Synthesis of 4,5-diazaspiro[2.3]hexanes and 1,2-diazaspiro[3.3]heptanes as hexahydropyridazine analogues.
Pancholi, Alpa K.; Iacobini, Gregory P.; Clarkson, Guy J.; Porter, David W.; Shipman, Michael; The Journal of organic chemistry  (2017) –; doi:10.1021/acs.joc.7b02622

data_4033271
_publ_section_title
;
 Synthesis of 4,5-diazaspiro[2.3]hexanes and 1,2-diazaspiro[3.3]heptanes
 as hexahydropyridazine analogues.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.7b02622
_journal_year                    2017
_chemical_formula_moiety         'C14 H22 F2 N2 O4'
_chemical_formula_sum            'C14 H22 F2 N2 O4'
_chemical_formula_weight         320.33
_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'
_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     dual
_audit_creation_date             2016-12-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.24 svn.r3356 for OlexSys, GUI svn.r5267)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.1203(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.02756(10)
_cell_length_b                   5.73781(4)
_cell_length_c                   21.00103(12)
_cell_measurement_reflns_used    26875
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.4270
_cell_measurement_theta_min      4.2370
_cell_volume                     1652.641(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.9991
_diffrn_measured_fraction_theta_max 0.9811
_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   -113.00 -13.00   1.00    1.00    --  -41.32 -57.00  90.00  100
  2  \w   -116.00 -17.00   1.00    1.00    --  -41.32 -37.00 150.00   99
  3  \w    -33.00  66.00   1.00    1.00    --   41.32 -37.00   0.00   99
  4  \w     57.00 130.00   1.00    1.00    --   41.32 178.00-180.00   73
  5  \w     13.00 114.00   1.00    1.00    --   41.32  57.00 -60.00  101
  6  \w     57.00 130.00   1.00    1.00    --   41.32 178.00-150.00   73
  7  \w     78.00 178.00   1.00    4.00    --  107.00  61.00-180.00  100
  8  \w     74.00 178.00   1.00    4.00    --  107.00  77.00 -90.00  104
  9  \w     34.00 121.00   1.00    4.00    --  107.00-125.00 -60.00   87
 10  \w     74.00 178.00   1.00    4.00    --  107.00  77.00 120.00  104
 11  \w     74.00 178.00   1.00    4.00    --  107.00  77.00  90.00  104
 12  \w     24.00 109.00   1.00    4.00    --  107.00 -94.00-180.00   85
 13  \w     74.00 178.00   1.00    4.00    --  107.00  77.00 150.00  104
 14  \w     74.00 178.00   1.00    4.00    --  107.00  77.00-150.00  104
 15  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 120.00  100
 16  \w     81.00 178.00   1.00    4.00    --  107.00  45.00 -30.00   97
 17  \w     74.00 178.00   1.00    4.00    --  107.00  77.00  60.00  104
 18  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 150.00  100
 19  \w     78.00 178.00   1.00    4.00    --  107.00  61.00  90.00  100
 20  \w     79.00 178.00   1.00    4.00    --  107.00  30.00 150.00   99
 21  \w     81.00 178.00   1.00    4.00    --  107.00  45.00 150.00   97
 22  \w     31.00 140.00   1.00    4.00    --  107.00 -77.00  60.00  109
 23  \w     81.00 178.00   1.00    4.00    --  107.00  45.00-180.00   97
 24  \w     81.00 178.00   1.00    4.00    --  107.00  45.00 120.00   97
 25  \w     79.00 178.00   1.00    4.00    --  107.00  30.00-150.00   99
 26  \w     81.00 178.00   1.00    4.00    --  107.00  45.00  90.00   97
 27  \w    -66.00  33.00   1.00    1.00    --  -41.32  37.00-120.00   99
 28  \w   -117.00  -9.00   1.00    1.00    --  -41.32 -77.00  30.00  108
 29  \w   -117.00  -9.00   1.00    1.00    --  -41.32 -77.00 -60.00  108
 30  \w   -117.00  -9.00   1.00    1.00    --  -41.32 -77.00-180.00  108
 31  \w    -32.00  67.00   1.00    1.00    --   41.32 -43.00-119.00   99
 32  \w     55.00 128.00   1.00    1.00    --   41.32-178.00   0.00   73
 33  \w     74.00 178.00   1.00    4.00    --  107.00  77.00   0.00  104
 34  \w     74.00 178.00   1.00    4.00    --  107.00  77.00-180.00  104
 35  \w     34.00 121.00   1.00    4.00    --  107.00-125.00  60.00   87
 36  \w     74.00 178.00   1.00    4.00    --  107.00  77.00 -30.00  104
 37  \w     78.00 178.00   1.00    4.00    --  107.00  61.00-150.00  100
 38  \w     74.00 178.00   1.00    4.00    --  107.00  77.00  30.00  104
 39  \w     74.00 178.00   1.00    4.00    --  107.00  77.00 -60.00  104
 40  \w     78.00 178.00   1.00    4.00    --  107.00  61.00  30.00  100
 41  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 -90.00  100
 42  \w     74.00 178.00   1.00    4.00    --  107.00  77.00-120.00  104
 43  \w     78.00 178.00   1.00    4.00    --  107.00  61.00-120.00  100
 44  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 -60.00  100
 45  \w     78.00 178.00   1.00    4.00    --  107.00  61.00   0.00  100
 46  \w     78.00 178.00   1.00    4.00    --  107.00  61.00  60.00  100
 47  \w     24.00 109.00   1.00    4.00    --  107.00 -94.00 -30.00   85
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0143974000
_diffrn_orient_matrix_UB_12      0.1033067000
_diffrn_orient_matrix_UB_13      0.0690702000
_diffrn_orient_matrix_UB_21      -0.0996384000
_diffrn_orient_matrix_UB_22      -0.0990012000
_diffrn_orient_matrix_UB_23      0.0065590000
_diffrn_orient_matrix_UB_31      0.0499560000
_diffrn_orient_matrix_UB_32      -0.2269897000
_diffrn_orient_matrix_UB_33      0.0285674000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0084
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            45210
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.604
_diffrn_reflns_theta_min         4.306
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.927
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75483
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.287
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.232
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.135
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     205
_refine_ls_number_reflns         3327
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0377P)^2^+0.7706P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0967
_refine_ls_wR_factor_ref         0.0968
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3302
_reflns_number_total             3327
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02622_si_002.cif
_cod_data_source_block           ap7
_cod_original_cell_volume        1652.64(2)
_cod_database_code               4033271
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C17(H17A,H17B)
2.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C4(H4A,H4B,H4C), C14(H14A,H14B,H14C), C13(H13A,H13B,
 H13C), C3(H3A,H3B,H3C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              7756
_shelx_hkl_checksum              38063
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.421
_oxdiff_exptl_absorpt_empirical_full_min 0.700