Single electron/energy transfer photocatalysis: α-/β-switchable synthesis of 3-deoxy-d-manno-oct-2-ulosonic acid <i>O</i>-glycosides.
Zhang, Jing-Dong; Jie, Jia-Long; Yan, Shu-Yi; Zhang, Hui; Chen, Jia-Meng; Wu, Jiang-Cheng; Qin, Lu-Yang; Liu, Guang-Jian; Su, Hong-Mei; Xing, Guo-Wen; Chemical science 16 (2025) 13070–13081; doi:10.1039/d5sc02980e

data_1574862
_publ_section_title
;
 Single electron/energy transfer photocatalysis:
 &#x3b1;-/&#x3b2;-switchable synthesis of 3-deoxy-d-manno-oct-2-ulosonic
 acid <i>O</i>-glycosides.
;
_journal_issue                   28
_journal_name_full               'Chemical science'
_journal_page_first              13070
_journal_page_last               13081
_journal_paper_doi               10.1039/d5sc02980e
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C46 H56 O17'
_chemical_formula_sum            'C46 H56 O17'
_chemical_formula_weight         880.90
_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
_audit_creation_date             2023-09-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-09-18 deposited with the CCDC.	2025-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.8007(19)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.0048(2)
_cell_length_b                   9.98913(19)
_cell_length_c                   20.5935(4)
_cell_measurement_reflns_used    10340
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      75.5230
_cell_measurement_theta_min      4.0630
_cell_volume                     2230.77(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.963
_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    -25.00   0.00   0.50    0.05    --  -46.80  24.00 166.00   50
  2  \w    -40.00  25.00   0.50    0.05    --  -46.80  37.00 -60.00  130
  3  \w     37.00 113.00   0.50    0.05    --  104.75-125.00 -30.00  152
  4  \w     39.00  72.00   0.50    0.05    --  104.75 -61.00-150.00   66
  5  \w     37.00  73.00   0.50    0.05    --  104.75 -61.00 -30.00   72
  6  \w     38.00  69.00   0.50    0.05    --  104.75 -61.00   0.00   62
  7  \w     32.00  57.00   0.50    0.05    --  104.75 -61.00  30.00   50
  8  \w    -27.00  23.00   0.50    0.05    --   46.80 -19.00-150.00  100
  9  \w    -22.00   3.00   0.50    0.05    --   46.80 -24.00   2.00   50
 10  \w     48.00  73.00   0.50    0.05    --  104.75 -61.00  60.00   50
 11  \w     42.00  67.00   0.50    0.05    --  104.75 -61.00  90.00   50
 12  \w     43.00  96.00   0.50    0.05    --  104.75 -77.00 150.00  106
 13  \w     91.00 176.00   0.50    0.05    --  104.75  15.00 120.00  170
 14  \w     98.00 124.00   0.50    0.05    --  104.75  24.00 166.00   52
 15  \w     35.00 104.00   0.50    0.05    --   46.80  24.00 166.00  138
 16  \w    -68.00 -30.00   0.50    0.05    -- -102.00  61.00   0.00   76
 17  \w    -69.00 -33.00   0.50    0.05    -- -102.00  61.00 -30.00   72
 18  \w    -76.00 -31.00   0.50    0.05    -- -102.00  77.00 -90.00   90
 19  \w    -67.00 -29.00   0.50    0.05    -- -102.00  61.00-120.00   76
 20  \w   -121.00 -51.00   0.50    0.05    --  -46.80 -24.00   2.00  140
 21  \w   -174.00 -98.00   0.50    0.05    -- -102.00 -24.00   2.00  152
 22  \w   -162.00-136.00   0.50    0.05    -- -102.00 -61.00 -90.00   52
 23  \w   -135.00 -85.00   0.50    0.05    -- -102.00 -61.00 -90.00  100
 24  \w   -116.00 -91.00   0.50    0.05    --  -46.80-125.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1410706000
_diffrn_orient_matrix_UB_12      -0.0045226000
_diffrn_orient_matrix_UB_13      -0.0042203000
_diffrn_orient_matrix_UB_21      0.0168463000
_diffrn_orient_matrix_UB_22      -0.0492608000
_diffrn_orient_matrix_UB_23      0.0718783000
_diffrn_orient_matrix_UB_31      0.0013096000
_diffrn_orient_matrix_UB_32      0.1460628000
_diffrn_orient_matrix_UB_33      0.0240616000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0374
_diffrn_reflns_av_unetI/netI     0.0391
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            16000
_diffrn_reflns_point_group_measured_fraction_full 0.766
_diffrn_reflns_point_group_measured_fraction_max 0.722
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.378
_diffrn_reflns_theta_min         4.077
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.837
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89611
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (Rigaku Oxford Diffraction, 2023)
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    1.311
_exptl_crystal_description       block
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.818
_refine_diff_density_min         -0.431
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 1619 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.11(11)
_refine_ls_extinction_coef       0.0010(3)
_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   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     575
_refine_ls_number_reflns         6750
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0548
_refine_ls_R_factor_gt           0.0491
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0869P)^2^+0.5831P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1348
_refine_ls_wR_factor_ref         0.1408
_reflns_Friedel_coverage         0.415
_reflns_Friedel_fraction_full    0.502
_reflns_Friedel_fraction_max     0.450
_reflns_number_gt                6036
_reflns_number_total             6750
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02980e2.cif
_cod_data_source_block           20230914b_auto
_cod_depositor_comments
'Adding full bibliography for 1574862--1574863.cif.'
_cod_original_cell_volume        2230.76(8)
_cod_database_code               1574862
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1O1
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.850
_diffrn_oxdiff_digest_frames
;
01f1099eeb649a1a11f5740e03969b0bae00050858b
;
_diffrn_oxdiff_digest_hkl
;
01522bfceef1bbe158f8ffa6b2eafa8bae3c8b
;
_reflns_odcompleteness_completeness 99.95
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C29-C28 = C30-C29 = C28-C27
 1.38 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C28) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
4.a Ternary CH refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C20(H20), C21(H21), C22(H22), C23(H23),
 C24(H24)
4.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C8(H8A,H8B), C9(H9A,H9B), C19(H19A,H19B), C25(H25A,H25B),
 C32(H32A,H32B), C39(H39A,H39B)
4.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C34(H34), C35(H35),
 C36(H36), C37(H37), C38(H38), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45)
4.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C16(H16A,H16B,
 H16C), C18(H18A,H18B,H18C), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              87465
_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 1.458
_oxdiff_exptl_absorpt_empirical_full_min 0.833