Magnesium hydride alkene insertion and catalytic hydrosilylation
García, Lucía; Dinoi, Chiara; Mahon, Mary F.; Laurent, Maron; Hill, Michael; Chemical Science  (2019) –; doi:10.1039/C9SC02056J

data_1552120
_publ_section_title
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 Magnesium hydride alkene insertion and catalytic hydrosilylation&#x00A0;
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_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02056J
_journal_year                    2019
_chemical_formula_moiety         'C35 H52 Mg N2'
_chemical_formula_sum            'C35 H52 Mg N2'
_chemical_formula_weight         525.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
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_audit_update_record
;
2019-04-25 deposited with the CCDC.    2019-07-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.4030(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.0530(3)
_cell_length_b                   20.7671(2)
_cell_length_c                   17.0951(2)
_cell_measurement_reflns_used    12840
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.3050
_cell_measurement_theta_min      3.7710
_cell_volume                     6579.88(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, 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  0.0391
_diffrn_reflns_av_unetI/netI     0.0405
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            51062
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.476
_diffrn_reflns_theta_min         3.196
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.625
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92749
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.060
_exptl_crystal_description       block
_exptl_crystal_F_000             2304
_exptl_crystal_size_max          0.203
_exptl_crystal_size_mid          0.136
_exptl_crystal_size_min          0.061
_refine_diff_density_max         0.423
_refine_diff_density_min         -0.411
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     749
_refine_ls_number_reflns         13116
_refine_ls_number_restraints     23
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0760
_refine_ls_R_factor_gt           0.0511
_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^)+(0.0696P)^2^+0.6241P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1390
_refine_ls_wR_factor_ref         0.1563
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9119
_reflns_number_total             13116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02056j2.cif
_cod_data_source_block           s19msh4-Compound-12
_cod_database_code               1552120
_shelxl_version_number           2014-3
_chemical_oxdiff_usercomment     'colorless crystal'
_olex2_refinement_description
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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. Restrained distances
 C31-C30 \\sim C31A-C30
 with sigma of 0.005
 C32A-C31A \\sim C32-C31
 with sigma of 0.005
 C33-C32 \\sim C33-C32A
 with sigma of 0.005
 Mg2-C65 \\sim Mg2-C65A
 with sigma of 0.005
 C66-C65 \\sim C66A-C65A
 with sigma of 0.005
 C70-C66 \\sim C70A-C66A
 with sigma of 0.005
 C16A-C15 \\sim C16-C15 \\sim C17-C15
 with sigma of 0.005
 C70-C69 \\sim C70A-C69
 with sigma of 0.005
 C70A-C66A \\sim C70-C66
 with sigma of 0.005
 C66A-C65A \\sim C66-C65
 with sigma of 0.005
 C67-C66A \\sim C67-C66
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C16A \\sim C16: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01
C31 \\sim C31A: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01
Uanis(C32A) = Uanis(C32)
Uanis(C66A) = Uanis(C66)
4. Others
 Sof(H30C)=Sof(H30D)=Sof(H33C)=Sof(H33D)=Sof(H35C)=Sof(H35D)=1-FVAR(1)
 Sof(H30A)=Sof(H30B)=Sof(H33A)=Sof(H33B)=Sof(H35A)=Sof(H35B)=FVAR(1)
 Fixed Sof: H15(0.6) H15A(0.4) C16(0.6) H16A(0.6) H16B(0.6) H16C(0.6) C31(0.9)
 H31(0.9) C32(0.9) H32A(0.9) H32B(0.9) C16A(0.4) H16D(0.4) H16E(0.4) H16F(0.4)
 C31A(0.1) H31A(0.1) C32A(0.1) H32C(0.1) H32D(0.1) H67A(0.75) H67B(0.75)
 H67C(0.25) H67D(0.25) H69A(0.75) H69B(0.75) H69C(0.25) H69D(0.25) C65(0.75)
 H65A(0.75) H65B(0.75) C66(0.75) H66(0.75) C70(0.75) H70A(0.75) H70B(0.75)
 C65A(0.25) H65C(0.25) H65D(0.25) C66A(0.25) H66A(0.25) C70A(0.25) H70C(0.25)
 H70D(0.25)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C15(H15A), C24(H24), C27(H27), C31(H31), C31A(H31A),
 C47(H47), C50(H50), C59(H59), C62(H62), C66(H66), C66A(H66A)
5.b Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C30(H30C,H30D), C33(H33A,H33B), C33(H33C,H33D), C34(H34A,
 H34B), C35(H35A,H35B), C35(H35C,H35D), C32(H32A,H32B), C32A(H32C,H32D),
 C67(H67A,H67B), C67(H67C,H67D), C68(H68A,H68B), C69(H69A,H69B), C69(H69C,H69D),
  C65(H65A,H65B), C70(H70A,H70B), C65A(H65C,H65D), C70A(H70C,H70D)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C37(H37),
 C43(H43), C44(H44), C45(H45), C55(H55), C56(H56), C57(H57)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C16A(H16D,H16E,H16F),
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C60(H60A,H60B,H60C), C61(H61A,
 H61B,H61C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C)
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