Sigmatropic rearrangement enables access to a highly stable spirocyclic nitroxide for protein spin labelling
Sowiński, Mateusz P.; Mocanu, Elena M.; Ruskin-Dodd, Hannah; McKay, Aidan P.; Cordes, David B.; Lovett, Janet E.; Haugland-Grange, Marius; Chemical Communications 61 (2025) 6755–6758; doi:10.1039/D5CC00472A

data_7134357
_publ_section_title
;
 Sigmatropic rearrangement enables access to a highly stable spirocyclic
 nitroxide for protein spin labelling
;
_journal_issue                   37
_journal_name_full               'Chemical Communications'
_journal_page_first              6755
_journal_page_last               6758
_journal_paper_doi               10.1039/D5CC00472A
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C17 H24 Cl3 N2 O2'
_chemical_formula_sum            'C17 H24 Cl3 N2 O2'
_chemical_formula_weight         394.73
_chemical_name_systematic
'2,2,2-trichloro-N-(15-methylene-7-azadispiro[5.1.58.26]pentadecan-14-yl) acetamide-7-N-oxyl'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-30
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-28 deposited with the CCDC.	2025-03-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.5135(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.68805(19)
_cell_length_b                   14.41773(19)
_cell_length_c                   10.39362(16)
_cell_measurement_reflns_used    11346
_cell_measurement_temperature    100
_cell_measurement_theta_max      75.1850
_cell_measurement_theta_min      3.5400
_cell_volume                     1856.17(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 42.94a (release 21-06-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'hybrid photon counting detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Dectris PILATUS P200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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     -9.00  89.00   0.50    0.50    --    0.00   9.00-180.00  196
  2  \w    -84.00  31.00   0.50    0.50    --    5.00  28.00 -30.00  230
  3  \w   -171.00 -88.00   0.50    2.50    --  -96.50  55.00  36.74  166
  4  \w   -174.00 -21.00   0.50    2.50    --  -96.50  46.00 -60.00  306
  5  \w    -58.00  -8.00   0.50    2.50    --  -96.50  55.00 125.14  100
  6  \w    -59.00 -33.00   0.50    2.50    --  -96.50  55.00  36.74   52
  7  \w    -74.00 -46.00   0.50    2.50    --  -96.50   0.00 -90.00   56
  8  \w   -139.00 -77.00   0.50    2.50    --  -96.50   0.00 -90.00  124
  9  \w   -185.00 -26.00   0.50    2.50    --  -96.50  55.00 -42.68  318
 10  \w   -183.00-131.00   0.50    2.50    --  -96.50  55.00 125.14  104
 11  \w   -184.00  -8.00   0.50    2.50    --  -96.50  55.00-145.68  352
 12  \w   -179.00-145.00   0.50    2.50    --  -96.50  55.00-102.37   68
 13  \w   -167.00-142.00   0.50    2.50    --  -96.50  55.00  -3.12   50
 14  \w   -179.00-153.00   0.50    2.50    --  -96.50  55.00  88.63   52
 15  \w   -108.00 -56.00   0.50    2.50    --  -96.50  55.00  88.63  104
 16  \w   -183.00-157.00   0.50    2.50    --  -96.50  55.00 144.46   52
 17  \w   -147.00 -98.00   0.50    2.50    --  -96.50  55.00 144.46   98
 18  \w    -60.00 -31.00   0.50    2.50    --  -96.50  55.00 144.46   58
 19  \w   -185.00  -8.00   0.50    2.50    --  -96.50  55.00-169.47  354
;
_diffrn_measurement_device       'AFC11: Quarter \c 4 circle'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200K'
_diffrn_measurement_method       'shutterless scans'
_diffrn_measurement_specimen_support Loop
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0541051000
_diffrn_orient_matrix_UB_12      0.0961675000
_diffrn_orient_matrix_UB_13      -0.0099493000
_diffrn_orient_matrix_UB_21      0.0583518000
_diffrn_orient_matrix_UB_22      0.0212260000
_diffrn_orient_matrix_UB_23      0.1429431000
_diffrn_orient_matrix_UB_31      0.0955931000
_diffrn_orient_matrix_UB_32      0.0414829000
_diffrn_orient_matrix_UB_33      -0.0501170000
_diffrn_radiation_monochromator  'Rigaku Osmic Confocal Optical System'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0626
_diffrn_reflns_av_unetI/netI     0.0366
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            19950
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.373
_diffrn_reflns_theta_min         3.568
_diffrn_source                   'Rotating Anode'
_diffrn_source_type              'Rigaku MM-007HF'
_exptl_absorpt_coefficient_mu    4.572
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60451
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.109a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.413
_exptl_crystal_description       needle
_exptl_crystal_F_000             828
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Diethyl ether'
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.600
_refine_diff_density_min         -0.356
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     221
_refine_ls_number_reflns         3799
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0404
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0640P)^2^+0.7920P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1045
_refine_ls_wR_factor_ref         0.1064
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3476
_reflns_number_total             3799
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc00472a2.cif
_cod_data_source_block           9
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7134357.cif.
;
_cod_original_sg_symbol_H-M      P21/c
_cod_database_code               7134357
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.477
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 N12-H12
 0.98 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C4(H4)
3.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C15(H15A,
 H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B)
3.c X=CH2 refined with riding coordinates:
 C11(H11A,H11B)
;
_shelx_res_checksum              20719
_shelx_hkl_checksum              84436