Alkene Synthesis by Photocatalytic Chemoenzymatically Compatible Dehydrodecarboxylation of Carboxylic Acids and Biomass
Nguyen, Vu T.; Nguyen, Viet D.; Haug, Graham C.; Dang, Hang T.; Jin, Shengfei; Li, Zhiliang; Flores-Hansen, Carsten; Benavides, Brenda S.; Arman, Hadi D.; Larionov, Oleg V.; ACS Catalysis 9 (2019) 9485–; doi:10.1021/acscatal.9b02951

data_4514632
_publ_section_title
;
 Alkene Synthesis by Photocatalytic Chemoenzymatically Compatible
 Dehydrodecarboxylation of Carboxylic Acids and Biomass
;
_journal_issue                   10
_journal_name_full               'ACS Catalysis'
_journal_page_first              9485
_journal_paper_doi               10.1021/acscatal.9b02951
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C23 H38 O3, 3/4(H2 O), C H4 O'
_chemical_formula_sum            'C24 H43.5 O4.75'
_chemical_formula_weight         407.83
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.747(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.5451(2)
_cell_length_b                   25.5594(4)
_cell_length_c                   15.6511(3)
_cell_measurement_reflns_used    28846
_cell_measurement_temperature    98(2)
_cell_measurement_theta_max      29.0640
_cell_measurement_theta_min      1.7990
_cell_volume                     4693.02(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28e (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      98(2)
_diffrn_detector                 'CCD plate'
_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    -97.00  24.00   1.00   30.00    --   -7.70 -64.00-134.00  121
  2  \w    -39.00  82.00   1.00   30.00    --   -7.70  64.00   1.00  121
  3  \w    -85.00  26.00   1.00   30.00    --    4.20 -38.00 120.00  111
  4  \w    -97.00  17.00   1.00   30.00    --   -7.70 -38.00  60.00  114
  5  \w    -37.00  67.00   1.00   30.00    --   -7.70  57.00-180.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0168424000
_diffrn_orient_matrix_UB_12      0.0083115000
_diffrn_orient_matrix_UB_13      0.0365664000
_diffrn_orient_matrix_UB_21      -0.0442488000
_diffrn_orient_matrix_UB_22      -0.0189113000
_diffrn_orient_matrix_UB_23      -0.0125442000
_diffrn_orient_matrix_UB_31      0.0376006000
_diffrn_orient_matrix_UB_32      -0.0185347000
_diffrn_orient_matrix_UB_33      0.0292187000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            76943
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.500
_diffrn_reflns_theta_min         1.910
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.078
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46797
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28e (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.154
_exptl_crystal_description       block
_exptl_crystal_F_000             1802
_exptl_crystal_recrystallization_method 'crystalized from methnaol'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.022
_refine_diff_density_min         -0.334
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 7205 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.23(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1102
_refine_ls_number_reflns         17398
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.099
_refine_ls_R_factor_all          0.0522
_refine_ls_R_factor_gt           0.0492
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0700P)^2^+1.6429P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1236
_refine_ls_wR_factor_ref         0.1257
_reflns_Friedel_coverage         0.949
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                16442
_reflns_number_total             17398
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b02951_si_002.cif
_cod_data_source_block           cd1794b
_cod_depositor_comments
;

2020-05-08
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C96 H173 O19'
_cod_original_formula_weight         1631.33
_cod_original_formula_moiety         '4(C23 H38 O3), 3(H2 O), 3(C H4 O), C H3 O'
_cod_original_formula_units_Z            2
_cod_database_code               4514632
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C30H20O2
_chemical_oxdiff_usercomment     VNS-177
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.969
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All O(H) groups, All O(H,H,H,H,H,H,H,H,H,H,H) groups
2. Restrained distances
 O17-H17
 0.95 with sigma of 0.02
3.a Free rotating group:
 O13(H13C), O14(H14C), O15(H15A)
3.b Ternary CH refined with riding coordinates:
 C77(H77), C58(H58), C75(H75), C12(H12A), C29(H29), C33(H33), C56(H56),
 C52(H52), C54(H54), C1(H1A), C31(H31), C47(H47), C7(H7A), C16(H16), C24(H24),
 C62(H62), C76(H76), C6(H6A), C39(H39), C79(H79), C53(H53), C10(H10A), C81(H81),
  C3(H3A), C35(H35), C30(H30), C8(H8A), C70(H70), C26(H26), C49(H49), C85(H85),
 C64(H64), C41(H41), C72(H72), C19(H19), C88(H88)
3.c Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C80(H80A,H80B), C17(H17A,H17B), C57(H57A,H57B), C11(H11A,
 H11B), C34(H34A,H34B), C78(H78A,H78B), C74(H74A,H74B), C13(H13A,H13B),
 C32(H32A,H32B), C5(H5A,H5B), C55(H55A,H55B), C40(H40A,H40B), C59(H59A,H59B),
 C28(H28A,H28B), C86(H86A,H86B), C63(H63A,H63B), C51(H51A,H51B), C60(H60A,H60B),
  C37(H37A,H37B), C82(H82A,H82B), C50(H50A,H50B), C27(H27A,H27B), C9(H9A,H9B),
 C4(H4A,H4B), C83(H83A,H83B), C36(H36A,H36B), C73(H73A,H73B)
3.d Aromatic/amide H refined with riding coordinates:
 C65(H65), C42(H42), C20(H20), C89(H89)
3.e X=CH2 refined with riding coordinates:
 C66(H66A,H66B), C43(H43A,H43B), C21(H21A,H21B), C90(H90A,H90B)
3.f Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C67(H67A,H67B,H67C), C44(H44A,H44B,H44C), C69(H69A,H69B,
 H69C), C87(H87A,H87B,H87C), C23(H23A,H23B,H23C), C92(H92A,H92B,H92C), C22(H22A,
 H22B,H22C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C68(H68A,H68B,H68C),
 C91(H91A,H91B,H91C), C93(H93A,H93B,H93C), C95(H95A,H95B,H95C), C94(H94A,H94B,
 H94C), C96(H96A,H96B,H96C)
3.g Idealised tetrahedral OH refined as rotating group:
 O8(H8), O1(H1), O6(H6), O10(H10), O2(H2), O18(H18), O16(H16A)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'
_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 1.835
_oxdiff_exptl_absorpt_empirical_full_min 0.726