Forced topochemistry of a solid-state Diels–Alder reaction by encapsulation in epoxy glue
Lau, T. A.; Khorasani, S.; Fernandes, M. A.; CrystEngComm 25 (2023) 3988–3997; doi:10.1039/D3CE00388D

data_7246823
_publ_section_title
;
 Forced topochemistry of a solid-state Diels--Alder reaction by
 encapsulation in epoxy glue
;
_journal_issue                   28
_journal_name_full               CrystEngComm
_journal_page_first              3988
_journal_page_last               3997
_journal_paper_doi               10.1039/D3CE00388D
_journal_volume                  25
_journal_year                    2023
_chemical_formula_moiety
;        
0.7994(C16 H14 N2 O4 S2), 0.7994(C14 H9 Br), 0.2006(C30 H23 Br N2 O4 S2)
;
_chemical_formula_sum            'C30 H23 Br N2 O4 S2'
_chemical_formula_weight         619.53
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-06
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-04-19 deposited with the CCDC.	2023-05-23 downloaded from the CCDC.
;
_cell_angle_alpha                64.094(2)
_cell_angle_beta                 78.975(2)
_cell_angle_gamma                62.088(2)
_cell_formula_units_Z            2
_cell_length_a                   11.4616(6)
_cell_length_b                   11.9174(6)
_cell_length_c                   11.9565(6)
_cell_measurement_reflns_used    9901
_cell_measurement_temperature    173.00
_cell_measurement_theta_max      28.01
_cell_measurement_theta_min      2.31
_cell_volume                     1297.97(12)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      173.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0600
_diffrn_reflns_av_unetI/netI     0.0355
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            49988
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.320
_diffrn_reflns_theta_min         1.894
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.786
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6675
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0771 before and 0.0588 after correction.
The Ratio of minimum to maximum transmission is 0.8951.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_description       rod
_exptl_crystal_F_000             632
_exptl_crystal_recrystallization_method 'Thermal solid-state reaction at 20degC'
_exptl_crystal_size_max          0.322
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.065
_refine_diff_density_max         1.211
_refine_diff_density_min         -0.687
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.115
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     377
_refine_ls_number_reflns         6432
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0816
_refine_ls_R_factor_gt           0.0693
_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^)+(0.0734P)^2^+3.9943P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1928
_refine_ls_wR_factor_ref         0.2008
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5353
_reflns_number_total             6432
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ce00388d2.cif
_cod_data_source_block           22talb11_90c_dc49b_fzgrt_12d9h_0f
_cod_depositor_comments
'Adding full bibliography for 7246822--7246827.cif.'
_cod_database_code               7246823
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.597
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Br1R-C1R \\sim Br1P-C1P \\sim Br2R-C8R
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S1P \\sim C6R: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
4. Rigid body (RIGU) restrains
 S1P, C6R
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 1*[Sof(S1R)+Sof(O1R)+Sof(O2R)+Sof(N1R)+Sof(C15R)+Sof(C16R)+Sof(C17R)+
 Sof(C18R)+Sof(C19R)+Sof(H19R)+Sof(C20R)+Sof(H20C)+Sof(H20D)+Sof(C21R)+
 Sof(H21C)+Sof(H21D)+Sof(C22R)+Sof(H22C)+Sof(H22D)+Sof(C1R)+Sof(C2R)+Sof(C3R)+
 Sof(H3R)+Sof(C4R)+Sof(H4R)+Sof(C5R)+Sof(H5R)+Sof(C6R)+Sof(H6R)+Sof(C7R)+
 Sof(C8R)+Sof(C9R)+Sof(C10R)+Sof(H10R)+Sof(C11R)+Sof(H11R)+Sof(C12R)+Sof(H12R)+
 Sof(C13R)+Sof(H13R)+Sof(C14R)]+1*[Sof(Br1P)+Sof(S1P)+Sof(S3P)+Sof(O1P)+
 Sof(O2P)+Sof(O5P)+Sof(O6P)+Sof(N1P)+Sof(N3P)+Sof(C1P)+Sof(C2P)+Sof(C3P)+
 Sof(H3P)+Sof(C4P)+Sof(H4P)+Sof(C5P)+Sof(H5P)+Sof(C6P)+Sof(H6P)+Sof(C7P)+
 Sof(C8P)+Sof(H8P)+Sof(C9P)+Sof(C10P)+Sof(H10P)+Sof(C11P)+Sof(H11P)+Sof(C12P)+
 Sof(H12P)+Sof(C13P)+Sof(H13P)+Sof(C14P)+Sof(C15P)+Sof(C16P)+Sof(C17P)+
 Sof(C18P)+Sof(C19P)+Sof(H19P)+Sof(C20P)+Sof(H20A)+Sof(H20B)+Sof(C21P)+
 Sof(H21A)+Sof(H21B)+Sof(C22P)+Sof(H22A)+Sof(H22B)+Sof(C31P)+Sof(C32P)+
 Sof(C33P)+Sof(C34P)+Sof(C35P)+Sof(H35P)+Sof(C36P)+Sof(H36A)+Sof(H36B)+
 Sof(C37P)+Sof(H37A)+Sof(H37B)+Sof(C38P)+Sof(H38A)+Sof(H38B)]=1 with esd of
 0.0001
 1*[Sof(Br1P)+Sof(S1P)+Sof(S3P)+Sof(O1P)+Sof(O2P)+Sof(O5P)+Sof(O6P)+Sof(N1P)+
 Sof(N3P)+Sof(C1P)+Sof(C2P)+Sof(C3P)+Sof(H3P)+Sof(C4P)+Sof(H4P)+Sof(C5P)+
 Sof(H5P)+Sof(C6P)+Sof(H6P)+Sof(C7P)+Sof(C8P)+Sof(H8P)+Sof(C9P)+Sof(C10P)+
 Sof(H10P)+Sof(C11P)+Sof(H11P)+Sof(C12P)+Sof(H12P)+Sof(C13P)+Sof(H13P)+
 Sof(C14P)+Sof(C15P)+Sof(C16P)+Sof(C17P)+Sof(C18P)+Sof(C19P)+Sof(H19P)+
 Sof(C20P)+Sof(H20A)+Sof(H20B)+Sof(C21P)+Sof(H21A)+Sof(H21B)+Sof(C22P)+
 Sof(H22A)+Sof(H22B)+Sof(C31P)+Sof(C32P)+Sof(C33P)+Sof(C34P)+Sof(C35P)+
 Sof(H35P)+Sof(C36P)+Sof(H36A)+Sof(H36B)+Sof(C37P)+Sof(H37A)+Sof(H37B)+
 Sof(C38P)+Sof(H38A)+Sof(H38B)]+1*[Sof(Br1R)+Sof(H8R)]+1*[Sof(Br2R)+Sof(H1R)]=1
 with esd of 0.0001
 Sof(S1R)=Sof(O1R)=Sof(O2R)=Sof(N1R)=Sof(C15R)=Sof(C16R)=Sof(C17R)=Sof(C18R)=
 Sof(C19R)=Sof(H19R)=Sof(C20R)=Sof(H20C)=Sof(H20D)=Sof(C21R)=Sof(H21C)=
 Sof(H21D)=Sof(C22R)=Sof(H22C)=Sof(H22D)=Sof(C1R)=Sof(C2R)=Sof(C3R)=Sof(H3R)=
 Sof(C4R)=Sof(H4R)=Sof(C5R)=Sof(H5R)=Sof(C6R)=Sof(H6R)=Sof(C7R)=Sof(C8R)=
 Sof(C9R)=Sof(C10R)=Sof(H10R)=Sof(C11R)=Sof(H11R)=Sof(C12R)=Sof(H12R)=Sof(C13R)=
 Sof(H13R)=Sof(C14R)=FVAR(1)
 Sof(S1P)=Sof(S3P)=Sof(O1P)=Sof(O2P)=Sof(O5P)=Sof(O6P)=Sof(N1P)=Sof(N3P)=
 Sof(C15P)=Sof(C16P)=Sof(C17P)=Sof(C18P)=Sof(C19P)=Sof(H19P)=Sof(C20P)=
 Sof(H20A)=Sof(H20B)=Sof(C21P)=Sof(H21A)=Sof(H21B)=Sof(C22P)=Sof(H22A)=
 Sof(H22B)=Sof(C31P)=Sof(C32P)=Sof(C33P)=Sof(C34P)=Sof(C35P)=Sof(H35P)=
 Sof(C36P)=Sof(H36A)=Sof(H36B)=Sof(C37P)=Sof(H37A)=Sof(H37B)=Sof(C38P)=
 Sof(H38A)=Sof(H38B)=0.5*FVAR(3)
 Sof(Br1P)=Sof(C1P)=Sof(C2P)=Sof(C3P)=Sof(H3P)=Sof(C4P)=Sof(H4P)=Sof(C5P)=
 Sof(H5P)=Sof(C6P)=Sof(H6P)=Sof(C7P)=Sof(C8P)=Sof(H8P)=Sof(C9P)=Sof(C10P)=
 Sof(H10P)=Sof(C11P)=Sof(H11P)=Sof(C12P)=Sof(H12P)=Sof(C13P)=Sof(H13P)=
 Sof(C14P)=FVAR(2)
 Sof(Br1R)=Sof(H8R)=FVAR(3)
 Sof(Br2R)=Sof(H1R)=FVAR(4)
 Fixed Uiso: S1P(0.04) S3P(0.04) O1P(0.04) O2P(0.04) O5P(0.04) O6P(0.04)
 N1P(0.04) N3P(0.04) C1P(0.04) C2P(0.04) C3P(0.04) C4P(0.04) C5P(0.04)
 C6P(0.04) C7P(0.04) C8P(0.04) C9P(0.04) C10P(0.04) C11P(0.04) C12P(0.04)
 C13P(0.04) C14P(0.04) C15P(0.04) C16P(0.04) C17P(0.04) C18P(0.04) C19P(0.04)
 C20P(0.04) C21P(0.04) C22P(0.04) C31P(0.04) C32P(0.04) C33P(0.04) C34P(0.04)
 C35P(0.04) H35P(0.04) C36P(0.04) H36A(0.04) H36B(0.04) C37P(0.04) H37A(0.04)
 H37B(0.04) C38P(0.04) H38A(0.04) H38B(0.04)
6.a Free rotating group:
 Br1P(S1P,S3P,O1P,O2P,O5P,O6P,N1P,N3P,C1P,C2P,C3P,C4P,C5P,C6P,C7P,C8P,C9P,C10P,
 C11P,C12P,C13P,C14P,C15P,C16P,C17P,C18P,C19P,C20P,C21P,C22P,C31P,C32P,C33P,
 C34P,C35P,H35P,C36P,H36A,H36B,C37P,H37A,H37B,C38P,H38A,H38B)
6.b Ternary CH refined with riding coordinates:
 C8P(H8P), C19P(H19P), C27R(H27R), C19R(H19R)
6.c Secondary CH2 refined with riding coordinates:
 C20P(H20A,H20B), C21P(H21A,H21B), C22P(H22A,H22B), C28R(H28A,H28B), C29R(H29A,
 H29B), C30R(H30A,H30B), C20R(H20C,H20D), C21R(H21C,H21D), C22R(H22C,H22D)
6.d Aromatic/amide H refined with riding coordinates:
 C3P(H3P), C4P(H4P), C5P(H5P), C6P(H6P), C10P(H10P), C11P(H11P), C12P(H12P),
 C13P(H13P), C1R(H1R), C3R(H3R), C4R(H4R), C5R(H5R), C6R(H6R), C8R(H8R),
 C10R(H10R), C11R(H11R), C12R(H12R), C13R(H13R)
;
_shelx_res_checksum              95946
_olex2_submission_special_instructions 'No special instructions were received'