(H95A,H95B), C96(H96A,H96B)
3.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C22(H22), C36(H36), C37(H37), C38(H38), C63(H63),
 C64(H64), C65(H65), C79(H79), C80(H80), C81(H81)
3.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C26(H26A,H26B,H26C), C28(H28A,
 H28B,H28C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C42(H42A,H42B,H42C),
 C44(H44A,H44B,H44C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C54(H54A,H54B,
 H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C59(H59A,
 H59B,H59C), C60(H60A,H60B,H60C), C69(H69A,H69B,H69C), C71(H71A,H71B,H71C),
 C74(H74A,H74B,H74C), C76(H76A,H76B,H76C), C85(H85A,H85B,H85C), C87(H87A,H87B,
 H87C), C90(H90A,H90B,H90C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C97(H97A,
 H97B,H97C)
;
_shelx_res_checksum              39586
_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 1.400
_oxdiff_exptl_absorpt_empirical_full_min 0.600