Readily accessible sp<sup>3</sup>-rich cyclic hydrazine frameworks exploiting nitrogen fluxionality.
Dean, Conor; Rajkumar, Sundaram; Roesner, Stefan; Carson, Nessa; Clarkson, Guy J.; Wills, Martin; Jones, Matthew; Shipman, Michael; Chemical science 11 (2020) 1636–1642; doi:10.1039/c9sc04849a

data_1556912
_publ_section_title
;
 Readily accessible sp<sup>3</sup>-rich cyclic hydrazine frameworks
 exploiting nitrogen fluxionality.
;
_journal_issue                   6
_journal_name_full               'Chemical science'
_journal_page_first              1636
_journal_page_last               1642
_journal_paper_doi               10.1039/c9sc04849a
_journal_volume                  11
_journal_year                    2020
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C22 H25 N3 O2'
_chemical_formula_sum            'C22 H25 N3 O2'
_chemical_formula_weight         363.45
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-30 deposited with the CCDC.	2019-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.8702(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.47130(5)
_cell_length_b                   9.02632(4)
_cell_length_c                   17.84198(7)
_cell_measurement_reflns_used    44954
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.3790
_cell_measurement_theta_min      3.5120
_cell_volume                     2005.951(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.998
_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   -114.00 -14.00   1.00    1.00    --  -41.94 -57.00-180.00  100
  2  \w    -33.00  66.00   1.00    1.00    --   41.94 -37.00  30.00   99
  3  \w      6.00  83.00   1.00    1.00    --   41.94 -99.00   0.00   77
  4  \w      7.00  33.00   1.00    1.00    --   41.94  84.00 -18.18   26
  5  \w      6.00  83.00   1.00    1.00    --   41.94 -99.00-150.00   77
  6  \w      9.00  42.00   1.00    1.00    --   41.94  78.00 -60.66   33
  7  \w     77.00 178.00   1.00    4.00    --  107.00  64.00 102.43  101
  8  \w     78.00 178.00   1.00    4.00    --  107.00  61.00-150.00  100
  9  \w     78.00 178.00   1.00    4.00    --  107.00  62.00-179.28  100
 10  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 -90.00  100
 11  \w     24.00 107.00   1.00    4.00    --  107.00 -94.00  30.00   83
 12  \w     78.00 178.00   1.00    4.00    --  107.00  61.00-120.00  100
 13  \w     80.00 178.00   1.00    4.00    --  107.00  49.00 155.49   98
 14  \w     76.00 178.00   1.00    4.00    --  107.00  72.00 -45.94  102
 15  \w     35.00 136.00   1.00    4.00    --  107.00 -61.00   0.00  101
 16  \w     97.00 178.00   1.00    4.00    --  107.00 125.00  60.00   81
 17  \w     34.00 112.00   1.00    4.00    --  107.00-125.00  30.00   78
 18  \w     75.00 178.00   1.00    4.00    --  107.00  73.00 -67.64  103
 19  \w   -114.00 -14.00   1.00    1.00    --  -41.94 -57.00  30.00  100
 20  \w    -33.00  66.00   1.00    1.00    --   41.94 -37.00-120.00   99
 21  \w      9.00  42.00   1.00    1.00    --   41.94  80.00 164.04   33
 22  \w      8.00  42.00   1.00    1.00    --   41.94  82.00   9.19   34
 23  \w     24.00 107.00   1.00    4.00    --  107.00 -94.00 -90.00   83
 24  \w     78.00 178.00   1.00    4.00    --  107.00  61.00  60.00  100
 25  \w     34.00 112.00   1.00    4.00    --  107.00-125.00 -90.00   78
 26  \w     78.00 178.00   1.00    4.00    --  107.00  61.00  90.00  100
 27  \w     78.00 178.00   1.00    4.00    --  107.00  61.00  30.00  100
 28  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 120.00  100
 29  \w     34.00 112.00   1.00    4.00    --  107.00-125.00-150.00   78
 30  \w     77.00 178.00   1.00    4.00    --  107.00  68.00 150.45  101
 31  \w     34.00 112.00   1.00    4.00    --  107.00-125.00-180.00   78
 32  \w    103.00 178.00   1.00    4.00    --  107.00  77.00 -30.00   75
 33  \w     76.00 178.00   1.00    4.00    --  107.00  69.00  41.07  102
 34  \w     78.00 178.00   1.00    4.00    --  107.00  61.00   0.00  100
 35  \w   -116.00 -18.00   1.00    1.00    --  -41.94 -37.00 -60.00   98
 36  \w      8.00  42.00   1.00    1.00    --   41.94  82.00-104.87   34
 37  \w      7.00  33.00   1.00    1.00    --   41.94  84.00 119.63   26
 38  \w      9.00  42.00   1.00    1.00    --   41.94  79.00-161.42   33
 39  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 150.00  100
 40  \w     79.00 178.00   1.00    4.00    --  107.00  55.00  76.38   99
 41  \w     76.00 178.00   1.00    4.00    --  107.00  72.00-137.31  102
 42  \w     81.00 178.00   1.00    4.00    --  107.00  45.00  30.00   97
 43  \w     81.00 178.00   1.00    4.00    --  107.00  45.00   0.00   97
 44  \w     24.00 107.00   1.00    4.00    --  107.00 -94.00  90.00   83
 45  \w     81.00 178.00   1.00    4.00    --  107.00  45.00 -60.00   97
 46  \w     80.00 178.00   1.00    4.00    --  107.00  51.00 142.90   98
 47  \w     76.00 178.00   1.00    4.00    --  107.00  71.00 163.91  102
 48  \w     24.00 107.00   1.00    4.00    --  107.00 -94.00-150.00   83
 49  \w     35.00 136.00   1.00    4.00    --  107.00 -61.00-150.00  101
 50  \w     81.00 178.00   1.00    4.00    --  107.00  45.00 -90.00   97
 51  \w   -116.00 -18.00   1.00    1.00    --  -41.94 -37.00  90.00   98
 52  \w    -87.00  -6.00   1.00    1.00    --  -41.94 125.00 120.00   81
 53  \w      7.00  33.00   1.00    1.00    --   41.94  84.00  57.18   26
 54  \w      8.00  34.00   1.00    1.00    --   41.94  83.00 147.98   26
 55  \w     81.00 169.00   1.00    4.00    --  107.00  45.00-120.00   88
 56  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 -60.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1034655000
_diffrn_orient_matrix_UB_12      0.0376667000
_diffrn_orient_matrix_UB_13      0.0397019000
_diffrn_orient_matrix_UB_21      -0.0318233000
_diffrn_orient_matrix_UB_22      -0.1109690000
_diffrn_orient_matrix_UB_23      0.0628279000
_diffrn_orient_matrix_UB_31      -0.0598644000
_diffrn_orient_matrix_UB_32      0.1240424000
_diffrn_orient_matrix_UB_33      -0.0441730000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            60499
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.631
_diffrn_reflns_theta_min         3.548
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.622
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39377
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.57a (Rigaku Oxford Diffraction, 2019)
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    1.203
_exptl_crystal_description       block
_exptl_crystal_F_000             776
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.108
_refine_diff_density_min         -0.162
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 3649 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
 Flack x: 0.01(6) Shelx 2018
 Hooft y: 0.01(3) Olex2
 Synthesised from a known chiral starting material
;
_refine_ls_abs_structure_Flack   0.01(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     493
_refine_ls_number_reflns         8067
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0283
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0444P)^2^+0.2036P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0739
_refine_ls_wR_factor_ref         0.0743
_reflns_Friedel_coverage         0.869
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                7973
_reflns_number_total             8067
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04849a2.cif
_cod_data_source_block           sr2
_cod_depositor_comments
;Adding full bibliography for 1556907--1556915.cif.

 Adding full bibliography for 1556907--1556915.cif.
;
_cod_database_code               1556912
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2'
_shelx_estimated_absorpt_t_max   0.907
_shelx_estimated_absorpt_t_min   0.826
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C113(H113), C213(H213)
2.b Secondary CH2 refined with riding coordinates:
 C110(H11A,H11B), C111(H11C,H11D), C112(H11E,H11F), C210(H21A,H21B), C211(H21C,
 H21D), C212(H21E,H21F)
2.c Aromatic/amide H refined with riding coordinates:
 C104(H104), C105(H105), C107(H107), C108(H108), C122(H122), C123(H123),
 C124(H124), C125(H125), C126(H126), C204(H204), C205(H205), C207(H207),
 C208(H208), C222(H222), C223(H223), C224(H224), C225(H225), C226(H226)
2.d Idealised Me refined as rotating group:
 C118(H11G,H11H,H11I), C119(H11J,H11K,H11L), C120(H12A,H12B,H12C), C218(H21G,
 H21H,H21I), C219(H21J,H21K,H21L), C220(H22A,H22B,H22C)
;
_shelx_res_checksum              61666
_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 1.941
_oxdiff_exptl_absorpt_empirical_full_min 0.688