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_1575573
_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 H138 Ca2 I2 N4, C6 H6'
_chemical_formula_sum            'C92 H144 Ca2 I2 N4'
_chemical_formula_weight         1640.06
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-13
_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            4
_cell_length_a                   21.0407(3)
_cell_length_b                   20.0279(2)
_cell_length_c                   20.3948(2)
_cell_measurement_reflns_used    19873
_cell_measurement_temperature    99.9(4)
_cell_measurement_theta_max      72.7360
_cell_measurement_theta_min      4.1600
_cell_volume                     8594.39(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_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    -70.00  32.00   1.00    4.00    --  -41.44  57.00  90.00  102
  2  \w     27.00  97.00   1.00    4.00    --   41.44-125.00 -90.00   70
  3  \w     75.00 177.00   1.00   16.00    --  104.37  61.00  60.00  102
  4  \w    103.00 178.00   1.00   16.00    --  104.37  77.00  90.00   75
  5  \w     22.00 106.00   1.00   16.00    --  104.37 -94.00 120.00   84
  6  \w    103.00 178.00   1.00   16.00    --  104.37  77.00 -60.00   75
  7  \w   -114.00 -13.00   1.00    4.00    --  -41.44 -57.00 150.00  101
  8  \w   -114.00 -13.00   1.00    4.00    --  -41.44 -57.00 -30.00  101
;
_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      0.0532203000
_diffrn_orient_matrix_UB_12      -0.0320143000
_diffrn_orient_matrix_UB_13      -0.0413299000
_diffrn_orient_matrix_UB_21      0.0486770000
_diffrn_orient_matrix_UB_22      0.0480878000
_diffrn_orient_matrix_UB_23      0.0307963000
_diffrn_orient_matrix_UB_31      0.0125916000
_diffrn_orient_matrix_UB_32      -0.0507389000
_diffrn_orient_matrix_UB_33      0.0552701000
_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  0.0386
_diffrn_reflns_av_unetI/netI     0.0264
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            33862
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.814
_diffrn_reflns_theta_min         3.739
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.124
_exptl_absorpt_correction_T_max  0.739
_exptl_absorpt_correction_T_min  0.453
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       block
_exptl_crystal_F_000             3480
_exptl_crystal_size_max          0.196
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.098
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.515
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     577
_refine_ls_number_reflns         8374
_refine_ls_number_restraints     685
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0302
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0274P)^2^+6.4229P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0702
_refine_ls_wR_factor_ref         0.0717
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7859
_reflns_number_total             8374
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05373k2.cif
_cod_data_source_block           hasj200228a
_cod_depositor_comments
'Adding full bibliography for 1575569--1575577.cif.'
_cod_original_cell_volume        8594.39(18)
_cod_database_code               1575573
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C92H144Ca2I2N4
_shelx_estimated_absorpt_t_max   0.542
_shelx_estimated_absorpt_t_min   0.336
_diffrn_oxdiff_digest_hkl
;
015cd1732b17a2e328bcbfb17387e144090f9b
;
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 C42A-C43A \\sim C43-C42 \\sim C40-C41 \\sim C40A-C41A
 with sigma of 0.02
 C39A-C42A \\sim C42-C39 \\sim C40A-C39A \\sim C40-C39
 with sigma of 0.02
 C28-C33 \\sim C28-C33A
 with sigma of 0.02
 C33-C39 \\sim C33A-C39A \\sim C34-C29A \\sim C34-C29
 with sigma of 0.02
 C31-C32A \\sim C31-C32
 with sigma of 0.02
 C32-C33 \\sim C32A-C33A
 with sigma of 0.02
 C30-C29 \\sim C30A-C29A
 with sigma of 0.02
 C31-C30 \\sim C31A-C30A
 with sigma of 0.02
 C33A-C29A \\sim C29-C33
 with sigma of 0.02
 C31-C28 \\sim C28-C31A
 with sigma of 0.02
 C32-C28 \\sim C28-C32A \\sim C30-C28 \\sim C28-C30A
 with sigma of 0.02
 C32A-C29A \\sim C29-C32 \\sim C33-C30 \\sim C33A-C30A
 with sigma of 0.02
3. Restrained planarity
 C39A, C33A, C32A, C31A, C30A, C29A, C28, C34
 with sigma of 0.07
 C39, C33, C28, C29, C30, C31, C32, C34
 with sigma of 0.07
4. Uiso/Uaniso restraints and constraints
C29 \\sim C28 \\sim C33A \\sim C39A \\sim C39 \\sim C33 \\sim C32A \\sim C32
\\sim C31A \\sim C31 \\sim C30A \\sim C30 \\sim C29A \\sim C34: within 4A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
C33A \\sim C32A \\sim C31A \\sim C31 \\sim C32 \\sim C33: within 3A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 3A
5. Rigid body (RIGU) restrains
 C44, C45, C46, C47, C48, C49
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C28, C33A, C39A, C39, C33, C32A, C32, C31A, C31, C30A, C30, C29, C34, C29A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H34a)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40a)=
 Sof(H40b)=Sof(C41)=Sof(H41a)=Sof(H41b)=Sof(H41c)=Sof(C42)=Sof(H42a)=Sof(H42b)=
 Sof(C43)=Sof(H43a)=Sof(H43b)=Sof(H43c)=Sof(C31A)=Sof(H31A)=Sof(C30A)=Sof(H30A)=
 Sof(C29A)=1-FVAR(1)
 Sof(C29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(H34)=Sof(C32A)=Sof(H32A)=
 Sof(C33A)=Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40c)=Sof(H40d)=Sof(C41A)=
 Sof(H41d)=Sof(H41e)=Sof(H41f)=Sof(C42A)=Sof(H42c)=Sof(H42d)=Sof(C43A)=
 Sof(H43d)=Sof(H43e)=Sof(H43f)=FVAR(1)
 Fixed Sof: C48(0.5) H48(0.5) C49(0.5) H49(0.5) C44(0.5) H44(0.5) C45(0.5)
 H45(0.5) C46(0.5) H46(0.5) C47(0.5) H47(0.5)
7.a Ternary CH refined with riding coordinates:
 C18(H18), C23(H23), C34(H34), C34(H34a), C39(H39), C39A(H39A)
7.b Secondary CH2 refined with riding coordinates:
 C19(H19a,H19b), C21(H21a,H21b), C24(H24a,H24b), C26(H26a,H26b), C35(H35a,
 H35b), C37(H37a,H37b), C40(H40a,H40b), C42(H42a,H42b), C40A(H40c,H40d),
 C42A(H42c,H42d)
7.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C30(H30), C31(H31), C32(H32), C32A(H32A),
 C48(H48), C49(H49), C44(H44), C45(H45), C46(H46), C47(H47), C31A(H31A),
 C30A(H30A)
7.d Fitted hexagon refined as free rotating group:
 C48(C49,C44,C45,C46,C47)
7.e Idealised Me refined as rotating group:
 C5(H5a,H5b,H5c), C6(H6a,H6b,H6c), C7(H7a,H7b,H7c), C9(H9a,H9b,H9c), C10(H10a,
 H10b,H10c), C11(H11a,H11b,H11c), C20(H20a,H20b,H20c), C22(H22a,H22b,H22c),
 C25(H25a,H25b,H25c), C27(H27a,H27b,H27c), C36(H36a,H36b,H36c), C38(H38a,H38b,
 H38c), C41(H41a,H41b,H41c), C43(H43a,H43b,H43c), C41A(H41d,H41e,H41f),
 C43A(H43d,H43e,H43f)
;
_shelx_res_checksum              82932
_olex2_date_sample_data_collection 2020-02-28
_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 1.334
_oxdiff_exptl_absorpt_empirical_full_min 0.827