Development of pharmaceutically relevant bio-based intermediates though aldol condensation and Claisen–Schmidt reactions of dihydrolevoglucosenone (Cyrene®)
Hughes, Liam; McElroy, Con R.; Whitwood, Adrian C.; Hunt, Andrew J.; Green Chemistry 20 (2018) 4423–; doi:10.1039/C8GC01227J

data_7230744
_publ_section_title
;
 Development of pharmaceutically relevant bio-based intermediates though
 aldol condensation and Claisen--Schmidt reactions of
 dihydrolevoglucosenone (Cyrene&#x00AE;)
;
_journal_issue                   19
_journal_name_full               'Green Chemistry'
_journal_page_first              4423
_journal_paper_doi               10.1039/C8GC01227J
_journal_volume                  20
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H11 Cl O3'
_chemical_formula_sum            'C13 H11 Cl O3'
_chemical_formula_weight         250.67
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-04-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2018-04-17 deposited with the CCDC.
2018-05-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.739(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.94601(13)
_cell_length_b                   5.17983(13)
_cell_length_c                   18.2456(5)
_cell_measurement_reflns_used    1783
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      70.2360
_cell_measurement_theta_min      7.2810
_cell_volume                     560.03(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -12.00  71.00   1.00    4.00    --   54.00 -37.00  90.00   83
  2  \w     37.00 130.00   1.00    8.00    --  108.00 -37.00  30.00   93
  3  \w     89.00 115.00   1.00    8.00    --  108.00-111.00 -30.00   26
  4  \w     60.00  87.00   1.00    4.00    --   54.00-126.00-127.00   27
  5  \w     38.00  75.00   1.00    8.00    --  108.00-111.00 -30.00   37
  6  \w     56.00  84.00   1.00    8.00    --  108.00-111.00  30.00   28
  7  \w     39.00 114.00   1.00    8.00    --  108.00 -50.00 -60.00   75
  8  \w    110.00 178.00   1.00    8.00    --  108.00 -12.00-150.00   68
  9  \w    139.00 176.00   1.00    8.00    --  108.00 111.00  30.00   37
 10  \w    134.00 173.00   1.00    8.00    --  108.00 111.00  90.00   39
 11  \w    111.00 138.00   1.00    8.00    --  108.00 178.00 150.00   27
 12  \w     58.00 103.00   1.00    8.00    --  108.00 178.00 150.00   45
 13  \w     56.00  90.00   1.00    4.00    --   54.00  57.00 -30.00   34
 14  \w     71.00 124.00   1.00    4.00    --   54.00  77.00-120.00   53
 15  \w     75.00 123.00   1.00    4.00    --   54.00  57.00-150.00   48
 16  \w     33.00  86.00   1.00    4.00    --   54.00  77.00-180.00   53
 17  \w     35.00 102.00   1.00    8.00    --  108.00 -12.00-150.00   67
 18  \w     47.00 113.00   1.00    8.00    --  108.00-111.00-180.00   66
 19  \w     -1.00  27.00   1.00    1.00    --    0.00 -77.00-150.00   28
 20  \w      1.00  94.00   1.00    4.00    --   54.00 -99.00 -60.00   93
 21  \w     23.00  72.00   1.00    4.00    --   54.00-125.00 120.00   49
 22  \w     48.00 113.00   1.00    8.00    --  108.00 -63.00 150.00   65
 23  \w     47.00  88.00   1.00    8.00    --  108.00-111.00 120.00   41
 24  \w     37.00 139.00   1.00    8.00    --  108.00 -25.00 120.00  102
 25  \w     -2.00  41.00   1.00    1.00    --    0.00  57.00-150.00   43
 26  \w    -55.00 -28.00   1.00    1.00    --    0.00 -77.00-150.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0182580000
_diffrn_orient_matrix_UB_12      0.2965307000
_diffrn_orient_matrix_UB_13      -0.0016487000
_diffrn_orient_matrix_UB_21      0.0052162000
_diffrn_orient_matrix_UB_22      0.0069527000
_diffrn_orient_matrix_UB_23      0.0845747000
_diffrn_orient_matrix_UB_31      0.2592185000
_diffrn_orient_matrix_UB_32      -0.0208637000
_diffrn_orient_matrix_UB_33      0.0054419000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0269
_diffrn_reflns_av_unetI/netI     0.0411
_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       -4
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            3274
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.075
_diffrn_reflns_theta_max         67.075
_diffrn_reflns_theta_min         4.864
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.974
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.665
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.487
_exptl_crystal_description       plate
_exptl_crystal_F_000             260
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Methanol'
_exptl_crystal_size_max          0.152
_exptl_crystal_size_mid          0.069
_exptl_crystal_size_min          0.019
_refine_diff_density_max         0.248
_refine_diff_density_min         -0.216
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 800 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     154
_refine_ls_number_reflns         1995
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0371
_refine_ls_R_factor_gt           0.0358
_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^)+(0.0569P)^2^+0.1061P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0920
_refine_ls_wR_factor_ref         0.0934
_reflns_Friedel_coverage         0.776
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                1929
_reflns_number_total             1995
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8gc01227j2.cif
_cod_data_source_block           jhc1705
_cod_depositor_comments
'Adding full bibliography for 7230738--7230745.cif.'
_cod_database_code               7230744
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C13 H11 Cl O3'
_chemical_oxdiff_usercomment     'Liam Hughs lmh4-Cl'
_reflns_odcompleteness_completeness 99.91
_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 Ternary CH refined with riding coordinates:
 C2(H2), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C10(H10), C12(H12), C13(H13)
;
_olex2_date_sample_data_collection 2017-04-21
_olex2_date_sample_submission    2017-04-05
_olex2_exptl_crystal_mounting_method 'oil on 75 micrometre micromount'
_olex2_submission_original_sample_id lmh4-Cl
_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 1.229
_oxdiff_exptl_absorpt_empirical_full_min 0.840