1,4-Refunctionalization of β-diketones to γ-keto nitriles via C–C single bond cleavage
Wu, Qi; Li, Yabo; Wang, Chenyang; Zhang, Jianye; Huang, Mengmeng; Kim, Jung Keun; Wu, Yangjie; Organic Chemistry Frontiers 5 (2018) 2496–; doi:10.1039/C8QO00556G

data_1554367
_publ_section_title
;
 1,4-Refunctionalization of \b-diketones to \g-keto nitriles via C--C
 single bond cleavage
;
_journal_issue                   16
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              2496
_journal_paper_doi               10.1039/C8QO00556G
_journal_volume                  5
_journal_year                    2018
_chemical_formula_moiety         'C10 H9 N O'
_chemical_formula_sum            'C10 H9 N O'
_chemical_formula_weight         159.18
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-11-17
_audit_creation_method
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Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-01-22 deposited with the CCDC.
2018-07-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.850(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.5235(7)
_cell_length_b                   5.5446(8)
_cell_length_c                   10.2976(10)
_cell_measurement_reflns_used    479
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      65.6740
_cell_measurement_theta_min      5.9500
_cell_volume                     423.23(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
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_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -52.00   35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   57.0000   90.0000 87

  2 omega -102.00  -15.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000  -60.0000 87

  3 omega  -32.00   55.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000  120.0000 87

  4 omega   18.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000 -120.0000 87

  5 omega  -33.00   65.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000  -90.0000 98

  6 omega   37.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -90.0000 54

  7 omega   88.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -120.0000 90

  8 omega   38.00   99.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -30.0000 61

  9 omega   38.00   99.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   60.0000 61

 10 omega   60.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000    0.0000 47

 11 omega   38.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  120.0000 70

 12 omega   36.00  133.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000   60.0000 97
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0813141000
_diffrn_orient_matrix_UB_12      -0.0821849000
_diffrn_orient_matrix_UB_13      0.1404290000
_diffrn_orient_matrix_UB_21      -0.1857092000
_diffrn_orient_matrix_UB_22      0.0284721000
_diffrn_orient_matrix_UB_23      0.0421523000
_diffrn_orient_matrix_UB_31      -0.0453781000
_diffrn_orient_matrix_UB_32      -0.2640190000
_diffrn_orient_matrix_UB_33      -0.0393953000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0187
_diffrn_reflns_av_unetI/netI     0.0445
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            1646
_diffrn_reflns_point_group_measured_fraction_full 0.750
_diffrn_reflns_point_group_measured_fraction_max 0.750
_diffrn_reflns_theta_full        67.025
_diffrn_reflns_theta_max         67.025
_diffrn_reflns_theta_min         4.358
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.653
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74072
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.249
_exptl_crystal_description       prism
_exptl_crystal_F_000             168
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.231
_refine_diff_density_min         -0.244
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 199 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1(3)
_refine_ls_extinction_coef       0.13(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     110
_refine_ls_number_reflns         1126
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0682
_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^)+(0.1321P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1904
_refine_ls_wR_factor_ref         0.2218
_reflns_Friedel_coverage         0.350
_reflns_Friedel_fraction_full    0.438
_reflns_Friedel_fraction_max     0.438
_reflns_number_gt                778
_reflns_number_total             1126
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8qo00556g2.cif
_cod_data_source_block           201711235a
_cod_original_cell_volume        423.23(9)
_cod_database_code               1554367
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H30N4O4
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.875
_reflns_odcompleteness_completeness 99.88
_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
2.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10)
;
_olex2_submission_special_instructions 'No special instructions were received'