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_1575574
_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         'C47 H77 Ca I N2 O, C5 H12'
_chemical_formula_sum            'C52 H89 Ca I N2 O'
_chemical_formula_weight         925.23
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-10
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-03-28 deposited with the CCDC.	2025-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.1405(3)
_cell_length_b                   16.1273(3)
_cell_length_c                   37.6114(9)
_cell_measurement_reflns_used    16855
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      28.4280
_cell_measurement_theta_min      2.3620
_cell_volume                     10396.9(4)
_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)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5806
_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  22.00   1.00   47.50    --  -10.86 -77.00 150.00   64
  2  \w    -62.00  36.00   1.00   47.50    --   11.80 -38.00-120.00   98
  3  \w     37.00  62.00   1.00   47.50    --   11.80-178.00 120.00   25
;
_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      -0.0049734000
_diffrn_orient_matrix_UB_12      0.0423971000
_diffrn_orient_matrix_UB_13      0.0044788000
_diffrn_orient_matrix_UB_21      -0.0162127000
_diffrn_orient_matrix_UB_22      0.0076308000
_diffrn_orient_matrix_UB_23      -0.0170362000
_diffrn_orient_matrix_UB_31      -0.0377622000
_diffrn_orient_matrix_UB_32      -0.0088568000
_diffrn_orient_matrix_UB_33      0.0067194000
_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  0.0534
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            45714
_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         25.681
_diffrn_reflns_theta_min         2.044
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.750
_exptl_absorpt_correction_T_max  0.895
_exptl_absorpt_correction_T_min  0.838
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.182
_exptl_crystal_description       block
_exptl_crystal_F_000             3968
_exptl_crystal_size_max          0.323
_exptl_crystal_size_mid          0.258
_exptl_crystal_size_min          0.188
_refine_diff_density_max         0.674
_refine_diff_density_min         -1.249
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     624
_refine_ls_number_reflns         9860
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0644
_refine_ls_R_factor_gt           0.0475
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0505P)^2^+13.7240P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1129
_refine_ls_wR_factor_ref         0.1263
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7689
_reflns_number_total             9860
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05373k2.cif
_cod_data_source_block           hasj220505b
_cod_depositor_comments
'Adding full bibliography for 1575569--1575577.cif.'
_cod_database_code               1575574
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C52H89CaIN2O
_shelx_estimated_absorpt_t_max   0.872
_shelx_estimated_absorpt_t_min   0.794
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.63
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C34 \\sim C37A \\sim C38A: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
C21 \\sim C22 \\sim C19A \\sim C20A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
Uanis(C41A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(H20D)=
 Sof(H20E)=Sof(H20F)=Sof(C21A)=Sof(H21C)=Sof(H21D)=Sof(C22A)=Sof(H22D)=
 Sof(H22E)=Sof(H22F)=1-FVAR(1)
 Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 FVAR(1)
 Sof(C5A)=Sof(H5D)=Sof(H5E)=Sof(H5F)=Sof(C6A)=Sof(H6D)=Sof(H6E)=Sof(H6F)=
 Sof(C7A)=Sof(H7D)=Sof(H7E)=Sof(H7F)=1-FVAR(2)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=
 Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(2)
 Sof(H40C)=Sof(H40D)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=1-FVAR(3)
 Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(3)
4.a Ternary CH refined with riding coordinates:
 C18(H18), C18A(H18A), C23(H23), C34(H34), C39(H39)
4.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C21(H21A,H21B), C19A(H19C,H19D), C21A(H21C,H21D), C24(H24A,
 H24B), C26(H26A,H26B), C35(H35A,H35B), C37A(H37A,H37B), C40(H40A,H40B),
 C40(H40C,H40D), C42(H42A,H42B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B),
  C47(H47A,H47B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B)
4.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C30(H30), C31(H31), C32(H32)
4.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C5A(H5D,H5E,H5F), C6A(H6D,
 H6E,H6F), C7A(H7D,H7E,H7F), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,
 H11B,H11C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C20A(H20D,H20E,H20F),
 C22A(H22D,H22E,H22F), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C36(H36A,H36B,
 H36C), C38A(H38A,H38B,H38C), C41(H41A,H41B,H41C), C41A(H41D,H41E,H41F),
 C43(H43A,H43B,H43C), C48(H48A,H48B,H48C), C52(H52A,H52B,H52C)
;
_shelx_res_checksum              1634
_olex2_date_sample_data_collection 2022-05-05
_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 1.563
_oxdiff_exptl_absorpt_empirical_full_min 0.787