Hydrodeoxygenation of isocyanates: snapshots of a magnesium-mediated CO bond cleavage
Yang, Yan; Anker, Mathew D.; Fang, Jian; Mahon, Mary F.; Maron, Laurent; Weetman, Catherine; Hill, Michael S.; Chem. Sci. 8 (2017) 3529–; doi:10.1039/C7SC00117G

data_1545370
_publ_section_title
;
 Hydrodeoxygenation of isocyanates: snapshots of a magnesium-mediated
 C&#xE001;O bond cleavage
;
_journal_issue                   5
_journal_name_full               'Chem. Sci.'
_journal_page_first              3529
_journal_paper_doi               10.1039/C7SC00117G
_journal_volume                  8
_journal_year                    2017
_chemical_formula_moiety         'C25 H43 B2 N O5'
_chemical_formula_sum            'C25 H43 B2 N O5'
_chemical_formula_weight         459.22
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-10-27
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-01-09 deposited with the CCDC.
2017-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.0273(4)
_cell_length_b                   12.4499(7)
_cell_length_c                   21.5324(9)
_cell_measurement_reflns_used    4868
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      27.0910
_cell_measurement_theta_min      3.7770
_cell_volume                     2688.1(2)
_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 16.1468
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Xcalibur, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0521
_diffrn_reflns_av_unetI/netI     0.0657
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            22144
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         3.276
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.076
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92040
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.135
_exptl_crystal_description       block
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.505
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.116
_refine_diff_density_max         0.165
_refine_diff_density_min         -0.154
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1448 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     426
_refine_ls_number_reflns         6057
_refine_ls_number_restraints     154
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0879
_refine_ls_R_factor_gt           0.0529
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0410P)^2^+0.0813P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0897
_refine_ls_wR_factor_ref         0.1010
_reflns_Friedel_coverage         0.757
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                4307
_reflns_number_total             6057
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc00117g2.cif
_cod_data_source_block           e16msh20
_cod_depositor_comments
'Adding full bibliography for 1545365--1545370.cif.'
_cod_database_code               1545370
_shelxl_version_number           2014-3
_chemical_oxdiff_usercomment     'colourless block'
_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
 C22A-C20A \\sim C22-C20 \\sim C23A-C20A \\sim C23-C20 \\sim C25-C21 \\sim
C25A-C21A \\sim C24-C21 ~
 C24A-C21A \\sim C3-C1 \\sim C4A-C1A \\sim C4-C1 \\sim C3A-C1A \\sim C5-C2
\\sim C5A-C2A \\sim C6-C2 \\sim C6A-
 C2A
 with sigma of 0.005
 O2-C2 \\sim O2-C2A \\sim O1-C1 \\sim O1-C1A \\sim O5-C21 \\sim O5-C21A \\sim
O4-C20 \\sim O4-C20A
 with sigma of 0.005
 C2-C1 \\sim C2A-C1A \\sim C21A-C20A \\sim C21-C20
 with sigma of 0.005
3. Others
 Fixed Sof: C1(0.65) C2(0.65) C3(0.65) H3A(0.65) H3B(0.65) H3C(0.65) C4(0.65)
 H4A(0.65) H4B(0.65) H4C(0.65) C5(0.65) H5A(0.65) H5B(0.65) H5C(0.65) C6(0.65)
 H6A(0.65) H6B(0.65) H6C(0.65) C20(0.65) C21(0.65) C22(0.65) H22A(0.65)
 H22B(0.65) H22C(0.65) C23(0.65) H23A(0.65) H23B(0.65) H23C(0.65) C24(0.65)
 H24A(0.65) H24B(0.65) H24C(0.65) C25(0.65) H25A(0.65) H25B(0.65) H25C(0.65)
 C1A(0.35) C2A(0.35) C3A(0.35) H3AA(0.35) H3AB(0.35) H3AC(0.35) C4A(0.35)
 H4AA(0.35) H4AB(0.35) H4AC(0.35) C5A(0.35) H5AA(0.35) H5AB(0.35) H5AC(0.35)
 C6A(0.35) H6AA(0.35) H6AB(0.35) H6AC(0.35) C20A(0.35) C21A(0.35) C22A(0.35)
 H22D(0.35) H22E(0.35) H22F(0.35) C23A(0.35) H23D(0.35) H23E(0.35) H23F(0.35)
 C24A(0.35) H24D(0.35) H24E(0.35) H24F(0.35) C25A(0.35) H25D(0.35) H25E(0.35)
 H25F(0.35)
4.a Ternary CH refined with riding coordinates:
 C14(H14), C17(H17)
4.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
4.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12)
4.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C15(H15A,
 H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C),
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C3A(H3AA,H3AB,H3AC), C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,H5AC), C6A(H6AA,
 H6AB,H6AC), C22A(H22D,H22E,H22F), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F),
 C25A(H25D,H25E,H25F)
;
_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 1.133
_oxdiff_exptl_absorpt_empirical_full_min 0.819