Skeletal rearrangements and structures of halosulfonamidation products of caryophyllene
Moskalik, Mikhail Yu.; Garagan, Ivan A.; Myasnikova, Valentina S.; Borodina, Tatyana N.; Shainyan, Bagrat A.; New Journal of Chemistry 50 (2026) 1935–1942; doi:10.1039/D5NJ03976B

data_7064321
_publ_section_title
;
 Skeletal rearrangements and structures of halosulfonamidation products of
 caryophyllene
;
_journal_issue                   4
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              1935
_journal_page_last               1942
_journal_paper_doi               10.1039/D5NJ03976B
_journal_volume                  50
_journal_year                    2026
_chemical_formula_moiety         'C24 H32 Br F3 N2 O2 S'
_chemical_formula_sum            'C24 H32 Br F3 N2 O2 S'
_chemical_formula_weight         549.48
_chemical_melting_point          480.3
_chemical_name_systematic
N-(6-bromo-1,1,7-trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)-N'-((4-(trifluoromethyl)phenyl)sulfonyl)acetimidamide
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-02-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-03-13 deposited with the CCDC.	2025-12-17 downloaded from the CCDC.
;
_cell_angle_alpha                90.113(4)
_cell_angle_beta                 93.196(4)
_cell_angle_gamma                93.055(4)
_cell_formula_units_Z            2
_cell_length_a                   10.3167(13)
_cell_length_b                   10.7257(14)
_cell_length_c                   11.5944(14)
_cell_measurement_reflns_used    9916
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      29.25
_cell_measurement_theta_min      2.57
_cell_volume                     1279.1(3)
_computing_cell_refinement       'SAINT V8.32B (BRUKER, 2016)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT V8.32B (BRUKER, 2016)'
_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)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker D8 VENTURE PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0778
_diffrn_reflns_av_unetI/netI     0.0847
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            61939
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.760
_diffrn_reflns_theta_min         2.574
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.733
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.2883
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1427 before and 0.0984 after correction.
The Ratio of minimum to maximum transmission is 0.3865.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.427
_exptl_crystal_description       prism
_exptl_crystal_F_000             568
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: chloroform'
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.595
_exptl_crystal_size_min          0.595
_refine_diff_density_max         0.693
_refine_diff_density_min         -0.442
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 3735 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.094(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     603
_refine_ls_number_reflns         14380
_refine_ls_number_restraints     399
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.0961
_refine_ls_R_factor_gt           0.0555
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0797P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1371
_refine_ls_wR_factor_ref         0.1505
_reflns_Friedel_coverage         0.984
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                9899
_reflns_number_total             14380
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03976b2.cif
_cod_data_source_block           3h
_cod_database_code               7064321
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.425
_shelx_estimated_absorpt_t_min   0.423
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(F2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F102) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F101) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F103) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F3) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F101)
\\sim Ueq, Uanis(F102) \\sim Ueq, Uanis(F103) \\sim Ueq: with sigma of 0.05 and
sigma for terminal atoms of 0.1
Uanis(C122) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C119) \\sim Ueq, Uanis(Br1A) \\sim Ueq, Uanis(C106) \\sim Ueq,
Uanis(C107) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C110) \\sim Ueq,
Uanis(C108) \\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C104) \\sim Ueq,
Uanis(C13A) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C103) \\sim Ueq,
Uanis(C19A) \\sim Ueq, Uanis(N101) \\sim Ueq, Uanis(C102) \\sim Ueq,
Uanis(C101) \\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C112) \\sim Ueq,
Uanis(C111) \\sim Ueq, Uanis(N102) \\sim Ueq, Uanis(C115) \\sim Ueq,
Uanis(S101) \\sim Ueq, Uanis(O102) \\sim Ueq, Uanis(O101) \\sim Ueq,
Uanis(C116) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C117) \\sim Ueq,
Uanis(C120) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C122) \\sim Ueq,
Uanis(F101) \\sim Ueq, Uanis(F103) \\sim Ueq, Uanis(F102) \\sim Ueq, Uanis(Br1)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C13) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C3) \\sim Ueq,
Uanis(C9A) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(N2) \\sim Ueq,
Uanis(C15) \\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O1) \\sim
Ueq, Uanis(C16) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C17) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq,
Uanis(C1) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(F103) \\sim Ueq, Uanis(F102) \\sim Ueq, Uanis(F101) \\sim Ueq,
Uanis(C122) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C122) \\sim Ueq, Uanis(F102) \\sim Ueq, Uanis(F101) \\sim Ueq,
Uanis(F103) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
3.a Ternary CH refined with riding coordinates:
 C3(H3), C6(H6), C9A(H9A), C103(H103), C106(H106), C19A(H19A)
3.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C8(H8A,H8B), C5(H5A,H5B), C4(H4A,H4B), C2(H2A,H2B), C9(H9B,
 H9C), C110(H11G,H11H), C105(H10C,H10D), C104(H10E,H10F), C108(H10G,H10H),
 C109(H10I,H10J), C102(H10K,H10L)
3.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C20(H20), C21(H21), N1(H1), C17(H17), N101(H101), C121(H121),
 C120(H120), C117(H117), C118(H118)
3.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C113(H11D,H11E,H11F), C115(H11I,H11J,H11K), C112(H11L,H11M,H11N),
 C111(H11O,H11P,H11Q)
;
_shelx_res_checksum              8709
_olex2_submission_special_instructions 'No special instructions were received'