<i>Ansa</i>-effects in alkaline earth metal octaphenylmetallocenophanes and a derived <i>ansa</i>-ferrocene.
Shephard, Angus C. G.; Bouammali, Amal; Delon, Aymeric; Guo, Zhifang; Chevreux, Sylviane; Niebel, Claude; Dautel, Olivier; Simler, Thomas; Deacon, Glen B.; Junk, Peter C.; Jaroschik, Florian; Dalton transactions (Cambridge, England : 2003) 54 (2025) 13918–13928; doi:10.1039/d5dt01881a

data_7719312
_publ_section_title
;
 <i>Ansa</i>-effects in alkaline earth metal octaphenylmetallocenophanes
 and a derived <i>ansa</i>-ferrocene.
;
_journal_issue                   37
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              13918
_journal_page_last               13928
_journal_paper_doi               10.1039/d5dt01881a
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C64 H52 Mg O, C7 H8, 0.2[C5H12]'
_chemical_formula_sum            'C72 H62.4 Mg O'
_chemical_formula_weight         967.93
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-06
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-06-16 deposited with the CCDC.	2025-08-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   45.8572(18)
_cell_length_b                   45.8572(18)
_cell_length_c                   13.3925(5)
_cell_measurement_reflns_used    17961
_cell_measurement_temperature    150
_cell_measurement_theta_max      26.70
_cell_measurement_theta_min      2.35
_cell_volume                     24389.8(16)
_computing_cell_refinement
;
X-Area Recipe 1.37.0.0 (STOE, 2021)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.175.0 (STOE, 2021)
;
_computing_data_reduction
;
X-Area Integrate 2.5.1.0 (STOE, 2021)
X-Area LANA 2.6.2.0 (STOE, 2021)
;
_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_temperature      150
_diffrn_detector                 'EIGER2 1M CDTE'
_diffrn_detector_area_resol_mean 13.33
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
 613 frames, detector distance = 60 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1258
_diffrn_reflns_av_unetI/netI     0.1498
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       54
_diffrn_reflns_limit_h_min       -53
_diffrn_reflns_limit_k_max       54
_diffrn_reflns_limit_k_min       -54
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            61003
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.026
_diffrn_reflns_theta_max         25.026
_diffrn_reflns_theta_min         2.350
_diffrn_source                   Axo_Mo
_diffrn_source_current           1.00
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_T_max  0.9836
_exptl_absorpt_correction_T_min  0.8895
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens in: F. R. Ahmed (Editor), "Crystallographic Computing", Munksgaard,
Copenhagen (1970), 255 - 270. Afterwards scaling of reflection intensities was
performed within STOE LANA. J. Koziskova, F. Hahn, J. Richter, J. Kozisek, Acta
Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Finally a spherical absorption correction was done within STOE LANA.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.186
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             9259
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.032
_exptl_crystal_size_rad          0.066
_refine_diff_density_max         0.242
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.978
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     659
_refine_ls_number_reflns         9553
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.978
_refine_ls_R_factor_all          0.1700
_refine_ls_R_factor_gt           0.0606
_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^)+(0.0481P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1269
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4501
_reflns_number_total             9553
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01881a2.cif
_cod_data_source_block           as223_2
_cod_depositor_comments
'Adding full bibliography for 7719312--7719315.cif.'
_cod_original_cell_volume        24390(2)
_cod_original_sg_symbol_H-M      'R -3'
_cod_original_formula_sum        'C72 H62.40 Mg O'
_cod_database_code               7719312
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.984
_olex2_refinement_description
;
1.a Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C31(H31A,H31B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,
 H63B), C64(H64A,H64B)
1.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25),
  C26(H26), C27(H27), C28(H28), C29(H29), C38(H38), C39(H39), C40(H40),
 C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C50(H50),
  C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58),
 C59(H59), C60(H60), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71)
1.c Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 147 electrons were 
found in a volume of 1647\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
0.2[C5H12] per Asymmetric Unit 
which account for 151 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              31959
_shelx_hkl_checksum              29275
_shelx_fab_checksum              19866
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '60.0 mm'
_stoe_detector_pixelsize_x       '0.075 mm'
_stoe_detector_pixelsize_y       '0.075 mm'
_stoe_detector_size_x            '8.0 cm'
_stoe_detector_size_y            '7.7 cm'
_stoe_evaluation_integration_a   10.1
_stoe_evaluation_integration_b   0.1
_stoe_evaluation_integration_ems 0.011
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 4
_stoe_evaluation_lana_bos_l_odd_max 1
_stoe_evaluation_lana_completeness 100.0
_stoe_evaluation_lana_dxs_max_order 3
_stoe_evaluation_lana_dys_max_order 3
_stoe_evaluation_lana_fs_max_order 3
_stoe_evaluation_lana_max_2theta_available 58.8
_stoe_evaluation_lana_max_2theta_desired 52.0
_stoe_evaluation_lana_mean_redundancy 6.2
_stoe_evaluation_lana_number_refls_after_or 66038
_stoe_evaluation_lana_number_refls_outliers 10710
_stoe_evaluation_lana_number_refls_total 76748
_stoe_evaluation_lana_number_refls_unique 10659
_stoe_evaluation_lana_number_refls_written 66038
_stoe_evaluation_lana_or_c1      0.035
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      0.7
_stoe_evaluation_lana_point_group -3
_stoe_evaluation_lana_table
;
2Theta           6.7   12.1   17.5   22.9   28.3   33.7   39.1   44.5   49.9
<Resolution>    5.37   3.32   2.33   1.76   1.45   1.23   1.06   0.94   0.85
N(total)         946   3249   4754   5423   8793  11584  13851  14713  13435
<Redundancy>    12.1   12.8    9.4    6.4    7.4    6.8    6.4    5.4    4.7
Complet. [%%]   100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0
<I/sigma>       37.9   30.7   13.2    8.2    3.7    2.5    1.5    0.6    0.3
R(int)         0.019  0.020  0.038  0.061  0.133  0.176  0.264  0.491  0.648
;
_stoe_measurement_identifier     AS223_2
_stoe_measurement_max_exposure_per_frame '300.0 s'
_stoe_measurement_mean_exposure_per_frame '300.0 s'
_stoe_measurement_min_exposure_per_frame '300.0 s'
_stoe_measurement_total_exposure_time '51.1 h'
_stoe_measurement_total_frame_number 613
_stoe_measurement_total_run_number 12
_stoe_measurement_tube_power     '50.0 W'