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_7246824
_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
'0.21(C14 H9 Br), 0.79(C30 H23 Br N2 O4 S2), 0.21(C16 H14 N2 O4 S2)'
_chemical_formula_sum            'C30 H23 Br N2 O4 S2'
_chemical_formula_weight         619.53
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-18
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-04-19 deposited with the CCDC.	2023-05-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 131.943(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.1661(11)
_cell_length_b                   11.7540(11)
_cell_length_c                   14.9001(12)
_cell_measurement_reflns_used    7973
_cell_measurement_temperature    173.00
_cell_measurement_theta_max      22.619
_cell_measurement_theta_min      2.201
_cell_volume                     2627.0(4)
_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      173.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.1477
_diffrn_reflns_av_unetI/netI     0.0401
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            52117
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.993
_diffrn_reflns_theta_max         24.993
_diffrn_reflns_theta_min         2.201
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.765
_exptl_absorpt_correction_T_max  0.7162
_exptl_absorpt_correction_T_min  0.5866
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1334 before and 0.1072 after correction.
The Ratio of minimum to maximum transmission is 0.8190.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.566
_exptl_crystal_description       rod
_exptl_crystal_F_000             1264
_exptl_crystal_recrystallization_method 'Thermal solid-state reaction at 20degC'
_exptl_crystal_size_max          0.286
_exptl_crystal_size_mid          0.078
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.835
_refine_diff_density_min         -0.431
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.122
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     343
_refine_ls_number_reflns         2305
_refine_ls_number_restraints     709
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.1315
_refine_ls_R_factor_gt           0.1082
_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^)+(0.1216P)^2^+16.8817P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2874
_refine_ls_wR_factor_ref         0.3122
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1758
_reflns_number_total             2305
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ce00388d2.cif
_cod_data_source_block           22talb36_90c_dc49b_fzgrt_133d5h_0f_1
_cod_depositor_comments
'Adding full bibliography for 7246822--7246827.cif.'
_cod_database_code               7246824
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.880
_shelx_estimated_absorpt_t_min   0.632
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C19P-C21P \\sim C19R-C21R \\sim C27R-C29R \\sim C27P-C29P
 with sigma of 0.005
 C22P-C19P \\sim C22P-C21P \\sim C21P-C20P \\sim C20P-C19P \\sim C30P-C27P
\\sim C30P-C29P \\sim C29P-
 C28P \\sim C28P-C27P
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Br1P \\sim S1P \\sim S2P \\sim O1P \\sim O2P \\sim O3P \\sim O4P \\sim N1P
\\sim N2P \\sim C1P \\sim C2P \\sim C3P \\sim C4P \\sim C5P \\sim C6P \\sim C7P
\\sim C8P \\sim C9P \\sim C10P \\sim C11P \\sim C12P \\sim C13P \\sim C14P
\\sim C15P \\sim C16P \\sim C17P \\sim C18P \\sim C19P \\sim C20P \\sim C21P
\\sim C22P \\sim C23P \\sim C24P \\sim C25P \\sim C26P \\sim C27P \\sim C28P
\\sim C29P \\sim C30P: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
Br1R \\sim C1R \\sim C2R \\sim C3R \\sim C4R \\sim C5R \\sim C6R \\sim C7R
\\sim C8R \\sim C9R \\sim C10R \\sim C11R \\sim C12R \\sim C13R \\sim C14R:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
S1R \\sim S2R \\sim O1R \\sim O2R \\sim O3R \\sim O4R \\sim N1R \\sim N2R \\sim
C15R \\sim C16R \\sim C17R \\sim C18R \\sim C19R \\sim C20R \\sim C21R \\sim
C22R \\sim C23R \\sim C24R \\sim C25R \\sim C26R \\sim C27R \\sim C28R \\sim
C29R \\sim C30R: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
4. Rigid body (RIGU) restrains
 Br1P, S1P, S2P, O1P, O2P, O3P, O4P, N1P, N2P, C1P, C2P, C3P, C4P, C5P, C6P,
 C7P, C8P, C9P, C10P, C11P, C12P, C13P, C14P, C15P, C16P, C17P, C18P, C19P,
 C20P, C21P, C22P, C23P, C24P, C25P, C26P, C27P, C28P, C29P, C30P
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Br1R, C1R, C2R, C3R, C4R, C5R, C6R, C7R, C8R, C9R, C10R, C11R, C12R, C13R, C14R
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S1R, S2R, O1R, O2R, O3R, O4R, N1R, N2R, C15R, C16R, C17R, C18R, C19R, C20R,
 C21R, C22R, C23R, C24R, C25R, C26R, C27R, C28R, C29R, C30R
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(Br1R)=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(H8R)=Sof(C9R)=Sof(C10R)=
 Sof(H10R)=Sof(C11R)=Sof(H11R)=Sof(C12R)=Sof(H12R)=Sof(C13R)=Sof(H13R)=
 Sof(C14R)=Sof(S1R)=Sof(S2R)=Sof(O1R)=Sof(O2R)=Sof(O3R)=Sof(O4R)=Sof(N1R)=
 Sof(N2R)=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(C23R)=Sof(C24R)=Sof(C25R)=Sof(C26R)=Sof(C27R)=Sof(H27R)=
 Sof(C28R)=Sof(H28C)=Sof(H28D)=Sof(C29R)=Sof(H29C)=Sof(H29D)=Sof(C30R)=
 Sof(H30C)=Sof(H30D)=0.5*(1-FVAR(2))
 Sof(Br1P)=Sof(S1P)=Sof(S2P)=Sof(O1P)=Sof(O2P)=Sof(O3P)=Sof(O4P)=Sof(N1P)=
 Sof(N2P)=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(C23P)=Sof(C24P)=Sof(C25P)=Sof(C26P)=Sof(C27P)=
 Sof(H27P)=Sof(C28P)=Sof(H28A)=Sof(H28B)=Sof(C29P)=Sof(H29A)=Sof(H29B)=
 Sof(C30P)=Sof(H30A)=Sof(H30B)=0.5*FVAR(2)
 Uiso(C1R)=Uiso(C2R)=Uiso(C3R)=Uiso(C4R)=Uiso(C5R)=Uiso(C6R)=Uiso(C7R)=
 Uiso(C8R)=Uiso(C9R)=Uiso(C10R)=Uiso(C11R)=Uiso(C12R)=Uiso(C13R)=Uiso(C14R)=
 Uiso(S1R)=Uiso(S2R)=Uiso(O1R)=Uiso(O2R)=Uiso(O3R)=Uiso(O4R)=Uiso(N1R)=
 Uiso(N2R)=Uiso(C15R)=Uiso(C16R)=Uiso(C17R)=Uiso(C18R)=Uiso(C19R)=Uiso(C20R)=
 Uiso(C21R)=Uiso(C22R)=Uiso(C23R)=Uiso(C24R)=Uiso(C25R)=Uiso(C26R)=Uiso(C27R)=
 Uiso(C28R)=Uiso(C29R)=Uiso(C30R)=FVAR(2)
6.a Free rotating group:
 Br1R(C1R,C2R,C3R,C4R,C5R,C6R,C7R,C8R,C9R,C10R,C11R,C12R,C13R,C14R), S1R(S2R,
 O1R,O2R,O3R,O4R,N1R,N2R,C15R,C16R,C17R,C18R,C19R,C20R,C21R,C22R,C23R,C24R,C25R,
 C26R,C27R,C28R,C29R,C30R)
6.b Ternary CH refined with riding coordinates:
 C8P(H8P), C19P(H19P), C27P(H27P), C19R(H19R), C27R(H27R)
6.c Secondary CH2 refined with riding coordinates:
 C20P(H20A,H20B), C21P(H21A,H21B), C22P(H22A,H22B), C28P(H28A,H28B), C29P(H29A,
 H29B), C30P(H30A,H30B), C20R(H20C,H20D), C21R(H21C,H21D), C22R(H22C,H22D),
 C28R(H28C,H28D), C29R(H29C,H29D), C30R(H30C,H30D)
6.d Aromatic/amide H refined with riding coordinates:
 C3R(H3R), C4R(H4R), C5R(H5R), C6R(H6R), C8R(H8R), C10R(H10R), C11R(H11R),
 C12R(H12R), C13R(H13R), C3P(H3P), C4P(H4P), C5P(H5P), C6P(H6P), C10P(H10P),
 C11P(H11P), C12P(H12P), C13P(H13P)
6.e Fitted hexagon refined as free rotating group:
 C2P(C3P,C4P,C5P,C6P,C7P), C9P(C10P,C11P,C12P,C13P,C14P)
;
_shelx_res_checksum              84536
_olex2_submission_special_instructions 'No special instructions were received'