Dibenzoazepine hydrazine is a building block for <i>N</i>-alkene hybrid ligands: exploratory syntheses of complexes of Cu, Fe, and Li.
Grasruck, Alexander; Schall, Kristina; Heinemann, Frank W.; Langer, Jens; Herrera, Alberto; Frieß, Sybille; Schmid, Günter; Dorta, Romano; Dalton transactions (Cambridge, England : 2003) 53 (2024) 8642–8656; doi:10.1039/d4dt00749b

data_7715940
_publ_section_title
;
 Dibenzoazepine hydrazine is a building block for <i>N</i>-alkene hybrid
 ligands: exploratory syntheses of complexes of Cu, Fe, and Li.
;
_journal_issue                   20
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              8642
_journal_page_last               8656
_journal_paper_doi               10.1039/d4dt00749b
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         '1(C30 H22 Cl2 Fe N4), C6 H6'
_chemical_formula_sum            'C36 H28 Cl2 Fe N4'
_chemical_formula_weight         643.37
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-05
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-03-07 deposited with the CCDC.	2024-04-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.3288(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8273(2)
_cell_length_b                   12.01604(12)
_cell_length_c                   20.6789(3)
_cell_measurement_reflns_used    12090
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      72.8810
_cell_measurement_theta_min      3.6060
_cell_volume                     3042.64(8)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.980
_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  29.00   1.00    4.00    --  -41.44  57.00 -30.00   97
  2  \w    -64.00  31.00   1.00    4.00    --  -41.44  38.00-120.00   95
  3  \w   -115.00 -10.00   1.00    4.00    --  -41.44 -77.00-150.00  105
  4  \w     24.00 109.00   1.00   20.00    --  105.04 -94.00-120.00   85
  5  \w     81.00 176.00   1.00   20.00    --  105.04  45.00 -90.00   95
  6  \w     94.00 177.00   1.00   20.00    --  105.04 125.00  90.00   83
  7  \w     24.00 109.00   1.00   20.00    --  105.04 -94.00-180.00   85
  8  \w     25.00 150.00   1.00   20.00    --  105.04 -15.00 120.00  125
  9  \w   -115.00 -10.00   1.00    4.00    --  -41.44 -77.00 -30.00  105
 10  \w      1.00  81.00   1.00    4.00    --   41.44 -99.00  60.00   80
 11  \w     74.00 178.00   1.00   20.00    --  105.04  77.00-180.00  104
 12  \w     94.00 177.00   1.00   20.00    --  105.04 125.00-150.00   83
 13  \w     77.00 130.00   1.00   20.00    --  105.04  61.00 -30.00   53
 14  \w     81.00 176.00   1.00   20.00    --  105.04  45.00 150.00   95
;
_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      -0.0621407000
_diffrn_orient_matrix_UB_12      -0.0905994000
_diffrn_orient_matrix_UB_13      0.0262950000
_diffrn_orient_matrix_UB_21      0.0497010000
_diffrn_orient_matrix_UB_22      -0.0898185000
_diffrn_orient_matrix_UB_23      -0.0349792000
_diffrn_orient_matrix_UB_31      0.0975376000
_diffrn_orient_matrix_UB_32      -0.0118882000
_diffrn_orient_matrix_UB_33      0.0646458000
_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  0.0379
_diffrn_reflns_av_unetI/netI     0.0268
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            23355
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.341
_diffrn_reflns_theta_min         3.637
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.841
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42477
_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            'clear brownish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_description       plate
_exptl_crystal_F_000             1328
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: 1,2-difluorobenzene, n-hexane'
_exptl_crystal_size_max          0.234
_exptl_crystal_size_mid          0.215
_exptl_crystal_size_min          0.086
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.369
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     503
_refine_ls_number_reflns         5980
_refine_ls_number_restraints     200
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0415
_refine_ls_R_factor_gt           0.0396
_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^)+(0.0568P)^2^+1.5495P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1030
_refine_ls_wR_factor_ref         0.1047
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5703
_reflns_number_total             5980
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00749b2.cif
_cod_data_source_block           rodo180421a
_cod_depositor_comments
'Adding full bibliography for 7715932--7715940.cif.'
_cod_original_cell_volume        3042.63(8)
_cod_database_code               7715940
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C30 H22 N4 Fe Cl2'
_shelx_estimated_absorpt_t_max   0.634
_shelx_estimated_absorpt_t_min   0.342
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Shared sites
{N2, N2B}
{N1, N1B}
{N3, N3A}
{N4, N4A}
{C1, C1B}
{C3, C3B}
{C4, C4B}
{C5, C5B}
{C6, C6B}
{C11, C11B}
{C12, C12B}
{C7, C7B}
{C13, C13B}
{C8, C8B}
{C14, C14B}
{C9, C9B}
{C15, C15B}
{C16, C16B}
{C10, C10B}
{C2, C2A}
{C24, C24A}
{C28, C28A}
{C17, C17A}
{C26, C26A}
{C18, C18A}
{C30, C30A}
{C19, C19A}
{C25, C25A}
{C20, C20A}
{C27, C27A}
{C21, C21A}
{C29, C29A}
{C22, C22A}
{C23, C23A}
3. Restrained distances
 Fe1A-Cl2A \\sim Fe1B-Cl2B \\sim Fe1-Cl2
 with sigma of 0.02
 Fe1B-Cl1B \\sim Fe1A-Cl1A \\sim Fe1-Cl1
 with sigma of 0.02
 C2A-C1A \\sim C2-C1 \\sim C2B-C1B
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Fe1A \\sim Cl1A \\sim Cl2A \\sim N1A \\sim N2A \\sim C1A \\sim C3A \\sim C4A
\\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim C9A \\sim C10A \\sim C11A \\sim
C12A \\sim C13A \\sim C14A \\sim C15A \\sim C16A: within 4A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 4A
Fe1B \\sim Cl1B \\sim Cl2B \\sim N4B \\sim N3B \\sim C17B \\sim C26B \\sim C22B
\\sim C30B \\sim C19B \\sim C24B \\sim C28B \\sim C2B \\sim C18B \\sim C20B
\\sim C23B \\sim C25B \\sim C27B \\sim C29B \\sim C21B: within 4A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 4A
Uanis(N2) = Uanis(N2B)
Uanis(N1) = Uanis(N1B)
Uanis(N3) = Uanis(N3A)
Uanis(N4) = Uanis(N4A)
Uanis(C1) = Uanis(C1B)
Uanis(C3) = Uanis(C3B)
Uanis(C4) = Uanis(C4B)
Uanis(C5) = Uanis(C5B)
Uanis(C6) = Uanis(C6B)
Uanis(C11) = Uanis(C11B)
Uanis(C12) = Uanis(C12B)
Uanis(C7) = Uanis(C7B)
Uanis(C13) = Uanis(C13B)
Uanis(C8) = Uanis(C8B)
Uanis(C14) = Uanis(C14B)
Uanis(C9) = Uanis(C9B)
Uanis(C15) = Uanis(C15B)
Uanis(C16) = Uanis(C16B)
Uanis(C10) = Uanis(C10B)
Uanis(C2) = Uanis(C2A)
Uanis(C24) = Uanis(C24A)
Uanis(C28) = Uanis(C28A)
Uanis(C17) = Uanis(C17A)
Uanis(C26) = Uanis(C26A)
Uanis(C18) = Uanis(C18A)
Uanis(C30) = Uanis(C30A)
Uanis(C19) = Uanis(C19A)
Uanis(C25) = Uanis(C25A)
Uanis(C20) = Uanis(C20A)
Uanis(C27) = Uanis(C27A)
Uanis(C21) = Uanis(C21A)
Uanis(C29) = Uanis(C29A)
Uanis(C22) = Uanis(C22A)
Uanis(C23) = Uanis(C23A)
5. Others
 1*[Sof(Fe1A)+Sof(Cl1A)+Sof(Cl2A)+Sof(N1A)+Sof(N2A)+Sof(N3A)+Sof(N4A)+Sof(C1A)+
 Sof(H1A)+Sof(C2A)+Sof(H2A)+Sof(C3A)+Sof(C9A)+Sof(H9A)+Sof(C10A)+Sof(H10A)+
 Sof(C11A)+Sof(H11A)+Sof(C12A)+Sof(H12A)+Sof(C4A)+Sof(C5A)+Sof(H5A)+Sof(C6A)+
 Sof(H6A)+Sof(C8A)+Sof(C7A)+Sof(C13A)+Sof(H13A)+Sof(C14A)+Sof(H14A)+Sof(C15A)+
 Sof(H15A)+Sof(C16A)+Sof(H16A)+Sof(C17A)+Sof(C18A)+Sof(C19A)+Sof(H19A)+
 Sof(C20A)+Sof(H20A)+Sof(C21A)+Sof(C22A)+Sof(C23A)+Sof(H23A)+Sof(C24A)+
 Sof(H24A)+Sof(C25A)+Sof(H25A)+Sof(C26A)+Sof(H26A)+Sof(C27A)+Sof(H27A)+
 Sof(C28A)+Sof(H28A)+Sof(C29A)+Sof(H29A)+Sof(C30A)+Sof(H30A)]+1*[Sof(Fe1B)+
 Sof(Cl1B)+Sof(Cl2B)+Sof(N4B)+Sof(N1B)+Sof(N3B)+Sof(N2B)+Sof(C17B)+Sof(C23B)+
 Sof(H23B)+Sof(C24B)+Sof(H24B)+Sof(C25B)+Sof(H25B)+Sof(C26B)+Sof(H26B)+
 Sof(C18B)+Sof(C13B)+Sof(H13B)+Sof(C22B)+Sof(C21B)+Sof(C27B)+Sof(H27B)+
 Sof(C28B)+Sof(H28B)+Sof(C29B)+Sof(H29B)+Sof(C30B)+Sof(H30B)+Sof(C15B)+
 Sof(H15B)+Sof(C19B)+Sof(H19B)+Sof(C1B)+Sof(H1B)+Sof(C3B)+Sof(C5B)+Sof(H5B)+
 Sof(C7B)+Sof(C9B)+Sof(H9B)+Sof(C11B)+Sof(H11B)+Sof(C2B)+Sof(H2B)+Sof(C4B)+
 Sof(C6B)+Sof(H6B)+Sof(C8B)+Sof(C10B)+Sof(H10B)+Sof(C12B)+Sof(H12B)+Sof(C14B)+
 Sof(H14B)+Sof(C16B)+Sof(H16B)+Sof(C20B)+Sof(H20B)]+1*[Sof(Fe1)+Sof(Cl1)+
 Sof(Cl2)+Sof(N2)+Sof(N3)+Sof(N1)+Sof(N4)+Sof(C8)+Sof(C9)+Sof(H9)+Sof(C10)+
 Sof(H10)+Sof(C11)+Sof(H11)+Sof(C12)+Sof(H12)+Sof(C13)+Sof(H13)+Sof(C6)+Sof(H6)+
 Sof(C1)+Sof(H1)+Sof(C2)+Sof(H2)+Sof(C3)+Sof(C5)+Sof(H5)+Sof(C7)+Sof(C14)+
 Sof(H14)+Sof(C4)+Sof(C15)+Sof(H15)+Sof(C16)+Sof(H16)+Sof(C17)+Sof(C18)+
 Sof(C19)+Sof(H19)+Sof(C20)+Sof(H20)+Sof(C21)+Sof(C22)+Sof(C23)+Sof(H23)+
 Sof(C24)+Sof(H24)+Sof(C25)+Sof(H25)+Sof(C26)+Sof(H26)+Sof(C27)+Sof(H27)+
 Sof(C28)+Sof(H28)+Sof(C29)+Sof(H29)+Sof(C30)+Sof(H30)]=1 with esd of 0.000001
 Sof(Fe1A)=Sof(Cl1A)=Sof(Cl2A)=Sof(N1A)=Sof(N2A)=Sof(N3A)=Sof(N4A)=Sof(C1A)=
 Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=
 Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=
 Sof(H6A)=Sof(C8A)=Sof(C7A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=
 Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=
 Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=
 Sof(H24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=
 Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=FVAR(1)
 Sof(Fe1)=Sof(Cl1)=Sof(Cl2)=Sof(N2)=Sof(N3)=Sof(N1)=Sof(N4)=Sof(C8)=Sof(C9)=
 Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=
 Sof(H13)=Sof(C6)=Sof(H6)=Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(C5)=
 Sof(H5)=Sof(C7)=Sof(C14)=Sof(H14)=Sof(C4)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=
 Sof(C17)=Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(C22)=
 Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=
 Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=FVAR(2)
 Sof(Fe1B)=Sof(Cl1B)=Sof(Cl2B)=Sof(N4B)=Sof(N1B)=Sof(N3B)=Sof(N2B)=Sof(C17B)=
 Sof(C23B)=Sof(H23B)=Sof(C24B)=Sof(H24B)=Sof(C25B)=Sof(H25B)=Sof(C26B)=
 Sof(H26B)=Sof(C18B)=Sof(C13B)=Sof(H13B)=Sof(C22B)=Sof(C21B)=Sof(C27B)=
 Sof(H27B)=Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(H29B)=Sof(C30B)=Sof(H30B)=
 Sof(C15B)=Sof(H15B)=Sof(C19B)=Sof(H19B)=Sof(C1B)=Sof(H1B)=Sof(C3B)=Sof(C5B)=
 Sof(H5B)=Sof(C7B)=Sof(C9B)=Sof(H9B)=Sof(C11B)=Sof(H11B)=Sof(C2B)=Sof(H2B)=
 Sof(C4B)=Sof(C6B)=Sof(H6B)=Sof(C8B)=Sof(C10B)=Sof(H10B)=Sof(C12B)=Sof(H12B)=
 Sof(C14B)=Sof(H14B)=Sof(C16B)=Sof(H16B)=Sof(C20B)=Sof(H20B)=FVAR(3)
6.a Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C2A(H2A), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C5A(H5A),
 C6A(H6A), C13A(H13A), C14A(H14A), C15A(H15A), C16A(H16A), C19A(H19A),
 C20A(H20A), C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A), C27A(H27A),
 C28A(H28A), C29A(H29A), C30A(H30A), C23B(H23B), C24B(H24B), C25B(H25B),
 C26B(H26B), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C9(H9),
  C10(H10), C13B(H13B), C11(H11), C27B(H27B), C28B(H28B), C29B(H29B),
 C30B(H30B), C12(H12), C13(H13), C6(H6), C1(H1), C15B(H15B), C2(H2), C19B(H19B),
  C1B(H1B), C5B(H5B), C5(H5), C9B(H9B), C11B(H11B), C14(H14), C15(H15),
 C2B(H2B), C16(H16), C6B(H6B), C19(H19), C10B(H10B), C20(H20), C12B(H12B),
 C14B(H14B), C16B(H16B), C23(H23), C24(H24), C20B(H20B), C25(H25), C26(H26),
 C27(H27), C28(H28), C29(H29), C30(H30)
6.b Fitted hexagon refined as free rotating group:
 C3A(C9A,C10A,C11A,C12A,C4A), C8A(C7A,C13A,C14A,C15A,C16A), C17B(C23B,C24B,
 C25B,C26B,C18B), C22B(C21B,C27B,C28B,C29B,C30B)
;
_shelx_res_checksum              5399
_olex2_date_sample_data_collection 2021-07-01
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.887
_oxdiff_exptl_absorpt_empirical_full_min 0.606