Synthesis and characterization of novel chiral derivatizing agents containing β-keto-anthracene adducts (KAAs) by <sup>1</sup>H-NMR: aromatic influence and chiral alcohol absolute configuration determination.
Intakaew, Neeranuth; Rithchumpon, Puracheth; Prommin, Chanatkran; Yimklan, Saranphong; Kungwan, Nawee; Thavornyutikarn, Praput; Meepowpan, Puttinan; Organic & biomolecular chemistry 17 (2019) 541–554; doi:10.1039/c8ob02662a

data_7156624
_publ_section_title
;
 Synthesis and characterization of novel chiral derivatizing agents
 containing \b-keto-anthracene adducts (KAAs) by <sup>1</sup>H-NMR:
 aromatic influence and chiral alcohol absolute configuration
 determination.
;
_journal_issue                   3
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              541
_journal_page_last               554
_journal_paper_doi               10.1039/c8ob02662a
_journal_volume                  17
_journal_year                    2019
_chemical_absolute_configuration rm
_chemical_formula_moiety         '4(C35 H30 O5)'
_chemical_formula_sum            'C140 H120 O20'
_chemical_formula_weight         2122.35
_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     dual
_audit_creation_date             2018-12-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-12-07 deposited with the CCDC.
2018-12-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.18(3)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   13.391(17)
_cell_length_b                   10.239(13)
_cell_length_c                   21.40(3)
_cell_measurement_reflns_used    3187
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      16.737
_cell_measurement_theta_min      2.543
_cell_volume                     2818(6)
_computing_cell_refinement       'SAINT V8.30C (?, 2016)'
_computing_data_reduction        'SAINT V8.30C (?, 2016)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0900
_diffrn_reflns_av_unetI/netI     0.1026
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            32630
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        21.178
_diffrn_reflns_theta_max         21.178
_diffrn_reflns_theta_min         2.089
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.083
_exptl_absorpt_correction_T_max  0.7446
_exptl_absorpt_correction_T_min  0.6669
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.251
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_recrystallization_method dichloromethane/hexane
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.105
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 1227 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.802
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     799
_refine_ls_number_reflns         6020
_refine_ls_number_restraints     144
_refine_ls_restrained_S_all      0.803
_refine_ls_R_factor_all          0.0839
_refine_ls_R_factor_gt           0.0410
_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^)+(0.0245P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0633
_refine_ls_wR_factor_ref         0.0717
_reflns_Friedel_coverage         0.861
_reflns_Friedel_fraction_full    0.965
_reflns_Friedel_fraction_max     0.965
_reflns_number_gt                3531
_reflns_number_total             6020
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob02662a2.cif
_cod_data_source_block           602103_3695_01r_0m
_cod_depositor_comments
'Adding full bibliography for 7156624--7156625.cif.'
_cod_original_cell_volume        2817(6)
_cod_database_code               7156624
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.966
_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
 C3"A-C4"A \\sim C5-C8"'
 with sigma of 0.02
 C3"A-C8"A \\sim C5-C8
 with sigma of 0.02
 C4"A-C5"A \\sim C8"'-C9
 with sigma of 0.02
 C8"A-C7"A \\sim C8-C11
 with sigma of 0.02
 C5"A-C6"A \\sim C9-C10
 with sigma of 0.02
 C6"A-C7"A \\sim C10-C11
 with sigma of 0.02
 O2A-C3"A \\sim O2A-C5
 with sigma of 0.04
 O2A-C2"A \\sim O2A-C7
 with sigma of 0.04
 C3"A-C2"A \\sim C5-C7
 with sigma of 0.04
 C3"A-C5"A \\sim C5-C9
 with sigma of 0.04
 C3"A-C7"A \\sim C5-C11
 with sigma of 0.04
 C4"A-C8"A \\sim C8"'-C8
 with sigma of 0.04
 C4"A-C6"A \\sim C8"'-C10
 with sigma of 0.04
 C8"A-C6"A \\sim C8-C10
 with sigma of 0.04
 C5"A-C7"A \\sim C9-C11
 with sigma of 0.04
 O2A-C1"A \\sim O2A-C6
 with sigma of 0.02
 C3"A-C1"A \\sim C5-C6
 with sigma of 0.02
 C1"A-C2"A \\sim C6-C7
 with sigma of 0.02
 C4"A-C1"A \\sim C8"'-C6
 with sigma of 0.04
 C1"A-C8"A \\sim C6-C8
 with sigma of 0.04
3. Restrained planarity
 C4"A, C5"A, C6"A, C7"A, C8"A, C3"A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C6 \\sim C1"A: within 2A with sigma of 0.0001 and sigma for terminal atoms of
0.0002
Uanis(C1"A) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 C5, C8"', C6, C7, C8, C9, C10, C11
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C3"A, C4"A, H4"A, C1"A, H1"A, C2"A, H2"A, H2"B, H2"C, C8"A, H8"A, C5"A, H5"A,
 C6"A, H6"A, C7"A, H7"A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(C5)=Sof(C8"')=Sof(H8"')=Sof(C6)=Sof(H1"')=Sof(C7)=Sof(H2"G)=Sof(H2"H)=
 Sof(H2"I)=Sof(C8)=Sof(H4"C)=Sof(C9)=Sof(H7"D)=Sof(C10)=Sof(H6"D)=Sof(C11)=
 Sof(H5"C)=1-FVAR(1)
 Sof(C3"A)=Sof(C4"A)=Sof(H4"A)=Sof(C1"A)=Sof(H1"A)=Sof(C2"A)=Sof(H2"A)=
 Sof(H2"B)=Sof(H2"C)=Sof(C8"A)=Sof(H8"A)=Sof(C5"A)=Sof(H5"A)=Sof(C6"A)=
 Sof(H6"A)=Sof(C7"A)=Sof(H7"A)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C10B(H10B), C9B(H9B), C1'(H1'), C1'A(H1'A), C2AA(H2AA), C1"B(H1"B),
 C5BA(H5BA), C1"A(H1"A), C6(H1"')
7.b Secondary CH2 refined with riding coordinates:
 C12B(H12A,H12B), C12A(H12C,H12D)
7.c Aromatic/amide H refined with riding coordinates:
 C5B(H5B), C8B(H8B), C7B(H7B), C4B(H4B), C6B(H6B), C7"'(H7"C), C6"'(H6"C),
 C3B(H3B), C2B(H2B), C5"'(H5"'), C1B(H1B), C5A(H5A), C15(H15), C3"'(H3"'),
 C4"B(H4"B), C3(H7"'), C7A(H7A), C4"'(H4"'), C2A(H2A), C4(H6"'), C4BA(H4BA),
 C3BA(H3BA), C6A(H6A), C8"B(H8"B), C18(H18), C5"B(H5"B), C1A(H1A), C19(H19),
 C3A(H3A), C4"A(H4"A), C6"B(H6"B), C7"B(H7"B), C8"A(H8"A), C5"A(H5"A),
 C6"A(H6"A), C7"A(H7"A), C8"'(H8"'), C8(H4"C), C9(H7"D), C10(H6"D), C11(H5"C)
7.d Idealised Me refined as rotating group:
 C4'B(H4'A,H4'B,H4'C), C2"B(H2"D,H2"E,H2"F), C4'A(H4'D,H4'E,H4'F), C2"A(H2"A,
 H2"B,H2"C), C7(H2"G,H2"H,H2"I)
;
_olex2_submission_special_instructions 'No special instructions were received'