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_1556907
_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 ad
_chemical_formula_moiety         'C23 H24 N2 O5 S'
_chemical_formula_sum            'C23 H24 N2 O5 S'
_chemical_formula_weight         440.50
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-07-30 deposited with the CCDC.	2019-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.4605(6)
_cell_length_b                   11.6596(2)
_cell_length_c                   6.11590(10)
_cell_measurement_reflns_used    10459
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.0630
_cell_measurement_theta_min      4.0070
_cell_volume                     2172.11(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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 1.000
_diffrn_measured_fraction_theta_max 0.997
_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   -112.00 -15.00   1.00    2.50    --  -41.80 -57.00-150.00   97
  2  \w    -68.00  28.00   1.00    2.50    --  -41.80  57.00-180.00   96
  3  \w      1.00  82.00   1.00    2.50    --   41.80 -99.00  90.00   81
  4  \w     32.00 137.00   1.00   25.00    --  106.00 -77.00-180.00  105
  5  \w     82.00 177.00   1.00   25.00    --  106.00  45.00 150.00   95
  6  \w     34.00 121.00   1.00   25.00    --  106.00-125.00-180.00   87
  7  \w     25.00 109.00   1.00   25.00    --  106.00 -94.00-180.00   84
  8  \w     82.00 177.00   1.00   25.00    --  106.00  45.00 -90.00   95
  9  \w     31.00 130.00   1.00   25.00    --  106.00 -30.00 150.00   99
 10  \w   -112.00 -15.00   1.00    2.50    --  -41.80 -57.00 120.00   97
 11  \w   -116.00 -10.00   1.00    2.50    --  -41.80 -77.00  60.00  106
 12  \w     36.00 134.00   1.00   25.00    --  106.00 -61.00 -60.00   98
 13  \w     78.00 176.00   1.00   25.00    --  106.00  61.00-150.00   98
 14  \w     82.00 177.00   1.00   25.00    --  106.00  45.00  90.00   95
 15  \w     78.00 176.00   1.00   25.00    --  106.00  61.00  30.00   98
 16  \w     78.00 109.00   1.00   25.00    --  106.00  61.00 -60.00   31
 17  \w     82.00 171.00   1.00   25.00    --  106.00  30.00   0.00   89
;
_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      -0.0504117000
_diffrn_orient_matrix_UB_12      -0.0093220000
_diffrn_orient_matrix_UB_13      -0.0115894000
_diffrn_orient_matrix_UB_21      -0.0039409000
_diffrn_orient_matrix_UB_22      0.1294558000
_diffrn_orient_matrix_UB_23      0.0468306000
_diffrn_orient_matrix_UB_31      0.0015990000
_diffrn_orient_matrix_UB_32      0.0249301000
_diffrn_orient_matrix_UB_33      -0.2470887000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0524
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            21406
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.432
_diffrn_reflns_theta_min         2.901
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.643
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63206
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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    1.347
_exptl_crystal_description       block
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.238
_refine_diff_density_min         -0.272
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1629 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Flack x: 0.004(13) Shelx2018
Hooft y: 0.005(10) Olex2
;
_refine_ls_abs_structure_Flack   0.004(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     341
_refine_ls_number_reflns         4351
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0386
_refine_ls_R_factor_gt           0.0362
_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^)+(0.0359P)^2^+0.5447P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0887
_refine_ls_wR_factor_ref         0.0904
_reflns_Friedel_coverage         0.711
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                4140
_reflns_number_total             4351
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04849a2.cif
_cod_data_source_block           rs4
_cod_depositor_comments
;Adding full bibliography for 1556907--1556915.cif.

 Adding full bibliography for 1556907--1556915.cif.
;
_cod_database_code               1556907
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2 S'
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.684
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
The NH and OH were located in a difference map. The OH was placed at a calculate position for the refinement 
but the hydrogen of the NH was given a Ueqiv 1.5 time the Uanis of N10 and refined with a DFIX restraint 
(as there is no suitable geometric restraint for this type of hydrogen to ride on the parent nitrogen). 
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, All C(H,H,H,H) groups, All O(H) groups
2. Restrained distances
 N10-H10
 0.9 with sigma of 0.02
3. Others
 Sof(C17A)=Sof(H17A)=Sof(C16A)=Sof(H16A)=Sof(C14A)=Sof(H14A)=Sof(C13A)=
 Sof(H13A)=Sof(C15A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=1-FVAR(1)
 Sof(C15)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=Sof(C17)=Sof(H17)=Sof(C16)=Sof(H16)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C7(H7A)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C21(H21A,H21B)
4.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C27(H27), C23(H23), C1(H1), C4(H4), C25(H25), C2(H2), C3(H3),
 C26(H26), C24(H24), C13(H13), C14(H14), C17(H17), C16(H16), C17A(H17A),
 C16A(H16A), C14A(H14A), C13A(H13A)
4.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C18A(H18D,H18E,H18F)
4.e Idealised tetrahedral OH refined as rotating group:
 O7(H7)
;
_shelx_res_checksum              16316
_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 1.509
_oxdiff_exptl_absorpt_empirical_full_min 0.490