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_7230743
_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         'C14 H14 O3'
_chemical_formula_sum            'C14 H14 O3'
_chemical_formula_weight         230.25
_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             2017-04-27
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.47958(16)
_cell_length_b                   7.89044(19)
_cell_length_c                   22.4589(6)
_cell_measurement_reflns_used    2604
_cell_measurement_temperature    109.9(2)
_cell_measurement_theta_max      70.8100
_cell_measurement_theta_min      7.0940
_cell_volume                     1148.25(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      109.9(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -21.00  69.00   1.00    1.00    --    0.00  57.00-180.00   90
  2  \w    -21.00  69.00   1.00    1.00    --    0.00  57.00  90.00   90
  3  \w    -16.00  84.00   1.00    1.00    --   54.00 -77.00 120.00  100
  4  \w    -19.00  98.00   1.00    1.00    --   54.00 -19.00  60.00  117
  5  \w     74.00 178.00   1.00    1.00    --  108.00  25.00  60.00  104
  6  \w    100.00 178.00   1.00    1.00    --  108.00 111.00 120.00   78
  7  \w    100.00 178.00   1.00    1.00    --  108.00 111.00  30.00   78
  8  \w     36.00 116.00   1.00    1.00    --  108.00-111.00-150.00   80
  9  \w    100.00 178.00   1.00    1.00    --  108.00 111.00 -90.00   78
 10  \w    -21.00  69.00   1.00    1.00    --    0.00  57.00 -90.00   90
 11  \w     33.00 123.00   1.00    1.00    --   54.00  57.00  90.00   90
 12  \w     28.00 126.00   1.00    1.00    --   54.00  37.00-150.00   98
 13  \w     78.00 109.00   1.00    1.00    --  108.00  77.00-180.00   31
;
_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      0.0335500000
_diffrn_orient_matrix_UB_12      0.0260586000
_diffrn_orient_matrix_UB_13      -0.0672907000
_diffrn_orient_matrix_UB_21      0.0401513000
_diffrn_orient_matrix_UB_22      -0.1912578000
_diffrn_orient_matrix_UB_23      -0.0074657000
_diffrn_orient_matrix_UB_31      -0.2319613000
_diffrn_orient_matrix_UB_32      -0.0293545000
_diffrn_orient_matrix_UB_33      -0.0109620000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0270
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            5107
_diffrn_reflns_point_group_measured_fraction_full 0.948
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.108
_diffrn_reflns_theta_min         3.937
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.759
_exptl_absorpt_correction_T_max  0.940
_exptl_absorpt_correction_T_min  0.800
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.332
_exptl_crystal_description       block
_exptl_crystal_F_000             488
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: ethanol'
_exptl_crystal_size_max          0.524
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.086
_refine_diff_density_max         0.157
_refine_diff_density_min         -0.190
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 687 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         2057
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0360
_refine_ls_R_factor_gt           0.0334
_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^)+(0.0465P)^2^+0.1783P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0839
_refine_ls_wR_factor_ref         0.0864
_reflns_Friedel_coverage         0.575
_reflns_Friedel_fraction_full    0.870
_reflns_Friedel_fraction_max     0.834
_reflns_number_gt                1943
_reflns_number_total             2057
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8gc01227j2.cif
_cod_data_source_block           jhc1708
_cod_depositor_comments
'Adding full bibliography for 7230738--7230745.cif.'
_cod_database_code               7230743
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C14 H14 O3'
_chemical_oxdiff_usercomment     'Liam Hughes lmh4Methyl'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.65
_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.a Ternary CH refined with riding coordinates:
 C2(H2), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C8(H8), C10(H10), C11(H11)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C)
;
_olex2_date_sample_data_collection 2017-04-25
_olex2_date_sample_submission    2017-04-05
_olex2_exptl_crystal_mounting_method 'oil on micromount'
_olex2_submission_original_sample_id lmh4Methyl
_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 1.238
_oxdiff_exptl_absorpt_empirical_full_min 0.588