1,3-Dianionic annulation of ketones with ketene dithioacetal: a modified route to 3-aryl/cyclopropyl-5-thiomethyl-phenols and 1-(methylthio)-9,10-dihydrophenanthren-3-ols
Shaw, Ranjay; Prakash, Prasoon; Althagafi, Ismail; Giri, Nand Gopal; Pratap, Ramendra; RSC Advances 13 (2023) 34299–34307; doi:10.1039/D3RA05421G

data_7247781
_publ_section_title
;
 1,3-Dianionic annulation of ketones with ketene dithioacetal: a modified
 route to 3-aryl/cyclopropyl-5-thiomethyl-phenols and
 1-(methylthio)-9,10-dihydrophenanthren-3-ols
;
_journal_issue                   48
_journal_name_full               'RSC Advances'
_journal_page_first              34299
_journal_page_last               34307
_journal_paper_doi               10.1039/D3RA05421G
_journal_volume                  13
_journal_year                    2023
_chemical_formula_moiety         'C21 H20 O3 S'
_chemical_formula_sum            'C21 H20 O3 S'
_chemical_formula_weight         352.45
_chemical_name_common
4,4''-dimethoxy-6'-(methylthio)-[1,1':4',1''-terphenyl]-2'-ol
_chemical_name_systematic
4,4''-dimethoxy-6'-(methylthio)-[1,1':4',1''-terphenyl]-2'-ol
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_Int_Tables_number      15
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-26
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-09-26 deposited with the CCDC.	2023-10-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.096(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.2427(13)
_cell_length_b                   5.4882(4)
_cell_length_c                   29.653(2)
_cell_measurement_reflns_used    3384
_cell_measurement_temperature    288(3)
_cell_measurement_theta_max      30.5030
_cell_measurement_theta_min      3.2940
_cell_volume                     3619.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      288(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.9243
_diffrn_measured_fraction_theta_max 0.4663
_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     21.00  70.00   0.50   10.00    --   -4.91  30.00  55.00   98
  2  \w    -17.00  25.00   0.50   10.00    --   -4.91 -99.00-120.00   84
  3  \w    -22.00  11.00   0.50   10.00    --   -4.91 -99.00   0.00   66
  4  \w    -23.00   6.00   0.50   10.00    --    5.23 -99.00 -30.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0198939000
_diffrn_orient_matrix_UB_12      0.0455164000
_diffrn_orient_matrix_UB_13      0.0166462000
_diffrn_orient_matrix_UB_21      -0.0247176000
_diffrn_orient_matrix_UB_22      -0.0208112000
_diffrn_orient_matrix_UB_23      -0.0146345000
_diffrn_orient_matrix_UB_31      -0.0032786000
_diffrn_orient_matrix_UB_32      -0.1191479000
_diffrn_orient_matrix_UB_33      0.0089400000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0816
_diffrn_reflns_av_unetI/netI     0.0895
_diffrn_reflns_Laue_measured_fraction_full 0.8966
_diffrn_reflns_Laue_measured_fraction_max 0.4436
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            8803
_diffrn_reflns_point_group_measured_fraction_full 0.8966
_diffrn_reflns_point_group_measured_fraction_max 0.4436
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         36.98
_diffrn_reflns_theta_min         3.30
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.195
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88796
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.69a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       block
_exptl_crystal_F_000             1489.854
_exptl_crystal_preparation
'The compund was prepared by the reaction of 1-(4-methoxyphenyl)-3,3-bis(methylthio)prop-2-en-1-one and 1-(4-methoxyphenyl)propan-2-one in NaH and DMF.'
_exptl_crystal_recrystallization_method
'A saturated solution of compound was prepared in hot methanol. After that the solution was cooled in 10 degree celcium for 2-3 days Without any disturbance which lead to the formation of crystal.'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.3940
_refine_diff_density_min         -0.5431
_refine_diff_density_rms         0.0971
_refine_ls_d_res_high            0.5907
_refine_ls_d_res_low             6.1732
_refine_ls_goodness_of_fit_ref   0.9715
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    34
_refine_ls_number_parameters     230
_refine_ls_number_reflns         4088
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.9715
_refine_ls_R_factor_all          0.1103
_refine_ls_R_factor_gt           0.0509
_refine_ls_shift/su_max          0.0004
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0543P)^2^+2.0950P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1128
_refine_ls_wR_factor_ref         0.1462
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              28
_reflns_limit_h_min              -28
_reflns_limit_k_max              7
_reflns_limit_k_min              0
_reflns_limit_l_max              46
_reflns_limit_l_min              0
_reflns_number_gt                2137
_reflns_number_total             4088
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3ra05421g2.cif
_cod_data_source_block           R-74_auto
_cod_depositor_comments
;

2025-01-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C2.471 H2.353 O0.353 S0.118'
_cod_original_formula_weight         41.466
_cod_original_formula_moiety         '0.118(C21 H20 O3 S)'
_cod_original_formula_units_Z            68
_cod_database_code               7247781
_chemical_oxdiff_formula         'C21 H20 O3 S1'
_chemical_oxdiff_usercomment     21-09-2023
_diffrn_oxdiff_ac3_digest_hkl    013b56eba7e7078052b3a80a56e3992cca502c
_diffrn_oxdiff_digest_frames
;
013f816df40bf75b992a8f6c9e3b86bf7a000256deb
;
_diffrn_oxdiff_digest_hkl
;
0175b2b982db0677c912aa6797ae02c9f4fa74
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C20(H20), C2(H2), C14(H14), C18(H18), C5(H5), C17(H17), C21(H21), C7(H7),
 C10(H10), C4(H4)
2.b Idealised Me refined as rotating group:
 C22(H22a,H22b,H22c), C1(H1a,H1b,H1c), C25(H25a,H25b,H25c)
2.c Idealised tetrahedral OH refined as rotating group:
 O24(H24)
;
_olex2_exptl_crystal_mounting_method
'At 35-40 degree celcius temperature the compound is sticky solid.'
_olex2_submission_original_sample_id R-74
_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 1.387
_oxdiff_exptl_absorpt_empirical_full_min 0.611