Redox deracemization of phosphonate-substituted dihydropyrimidines.
Meng, Fan-Jie; Shao, Bing-Ru; Velopolcek, Maria K.; Guo, Xuan; Feng, Guang-Shou; Shi, Lei; Organic & biomolecular chemistry 19 (2021) 10570–10574; doi:10.1039/d1ob02079j

data_7158421
_publ_section_title
;
 Redox deracemization of phosphonate-substituted dihydropyrimidines.
;
_journal_issue                   48
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10570
_journal_page_last               10574
_journal_paper_doi               10.1039/d1ob02079j
_journal_volume                  19
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H27 N2 O6 P'
_chemical_formula_sum            'C20 H27 N2 O6 P'
_chemical_formula_weight         422.40
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-05-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-31 deposited with the CCDC.	2021-11-26 downloaded from the CCDC.
;
_cell_angle_alpha                92.649(3)
_cell_angle_beta                 93.232(3)
_cell_angle_gamma                92.618(3)
_cell_formula_units_Z            5
_cell_length_a                   9.4275(8)
_cell_length_b                   10.8201(8)
_cell_length_c                   27.124(2)
_cell_measurement_reflns_used    9791
_cell_measurement_temperature    190.0
_cell_measurement_theta_max      60.426
_cell_measurement_theta_min      3.770
_cell_volume                     2756.2(4)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      190.0
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0463
_diffrn_reflns_av_unetI/netI     0.0648
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            35334
_diffrn_reflns_point_group_measured_fraction_full 0.896
_diffrn_reflns_point_group_measured_fraction_max 0.839
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         60.593
_diffrn_reflns_theta_min         1.421
_diffrn_source_current           2.85
_diffrn_source_power             0.1986735
_diffrn_source_voltage           69.71
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.925
_exptl_absorpt_correction_T_max  0.7519
_exptl_absorpt_correction_T_min  0.6527
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1436 before and 0.0907 after correction.
The Ratio of minimum to maximum transmission is 0.8681.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.272
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.332
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 6991 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.049(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1565
_refine_ls_number_reflns         21189
_refine_ls_number_restraints     131
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0540
_refine_ls_R_factor_gt           0.0462
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0565P)^2^+0.3149P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1172
_refine_ls_wR_factor_ref         0.1243
_reflns_Friedel_coverage         0.715
_reflns_Friedel_fraction_full    0.797
_reflns_Friedel_fraction_max     0.699
_reflns_number_gt                18437
_reflns_number_total             21189
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob02079j3.cif
_cod_data_source_block           a
_cod_depositor_comments
'Adding full bibliography for 7158421--7158422.cif.'
_cod_database_code               7158421
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.913
_shelx_estimated_absorpt_t_min   0.897
_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
 C24A-C25 \\sim C24-C25 \\sim C26A-C25 \\sim C26-C25
 with sigma of 0.02
 C81-C82 \\sim C83-C82
 with sigma of 0.02
 C2-C1A \\sim C3A-C2
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C4 \\sim C4A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C24 \\sim C24A \\sim C26 \\sim C26A: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
C14 \\sim C14A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C3A \\sim C3: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C84 \\sim C85 \\sim C86: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
C81 \\sim C83 \\sim C83A \\sim C81A: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
O3A \\sim O3B: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
O2A \\sim O2B: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
Uanis(C24) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C26A)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C1A) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3A) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(H7B)=Sof(O1A)=Sof(P1A)=1-FVAR(1)
 Sof(P1)=Sof(O1)=Sof(H7A)=FVAR(1)
 Sof(H87A)=Sof(P6)=Sof(O31)=1-FVAR(2)
 Sof(P4)=Sof(O19)=Sof(H87)=FVAR(2)
 Sof(H5B)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=1-FVAR(3)
 Sof(H5A)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(3)
 Sof(O6A)=Sof(C13A)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=1-FVAR(4)
 Sof(C14)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C13)=Sof(O6)=FVAR(4)
 Sof(H2B)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=
 Sof(H1AC)=1-FVAR(5)
 Sof(H2A)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(H3C)=FVAR(5)
 Sof(C62A)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63A)=Sof(H63D)=Sof(H63E)=
 Sof(H63F)=Sof(C61A)=Sof(H61A)=1-FVAR(6)
 Sof(C61)=Sof(H61)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C62)=Sof(H62D)=
 Sof(H62E)=Sof(H62F)=FVAR(6)
 Sof(H82A)=Sof(C83A)=Sof(H83D)=Sof(H83E)=Sof(H83F)=Sof(C81A)=Sof(H81D)=
 Sof(H81E)=Sof(H81F)=1-FVAR(7)
 Sof(H82)=Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=Sof(C81)=Sof(H81A)=Sof(H81B)=
 Sof(H81C)=FVAR(7)
 Sof(O24A)=Sof(C91A)=Sof(C92A)=Sof(H92A)=Sof(H92B)=Sof(H92C)=1-FVAR(8)
 Sof(C92)=Sof(H92D)=Sof(H92E)=Sof(H92F)=Sof(C91)=Sof(O24)=FVAR(8)
 Sof(H25A)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C24A)=Sof(H24D)=
 Sof(H24E)=Sof(H24F)=1-FVAR(9)
 Sof(H25)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C24)=Sof(H24A)=Sof(H24B)=
 Sof(H24C)=FVAR(9)
 Sof(O3B)=Sof(O2B)=1-FVAR(10)
 Sof(O2A)=Sof(O3A)=FVAR(10)
 Sof(O20B)=1-FVAR(11)
 Sof(O20A)=FVAR(11)
5.a Ternary CH refined with riding coordinates:
 C42(H42), C72(H72), C27(H27), C65(H65), C47(H47), C22(H22), C7(H7A), C7(H7B),
 C45(H45), C2(H2B), C2(H2A), C25(H25), C25(H25A), C87(H87), C87(H87A), C61(H61),
  C82(H82), C82(H82A), C85(H85), C5(H5A), C5(H5B), C61A(H61A)
5.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C73(H73), C28(H28), C36(H36), C40(H40), C56(H56), C76(H76),
 C48(H48), C39(H39), C77(H77), C37(H37), C97(H97), C20(H20), C78(H78), C8(H8),
 C60(H60), C57(H57), C19(H19), C38(H38), C18(H18), C96(H96), C88(H88), C59(H59),
  C100(H100), C17(H17), C80(H80), C79(H79), C98(H98), C58(H58), C99(H99)
5.c Idealised Me refined as rotating group:
 C51(H51A,H51B,H51C), C94(H94A,H94B,H94C), C12(H12A,H12B,H12C), C41(H41A,H41B,
 H41C), C43(H43A,H43B,H43C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C66(H66A,
 H66B,H66C), C54(H54A,H54B,H54C), C32(H32A,H32B,H32C), C68(H68A,H68B,H68C),
 C64(H64A,H64B,H64C), C70(H70A,H70B,H70C), C6(H6A,H6B,H6C), C46(H46A,H46B,H46C),
  C34(H34A,H34B,H34C), C44(H44A,H44B,H44C), C83(H83A,H83B,H83C), C14A(H14A,H14B,
 H14C), C62A(H62A,H62B,H62C), C3A(H3AA,H3AB,H3AC), C86(H86A,H86B,H86C),
 C84(H84A,H84B,H84C), C63(H63A,H63B,H63C), C92A(H92A,H92B,H92C), C26(H26A,H26B,
 H26C), C1(H1A,H1B,H1C), C4(H4A,H4B,H4C), C81(H81A,H81B,H81C), C4A(H4AA,H4AB,
 H4AC), C14(H14D,H14E,H14F), C1A(H1AA,H1AB,H1AC), C3(H3A,H3B,H3C), C24(H24A,
 H24B,H24C), C62(H62D,H62E,H62F), C63A(H63D,H63E,H63F), C83A(H83D,H83E,H83F),
 C81A(H81D,H81E,H81F), C92(H92D,H92E,H92F), C26A(H26D,H26E,H26F), C24A(H24D,
 H24E,H24F)
;
_shelx_res_checksum              93730
_olex2_submission_special_instructions 'No special instructions were received'