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_1556910
_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 H21 N3 O2, 0.125(H2 O)'
_chemical_formula_sum            'C22 H21.25 N3 O2.125'
_chemical_formula_weight         361.67
_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   mixed
_audit_creation_date             2019-02-26
_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                 93.0169(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.18405(5)
_cell_length_b                   9.71457(5)
_cell_length_c                   18.82762(9)
_cell_measurement_reflns_used    29109
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.3780
_cell_measurement_theta_min      4.3180
_cell_volume                     1860.104(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.40a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.40a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.40a (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 0.996
_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 -68.00 31.00 1.00 4.00 -- -41.82 45.00 110.00 99 2 \w -114.00 -14.00 1.00 4.00 -- -41.82 -57.00 150.00 100 3 \w 57.00 131.00 1.00 4.00 -- 41.82 178.00 60.00 74 4 \w 57.00 131.00 1.00 4.00 -- 41.82 178.00 -90.00 74 5 \w 17.00 116.00 1.00 4.00 -- 41.82 37.00 -30.00 99 6 \w 17.00 116.00 1.00 4.00 -- 41.82 37.00-120.00 99 7 \w 74.00 178.00 1.00 16.00 -- 107.00 77.00 120.00 104 8 \w 24.00 110.00 1.00 16.00 -- 107.00 -94.00 -30.00 86 9 \w 74.00 178.00 1.00 16.00 -- 107.00 77.00 150.00 104 10 \w 78.00 178.00 1.00 16.00 -- 107.00 61.00-120.00 100 11 \w 78.00 178.00 1.00 16.00 -- 107.00 61.00-150.00 100 12 \w 34.00 118.00 1.00 16.00 -- 107.00-125.00 -30.00 84 13 \w 94.00 178.00 1.00 16.00 -- 107.00 125.00 0.00 84 14 \w 74.00 178.00 1.00 16.00 -- 107.00 77.00-120.00 104 15 \w 74.00 178.00 1.00 16.00 -- 107.00 77.00-150.00 104 16 \w 78.00 178.00 1.00 16.00 -- 107.00 61.00-180.00 100 17 \w 35.00 136.00 1.00 16.00 -- 107.00 -61.00 -30.00 101 18 \w 74.00 178.00 1.00 16.00 -- 107.00 77.00-180.00 104 19 \w 94.00 178.00 1.00 16.00 -- 107.00 125.00 30.00 84 20 \w 81.00 178.00 1.00 16.00 -- 107.00 45.00 110.00 97 21 \w -114.00 -14.00 1.00 4.00 -- -41.82 -57.00 30.00 100 22 \w -118.00 -9.00 1.00 4.00 -- -41.82 -77.00 -30.00 109 23 \w -66.00 33.00 1.00 4.00 -- -41.82 37.00-120.00 99 24 \w -118.00 -9.00 1.00 4.00 -- -41.82 -77.00-150.00 109 25 \w -118.00 -9.00 1.00 4.00 -- -41.82 -77.00 90.00 109 26 \w 9.00 118.00 1.00 4.00 -- 41.82 77.00 -30.00 109 27 \w 81.00 178.00 1.00 16.00 -- 107.00 45.00 -30.00 97 28 \w 78.00 178.00 1.00 16.00 -- 107.00 61.00 60.00 100 29 \w 74.00 178.00 1.00 16.00 -- 107.00 77.00 -90.00 104 30 \w 74.00 178.00 1.00 16.00 -- 107.00 77.00 -30.00 104 31 \w 78.00 178.00 1.00 16.00 -- 107.00 61.00 30.00 100 32 \w 94.00 178.00 1.00 16.00 -- 107.00 125.00 -90.00 84'
_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      -0.0544785000
_diffrn_orient_matrix_UB_12      0.0722652000
_diffrn_orient_matrix_UB_13      0.0650689000
_diffrn_orient_matrix_UB_21      -0.1190733000
_diffrn_orient_matrix_UB_22      0.0511032000
_diffrn_orient_matrix_UB_23      -0.0465648000
_diffrn_orient_matrix_UB_31      -0.0761721000
_diffrn_orient_matrix_UB_32      -0.1315775000
_diffrn_orient_matrix_UB_33      0.0176563000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0176
_diffrn_reflns_av_unetI/netI     0.0104
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            35330
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.526
_diffrn_reflns_theta_min         4.347
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.679
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37742
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.40.40a (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    1.291
_exptl_crystal_description       block
_exptl_crystal_F_000             765
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.135
_refine_diff_density_min         -0.195
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 3337 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Flack x: -0.05(3) Shelx
Hooft y: -0.04(2) Olex2
This is OK as the structure contains no heavy atoms in it, additionally the assignment of stereochemistry has 
been made by reference to an unchanging chiral centre in the synthetic procedure.
;
_refine_ls_abs_structure_Flack   -0.05(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     496
_refine_ls_number_reflns         7385
_refine_ls_number_restraints     37
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0259
_refine_ls_R_factor_gt           0.0257
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0408P)^2^+0.2075P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0679
_refine_ls_wR_factor_ref         0.0682
_reflns_Friedel_coverage         0.859
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.969
_reflns_number_gt                7318
_reflns_number_total             7385
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04849a2.cif
_cod_data_source_block           cd7
_cod_depositor_comments
;
 Adding full bibliography for 1556907--1556915.cif.

2022-11-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_weight         723.34
_cod_original_formula_moiety         '2(C22 H21 N3 O2), 0.25(H2 O)'
_cod_original_formula_units_Z            2
_cod_original_cell_volume        1860.102(16)
_cod_original_formula_sum        'C44 H42.50 N6 O4.25'
_cod_database_code               1556910
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2'
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.854
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
A small amount of electron density was modelled as a partially occupied 
water 25% occupancy and is the source of the fractional formula. 
A RIGU restraint was used to give some of the atoms of one of the phenyl rings 
less extreme elliptical thermal parameters.

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 O(H,H) groups
2. Rigid body (RIGU) restrains
 C211, C212, C213, C214, C215, C216
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Others
 Fixed Sof: O1(0.25) H1A(0.25) H1B(0.25)
4.a Free rotating group:
 O1(H1A,H1B)
4.b Ternary CH refined with riding coordinates:
 C110(H110), C210(H210)
4.c Secondary CH2 refined with riding coordinates:
 C109(H10A,H10B), C209(H20A,H20B), C208(H20C,H20D), C108(H10C,H10D)
4.d Aromatic/amide H refined with riding coordinates:
 C120(H120), C119(H119), C223(H223), C116(H116), C222(H222), C204(H204),
 C123(H123), C104(H104), C219(H219), C203(H203), C114(H114), C212(H212),
 C115(H115), C205(H205), C103(H103), C105(H105), C220(H220), C122(H122),
 C202(H202), C113(H113), C213(H213), C112(H112), C102(H102), C214(H214),
 C216(H216), C215(H215)
4.e Idealised Me refined as rotating group:
 C124(H12A,H12B,H12C), C224(H22A,H22B,H22C)
;
_shelx_res_checksum              68994
_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 2.001
_oxdiff_exptl_absorpt_empirical_full_min 0.695