Explorations into the sustainable synthesis of cyclic and polymeric carbonates and thiocarbonates from eugenol-derived monomers and their reactions with CO2, COS, or CS2
Sengoden, Mani; Bhat, Gulzar A.; Darensbourg, Donald J.; Green Chemistry 24 (2022) 2535–2541; doi:10.1039/D2GC00327A

data_7244545
_publ_section_title
;
 Explorations into the sustainable synthesis of cyclic and polymeric
 carbonates and thiocarbonates from eugenol-derived monomers and their
 reactions with CO2, COS, or CS2
;
_journal_issue                   6
_journal_name_full               'Green Chemistry'
_journal_page_first              2535
_journal_page_last               2541
_journal_paper_doi               10.1039/D2GC00327A
_journal_volume                  24
_journal_year                    2022
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C15 H20 O3 S'
_chemical_formula_sum            'C15 H20 O3 S'
_chemical_formula_weight         280.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc29yg80
_audit_creation_date             2021-10-07
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6405)
;
_audit_update_record
;
2022-01-20 deposited with the CCDC.	2022-02-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.6035(6)
_cell_length_b                   7.9904(2)
_cell_length_c                   16.8357(5)
_cell_measurement_reflns_used    9601
_cell_measurement_temperature    110.00
_cell_measurement_theta_max      27.495
_cell_measurement_theta_min      2.975
_cell_volume                     2906.19(14)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      110.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Quest (PHOTON III)'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0666
_diffrn_reflns_av_unetI/netI     0.0311
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            159949
_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         27.516
_diffrn_reflns_theta_min         1.885
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.224
_exptl_absorpt_correction_T_max  0.3787
_exptl_absorpt_correction_T_min  0.3348
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1808 before and 0.0897 after correction.
The Ratio of minimum to maximum transmission is 0.8841.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.492
_exptl_crystal_size_mid          0.457
_exptl_crystal_size_min          0.247
_refine_diff_density_max         0.404
_refine_diff_density_min         -0.464
_refine_diff_density_rms         0.094
_refine_ls_abs_structure_details
;
 Flack x determined using 2763 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.48(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     368
_refine_ls_number_reflns         6672
_refine_ls_number_restraints     273
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0599
_refine_ls_R_factor_gt           0.0555
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0782P)^2^+3.0665P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1589
_refine_ls_wR_factor_ref         0.1629
_reflns_Friedel_coverage         0.932
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                6090
_reflns_number_total             6672
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2gc00327a2.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 7244542--7244545.cif.'
_cod_database_code               7244545
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.898
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C14C, C14D}
3. Restrained distances
 C14A-C13 \\sim C14-C13
 with sigma of 0.02
 S1A-C15A \\sim S1-C15
 with sigma of 0.01
 C15A-C14A \\sim C15-C14
 with sigma of 0.01
 S1-C14 \\sim S1A-C14A
 with sigma of 0.01
 S1D-C15D \\sim S1C-C15C
 with sigma of 0.01
 C15C-C14C \\sim C15D-C14D
 with sigma of 0.01
 S1D-C14D \\sim S1C-C14C
 with sigma of 0.01
 C14C-C13C \\sim C14D-C13C
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
S1 \\sim C13 \\sim C14 \\sim C15 \\sim S1A \\sim C14A \\sim C15A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
S1C \\sim C13C \\sim C14C \\sim C15C \\sim S1D \\sim C14D \\sim C15D: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C14A) = Uanis(C14)
Uanis(S1) = Uanis(S1A)
Uanis(S1D) = Uanis(S1C)
Uanis(C14C) = Uanis(C14D)
Uanis(C15D) = Uanis(C15C)
Uanis(C15) = Uanis(C15A)
5. Rigid body (RIGU) restrains
 S1, C13, C14, C15, S1A, C14A, C15A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S1C, C13C, C14C, C15C, S1D, C14D, C15D
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Others
 Sof(H13C)=Sof(H13D)=Sof(S1A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15C)=
 Sof(H15D)=1-FVAR(1)
 Sof(S1)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 FVAR(1)
 Sof(H13G)=Sof(H13H)=Sof(S1D)=Sof(C14D)=Sof(H14D)=Sof(C15D)=Sof(H15G)=
 Sof(H15H)=1-FVAR(2)
 Sof(S1C)=Sof(H13E)=Sof(H13F)=Sof(C14C)=Sof(H14C)=Sof(C15C)=Sof(H15E)=
 Sof(H15F)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C14(H14), C14C(H14C), C14A(H14A), C14D(H14D)
7.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C13(H13C,H13D), C15(H15A,H15B), C13C(H13E,H13F), C13C(H13G,
 H13H), C15C(H15E,H15F), C15A(H15C,H15D), C15D(H15G,H15H)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C3C(H3C), C4C(H4C), C6C(H6C)
7.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C7C(H7CA,H7CB,H7CC), C10C(H10D,H10E,H10F), C11C(H11D,H11E,H11F),
 C12C(H12D,H12E,H12F)
;
_shelx_res_checksum              5467
_shelx_hkl_checksum              12597
_olex2_submission_special_instructions 'No special instructions were received'