Synthesis of 2,5-Bis(spirocyclohexane)-Substituted Nitroxides of Pyrroline and Pyrrolidine Series, Including Thiol-Specific Spin Label: An Analogue of MTSSL with Long Relaxation Time
Igor A. Kirilyuk; Yuliya F. Polienko; Olesya A. Krumkacheva; Rodion K. Strizhakov; Yurii V. Gatilov; Igor A. Grigor'ev; Elena G. Bagryanskaya; Journal of Organic Chemistry 77 (2012) 8016–8027; doi:10.1021/jo301235j

data_4027514
_publ_contact_author_address
;Novosibirsk Institute of Organic Chemistry SB RAS, 
Lavrentjev Ave. 9, 630090, Novosibirsk, Russian Federation
;
_publ_contact_author_email       gatilov@nioch.nsc.ru
_publ_contact_author_name        'Dr. Yu.V. Gatilov'
_publ_section_title
;
 Synthesis of 2,5-Bis(spirocyclohexane)-Substituted Nitroxides of
 Pyrroline and Pyrrolidine Series, Including Thiol-Specific Spin Label: An
 Analogue of MTSSL with Long Relaxation Time
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              8016
_journal_page_last               8027
_journal_paper_doi               10.1021/jo301235j
_journal_volume                  77
_journal_year                    2012
_chemical_formula_moiety         'C16 H25 N2 O4, 0.25(C4 H8 O2)'
_chemical_formula_sum            'C17 H27 N2 O4.5'
_chemical_formula_weight         331.41
_chemical_melting_point          442.6
_chemical_name_systematic
; 
 (14R(S),15R(S))-14-Carbamoyl-15-carboxy-7-
azadispiro[5.1.5.2]pentadecane-7-oxyl ethyl acetate solvate
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 101.0230(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            16
_cell_length_a                   19.3600(7)
_cell_length_b                   19.1405(7)
_cell_length_c                   20.7892(6)
_cell_measurement_reflns_used    9864
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      24.79
_cell_measurement_theta_min      2.33
_cell_volume                     7561.5(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0596
_diffrn_reflns_av_sigmaI/netI    0.0513
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            84700
_diffrn_reflns_theta_full        26.05
_diffrn_reflns_theta_max         26.05
_diffrn_reflns_theta_min         1.07
_exptl_absorpt_coefficient_mu    0.084
_exptl_absorpt_correction_T_max  0.9878
_exptl_absorpt_correction_T_min  0.7964
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS-2008/1
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.164
_exptl_crystal_description       prism
_exptl_crystal_F_000             2864
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.213
_refine_diff_density_min         -0.411
_refine_diff_density_rms         0.154
_refine_ls_extinction_coef       0.0082(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     859
_refine_ls_number_reflns         14879
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.1168
_refine_ls_R_factor_gt           0.0742
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1401P)^2^+5.8919P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1977
_refine_ls_wR_factor_ref         0.2377
_reflns_number_gt                9845
_reflns_number_total             14879
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo301235j_si_001_1.cif
_cod_data_source_block           compound18_kiril
_cod_original_sg_symbol_H-M      'P 1 21/c 1 '
_cod_original_formula_sum        'C17 H27 N2 O4.50'
_cod_database_code               4027514