A novel type of organometallic 2-R-2,4-dihydro-1H-3,1-benzoxazine with R = [M(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>)(CO)<sub>3</sub>] (M = Re or Mn) units. Experimental and computational studies of the effect of substituent R on ring-chain tautomerism.
Oyarzo, Juan; Bosque, Ramón; Toro, Patricia; Silva, Carlos P.; Arancibia, Rodrigo; Font-Bardía, Mercè; Artigas, Vania; Calvis, Carme; Messeguer, Ramon; Klahn, A. Hugo; López, Concepción; Dalton transactions (Cambridge, England : 2003) 48 (2019) 1023–1039; doi:10.1039/c8dt03265c

data_7048358
_publ_section_title
;
 A novel type of organometallic 2-R-2,4-dihydro-1H-3,1-benzoxazine with R
 = [M(\h<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>)(CO)<sub>3</sub>] (M = Re
 or Mn) units. Experimental and computational studies of the effect of
 substituent R on ring-chain tautomerism.
;
_journal_issue                   3
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1023
_journal_page_last               1039
_journal_paper_doi               10.1039/c8dt03265c
_journal_volume                  48
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H17 Fe N O'
_chemical_formula_sum            'C18 H17 Fe N O'
_chemical_formula_weight         319.17
_chemical_melting_point          96
_chemical_name_systematic        6a
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-01-16
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3461 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-07-27 deposited with the CCDC.
2018-12-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.7714(15)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.9213(2)
_cell_length_b                   7.5337(3)
_cell_length_c                   16.2535(7)
_cell_measurement_reflns_used    9921
_cell_measurement_temperature    170.0
_cell_measurement_theta_max      26.40
_cell_measurement_theta_min      2.52
_cell_volume                     720.00(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0258
_diffrn_reflns_av_unetI/netI     0.0236
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            16003
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.416
_diffrn_reflns_theta_min         2.524
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.044
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.7000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0599 before and 0.0534 after correction.
The Ratio of minimum to maximum transmission is 0.9391.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.472
_exptl_crystal_description       block
_exptl_crystal_F_000             332
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.287
_refine_diff_density_min         -0.204
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.023(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.968
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     165
_refine_ls_number_reflns         2941
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.968
_refine_ls_R_factor_all          0.0247
_refine_ls_R_factor_gt           0.0229
_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^)+(0.0330P)^2^+0.2690P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0559
_refine_ls_wR_factor_ref         0.0569
_reflns_Friedel_coverage         0.854
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                2831
_reflns_number_total             2941
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt03265c2.cif
_cod_data_source_block           va_jom_fc30_06_17_170k_0m
_cod_depositor_comments
'Adding full bibliography for 7048356--7048358.cif.'
_cod_database_code               7048358
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.903
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.977(18)
 0.023(18)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C17) = Uanis(C16) = Uanis(C15) = Uanis(C14) = Uanis(C18) = Uanis(C17A) =
Uanis(C16A) = Uanis(C15A) = Uanis(C14A) = Uanis(C18A)
4. Others
 Sof(C17A)=Sof(H17A)=Sof(C16A)=Sof(H16A)=Sof(C15A)=Sof(H15A)=Sof(C14A)=
 Sof(H14A)=Sof(C18A)=Sof(H18A)=1-FVAR(1)
 Sof(C17)=Sof(H17)=Sof(C16)=Sof(H16)=Sof(C15)=Sof(H15)=Sof(C14)=Sof(H14)=
 Sof(C18)=Sof(H18)=FVAR(1)
5.a Riding coordinates:
 N1(H1)
5.b Ternary CH refined with riding coordinates:
 C6(H6)
5.c Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B)
5.d Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2), C3(H3), C4(H4), C8(H8), C9(H9), C10(H10), C11(H11), C17(H17),
  C16(H16), C15(H15), C14(H14), C18(H18), C17A(H17A), C16A(H16A), C15A(H15A),
 C14A(H14A), C18A(H18A)
5.e Fitted pentagon refined as free rotating group:
 C17(C16,C15,C14,C18), C17A(C16A,C15A,C14A,C18A)
;
_olex2_submission_special_instructions 'No special instructions were received'