Reduction of 1,3,5,7-Cyclooctatetraene by a Molecular Calcium Hydride: An Even Electron Polarised Insertion/Deprotonation Mechanism
Hill, Michael; Mahon, Mary F.; Wilson, Andrew; Laurent, Maron; Dinoi, Chiara; Richards, Emma; Chemical Communications  (2019) –; doi:10.1039/C9CC02418B

data_7123310
_publ_section_title
;
 Reduction of 1,3,5,7-Cyclooctatetraene by a Molecular Calcium Hydride: An
 Even Electron Polarised Insertion/Deprotonation Mechanism
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC02418B
_journal_year                    2019
_chemical_formula_moiety         'C66 H90 Ca2 N4'
_chemical_formula_sum            'C66 H90 Ca2 N4'
_chemical_formula_weight         1019.57
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-04-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.18 svn.r3501 for OlexSys, GUI svn.r5488)
;
_audit_update_record
;
2019-03-27 deposited with the CCDC.    2019-04-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.412(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.7014(4)
_cell_length_b                   10.3339(3)
_cell_length_c                   19.8975(5)
_cell_measurement_reflns_used    19723
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      72.9120
_cell_measurement_theta_min      3.5920
_cell_volume                     3020.21(14)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0617
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            37686
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.327
_diffrn_reflns_theta_min         3.665
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.939
_exptl_absorpt_correction_T_max  0.954
_exptl_absorpt_correction_T_min  0.884
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.121
_exptl_crystal_description       block
_exptl_crystal_F_000             1108
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.134
_refine_diff_density_max         0.328
_refine_diff_density_min         -0.200
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         6031
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0423
_refine_ls_R_factor_gt           0.0401
_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^)+(0.0587P)^2^+0.6582P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1042
_refine_ls_wR_factor_ref         0.1068
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5651
_reflns_number_total             6031
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc02418b2.cif
_cod_data_source_block           s18msh24
_cod_database_code               7123310
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_usercomment     'colourless block'
_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.a Ternary CH refined with riding coordinates:
 C8(H8), C15(H15), C27(H27), C20(H20)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C13(H13), C12(H12), C25(H25), C11(H11), C23(H23), C24(H24)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C5(H5A,H5B,H5C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C),
 C17(H17A,H17B,H17C), C22(H22A,H22B,H22C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C16(H16A,H16B,H16C), C21(H21A,H21B,H21C)
;
_olex2_submission_special_instructions 'No special instructions were received'