C(21)-Di- and monofluorinated scaffold for thevinol/orvinol-based opioid receptor ligands.
Zelentsova, Maria V.; Sandulenko, Irina V.; Ambartsumyan, Asmik A.; Danshina, Anastasia A.; Moiseev, Sergey K.; Organic & biomolecular chemistry 21 (2023) 9091–9100; doi:10.1039/d3ob01577g

data_7159621
_publ_section_title
;
 C(21)-Di- and monofluorinated scaffold for thevinol/orvinol-based opioid
 receptor ligands.
;
_journal_issue                   45
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9091
_journal_page_last               9100
_journal_paper_doi               10.1039/d3ob01577g
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C24 H31 F2 N O4, H2 O, C2 H6 O'
_chemical_formula_sum            'C26 H39 F2 N O6'
_chemical_formula_weight         499.58
_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'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-08-31
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-09-11 deposited with the CCDC.	2023-10-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.5587(9)
_cell_length_b                   10.1828(8)
_cell_length_c                   24.801(2)
_cell_measurement_reflns_used    9876
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.66
_cell_measurement_theta_min      2.16
_cell_volume                     2414.0(4)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Quest D8'
_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  0.1520
_diffrn_reflns_av_unetI/netI     0.0659
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_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       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            59479
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.997
_diffrn_reflns_theta_min         1.642
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.106
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5995
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1368 before and 0.0797 after correction.
The Ratio of minimum to maximum transmission is 0.8035.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.375
_exptl_crystal_description       needle
_exptl_crystal_F_000             1072
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.443
_refine_diff_density_min         -0.608
_refine_diff_density_rms         0.116
_refine_ls_abs_structure_details
;
 Flack x determined using 1821 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.33(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.142
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     332
_refine_ls_number_reflns         5837
_refine_ls_number_restraints     101
_refine_ls_restrained_S_all      1.146
_refine_ls_R_factor_all          0.1132
_refine_ls_R_factor_gt           0.0982
_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^)+14.5778P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2223
_refine_ls_wR_factor_ref         0.2272
_reflns_Friedel_coverage         0.766
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4932
_reflns_number_total             5837
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01577g2.cif
_cod_data_source_block           38
_cod_depositor_comments
'Adding full bibliography for 7159615--7159624.cif.'
_cod_database_code               7159621
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.989
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All O(H) groups, All O(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1S-C1S \\sim O1S-C1'S
 with sigma of 0.02
 O1S-C1S \\sim O1'S-C1'S
 with sigma of 0.02
 O1'S-H1'S \\sim O1S-H1S
 with sigma of 0.02
 C2S-C1S \\sim C2'S-C1'S
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C19) \\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
Uanis(O1S) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O1) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C19) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C22) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C1S) \\sim Ueq, Uanis(C1'S) \\sim Ueq, Uanis(C2'S) \\sim Ueq, Uanis(C2S)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C12) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
Uanis(C4) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(O1S) = Uanis(O1'S)
Uanis(C1'S) = Uanis(C1S)
Uanis(C2'S) = Uanis(C2S)
4. Others
 Sof(O1S)=Sof(H1S)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=
 Sof(H2SC)=1-FVAR(1)
 Sof(O1'S)=Sof(H1'S)=Sof(C1'S)=Sof(H1'A)=Sof(H1'B)=Sof(C2'S)=Sof(H2'A)=
 Sof(H2'B)=Sof(H2'C)=FVAR(1)
5.a Riding coordinates:
 O4(H4), O2S(H2SD,H2SE), O1S(H1S), O1'S(H1'S)
5.b Ternary CH refined with riding coordinates:
 C5(H5), C7(H7), C9(H9), C22(H22)
5.c Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B), C15(H15A,H15B), C16(H16A,H16B), C18(H18A,H18B),
 C19(H19A,H19B), C1S(H1SA,H1SB), C1'S(H1'A,H1'B)
5.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2)
5.e Idealised Me refined as rotating group:
 C17(H17A,H17C,H17B), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C2S(H2SA,H2SB,H2SC), C2'S(H2'A,H2'B,H2'C)
;
_shelx_res_checksum              31747
_olex2_submission_special_instructions 'No special instructions were received'